Production of 1,4 - Butanediol From Renewable Resources

Production of 1,4-Butanediol from
Renewable Resources
Hamed Al-Jabri 12131822

Diarmaid Beecher 14170604
Mark Fitzpatrick 14159198
Ryan Kiernan 14141248
Eoin Sheehan 14154579
Chemical & Biochemical Engineering, LM115

Final Year Design Project, CG4097/98
University of Limerick, 2018
Date Submitted: April 2018
Acknowledgements
We would like to acknowledge the following people for their advice and support
throughout the course of this design project, without which, this design project
would not have been possible:
Prof. Åke C Rasmuson
Dr. Witold Kwapinski
We would all like to thank our families & friends for their support throughout the
course of this project.
Finally we would like to acknowledge Mr. Edmond Kennedy for his insight into
industrial practices.
-1-
Introduction
The following report was produced with the intention to provide value and guidance in the
situation of the production of a 1,4-butanediol processing plant. BDO is an important
intermediate in the production of polymers like PBT, and PBS, and of solvents like THF. In
the scenario where an individual may be interested in investigating the possibility of creating
the processing plant, he/she will look to see the feasibility, locations, sources, unit operations,
costs, utilities, profits and investments necessary.
From this report, it will be evident what the possible alternatives to produce BDO will be, with
a background into the alternative raw materials and locations, detailed analysis on unit
operations, mass and energy balances, process controls, health and safety, environmental
analysis and a detailed economic and cost analysis.
The chosen process was done so with cost, time, efficiency and yield being taken into
consideration. Chapter 1 shows several locations that were investigated to locate the
manufacturing plant, taking the source of raw material into consideration and distance to the
market. Along with this, a number of potential avenues were investigated to produce the final
product, via different pre-treatment processes, purification and synthesis routes. All are
essential in determining the most efficient, and cost effective route.
-2-
Abstract
The following Design Project Report has been completed as part of the Final Year Chemical
and Biochemical Engineering Design Project for the B.Eng. in Chemical & Biochemical
Engineering. This is a group project and aims to give the students the opportunity to experience
a realistic design process, work as a team and to utilise the skills and knowledge that has been
obtained over the past four years throughout the degree programme.
The report is based on the design a plant for the production of 1, 4-butanediol, from renewable
resources. 1, 4-butanediol (BDO) is an important intermediate in the production of polymers
like polybutylene terephthalic acid (PBT) and polybutylene succinate (PBS), and of solvents
like tetrahydrofuran (THF). BDO can be obtained by the conversion of succinic acid, which is
one of the most attractive platform chemicals for establishing the ‘green’ chemical industry.
For the following report, Corn Stover, a non-edible renewable resource was chosen.
With several processing routes to choose from, our group decided to choose the Davy Method
for the production of BDO from succinic acid. Four steps are undertaken in this method: Two
esterification steps of succinic acid to the to the intermediary dimethyl succinate, followed by
two Hydrogenolysis steps to convert this ester to our desired product of 1,4-butanediol.
The full process from start to finish is discussed, including the design of an Ammonia Fibre
Expansion pre-treatment process to expose the desired glucan and later converted to glucose;
a fermenter to convert the glucose to succinic acid; a crystalliser to purify the produced succinic
acid; a fixed bed reactor for the esterification of succinic acid; and a Plug Flow Reactor for the
Hydrogenolysis of dimethyl succinate and purification of our product, 1,4-butanediol.
With corn stover being our raw material of choice, this with a large market for BDO in the
USA is the incentives to locate in Iowa, USA. Utilising stover for succinic acid production has
the benefits of avoiding competition with food production, being relatively cheap and widely
available, and giving the highest succinic acid concentration, productivity, and yield out of all
researched raw materials. The United States and China were the top two producers of corn at
360,302 and 215,000 MT respectively in 2017, justifying our choice to locate in the US.
The production rate of our BDO works out to be 70227 tonne per annum with the selected
process. These results in 287,000 tonne of raw material (corn stover) needed per annum. After
the economic analysis was conducted, the selling price of BDO worked out to be $3.25/kg with
a production cost of $0.92 per kg. A total net cash flow at the end of the projected 10 years is
estimated to be $468,000,000.
Material and energy integration was an important factor to consider when designing the
process, to ensure maximum efficiency for the production plant. Throughout our process, lines
with steam were redirected to be further utilised in heating for other operations. As well as this,
a by-product of the pre-treatment process, lignin, will be retrieved and sold.
-3-
Chapter 1 Literary Review ...................................................................................................5
Chapter 2 Process Description ........................................................................................ 22
Chapter 3 Mass & Energy Balances ............................................................................... 31
Chapter 4 Individual Unit Operation ............................................................................ 61
Chapter 4.1 Design of an Ammonia Fibre Expansion Unit for Pre-Treatment of Corn
Stover ................................................................................................................................... 62
Chapter 4.2 Design of a Semi-Batch Fermenter for the Fermentation of Succinic Acid88
Chapter 4.3 Design of a Batch Cooling Crystallizer for the Purification of Succinic Acid
............................................................................................................................................ 104
Chapter 4.4 Design of a Catalytic Fixed Bed Reactor for the Esterification of Succinic
Acid to Dimethyl Succinate .............................................................................................. 128
Chapter 4.5 Design of a Continuous Plug Flow Reactor for the Hydrogenolysis of
Dimethyl Succinate to 1,4-Butanediol ............................................................................ 143
Chapter 5 Process Control ............................................................................................. 164
Chapter 6 Health & Safety and EIA ............................................................................. 178
Chapter 7 Economics ........................................................................................................ 200
Chapter 8 Conclusion ....................................................................................................... 215
-4-
Chapter 1 Literary Review
Author: All Members
1.1 Description of Products .................................................................................................7
1.1.1 1,4-Butanediol ............................................................................................................... 7
1.1.2 Succinic Acid ................................................................................................................ 8
1.2 Synthesis Routes ...............................................................................................................9
1.2 1 Current Industrial Standard ........................................................................................... 9
1.2.2 Fermentation via E. Coli ............................................................................................. 10
1.2.3 Fermentation via A. Succinogenes .............................................................................. 10
1.2.4 Ruthenium Nanoparticles Catalysed Hydrogenation of Succinic Acid ...................... 11
1.2.5 Davy Method of Succinic Acid to 1,4-butanediol: ..................................................... 11
1.3 Methods of Pre-Treating ............................................................................................ 12
1.3.1 Liquid Hot Water (LHW) ............................................................................................ 12
1.3.2 Milling ......................................................................................................................... 12
1.3.3 Alkaline Hydrolysis (NaOH/Ca(OH)2/AFEX)............................................................ 12
1.4 Environmental Benefits of Bio-Based BDO ........................................................ 12
1.5 Biomass Selection.......................................................................................................... 13
1.5 1 Wheat .......................................................................................................................... 13
1.5.2 Cane Molasses ............................................................................................................. 14
1.5.3 Corn Stover ................................................................................................................. 14
1.6 Plant Location ................................................................................................................ 15
1.7 Processing Overview.................................................................................................... 16
1.7.1 Corn Pre-treatment ...................................................................................................... 16
1.7.2 Corn Fermentation....................................................................................................... 16
1.7.3 Succinic Acid Purification .......................................................................................... 17
1.7.4 Succinic Acid Esterification ........................................................................................ 17
1.7.5 Hydrogenolysis of Dimethyl Succinate ...................................................................... 17
1.8 Market for BDO............................................................................................................... 18
1.9 Plant Size ........................................................................................................................... 19
1.10 References ..................................................................................................................... 20
-6-
1.1 Description of Products
1.1.1 1,4-Butanediol
1,4-butanediol (BDO) is a colourless, viscous liquid, industrially used as a solvent and in the
manufacture of plastics, polyurethanes, γ-butyrolactone, and elastic fibres such as those in
Spandex. In the presence of phosphoric acid and high temperature, it dehydrates to the
important solvent tetrahydrofuran (THF)[1]. BDO has a molecular formula of C4H10O2 or
HO(CH2)4OH and a molecular weight of 90g/mol. 1,4-butanediol is classified as a subclass of
alcoholic compounds called diols, which are named due to the presence of two alcohol (OH-)
substitutions in their structure. 1,4-butanediol is named for this reason, with the alcohol
substitutions located at R1 and R4.[2, 3]
Figure 1.1: Uses of 1,4-Butanediol
-7-
1.1.2 Succinic Acid
Succinic acid, a water soluble, colourless crystal, also known as butanedioc acid or 1,2-
ethanedicarboxylic acid occurs in nature in various forms of its ester. With a molecular formula
of C4H6O4, boiling point of 235°C, melting point of 184°C and a weight of 118.088g/mol,
succinic acids main purpose is a chemical intermediate, in medicine, the manufacture of
lacquers, and to make perfume esters. Before modern manufacturing practices, succinic acid
was manufactured by catalytic hydrogenation of maleic anhydride. [4]
Figure 1.2: Succinic Acid Derivatives [5]
‘Bio-based succinic acid’ has the same the chemical equivalence to conventionally produced
succinic acid, and is suitable for the same applications. Most importantly, bio-based succinic
production avoids the use of the fossil fuel route and instead takes advantage of fermentation
process. Fermentation is an energy-deriving reaction, and is more specifically carried out by
bacterial and fungal cells that pose specific genes necessary. [5]
-8-
1.2 Synthesis Routes
Figure 1.3: Schematic of BDO synthesis routes
1.2.1 Current Industrial Standard

The industry standard for manufacturing 1,4-butanediol is based on Reppe Chemistry. This is
the original method of production and requires the use of fossil fuels. Acetylene, derived from
coal, natural gas or oil, is reacted with formaldehyde to form butynediol. This butynediol is
then hydrogenated to form BDO under high pressure. [6]
Figure 1.4: Hydrogenation of Butynediol [1]
From our design brief the aim is to design a plant that produces Bio-BDO by using renewable
resources. This is the petrochemical method so it is automatically disqualified from being used
in our plant.
-9-
1.2.2 Fermentation via E. Coli
There have been several reports into the first direct bio-catalytic routes to BDO from renewable
carbohydrate feedstocks, leading to a strain of escherichia coli capable of producing 18 g l−1
of this highly reduced, non-natural chemical. In these studies, an accurate genome-scale
metabolic model of E.coli along with bio-pathway prediction algorithms were used to prioritize
specific BDO pathways that are predicted to lead to optimal performance.
E.coli synthesis of 1,4-butanediol entails the reduction of highly oxidized starting material,
carbohydrates, into a more reduced target molecule. [7]
When using corn stalk hydrolysate as the substrate; E. coli gave a succinic acid concentration
of 36.55 g L-1, productivity of 0.508 g L-1 h-1, and yield of 0.83 g g-1, whereas Actinobacillus
succinogenes gave a succinic acid concentration of 66.2 g L-1, productivity of 0.66 g L-1 h-1,
and yield of 1.38 g g-1.
BDO is a non-natural compound not synthesized by any known organism, so there are no
complete biosynthetic pathways that would be suitable or relevant for BDO production in our
report. For this reason, this specific synthesis route was discarded.
Figure 1.5: BDO biosynthetic pathways introduced into E. coli
1.2.3 Fermentation via A. Succinogenes

Research into using E. coli as a fermentation bacteria showed succinic acid concentration,
productivity, and yields to be lower than that of the method using genetically modified bacteria
designed to produce succinic acid. When using corn stalk hydrolysate as the substrate; E. coli
gave a succinic acid concentration of 36.55 g L-1, productivity of 0.508 g L-1 h-1, and yield of
0.83 g g-1 substrate, whereas Actinobacillus succinogenes gave a succinic acid concentration
of 66.2 g L-1, productivity of 0.66 g L-1 h-1, and yield of 1.38 g g-1 substrate. Production of 1,4-
butanediol using Actinobacillus Succinogenes as the bacteria requires two stages with succinic
acid as an intermediary. The first stage in this process is the fermentation of glucose to produce
succinic acid followed by a hydrogenation reaction to produce 1,4-butanediol. We have chosen
this method as it fulfils the scope of our design brief, rates of conversions are high and it is a
new emerging technology that is still to be fully developed. Each stage of the process is further
- 10 -
developed further down in this report. Bio-based succinic acid is produced from the most
abundant sugars present in the plant biomass, most commonly glucose. [4]
1.2.4 Ruthenium Nanoparticles Catalysed Hydrogenation of Succinic Acid

Ruthenium is very well known active material in the hydrogenation of several chemicals and
several papers discussed its size-dependent surface atomic numbers of its hydrogenation
activity. Chung [8] reported the successful use of Ru NPs/SiO2 for the hydrogenation of
succinic acid directly to 1,4-butanediol (BDO), with the selectivity to BDO controllable by
adjusting the reaction temperature. No kinetic data was published using this direct pathway,
and due to the high cost of large quantities of ruthenium ($7,000 per kg), this process was not
selected.
1.2.5 Davy Method of Succinic Acid to 1,4-Butanediol:

Johnson Matthey developed a two-step process for the conversion of succinic acid to 1,4-
butanediol. The succinic acid first under goes esterification to dimethyl succinate, at low
temperature followed by a high temperature hydrogenolysis to 1,4-butanediol. The purpose of
the esterification step is to convert the acidic feed to a non‐acidic intermediate ester, which is
much easier to convert to 1,4-butanediol compared to the acidic feed. This two-step method
requires two reaction vessels and purification processes, but utilises relatively cheap catalysts
to balance the additional vessel capital costs. [9] Thus this method has been selected for our
processing plant.
- 11 -
1.3 Methods of Pre-Treating
1.3.1 Liquid Hot Water (LHW)
Involves pre-treatment by direct contact with compressed water at high temperature and
pressure. Carried out for up to 15 min between 200-230°C. Results in complete hemicellulose
removal and up to 60% lignin removal. Disregarded by the group due to the unfavourably high
loss of cellulose (up to 22%) and overall loss of biomass (40% to 60%). [10]
1.3.2 Milling
“The size reduction is a necessary step to eliminate mass and heat-transfer limitations during
hydrolysis reactions”. Literature indicated that milling was necessary for good hydrolysis
downstream. It also increases the surface area of solids. [11]
1.3.3 Alkaline Hydrolysis (NaOH/Ca(OH)2/AFEX™):

Most effective for lignin removal. Calcium or sodium hydroxide hydrolysis occurs under
relatively mild conditions, resulting in elongated reaction times [12].
1.4 Environmental Benefits of Bio-Based BDO

There is many environmental benefits of producing Bio-BDO over traditional acetylene.
Estimates made by Novament, an Italian producer of Bio-BDO, suggests a 56% reduction in
greenhouse gas emissions versus conventional processes. This is more conservative than a 2015
report submitted by E4Tech Consultancy to the European Commission Director General for
Energy suggesting a decrease in CO2 emissions of 70-117% compared to petro-based BDO. A
2006 report (The BREW Project) into the production of bulk chemicals from biologic feedstock
prepared under the European Commission’s GROWTH Programme reported a 30% saving in
Non-Renewable Energy Use when producing Bio-BDO at the time of writing their report. They
also predicted a future saving of up to 60%, which is in agreement with E4Tech reporting
preliminary life cycle assessments to indicate that bio-based BDO may use 60-87% less fossil
energy. Further, the bio-based fermentation process requires no organic solvent and can use
recycled water, further improving its environmental credentials. [13]
- 12 -
1.5 Biomass Selection
Theoretically, any raw biomass can be used to produce succinic acid. However, each biomass
brings with it a different concentration, productivity and yield for succinic acid, which is why
each must be studied to determine the most efficient and suitable feedstock.
1.5.1 Wheat
Wheat straw is a major cereal crop, and provides a staple food for humans and animals around
the globe. The global production of dry wheat is about 529MMT. Asia and Europe are the
primary production regions, with 43% and 32% respectively. The average yield of wheat
production in China averages at 3.4 dry Tonnes ha-1. [14]
Figure 1.6: Types of Cereals produced in the E.U. [15]
Wheat constitutes an ideal source for feedstock production as it contains all the necessary
nutrients to induce microbial growth and product formation. [16] However, the main drawback
is wheats consumption in the food industry and production is not at the same level for all
countries worldwide. In total, the required amount of wheat was 82.1% of the annual world
consumption, meaning that this magnitude renders the exploitation of the current world wheat
supplies, as the primary use of wheat is in the food industry. [15]
Furthermore, a second drawback is that hinders the implementation of wheat for chemical
production is it low annual reserves. [15] Past trends have shown annual disappearances of
wheat production, so there is no guarantee of a safe and secure supply of the feedstock.
The average price per kg of wheat is $0.145, giving it some economic advantage over glucose
syrup and sucrose, which are $0.580/kg and $0.261/kg respectively. [14]
- 13 -
1.5.2 Cane Molasses
A strong candidate for the manufacture of 1,4-butanediol is the cane molasses. Brazil is seen
as the favoured location for sourcing this product as it leads the world in production of sugar
cane - cane molasses being a by-product of the sugar-cane plant. The USDA estimated that in
2016/17 production would peak at 680MMT.[17] Cane molasses have a sugar content of about
50% of which 80% can be converted succinic acid during fermentation. [18] The cost of
purchasing sugar cane is approximately $22.68/ton.[17] This sugarcane is processed by cutting
the stalks and roller pressing the juice out of the pulp, carbon dioxide and milk are the added
to the juice to remove non-sugar plant materials, water is removed under a vacuum to leave a
syrup, this syrup is fed seed crystals to promote crystal growth, and finally is centrifuged
splitting the sugar from the molasses. Purchasing processed cane molasses would cost
$210/tonne. [19]
The processing of sugar cane would add unnecessary complexity to the pretreatment, in
comparison to that of other raw materials, while costing more compared to raw materials, i.e.
wheat has an approximate price of 140$/ tonne. Using molasses would also interfere with the
food market as molasses is used in foodstuffs. [20]
1.5.3 Corn Stover

When harvesting corn, the corn stover (consisting of the cobs, husks, stalks, leaves, and tassels
of the corn plant) typically is not removed from the field. Utilising stover for succinic acid
production has the benefits of avoiding competition with food production, being relatively
cheap and widely available, and giving the highest succinic acid concentration, productivity,
and yield out of all researched raw materials. Other uses for corn stover are for bioethanol
production and fibreboard. [21]
The drawback of using corn stover, however, is that when it is removed, nutrients that would
otherwise be returned to the soil are also removed. A suggested remedy for this is that the value
of these nutrients would be calculated into the value of the corn stover, and using a price index
to vary the price of corn stover with that of fertiliser.
In terms of production, the United States and China were the top two producers of corn at
360,302 and 215,000 MT respectively in 2017.[22] China varies between being the second
largest exporter of corn and being a significant importer, this is dependent on government
policy as corn prices are typically higher than the rest of the world. [23] Despite China currently
having a large production of corn and being the biggest consumer of 1,4-butanediol, we chose
to source our raw material from the American Midwest for a stable supply of stover. To lower
transport costs for our raw material we also chose to locate our plant in the Midwest, this also
gives the advantage of a stable market for our 1,4-butanediol.
- 14 -
.
Figure 1.7: Corn production by county, USDA 2016
1.6 Plant Location

For our plant location we chose to base our plant in the state of Iowa. As seen in Figure 1.7
Iowa is in the centre of the “corn belt” region of the United Stated and has much of the state
area producing corn, this gives the advantage of reducing transport time, costs, and
emissions. Locating our plant in Iowa also gives the advantage of a stable market for our 1,4-
butanediol (Chapter 1.8), and for exporting our product abroad we have the option of using
ports at Chicago, Illinois, or St. Louis, Missouri.
Figure 1.8: Iowa Location [24]
- 15 -
1.7 Processing Overview
1.7.1 Corn Pre-treatment
Alkaline pre-treatment is one of the several chemical pre-treatment technologies that employs
various alkaline reagents including sodium hydroxide, calcium hydroxide, potassium
hydroxide, ammonia hydroxide and sodium hydroxide. The process involves the breakdown of
the interior linkages in lignin and glyosidic bonds, and is most effective in agricultural residues
as the lignin content is lower. [25] For the selected pre-treatment process for our design process,
ammonia will be the reagent used, in an AFEX process (ammonia fibre expansion). The AFEX
pre-treatment will improve the accessibility of cellulose and hemicelluloses to enzymes during
hydrolysis by breaking down the ester linkages and other lignin carbohydrate complex (LCC)
bonds and the sugar produced by this process is found to be highly fermentable.
Figure 1.9: Inner linkages of the corn stover biomass exposed via pre-treatment
There are certain parameters that must be met to ensure an efficient and successful pre-
treatment. These include having the reactor condition between 60-100oC, with an ammonia to
biomass ratio of 1:1. The internal pressure must be increased to 21bar, which will allow the
above mechanism to take place, and expose the inner sugars. The residence time will be
calculated in detail in Chapter 4.1, and will be determined to ensure maximum efficiency for
the pre-treatment process. [26]
1.7.2 Corn Fermentation

The fermentation of glucose into succinic acid is a function of the Tricarboxylic Acid cycle of
which succinic acid is a metabolite, Figure 1.10. In theory this method can produce 2 moles of
succinic acid from one mole of glucose in the presence of carbon dioxide. In reality side
products are formed in the process which are composed of acetic acid, lactic acid, and formic
acid. [27]
- 16 -
Figure 1.10: A. Succinogenes production pathway [28]
1.7.3 Succinic Acid Purification

The fermentation procedure produces a large feed from which the succinic acid must be
purified. This feed is composed of succinic acid, acetic acid, lactic acid, and formic acid
dissolved in water. It is essential to remove these impurities so that pure succinic acid can be
supplied to the esterification. Reduction of pH to 1.5 decreases the solubility of succinic acid
without reducing the solubility of the other components allowing for selective crystallization
of succinic acid with a 99.99% purity. [4]
1.7.4 Succinic Acid Esterification

The first reaction with methanol
converts the SA feed to a mono‐ester.
The mono‐ester then further reacts with
the excess of methanol to form dimethyl
succinate.[9]
1.7.5 Hydrogenolysis of Dimethyl Succinate

The second stage in 1,4-butanediol production is hydrogenolysis and hydrogenation of the
dimethyl ester. This again takes place in two steps:
Dimethyl succinate undergoes
hydrogenolysis to form another
intermediary M4-HB releasing
methanol that will be recycled back into
the esterification step. [9]
Subsequent hydrogenation of methyl
4-hydroxybutanoate produces the
desired 1,4-butanediol, and releasing
methanol. [5]
- 17 -
1.8 Market for BDO
Figure 1.11: Global Consumption of 1,4-Butanediol [29]
Consumption of 1,4-butanediol is the highest in China and East Asian nations with a rate of
63%, followed by the United States and then Europe. [29] In 2013, the global output of BDO
was 2 million metric tonnes and this is expected to rise to 3 million metric tonnes by 2024.[30]
This accounts for a consumption of over 320000 tonnes in the US alone. Currently the market
for BDO is valued at $6.19 billion but this value is forecasted to grow at a rate of 7.7%. [31]
The market in the US remains stable whereas China, in 2014, experience a period of
oversaturation with the production outpacing demand causing a collapse in price. [32] This
could happen again making the US to be a suitable market. By producing Bio-BDO production
costs will be 15-30% lower relative to petro-chemically produced BDO and will remain
competitive down to a price of 45$ per barrel of oil. [33] 1,4-butanediol is currently priced at
$3250 per tonne, Figure 1.12, in America. Other solvents that have similar uses include THF,
NMP and 2-Pyrrolidone. The price of these solvents is similar to our product with their prices
being $3307, $2800, and $3000 respectively [29]
- 18 -
Figure 1.12: BDO price per region [29]
1.9 Plant Size

The production rate of our plant is based on other 1,4-butanediol producing companies such as
BioAmber, LyondellBasell, and International Specialty Products Ltd, which have an
approximate annual output of 60,000-70,000 tonnes per year. Accounting for conversion and
material being recycled in the process the estimated corn stover consumed is 287,000 tonnes
per annum. [34, 35]
- 19 -
1.10 References
1. Plotkin, J.S. The Many Lives of BDO. 2016 [cited 2017 20 September]; Available
from: https://www.acs.org/content/acs/en/pressroom/cutting-edge-chemistry/the-
many-lives-of-bdo.html.
2. psychonautwiki. 1,4-Butanediol. Available from: https://psychonautwiki.org/wiki/1,4-
Butanediol.
3. PubChem. 1,4-butanediol. [cited 2017 25 September].
4. Sudeep Vaswani. Process Economic Programe review: Bio-based Succinic Acid.
2010; Available from: https://www.ihs.com/pdf/RW2010-
14_220240110917062932.pdf.
5. Ebert, J. The Quest to Commercialize Biobased Succinic Acid. Biomass Magazine;
Available from: http://biomassmagazine.com/articles/1228/the-quest-to-
commercialize-biobased-succinic-acid/.
6. Ingram, A. and B. Le. PREP Report: 1,4-Butanediol/Tetrahydrofuran(BDO/THF).
2013 [cited 2017; Available from:
http://thinking.nexant.com/sites/default/files/report/field_attachment_abstract/201304/
2012_3_abs.pdf.
7. Yim, H., et al., Metabolic engineering of Escherichia coli for direct production of 1,4-
butanediol. Vol. 7. 2011. 445-52.
8. Chung, S.H., Hydrogenation of Succinic Acid Using Ruthenium Nanoparticles
Embedded Catalysts. 2012.
9. Johnson Matthey Group, Process description: Butanediol (BDO). 2017: DAVY
website.
10. Harmsen. Literature Review of Physical and Chemical Pretreatment Processes for
Lignocellulosic Biomass Available from:
https://www.ecn.nl/docs/library/report/2010/e10013.pdf.
11. Li, H. Chemical composition and characterization of cellulose for Agave as a fast-
growing, drought-tolerant biofuels feedstock. 2012; Available from:
http://pubs.rsc.org/en/content/articlehtml/2012/ra/c2ra20557b.
12. Schell, D.J. Milling of lignocellulosic biomass. 1994; Available from:
https://link.springer.com/article/10.1007%2FBF02941795#citeas.
13. E4tech, RE-CORD, and WUR, From the Sugar Platform to biofuels and
biochemicals. 2015, Final Report for the European Comission.
14. Kim, S. and B.E. Dale, Global potential bioethanol production from wasted crops and
crop residues. Biomass and Bioenergy, 2004. 26(4): p. 361-375.
15. Eurostat. Agricultural Production - Crops. European Comission October 2016 [cited
2017 1 October].
16. Koutinas, A.A., R. Wang, and C. Webb, Evaluation of wheat as generic feedstock for
chemical production. Industrial Crops and Products, 2004. 20(1): p. 75-88.
17. Barros, S., Global Agricultural Information Network Report on Brazilian Sugar.
2016, USDA Foreign Agricultural Service.
18. Liu, Y.-P., et al., Economical succinic acid production from cane molasses by
Actinobacillus succinogenes. Bioresource Technology, 2008. 99(6): p. 1736-1742.
19. Commodity BR. Sugar Cane Molasses. 2017 [cited 2017 5 October ]; Available
from: https://www.go4worldbusiness.com/pref_product/view/768962/sugar-cane-
molasses.html.
20. Sugar Association. Refining and Processing Sugar. [cited 2017 10 September];
Available from: https://www.sugar.org/images/docs/refining-and-processing-
sugar.pdf.
- 20 -
21. Lin, C.S.K., et al., Wheat-based biorefining strategy for fermentative production and
chemical transformations of succinic acid. Biofuels, Bioproducts and Biorefining,
2012. 6(1): p. 88-104.
22. United States Department of Agriculture. Grain: World Markets and Trade.
September 2017 [cited 2017 3rd October]; Available from:
https://apps.fas.usda.gov/psdonline/circulars/grain-corn-coarsegrains.pdf.
23. Capehart, T. Corn Trade. Thursday, September 14, 2017 [cited 2017 1st October];
Available from: https://www.ers.usda.gov/topics/crops/corn/trade/.
24. Maps.com, U.S. Map United States. Available from: http://www.united-states-
map.com/usa7241z.htm.
25. Chen, Y., et al., Understanding of alkaline pretreatment parameters for corn stover
enzymatic saccharification. Biotechnology for Biofuels, 2013. 6(1): p. 8.
26. Lau, M.W. and B.E. Dale, Cellulosic ethanol production from AFEX-treated corn
stover using Saccharomyces cerevisiae 424A(LNH-ST). Proceedings of the National
Academy of Sciences, 2009. 106(5): p. 1368-1373.
27. Rengesh Balakrishnan. Batch, Fed-Batch, Continuous Cultivation. LinkedIn
SlideShare 2016 [cited 2017 September]; Available from:
https://www.slideshare.net/RengeshBalakrishnan/batch-fedbatch-continuous-
cultivation-57209876.
28. Cheng, K.-K., et al., Biotechnological production of succinic acid: current state and
perspectives. Biofuels, Bioproducts and Biorefining, 2012. 6(3): p. 302-318.
29. IHS Markit. 1,4-Butanedoil. May 2016 [cited 2017 7 September]; Available from:
https://www.ihs.com/products/butanediol-chemical-economics-handbook.html.
30. Sherry James. 1,4 Butanediol Market Demand Expected to Reach 3,030 kilo tons by
2024. LinkedIn Pulse 2017 [cited 2017 28 September]; Available from:
https://www.linkedin.com/pulse/14-butanediol-market-demand-expected-reach-3030-
kilo-tons-james/.
31. Grand View Research, 1,4 Butanediol (BDO) Market Analysis By Application
(Tetrahydrofuran (THF), Polybutylene Terephthalate (PBT), Gamma-Butyrolactone
(GBL), Polyurethane (PU)), By Region (North America, Europe, Asia Pacific, CSA,
MEA), And Segment Forecasts, 2014 - 2025, in Report ID: 978-1-68038-084-2. 2017.
32. Frankly Inc. Butanediol Market 2017-2021 Demand, Trends, Growth and
Manufacturers BASF, Dairen Chemical, LyondellBasell, Ashland Report say a new
Research Report at ReportsnReports. 2017 [cited 2017 25 October]; Available from:
http://www.erienewsnow.com/story/36032909/butanediol-market-2017-2021-
demand-trends-growth-and-manufacturers-basf-dairen-chemical-lyondellbasell-
ashland-report-say-a-new-research-report-at.
33. Tecnon ObiChem. 1,4-Butanediol. Chemical Market Insight And Foresight 2013
[cited 2017 9 September]; Available from:
http://www.orbichem.com/userfiles/CNF%20Samples/bdo_13_11.pdf.
34. Kirschner, M. Chemical Profile: 1,4-Butanediol. ICIS Chemical Business 2009 [cited
2017 15 September]; Available from:
https://www.icis.com/resources/news/2009/03/02/9195785/chemical-profile-1-4-
butanediol/.
35. Bio Amber Inc. Bioamber Secures Best-In-Class Technology For Planned BDO/THF
Plants. 2015 [cited 2017 15 September]; Available from: http://investor.bio-
amber.com/2015-04-08-BioAmber-Secures-Best-In-Class-Technology-for-Planned-
BDO-THF-Plants.
- 21 -
Chapter 2 Process Description
Author: All Members
2.1 Process Flow Diagram ................................................................................................. 24
2.2 Process Description ...................................................................................................... 25
2.2.1 Corn Pre-treatment ...................................................................................................... 25
2.2.2 Fermentation to Succinic Acid & Purification ............................................................ 26
2.2.3 Succinic Acid Esterification ........................................................................................ 27
2.2.4 Hydrogenolysis of Dimethyl Succinate ...................................................................... 28
2.3 Scheduling ........................................................................................................................ 29
- 23 -
2.1 Process Flow Diagram
Hoist
S111
S107 S108
S106
X102
R101
S110
S102 S109 S112
Corn S103 S104
CM101 R102
Stover X101
S101
S105
ST101
Shed H101 S113
S218
S205 S208
S214 S220 S223

S206 S222
S203 S213 LLE201
S212 MX201
X203 ST201 UF202
F201 S215 S216 S217
S204 S211 P201 S221
S207 X205
X204 S219
CR201
S209 S210
ST202 S311
S313
S312
PU303 X303 S309 DC
S307 S308 302
S301 X302
PU302
S310
S304 S306 DC
MX301
S305 301
S303 S316
PU301 R301
S302
S314
DC
X304 S315 303
S319
S318 S317
PU304 X305
X301
S334 S203
X202 S201
S336
S335 X201
S342
Hydrogen VLS302
CM301 S202
CM303
S410
S337
Steam
1,4-butanediol
S320 S404 S402 S338
S339 X308 S333
S323 TV301
S321 S322 DC
S324 S325 S326 S327 S328
X307 304
X306 FU301 S409
R302 VLS301
S340
S403 Condensate
S331
S341 S332 CM302
S329
Figure 2.1: Overall Plant layout
Gold Line Corn stover

Green Line Glucose
Purple Line Succinic acid
Blue Line Dimethyl succinate
Pink Line 1,4-butanediol
- 24 -
2.2 Process Description
2.2.1 Corn Pre-Treatment
Hoist
Enzymes
Ammonia Steam
Out Out
X102
Ammonia
R101 Solid
Waste
In
Corn X103
CM101 Steam R102

Stover X101 in
ST101
Shed H101
Liquid
Product
Figure 2.2: Pre-treatment of corn stover
To produce 1,4-butanediol, the initial processing stages are pre-treatment of the raw material
being used. In our design project, our initial raw material is corn stover. The stover is taken
and pre-treated using an ammonia fibre expansion process. The objective of the pre-treatment
is to break the outer cellulose exterior of the stover, and break the internal covalent cross-
linkages between cell walls. From here, the inner sugars such as glucan and xylan are exposed
and will later be converted to glucose and xylan in the hydrolysis stage of processing.
The initial step is to fill containers with the milled corn stover, via the hopper H101 to a density
of 100kg/m3. From here the containers (five in total) are passed on a conveyor belt to the
reactor, where a latch is opened and containers are hoisted up into the reactor, stacking on top
of each other. The latch is closed once loaded, and all seals closed and locked. As shown in
Figure 2.2, the initial process is a pre-steam through the beds of biomass to heat the biomass
and remove any entrained air. Next ammonia is fed from on-site storage tanks and compressed
to 21 bar. The pressurisation of ammonia increases its temperature to 160°C, so X101 cools it
back to the desired 137°C inlet temperature. The ammonia is held in the AFEX reactor at 21bar
and 137°C for 39 minutes. The ammonia is released back to the on-site storage tank, being
cooled back to 25°C in X102 as it exits R101. Once the vessel is depressurised, a final purge
of steam is passed through to ensure no ammonia is left within the vessel.
After the AFEX process is complete, the biomass is removed and transferred semi-batch
directly into an enzymatic hydrolysis (R102). This process converts the exposed glucan and
xylan to glucose and xylan, using Cellic CTec 3 and Cellic HTec 3 maintained at 50°C for 72
hours. A 90.67% glucan to glucose conversion and a 75.93% xylan to xylose conversion is
obtained. The liquid sugar solution is drained from R102, to the intermediate storage tank
ST101. The solid waste lignin is removed, dried and sold for further processing.
Eoin Sheehan - 25 -
2.2.2 Fermentation to Succinic Acid & Purification
X202
X201
LLE201
X203 F201 ST201
P201 X205
X204
CR201
ST202
Figure 2.3: Fermentation of glucose to succinic acid & its Purification
The function of the fermentation step is to form the intermediate product succinic acid from
glucose. The glucose is fed from ST101 into the fermenter (F201) along with carbon dioxide
and ammonia, and the biological reaction takes place using actinobacillus succinogenes. The
fermentation takes place at 1 bar, 37°C, and takes 48 hours. Any excess carbon dioxide leaves
in the off-gas. There are five fermenters in this step working in parallel, only one is shown in
Figure 2.3. The feed passes through a heat exchanger to raise the feed temperature form
ambient, 25°C, to the required temperature. Cooling is supplied a propylene glycol jacket
which is supplied at 5°C and leaves at 35°C.
The outlet stream passes through a filter where all solid biomass is removed and transferred to
the thermal oxidiser FU201, and the succinic acid containing filtrate is stored in ST201. The
heat generated from the thermal oxidiser (FU201) will be used to create steam which is required
for plant wide heating.
Hydrochloric acid is added in the mixer (MX201) to reduce the pH of the feed from 7 down to
1.5 where crystallization is favoured. This stream is passed along to the crystallizer (CR201)
which operates at atmospheric pressure. The crystallizer operates via cooling mode with the
temperature reduced from 52°C to 20°C. The crystallizer is cooled via propylene glycol being
fed into a cooling jacket at 5°C and exiting at 15°C. Following the crystallization step the
succinic acid crystals are filtered out to be sent to the esterification process. The filtrate is
passed through a liquid-liquid extractor to recover hydrochloric acid which is then recycled
back to the mixer.
Ryan Kiernan - 26 -
2.2.3 Succinic Acid Esterification
Figure 2.4: Esterification reactor & DMS purification flow sheet
The function of the fixed bed reactor (R301) is to convert succinic acid into DMS which is to
be further converted into our desired product 1,4-butanediol downstream.
Succinic acid (SA) crystals, methanol, and recycle streams are mixed in a continuous stirred
tank mixer (MX301). Low solubility of SA in methanol requires an excess of methanol in the
feed (5:1 molar ratio) and mixing temperatures above 50°C. The dissolved SA and methanol is
pumped from the reactor at 300kPa and heated to 90°C in X301, before entering R301.
The reactor outlet contains dimethyl succinate (DMS), intermediary monomethyl succinate
(MMS), unreacted SA and methanol, and water by-product. These components are separated
via three distillation columns. The first distillation column (DC301) separates the low boiling
water and methanol from the high boilers. This water and methanol are cooled in X302 and
enter DC302 to remove the water, which is sent to waste. The methanol leaving the condenser
of DC302 is recycled back to MX301.
The bottoms outlet of DC301 is heated before entering DC303, where the DMS is purified and
sent downstream to the hydrogenolysis. The remaining intermediary MMS and unreacted SA
are cooled in X305 to 60°C and are recycled to MX301 for reprocessing.
Diarmaid Beecher - 27 -
2.2.4 Hydrogenolysis of Dimethyl Succinate
Methanol
X202
DMS X201
X301
CM301 VLS302
Hydrogen CM303
Steam
X308
1,4-
TV301
DC butanediol
X307 304
X306 FU301 R302 VLS301
Condensate
CM302
Figure 2.5: Hydrogenolysis reactor and 1,4-butanediol purification flow sheet
Hydrogenolysis of dimethyl succinate, is the final reaction step in the conversion of raw corn
stover to 1,4-butanediol.
A continuous flow of gaseous dimethyl succinate from the esterification is compressed to 5 bar
in CM301, and is mixed with hydrogen and other gas phase recycled reactants. This stream is
then preheated from 508K to 510K in X306, by cooling the warm reactant coolant exiting the
reactor. The furnace (FU301) burning natural gas then raises the reactor feed to the required
reaction temperature of 545K.
Hydrogenolysis of the DMS takes place in the plug flow reactor R302. DMS reacts with
hydrogen to produce methyl 4-hydroxybutanoate, which subsequently reacts with more
hydrogen, to produce the 1,4-butanediol product, with methanol as the by-product.
On exiting the reactor, the reaction products are cooled to 503K, by preheating the hydrogen
feed in X307. The throttle valve (TR301) then drops the pressure from 4.5 bar to atmospheric.
X308 then cools the reaction products from 503K to 463K condensing out the high boiling
BDO, unreacted DMS and M4HB. The heat released from this condensation is reutilised for
10bar steam production.
The liquid phase components are separated from the highly volatile methanol and hydrogen in
the first vapour liquid separator (VLS301). Liquid phase BDO, M4HB and DMS enters DC304
at 470K. 99% purity BDO exits as the bottoms of DC304, at 483K, where it is cooled to 315K
by X201. The DMS and MHB exits as the vapour distillate from DC304, and is compressed
back to 5 bar in CM302.
The low boiling hydrogen and methanol exit the top of VLS301, and are cooled to 398K by
X201. The partial condenser X202, cools the hydrogen and methanol from 398K to
333k condensing out the lower volatility methanol. The gaseous hydrogen is then removed
from the liquid methanol in VLS302. The methanol is recycled back to MX301 in the
esterification process to be reused. The recycled hydrogen is compressed to 5 bar and is added
to with fresh hydrogen feed, and then preheated in X307 to 477K, before being reused in the
reaction.
Mark Fitzpatrick - 28 -
2.3 Scheduling
The pre-treatment, fermentation, and purification of succinic acid takes place on a batch/fed-
batch basis. The scheduling is based on the fermenter operating and down time which totals 72
hours. This can be seen in Figure 2.6 where the gold bar represents the time from the corn
stover is supplied to the AFEX through to leaving the crystallizer, and the red bar represents
the operations within each unit.
1. AFEX – Each AFEX run takes 1 hour total before being supplied to the Enzymatic
Hydrolysis.
2. Enzymatic Hydrolysis takes 72 hours to complete and operates on a fed batch basis,
therefore 72 runs of the AFEX can be completed to supply the Hydrolysis. The
Hydrolysis is scheduled to start 1 hour after the first AFEX run takes place.
3. The product from the Enzymatic Hydrolysis is transferred to the Storage Tank
(ST101) where the glucose is ready to be added to thon fermenter.
4. All 5 fermenters are fed-batch and feeding of fermenter 1 begins when glucose is in
the storage tank. Each fermenter has a down time of 24 hours to allow for emptying,
cleaning, and any maintenance etc.
5. Each fermenter is staggered so that each begins 6 hours after the previous fermenter
has begun. This is set so that fermenter 5, the last fermenter is finished when the batch
storage in the first storage tank finishes.
6. The operating time for each fermenter is 48 hours and when fermenter 1 finishes it
empties into the second storage tank. Each successive fermenter will finish such that
the tank will be filled within 24 hours.
7. The crystallizer is will begin simultaneously with the storage tank ST201 being filled.
Each cycle of the Crystallizer is calculated to be 5 hours, see Chapter 4.3, therefore
the crystallizer is operated 14 times to empty the storage tank. A downtime of two is
applied to make up time to 72 hours. Any small maintenance can take place during
this time.
8. After crystallization, the esterification & hydrogenolysis are run continuously
therefore scheduling is not required.
Ryan Kiernan - 29 -
day 1 2 3 4 5 6 7 8 9 10 11 day
h 8 16 24 32 40 48 56 64 72 80 88 96 104 112 120 128 136 144 152 160 168 176 184 192 200 208 216 224 232 240 248 256 264 h
Complete Recipe
Ryan Kiernan
AFEX in R101
AFEX AFEX (72.00 h)
EnzHydraul in R102
Enzymatic Hydraulysis Enzymatic Hydraulysis (72.00 h)
Storage 1 in ST 101
Storage Storage (72.00 h)
Fermentation 1 in F201
Fermentation Fermentation (48.00 h)
Downtime Downtime (24.00 h)
Figure 2.6: Scheduling of Batch Operations

Storage 2 in ST 201
Storage Storage (72.00 h)
Crystallizer in CR201
Crystallize Crystallize (70.00 h)
- 30 -
Chapter 3 Mass & Energy Balances
Author: All Members
3.1 Aims..................................................................................................................................... 34
3.2 Assumptions .................................................................................................................... 34
3.3 Abbreviations .................................................................................................................. 34
3.4 Equations .......................................................................................................................... 35
3.5 Calculations ...................................................................................................................... 37
3.5.1 AFEX Reactor R101 ................................................................................................... 37
3.5.2 Enzymatic Hydrolysis R102........................................................................................ 38
3.5.3 Fermenter F201 ........................................................................................................... 39
3.5.4 Filter UF201 ................................................................................................................ 40
3.5.5 Mixer MX201.............................................................................................................. 41
3.5.6 Crystallizer CR201 ...................................................................................................... 42
3.5.7 Filter UF202 ................................................................................................................ 43
3.5.8 Liquid-Liquid Extractor LLE201 ................................................................................ 43
3.5.9 Mixer M301................................................................................................................. 44
3.5.11 Fixed Bed Reactor R301 ........................................................................................... 44
3.5.12 Distillation Column DC301 ...................................................................................... 46
3.5.15 Plug Flow Reactor R302 ........................................................................................... 49
3.5.16 VLE Separator VLS301 ............................................................................................ 49
3.5.18 VLE Separator VLS302 ............................................................................................ 50
3.5.19 Heat Exchangers & Condensers ................................................................................ 51
3.5.20 Pumps ........................................................................................................................ 52
3.5.21 Compressors .............................................................................................................. 53
3.5.22 Throttle ...................................................................................................................... 53
3.5.23 T-Joints ...................................................................................................................... 54
3.6 Overall Mass Balance ................................................................................................... 55
3.7 Mass Integration ............................................................................................................ 56
3.7.1 Recycling ..................................................................................................................... 56
3.7.2 S111 Lignin Waste Stream .......................................................................................... 56
3.7.3 S223 Waste Stream ..................................................................................................... 56
3.7.4 S210 Cell Waste Stream .............................................................................................. 56
3.8 Energy Integration ........................................................................................................ 57
- 32 -
3.9 Steam Requirements .................................................................................................... 58
3.9.1 Condenser X306 .......................................................................................................... 58
3.9.2 S210 Cell Waste Stream .............................................................................................. 59
3.10 References ..................................................................................................................... 60
- 33 -
3.1 Aims
The aims of the Mass & Energy Balances are:
 Quantify the material required by each Unit Operation.
 Quantify the energy required by each Unit Operation.
 Identify any areas where heat can be recycled reducing our energy consumption.
3.2 Assumptions
1. No nuclear reactions take place; thus, mass is conserved.
2. Perfect separation is achieved in filters.
3. No loss of material in piping.
4. 100% Recycle of material can be achieved.
5. Water basis is assumed for the calculation of the required amount of hydrochloric acid.
6. Density of hydrochloric acid is equal to that of water.
7. 100% efficiency in each Unit Operation.
8. Due to a lack of available data, some heat capacities were assumed to be those of similar
compounds.
9. Change in heat capacity due to temperature change is negligible.
10. Change in temperature due to change in pressure through pumps in negligible
11. Heat capacity of hydrochloric acid is equal to water.
12. The thermodynamic properties of hexanoic acid are used in place of methyl-4-
hydroxybutanoate (MHB), due to insufficient information on this rarely used chemical.
3.3 Abbreviations
Full Name Abbreviation
Succinic acid SA
Methanol MeOH
Monomethyl succinate MMS
Dimethyl succinate DMS
Methyl 4-hydroxybutanoate MHB
1,4-butanediol BDO
- 34 -
3.4 Equations
For this report our process was operating at steady state, thus we had no accumulation for any
of our mass & energy balances.
𝑇𝑜𝑡𝑎𝑙 𝑀𝑎𝑠𝑠 𝐼𝑛 = 𝑇𝑜𝑡𝑎𝑙 𝑀𝑎𝑠𝑠 𝑂𝑢𝑡 𝐸𝑞𝑛. 1

1
∆𝐻 + ∆𝑢2 + 𝑔∆𝑧 = 𝑊𝑠 + 𝑄 𝐸𝑞𝑛. 2
2
In this report we assumed no change in elevation or frictional forces, removing the kinetic and
potential energy terms. This left us with enthalpy change, shaft work, and heat transfer as
represented by the following:
∆𝐻 = 𝑊𝑠 + 𝑄 𝐸𝑞𝑛. 3
Eqn. 3 is dependent on the technology that is being used. In the case of a pump, heat transfer
is negligible, Q = 0. Enthalpy change is equal to the volumetric flow times the change in
pressure:
∆𝐻 = 𝑊𝑠 = 𝑉̇ ∆𝑃 𝐸𝑞𝑛. 4
In the case of heat exchangers where no work is performed, Ws = 0. In this case only heat is
changed, therefore the heat supplied is a function of the mass flow, specific heat capacity and
the change in temperature:
𝑛
̇ ∆𝐻̇ = (∑ 𝑚𝑖 𝑐𝑝,𝑖 ) ∆𝑇 𝐸𝑞𝑛. 5
𝑄=
𝑖=1
For vapour-liquid separators and mixing vessels:
∆𝐻 = 0 𝐸𝑞𝑛. 6
For condensers:
𝑄 = 𝑚̇∆𝐻𝑐𝑜𝑛𝑑 𝐸𝑞𝑛. 7
For compressors:
𝛾
𝑊𝑠 = 𝑚̇𝑅𝑇1 [(𝑃2 /𝑃1 )(𝛾−1)/𝛾 − 1 ] 𝐸𝑞𝑛. 8
𝛾−1
𝑃2 𝛾−1
𝑇2 = 𝑇1 ( ) 𝛾 𝐸𝑞𝑛. 9
𝑃1
- 35 -
Hess’s law is used to calculate the total enthalpy of the reaction:
∆𝐻𝑟𝑥𝑛,298 = (∑ 𝑛∆𝐻𝑓,298 ) − (∑ 𝑛∆𝐻𝑓,298 ) 𝐸𝑞𝑛. 10

𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
The above is used with standard enthalpy values at 25°C. We operate significantly above this
temperature throughout the process. In order to account for this change we make use of
Kirchhoff’s Law, describes the enthalpy of a reaction's variation with temperature changes.
𝑇
∆𝐻𝑟𝑥𝑛, 𝑇 = ∆𝐻𝑟𝑥𝑛,298 + ∫ ∆𝐶𝑝 𝑑𝑇 Eq. 11
298
Alternatively if the heat of formation of reactants and products isn’t known then the energy
released when they undergo complete combustion can be used to calculate the enthalpy of
reaction.
∆𝐻𝑟𝑥𝑛 = ∑(𝑛∆𝐻𝑐 )𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 − ∑(𝑛∆𝐻𝑐 )𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝐸𝑞𝑛. 12
Distillation columns:
𝑄𝑟𝑒𝑏𝑜𝑖𝑙 = ∆𝐻𝑣𝑎𝑝 𝐷(𝑅 + 1) + 𝐹(𝐻𝑓𝑠 − 𝐻𝑓 ) 𝐸𝑞𝑛. 13
𝑄𝑐𝑜𝑛𝑑 = −∆𝐻𝑐𝑜𝑛𝑑 𝐷(𝑅 + 1) 𝐸𝑞𝑛. 14

Where:
𝐹(𝐻𝑓𝑠 − 𝐻𝑓 ) = 𝑚̇𝐶𝑝 (𝑇𝑏 − 𝑇𝑓 ) 𝐸𝑞𝑛. 15
D Top product kmol/s

R Reflux ratio
F Feed kmol/s
- 36 -
3.5 Calculations
3.5.1 AFEX Reactor R101
Figure 3.1: AFEX Reactor R101
Mass Balance
AFEX reactor is operated at a rate of 1 batch per hour.
In
Stream Corn Stover, Ammonia, Steam, Total,
kg/h kg/h kg/h kg/batch
S101 35288 -- -- 35288
S104 -- 35288 -- 35288
S105 -- -- 20919.6 20919.6
Out
Stream Glucan, Xylan, Ammonia, Steam, Other, Total,
kg/h kg/h kg/h kg/h kg/h kg/batch
S106 -- -- 35288 -- -- 35288
S108 -- -- -- 20919.6 -- 20919.6
S109 15725 4881.3 -- -- 14643.7 35250
This unit op is covered in greater detail in Chapter 4.1.
- 37 -
3.5.2 Enzymatic Hydrolysis R102
Figure 3.2: Enzymatic Hydrolysis R102
Mass Balance
Enzymatic Hydrolysis is operated on a fed batch basis for 72 hours
In
Stream Glucan, Xylan, Other, Enzymes Total Total
kg/h kg/h kg/h kg/h kg/h kg/batch
S110 15725 4881 14643 -- 35250 2538000
S111 -- -- -- 60 60 4323
Out
Stream Glucose Xylose Other Lignin Total
kg/batch kg/batch kg/Batch kg/Batch kg/Batch
S112 -- -- 187646 855979 1047956
S113 1029146 266853 198367 -- 1494367
Energy Conversion
The energy conversion in R102 is detailed in Chapter 4.1.
- 38 -
3.5.3 Fermenter F201
Figure 3.3: Fermenter F201
Refer to Chapter 4.2: Unit Operation for more information

Mass Balance
In (kg/batch)
Stream Glucose Water Ammonia CO2 Total
S205 258025 761785 1019810
S206 63200 63200
S207 48783 48783
Total 1131793
Out (kg/batch)
Stream Biomass Water Succinic Acetic Lactic Formic CO2 Total
Acid Acid Acid Acid
S208 168 168
S209 20273 873600 174720 40547 12533 9952 1131625
- 39 -
Energy Conversion
Molar Mass,
Component Δhc, MJ/kmol nΔhc, MJ
kg/kmol
Glucose 180 -2805 -4020893
Water 18 - -
Ammonia 17 -382.6 -1097909
CO2 46 - -
Biomass 25.2 -552 -444084
Succinic Acid 118 -1491 -2207691
Acetic Acid 60 -874.2 -591240
Lactic Acid 90 -1368.3 -190537
Formic Acid 46 -254.6 -55084
∑(𝑛∆ℎ𝑐 )𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = − 4020893 − 1097909 = −5118802𝑀𝐽
∑(𝑛∆ℎ𝑐 )𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 = − 444084 − 2207691 − 591240 − 190537 − 55084 = 3488636𝑀𝐽
∆𝐻𝑟𝑥𝑛 = −5118802 − (−3488636) = −1630166𝑀𝐽

1630166
𝑄 = −∆𝐻𝑟𝑥𝑛 = 1630166𝑀𝐽 = = 9.434𝑀𝑊 𝑝𝑒𝑟 𝑓𝑒𝑟𝑚𝑒𝑛𝑡𝑒𝑟
48 ∗ 3600
This unit op is covered in greater detail in Chapter 4.2.
3.5.4 Filter UF201

Mass Balance
Perfect separation is achieved in filters, therefore all biomass is removed. As shown in the table
below.
In (kg/batch)
Stream Biomass Water Succinic Acetic Lactic Formic Total
Acid Acid Acid Acid
S209 20273 873600 174720 40547 12533 9952 1131625
Out (kg/batch)
Stream Biomass Water Succinic Acetic Lactic Formic Total
Acid Acid Acid Acid
S210 20273 20273
S211 873600 174720 40547 12533 9952 1111352
Energy Conversion
No energy conversion takes place in UF201.
- 40 -
3.5.5 Mixer MX201
Mass Balance
Hydrochloric Acid must be added to the crystallizer feed in order to reduce the pH to 1.5 where
crystallization of succinic acid is favored. At this point succinic acid is only 4% miscible
whereas all other organic acid are completely immiscible. The amount of hydrochloric acid
required is calculated below.
A water basis is assumed for this calculation:
10−𝑌 − 10−𝑋
𝑄𝑢𝑎𝑛𝑡𝑖𝑡𝑦 𝐻𝐶𝑙 𝑛𝑒𝑒𝑑𝑒𝑑 =
10−𝑍 − 10−𝑋
Where X=pH of Original Solution, Y=pH required, Z=pH of HCl added.
10−1.5 − 10−6.5 𝐿 𝐻𝐶𝑙 𝐾𝑔 𝐻𝐶𝑙
𝐻𝐶𝑙 = = 0.316 = 0.316
10−1 − 10−6.5 𝐿 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝐿 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛
1L of Water = 1Kg of Water → 1000/18=55.55 Moles/Liter
𝐾𝑔 𝐻𝐶𝑙
0.316
𝐿 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 0.57 𝐾𝑔
𝑀𝑜𝑙𝑒𝑠 𝐾𝑚𝑜𝑙𝑒
55.55 𝐿𝑖𝑡𝑟𝑒
Molar mass of solution is 21.79 Kg/Kmole

𝐾𝑔 𝐻𝐶𝑙
0.57
𝐾𝑚𝑜𝑙𝑒 = 0.026 𝐾𝑔 𝐻𝐶𝑙
𝐾𝑔 𝐾𝑔 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛
21.79
𝐾𝑚𝑜𝑙𝑒
𝐻𝐶𝑙 𝑝𝑒𝑟 𝐶𝑦𝑐𝑙𝑒 = 0.026 ∗ 396911.379 = 10368𝐾𝑔 𝐻𝐶𝑙
In
Stream Water, Succinic Acetic Lactic Formic HCl, Total,
kg Acid, kg Acid, kg Acid, kg Acid, kg kg kg
S213 312000 62400 14481 4476 3554 396911
S214 208 208
S221 10160 10160
Out
S215 312000 62400 14481 4476 3554 10368 407279
- 41 -
3.5.6 Crystallizer CR201
Mass Balance
In
Stream Water, Succinic Succinic Acetic Lactic Formic HCl, Total,
kg Acid, kg Acid Acid, Acid, Acid, kg kg
Crystals, kg kg kg
kg
S216 312000 62400 14481 4476 3554 10368 407279
Out
Stream Water, Succinic Succinic Acetic Lactic Formic HCl, Total,
kg Acid, kg Acid Acid, Acid, Acid, kg kg
Crystals, kg kg kg
kg
S217 312000 4342 58058 14481 4476 3554 10368 407279
Energy Balance
The crystallizer requires 3172kW of heat to be removed to reduce the solution temperature
from 50°C to 20°C. This was calculated in detail in Chapter 4.3.
- 42 -
3.5.7 Filter UF202
Mass Balance
Perfect Separation is achieved in filters, therefore all crystals are separated.
In (x103 kg)
Stream Water Succinic Succinic Acetic Lactic Formic HCl Total
Acid Acid Crystals Acid Acid Acid
S217 312 4.3 58 14.5 4.4 3.5 10.4 407
3
Out (x10 kg)
Stream Water Succinic Succinic Acetic Lactic Formic HCl Total
Acid Acid Crystals Acid Acid Acid
S219 312 4.3 14.5 4.4 3.5 10.4 349
S218 58 58
Energy Conversion
No energy conversion takes place in UF202.
3.5.8 Liquid-Liquid Extractor LLE201

Mass Balance
The addition of extraction solvent TDA has the ability to separate 98% of Hydrochloric Acid
from the filtered solution. The recommended quantity of extraction solvent to be used is
Vorg/Vaq = 1.5
349221
𝑉𝑜𝑟𝑔 = 1.5𝑉𝑎𝑞 = 1.5 ( ) = 406.7𝑚3
1288
𝑀𝑎𝑠𝑠 = 406.7 ∗ 810 = 329428.19𝐾𝑔
𝐻𝐶𝑙𝑒𝑥𝑡𝑟𝑎𝑐𝑡 = 10368 ∗ 0.98 = 10160.64𝐾𝑔
𝐻𝐶𝑙𝑟𝑎𝑓𝑓 = 10368 ∗ 0.2 = 207.36 𝐾𝑔

In x103
Stream Water, Succinic Acetic Lactic Formic HCl, TDA, Total,
Kg Acid, Acid, Acid, Acid, Kg Kg Kg
Kg Kg Kg Kg
S219 312 4.342 14.481 4.476 3.554 10.368 349.221
S220 329.428 329.428
Out x103
S223 312 4.342 14.481 4.476 3.554 .208 339.061
S222 329.428 329.428
S221 10.16 10.16
- 43 -
3.5.10 Mixer M301
Mass Balance
In
Stream Succinic Methanol, Water, MMS, DMS, Total,
Acid, Kg/s Kg/s Kg/s Kg/s Kg/s Kg/s
S301 3.126 3.126
S302 0.006 0.006
S313 2.589 0.015 2.604
S342 1.689 1.689
S319 0.032 0.304 0.336
Out
Acid, Kg/s Kg/s Kg/s Kg/s Kg/s Kg/s
S303 3.158 4.284 0.015 0.304 7.761
Energy Conversion
All streams are 60°C entering mixer. No energy calculations required
3.5.11 Fixed Bed Reactor R301
Figure 3.4: Reactor R301
See Chapter 4.4: Unit Operation for further information

Mass Balance
Reactor R301 is an esterification reactor used to convert succinic acid (SA) to dimethyl
succinate (DMS). This this is a two-step reaction where SA is first converted to monomethyl
succinate (MMS) which is then further reacted to form DMS. 99% Conversion of SA is
achieved, with a selectivity to DMS of 92%, the remaining 8% stays as the intermediary MMS
and is later recycled.
Reaction step 1: SA + 𝑀𝑒𝑂𝐻 → 𝑀𝑀𝑆 + 𝐻2 𝑂
Reaction step 2: 𝑀𝑀𝑆 + 𝑀𝑒𝑂𝐻 → 𝐷𝑀𝑆 + 𝐻2 O
- 44 -
Reaction Step 1:
99% of the SA is reacted with one mole of methanol generating one mole MMS and one mole
of H2O.
𝑆𝐴 𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 = (0.032 + 3.126) ∗ 0.99 = 3.126 𝑘𝑔/𝑠
32
𝑀𝑒𝑂𝐻 𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 (1) = 3.126 ∗ = 0.848 𝑘𝑔/𝑠
118
132
𝑀𝑀𝑆 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = 3.126 ∗ = 3.497 𝑘𝑔/𝑠
118
18
𝐻2 𝑂 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 (1) = 3.126 ∗ = 0.477 𝑘𝑔/𝑠
118
Reaction Step 2:
92% of the MMS is reacted with one mole methanol generating one mole DMS and one mole
H2O.
𝑀𝑀𝑆 𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 = (0.304 + 3.497) ∗ 0.92 = 3.497 𝑘𝑔/𝑠
32
𝑀𝑒𝑂𝐻 𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 (2) = 3.497 ∗ = 0.848 𝑘𝑔/𝑠
132
146
𝐷𝑀𝑆 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = 3.497 ∗ = 3.868 𝑘𝑔/𝑠
132
18
𝐻2 𝑂 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 (2) = 3.497 ∗ = 0.477 𝑘𝑔/𝑠
132
Using the general mass balance equation:
𝑂𝑢𝑡𝑝𝑢𝑡 = 𝐼𝑛𝑝𝑢𝑡 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 − 𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛
𝑆𝐴 𝑂𝑢𝑡𝑝𝑢𝑡 = 3.158 − 3.126 = 0.032 𝑘𝑔/𝑠
𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑂𝑢𝑡𝑝𝑢𝑡 = 4.284 − (0.848 + 0.848) = 2.589 𝑘𝑔/𝑠
𝑀𝑀𝑆 𝑂𝑢𝑡𝑝𝑢𝑡 = 0.304 + 3.497 − 3.497 = 0.304 𝑘𝑔/𝑠
𝐻2 𝑂 𝑂𝑢𝑡𝑝𝑢𝑡 = 0.015 + (0.477 + 0.477) = 0.969 𝑘𝑔/𝑠
𝐷𝑀𝑆 𝑂𝑢𝑡𝑝𝑢𝑡 = 3.868 𝑘𝑔/𝑠
In
Acid, Kg/s Kg/s Kg/s Kg/s Kg/s
Kg/s
S305 3.158 4.284 0.015 0.304 0 7.7612
Out
Kg/s
S306 0.032 2.589 0.969 0.304 3.868 7.7612
- 45 -
Energy Conversion
The reaction enthalpies in R301 are low, so the reactor is operated adiabatically. This is covered
in greater detail in Chapter 4.4.
3.5.12 Distillation Column DC301
Figure 3.5: Distillation Column DC301
Mass Balance
In
Acid, kg/s kg/s kg/s kg/s kg/s kg/s
S306 0.03 2.59 0.97 0.3 3.86 7.76
Out
Acid, kg/s kg/s kg/s kg/s kg/s kg/s
S307 2.59 0.97 3.56
S314 0.03 0.3 3.86 4.20
Energy Conversion
To calculate the heat duties of the reboiler and condensers Eqn. 13, 14 and 15 were used.
Reflux ratio, R, is taken from [1]. Tf is selected as a temperature close to the boiling point of
the least volatile component to be distilled. Tb is determined using a VLE curve, where more
than two components exist in the feed, it is treated as a binary mixture of the least volatile
component to be distilled and the most volatile component to be removed in the bottoms (e.g.
for column DC301 it’s treated as a binary mixture of water and DMS).
- 46 -
Methanol VLE Curve
105
100
Temperature (C) 95
90
85
80
75
70
65
60
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fraction MeOH
Figure 3.6: Determination of Tb using VLE curve for DC302
The method of calculating the duties for distillation column DC301 is as follows:
𝑄𝑟𝑒𝑏𝑜𝑖𝑙 = (𝑚̇𝑀𝑒𝑂𝐻 ∗ ℎ𝑣𝑎𝑝 𝑀𝑒𝑂𝐻 + 𝑚̇𝐻2𝑂 ∗ ℎ𝑣𝑎𝑝 𝐻2 𝑂 ) ∗ (𝑅 + 1) + ∑ 𝑚̇𝐶𝑝 (𝑇𝑏 − 𝑇𝑓 )
mMeOH 2.589 kg/s R 0.15

Latent Heat of MeOH 1085 kJ/kg Tb 95 °C
mH2O 0.969 kg/s Tf 90 °C
Latent Heat of H2O 2338 kJ/kg
𝑄𝑟𝑒𝑏𝑜𝑖𝑙 = (2.589 ∗ 1085 + 0.969 ∗ 2338) ∗ (0.15 + 1) + 94.72

𝑄𝑟𝑒𝑏𝑜𝑖𝑙 = 5927 𝑘𝑊
𝑄𝑐𝑜𝑛𝑑 = (𝑚̇𝑀𝑒𝑜𝐻 ∗ ℎ𝑐𝑜𝑛𝑑 𝑀𝑒𝑂𝐻 + 𝑚̇𝐻20 ∗ ℎ𝑐𝑜𝑛𝑑 𝐻2 𝑂 ) ∗ (𝑅 + 1)
𝑄𝑐𝑜𝑛𝑑 = (2.589 ∗ 1085 + 0.969 ∗ 2338) ∗ (0.15 + 1)

𝑄𝑐𝑜𝑛𝑑 = −5836 𝑘𝑊
- 47 -
Mass Balance
In
Kg/s
S309 2.589 0.969 3.5572
Out
Kg/s
S310 0.954 0.954
S311 2.589 0.015 2.604
Energy Conversion
mMeOH 2.589 kg/s R 1.22
Latent Heat of MeOH 1085 kJ/kg Tb 72 °C
Tf 60 °C

Mass Balance
In
Kg/s
S315 0.032 0.304 3.868 4.204
Out
Kg/s
S316 3.868 3.868
S317 0.032 0.304 0.336
Energy Conversion
mDMS 3.868 kg/s R 0.31
Latent Heat of DMS 388 kJ/kg Tb 206 °C
Tf 195 °C
- 48 -
3.5.15 Plug Flow Reactor R302
Mass Balance
Reactor R302 is Hydrogenolysis reactor used to convert Dimethyl Succinate (DMS) to our
final product 1,4-Butanediol (BDO). This this is a two-step reaction where DMS is first
converted to Methyl 4-hydroxybutanoate (MHB) which is then further reacted to form BDO.
100% Conversion of DMS is achieved, with a selectivity to BDO of 93%, the remaining 7%
stays as the intermediary MHB and is later recycled.
Reaction step 1: 𝐷𝑀𝑆 + 2𝐻2 → 𝑀𝐻𝐵 + 𝑀𝑒𝑂𝐻
Reaction step 2: 𝑀𝐻𝐵 + 2𝐻2 → 𝐵𝐷𝑂 + 𝑀𝑒𝑂𝐻
In
Stream DMS, Hydrogen, Methanol, MHB, 1,4-BDO, Total,
Kg/s Kg/s Kg/s Kg/s Kg/s Kg/s
S323 3.871 0.481 0.011 0.210 0.024 4.597
Out
Kg/s Kg/s Kg/s Kg/s Kg/s Kg/s
S324 0.004 0.268 1.700 0.234 2.391 4.597
Energy Conversion
The energy conversion for R302 is covered in Chapter 4.5
3.5.16 VLE Separator VLS301

Mass Balance
In
kg/s kg/s kg/s kg/s kg/s kg/s
S327 0.004 0.268 1.700 0.234 2.391 4.597
Out
kg/s kg/s kg/s kg/s kg/s kg/s
S328 0.004 0.000 0.009 0.234 2.391 2.637
S333 0.000 0.268 1.691 0.000 0.000 1.960
Energy Balance
No energy conversion occurs in vapour liquid separators.
- 49 -
Mass Balance
In
Stream DMS, Hydrogen, kg/s Methanol, MHB, 1,4-BDO,
kg/s kg/s kg/s kg/s
S328 0.004 0.008 0.234 2.391 2.637
Out
Stream DMS, Hydrogen, kg/s Methanol, MHB, 1,4-BDO,
kg/s kg/s kg/s kg/s
S329 0.000 0.000 0.023 2.367 3.868
S331 0.00348 0.008 0.211 0.024 0.246
Energy Conversion
mDMS 3.868 kg/s R 0.31
Latent Heat of DMS 388 kJ/kg Tb 206 °C
Tf 195 °C
𝑄𝑟𝑒𝑏𝑜𝑖𝑙 = 552.23 𝑘𝑊
𝑄𝑐𝑜𝑛𝑑 = 368.42 𝑘𝑊
3.5.18 VLE Separator VLS302

Mass Balance
In
Stream Hydrogen, Kg/s Methanol, Kg/s Total, Kg/s
S335 0.268 1.691 1.960
Out
Stream Hydrogen, kg/s Methanol, kg/s Total, kg/s
S336 0.268 0.003 0.271
S342 0.000 1.688 1.688
Energy Conversion
No energy conversion occurs in vapour liquid separators.
- 50 -
3.5.19 Heat Exchangers & Condensers
Mass Balance
No mass conversion occurs in heat exchangers.
Energy Conversion
For Condenser X308:
𝑄 = ∑(𝑚̇𝐶𝑝 )∆𝑇 + ∑(𝑚̇ℎ𝑣𝑎𝑝 )
∑(𝑚̇𝐶𝑝 ) = (2205 ∗ 0.004) + (16403.51 ∗ 0.268) + (1375 ∗ 1.7) + (444.85 ∗ 0.234)

+ (4590.14 ∗ 2.39)
∑(𝑚̇ℎ𝑣𝑎𝑝 ) = (1153.5 ∗ 0.009) + (7784.8 ∗ 0.234) + (6488.68 ∗ 2.39)
𝑄 = 11779(503 − 463) + 17343306.73

𝐽
𝑄 = 17814479 = 17814𝑘𝑊
𝑠
Mass Integrated Streams
Symbol Cold Cold Outlet M.CP Hot inlet Hot m.CP

Inlet (K) (K) (K) Outlet (K)
X201 298 305 101043 463 398 4937
X202 305 310 101043 398 333 7241
X301 333 363 15.612 463 398 7241
X306 508.4 510.2 9287.27 543 540 5627.1
X307 417.8 477.6 7879.13 543 503 11779.3
Coolers
Symbol Hot inlet (K) Hot Outlet (K) M.CP Q, kW
X302 430 333 10600 1028

X303 353 333 2603 52
X305 500 333 650 109
X101 432 410 32377 730
X102 410 298 32377 3626
- 51 -
Heaters
Symbol Hot inlet (K) Hot Outlet Heat Required Steam Required
(K) kW (Kg/s)
X203 298 310 17.77 0.01
X204 298 310 35.41 0.01
X205 310 325 3611 1.48
X304 368 479 306 0.12
3.5.20 Pumps
Mass Balance
No mass conversion occurs in pumps.
Energy Conversion
Eqn 3 is used to calculate the power needed to pump a liquid to a specific pressure. A sample
calculation of this is shown below for PU201 which has a 59L/s volumetric flow and is
increasing in pressure by 20kPa.
𝑄 = 𝑉𝑑𝑃
𝑄 = 59/1000 ∗ (20) = 5.9𝑘𝑊
Item Volumetric Flow, L/s Pressure increase, kPa Q, kW
PU201 59 20 5.9
PU301 8 199 1.528
PU302 12 10 0.123
PU303 3 11 0.036
PU304 0.3 11 0.003
PU305 5 199 0.995
Total 8.585
- 52 -
3.5.21 Compressors
Mass Balance
No mass conversion occurs in compressors.
Energy Conversion
Eqn 8 is used to calculate the power needed to pressurise a gas stream under assumed adiabatic
conditions. Eqn. 9 then calculates the increase in temperature of the stream due to the adiabatic
compression. A sample calculation for DMS compressor CM301 is shown below:
P1 = 1bar, P2 = 5bar, γ = 1.03, R = 0.057kJ/kg.K, T1 = 500K, m = 3.18 kg/s
1.37−1
1.03 5 1.37
𝑊𝑠 = 3.18 ∙ 0.057 ∙ 500 ∙ [( ) − 1 ] = 282𝑘𝑊
1.03 − 1 1
1.03−1
5 1.03
𝑇2 = 500 ( ) = 536𝐾
1
Number Mass Flow Pressure in Pressure out Temp In Temp Out Q
kg/s bar bar K K kW
CM101 14.9 4 21 298 432 4355
CM301 3.18 1 5 500 536 282
CM302 0.27 1 5 483 509 17
CM303 0.28 1 5 333 512 747
Total 5401
3.5.22 Throttle Valve

Mass Balance
No mass conversion occurs in throttle valve.
Energy Conversion
The pressure of stream S324 is being reduced from 4.5 bar to 1 bar by expanding the gas at the
outlet of a throttle valve. The Joule-Thomson effect describes the temperature of a real gas
when it is forced through an expansion like this. Most chemicals cool when expanded, however
hydrogen is one of the few that warm up. As S324 is a mix of hydrogen, BDO and methanol,
Aspen HYSYS was used to simulate the temperature change when S324 passes through throttle
valve (TR301).
Compound Mass Flow Pressure in Pressure out Temp In Temp Out
kg/s bar bar K K
Hydrogen 0.27
1,4-butanediol 2.39
Methanol 1.7 4.5 1 503 502
M4-HB 0.234
DMS 0.003
- 53 -
3.5.23 T-Joints
T-Joints are used to bring two gas phase streams together. The mass entering must equal the
mass exiting, and the resulting temperature can be calculated by balancing the heat entering in
the separate streams to the heat leaving in the combined stream.
(𝑚̇𝐶𝑝𝑖𝑛1 ∙ 𝑇𝑖𝑛1 ) + (𝑚̇𝐶𝑝𝑖𝑛2 ∙ 𝑇𝑖𝑛2 )
𝑇𝑜𝑢𝑡 =
𝑚̇𝐶𝑝𝑜𝑢𝑡
T-Joint 1:
Stream DMS Hydrogen Methanol M4-HB BDO Total ΣmCp Temp
kg/s kg/s kg/s kg/s kg/s kg/s kJ/s K
In
S320 3.87 0 0 0 0 3.87 8528 536
S341 0 0.48 0.01 0.21 0.02 4.59 8353 479
Out
S321 3.87 0.48 0.01 0.21 0.02 4.59 16881 508
T-Joint 2:
In
S337 0 0.268 0.002 0 0 0.270 4401 512
S338 0 0.212 0 0 0 0.212 3485 298
Out
S339 0 0.48 0.002 0 0 0.482 7887 417
T-Joint 3:
In
S340 0 0.48 0.002 0 0 0.482 7887 477
S332 0 0.008 0.21 0.024 465 509
Out
S341 0 0.48 0.01 0.21 0.02 4.59 8353 479
- 54 -
3.6 Overall Mass Balance
IN OUT
tonnes per year tonnes per year
Corn Stover 286590
Enzymes 486
Solid Lignin 117972
Liquids 23320
Water 430408
Carbon dioxide 35612
Ammonia 27562
Biomass 11454
Hydrochloric acid
Acids & water 536065
Methanol 49792
Water 28020
Hydrogen 6226
Methanol 49609
1,4-butanediol 70237
Total 836677 836677
The above table represents the overall mass balance of our designed 1, 4-butanediol processing
plant. On first view, it is clear that our design balances, with 836,677 tonne/year going in and
836,677tonne/year coming out. From the pre-treatment and enzymatic hydrolysis processes,
286,590 ton/year of corn stover, 27562tn/year of Ammonia and 486 tonne/year enzymes are
being used to convert the exposed glucan to glucose. Solid lignin is a by-product material of
these processes, 117972tn/year, and will be exported and sold. 430,408tn/year of water is being
used throughout, which will be taken from water sources in the locality. The crystalliser will
purify the succinic acid, and will output 536,065tn/year of acids and water. The latter stages of
the process will involve 49,792tn/year of methanol and 6,226tn/year hydrogen to produce
70,237tn/year of our desired product, 1,4-butandiol. Having an efficient mass and energy
integration system in place, there will be minimal waste of mass or energy onsite, with recycle
streams and heat integration appropriately installed. The 49,609tn/year of methanol will be
recycled onsite to the esterification stages of the process.
- 55 -
3.7 Mass Integration
3.7.1 Recycling
In the design of the 1,4-butanediol production process, recycling of any possible material was
evaluated and accounted for. The addition of recycle streams in the process are used to reduce
the material cost of the process, especially as some of the chemicals used in the process are
quite expensive to be constantly purchasing, namely methanol & hydrochloric acid.
 A recycle stream, S221, can be found between LLE201 and MX201 recycling back recovered
hydrochloric acid.
 S342 recycles methanol from VLS302 back to MX301 for reuse in the esterification reaction.
 S317 recycles unreacted SA and intermediary MMS from DC303 for reuse in the esterification
reaction.
 S336 recycles hydrogen from VLS302 for reuse in the hydrogenolysis reaction.
 S331 recycles unreacted DMS and intermediary MHB from DC304 for reuse in the
hydrogenolysis reaction.
3.7.2 S111 Lignin Waste Stream

The waste stream from the enzymatic hydrolysis contains a large quantity of lignin which is a
valuable resource that can be reused in other processes. Uses of lignin include crack filling
material for asphalt, as a board binder, and for use in carbon fibre manufacturing. Lignin has a
price of $500 per tonne and for this reason will be sold off.
3.7.3 S223 Waste Stream

The waste stream S223 contain a large quantity of acids that would be too difficult to extract
onsite so this will be treated by an off-site waste management company.
3.7.4 S210 Cell Waste Stream

The waste stream from S210 containing biomass will be incinerated in FU201 and the heat
generated will be used to create steam that is required for the process.
- 56 -
3.8 Energy Integration
3.8.1 X201
X201 integrates the heat removed in cooling our
final product 1,4-butanediol to 40°C for export off-
site, to heating our glucose on route to the
fermenter (F201).
3.8.2 X202
X202 then further heats the glucose to the
fermenter operating temperature of 37°C, by
reutilising the heat to be removed when condensing
methanol out of a hydrogen/methanol vapour
mixture.
3.8.3 X301
The succinic acid dissolved in methanol is heated
from 60°C to 90°C at 300kPa, before entering
R301. The cooling of methanol/hydrogen vapour
mixture from 190°C to 125°C provides this heat.
3.8.4 X306
S403 is the coolant exiting R302. Heat gained
from cooling the reactor is transferred to the
reactor feed S321.
3.8.5 X307
Stream S324 exiting the reactor is used to preheat
the recycled and fresh hydrogen that is flowing to
the reactor.
3.9 Steam Requirements
3.9.1 Condenser X308
Stream S326 passing through condenser X308 generates 17,814kW of heat which is cooled by
water at 80°C. This creates steam at 180°C and 10 bar. The steam that is generated here can be
used for heating in heat exchangers and reboilers of distillation columns
Using steam tables:
𝑆𝑡𝑒𝑎𝑚 @ 180℃ = 2778.2𝑘𝐽/𝑘𝑔
𝐶𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑒 @80℃ = 334.88𝑘𝐽/𝑘𝑔
𝐸𝑛𝑒𝑟𝑔𝑦 𝑟𝑒𝑙𝑒𝑎𝑠𝑒𝑑 𝑏𝑦 1𝑘𝑔 𝑜𝑓 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑖𝑛𝑔 𝑠𝑡𝑒𝑎𝑚 = 2443.32𝑘𝐽/𝑘𝑔
17814
𝑆𝑡𝑒𝑎𝑚 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑 𝑏𝑦 𝑋308 = = 7.29𝑘𝑔/𝑠
2443.32
This steam will able to supply the necessary heat to the following units:
Unit Heat Required, kW Steam Required, kg/s
X205 3611 1.478
X203 17.77 0.007
X204 35.41 0.14
DC301 5927 2.426
DC302 6367 2.606
Ryan Kiernan - 58 -
3.9.2 S210 Cell Waste Stream
It is planned to incinerate the cell waste stream form S210 in FU210. The biomass has an
elemental formula CH1.8O0.5N0.2, Molar Mass 25.9 kg/kmole, and a heat of combustion -552
kJ/gmol. The Eqn. for the combustion of biomass is given by:
10𝐶𝐻1.8 𝑂0.5 𝑁0.2 + 13𝑂2 → 10𝐶𝑂2 + 2𝑁𝑂 + 9𝐻2 𝑂 ∆ℎ𝑐𝑜 = −522𝑘𝐽/𝑔𝑚𝑜𝑙
Currently 101367Kg (3913.73 kmoles) of biomass is generated per fermentation batch.
 CO2 = 3913.73*44 = 172204.12 kg
 NO = (3913.73/10)*2*30 = 23482.38 kg
 H2O = (3913.73/10)*9*18 = 63402.43 kg
The heat produced during combustion is:
 3913.73*-522 = -2,042,967 MJ
Over a 72 hour fermentation period this equals
 -2042967/(72*3600) = -7.88 MJ/s or 7.88 MW
High pressure steam at 40 bar and 250°C is required from this combustion as this will be
supplying heating to units at high temperatures.
𝑆𝑡𝑒𝑎𝑚 @ 250℃ = 2801.5𝑘𝐽/𝑘𝑔
𝐶𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑒 @80℃ = 334.88𝑘𝐽/𝑘𝑔
𝐸𝑛𝑒𝑟𝑔𝑦 𝑟𝑒𝑙𝑒𝑎𝑠𝑒𝑑 𝑏𝑦 1𝑘𝑔 𝑜𝑓 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑖𝑛𝑔 𝑠𝑡𝑒𝑎𝑚 = 2466.62𝑘𝐽/𝑘𝑔
7881.82
𝑆𝑡𝑒𝑎𝑚 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑 𝑏𝑦 𝑏𝑜𝑖𝑙𝑒𝑟 = = 3.19𝑘𝑔/𝑠
2443.32
This steam will able to supply the necessary heat to the following units:
Unit Heat Required, kW Steam Required, kg/s
X304 306 0.124
DC303 2048 0.83
DC304 552 0.224
Figure 3.7: High pressure steam requirements
The total steam required in the above table is 1.178 kg/s, meaning that 2.017 kg/s of steam is
left unused.
High Pressure steam at 250°C is also required by the AFEX reactor at a flow rate of 5.83kg/s.
The extra steam generated by the incinerator can be supplied to the AFEX however a second
source of steam needs to be identified to supply the remaining 3.813kg/s steam.
The combustion of natural gas has been chosen to generate the second source of steam for the
AFEX. The eqn for the combustion of natural gas is given by:
𝐶𝐻4 + 2𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂 ∆ℎ𝑐 = −802.3𝑘𝐽/𝑚𝑜𝑙
The heat of combustion per kg of natural gas is 50143 kJ/kg. Thus equating the flow of natural
gas to the flow of steam gives:
(50143)(𝑁𝑎𝑡𝑢𝑟𝑎𝑙 𝐺𝑎𝑠 𝑓𝑙𝑜𝑤 𝑅𝑎𝑡𝑒) = (2466.62)(3.813)
𝑁𝑎𝑡𝑢𝑟𝑎𝑙 𝐺𝑎𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 0.187𝑘𝑔/𝑠
Ryan Kiernan - 59 -
3.10 References
[1] Perry's Chemical Engineers' Handbook. New York: McGraw-Hill, 1984. Print.
[2] Richardson, J. F., Harker, J. H., Backhurst, J. R., & Coulson, J. M. (2002). Coulson and
Richardson's chemical engineering: Vol. 2. Oxford: Butterworth-Heinemann.
Figures retrieved from:
 SuperPro Designer
 Aspen Plus
 Aspen HYSYS
- 60 -
Chapter 4 Individual Unit Operation
Author: All Members
Chapter 4.1 Design of an Ammonia Fibre Expansion
Unit for Pre-Treatment of Corn Stover
Author: Eoin Sheehan
4.1.1 SCOPE OF THE DESIGN ..................................................................................................... 64
4.1.2 MECHANISM OF REACTION ........................................................................................... 64
4.1.3 PROCESS SELECTION ...................................................................................................... 65
4.1.4 VESSEL & MATERIAL SELECTION................................................................................ 66
4.1.5 ASSUMPTIONS ................................................................................................................. 67
4.1.6 SAFETY CONSIDERATIONS ............................................................................................ 67
4.1.7 ADVANTAGES OF AFEX PRE-TREATMENT PROCESS .............................................. 68
4.1.8 SANITY CHECK ................................................................................................................ 68
4.1.9 DETAILS OF THE SELECTED AFEX PROCEDURE ...................................................... 68
4.1.10 NOMENCLATURE .......................................................................................................... 70
4.1.11 AFEX DESIGN .............................................................................................................. 71
4.1.11.1 Determining the Residence Time ........................................................................... 71
4.1.11.2 Sizing of the Reactor .............................................................................................. 72
4.1.11.3 Determining the Volumes of reactors .................................................................... 73
4.1.11.4 Diameter and Height of the Reactor ....................................................................... 74
4.1.11.5 Determining the Biomass Container Size .............................................................. 75
4.1.11.6 Cross-Reference Volume Calculations .................................................................. 77
4.1.11.7 Vessel Size Comparisons ....................................................................................... 78
4.1.11.8 Vessel Thickness .................................................................................................... 78
4.1.11.9 Final Dimensions of Unit Operation ...................................................................... 79
4.1.11.10 Other working operations around the Unit Op ..................................................... 80
4.1.11.11 Hoist System to load with biomass containers ..................................................... 80
4.1.11.12 Cost Analysis........................................................................................................ 81
4.1.11.13 Cost summary....................................................................................................... 81
4.1.12 ENZYMATIC HYDROLYSIS ........................................................................................... 82
4.1.12.1 Energy Balance ...................................................................................................... 83
4.1.13 CONCLUSIONS ............................................................................................................... 84
4.1.14 APPENDIXES .................................................................................................................. 85
4.1.15 References .................................................................................................................. 87
Eoin Sheehan - 63 -
4.1.1 SCOPE OF THE DESIGN
This chapter details the design process of the ammonia fibre expansion unit, AFEX, for the
pre-treatment of corn-stover. The AFEX unit involves the charging of feedstock with ammonia
under high pressures, with a rapid de-pressurisation which in return breaks the feedstock
particles, lignin in particular, and makes it more favourable for the fermentation process later
on.
The aim of this design is to quantitatively measure the main parameters of the pressure vessel,
which affect the costing of the unit operation. There is a significant pressure drop within the
vessel, with a change of 1700kPa after expansion. Materials chosen will need to be suited to
withstand such pressures, and adequate safety features like relief valves and bursting discs will
be essentially for overall safety precautions. At the end of this section, I will hope to have found
and quantified the:
1. Type of vessel needed for the operation;
2. Appropriate size for the vessel;
3. Material selection;
4. Internal kinetic and the operating parameters & conditions;
5. Full flowsheet of the operations involved with the AFEX reactor.
4.1.2 MECHANISM OF REACTION

The main aim of pretreatment is to make the inner carbohydrate molecules, celluose,
hemicelluose and lignin, more accessible for enzmatic hydrolysis. The ammonia will be pre-
pressurised initially in an external vessel, which will be fed into the main AFEX tank which
has the biomass and water inside, at a certain temperature. As the ammonia is charged into the
vessel the temperature and pressure will increase. After a calculated residence time, the
pressrue will be released from the vessel and biomass washed with steam to strip any excess
ammonia.
No chemcial conversions take place, only an energy conversion across the reactor itself. Once
the residual time is completed, the biomass, ammonia and water is removed and passed on to
the next process.
The ammonia and water are easily seperated in a stripper, where the ammonia is recycled back
to the beginning into the pressuried vessel for the next batch of biomass.
Major process parameters are the temperature of the reaction, residence time, ammonia loading,
and water loading. This process de-crystallizes the cellulose, hydrolyses hemicellulose,
removes and depolymerizes lignin, and increases the size and number of micropores in the cell
wall, thereby significantly increasing the rate of enzymatic hydrolysis later on.
Eoin Sheehan - 64 -
Using literature to find a relevant rate constant, a residence time will be calculated for the
AFEX pretreatment and further used in several calculations for vessel size, thickness, height
etc.
The internal breakdown of the biomass is as follows:
• The formation of hydroxide ion catalyses various thermochemical reactions inside the
biomass structure.
• As a result of the thermochemical reactions, the compounds lignin and hemicellulose will be
extracted and redeposited on the surface of the biomass cell wall.
• These alterations in the lignocellulosic biomass structure enhance the accessibility of
cellulose for the enzymes during the hydrolysis process. [2]
Figure 4.1: Feedstock Breakdown from Pre-Treatment
4.1.3 PROCESS SELECTION:

The ammonia fibre expansion process was originally going to be processed in two separate
vessels. Initially, the biomass would be mixed with water and then charged with ammonia into
the pressurised vessel. After the residence time of the ammonia soaking, it would be passed
onto an ammonia stripper where steam would pass through the biomass and remove any excess
ammonia on the biomass.
Alternatively, I found a paper that illustrated a vessel that combined both mechanisms in one.
The biomass will be compressed into baskets to obtain a certain density, and placed within a
packed bed vessel under each other. The number of baskets per reactor will be calculated. From
here, a number of steps are taken to wash, charge and strip the biomass using steam and
ammonia inputs. The ammonia is still recycled and re-used in the process for the next batch.
Having evaluated both below, I will continue to use the latter option as there is less
complexities from moving the biomass from one vessel to another, and seems to be a more
promising treatment for my unit operation.
Eoin Sheehan - 65 -
4.1.4 VESSEL & MATERIAL SELECTION
To begin, any AFEX vessel will need to be a pressurised vessel. Having chosen the second
alternative process, a packed bed reactor will be the vessel in design. Some structural elements
will come into consideration, as ammonia is the component being used so certain material may
not be applicable will not last a long time with the exposure to the ammonia, pressures or
temperatures.
In choosing the materials for the vessel, several parameters and conditions must be evaluated
prior to choosing. Certain operational requirements for a pressure vessel include operating
pressure, fluid conditions, external loads and transient conditions. Once these have been
quantified, functional requirements can be determined, which will include the size, shape and
support of the vessel.
Also with the holding of ammonia at high temperatures, certain materials will be more suitable
than others. From a ‘chemical compatibility guide for metallic materials’ list, it stated that brass
or aluminium bronze were not recommended. However, stainless steel, carbon steel and
aluminium were all acceptable. For this unit operation, I will be choosing #316 stainless steel
as my construction material for the AFEX vessel. [5]
As the AFEX reaction is carried out at elevated temperatures close to ammonias critical
temperature and the critical pressure of ammonia can be reached, certain vessels, piping and
transductors must be chosen. All temperature and pressure gauges will have to be of the same
material, as it is also important to check the specification of every part of the reactor for its
compatibility with liquid and gaseous ammonia, i.e. polytetrafluorethylene (PFTE) is a good
material to use for seals.
Schematic Label Meaning Schematic Label Instrument

S101 Ammonia in X101 Cooler
S102 Compressed Ammonia X102 Cooler
S103 Ammonia CM101 Compressor
S104 Steam in R101 AFEX Reactor
S105 Ammonia Out R102 Hydrolysis Reactor
S106 Cooled Ammonia H101 Hoist System
S107 Steam Out ST101 Storage Tank
S108 Biomass Outlet
S109 Enzyme Feed
S110 Liquid Product
S111 Solid Waste
Eoin Sheehan - 66 -
Figure 4.2: Full Schematic of the AFEX procedure
4.1.5 ASSUMPTIONS
Below are basic assumptions to facilitate the design:
 100% ammonia is recycled and returned to the beginning

 Weight ratio of 1:1 of biomass to ammonia is used
 Batch process is undertaken
 100% of biomass is retained and passed on.
 Ammonia is pumped from a storage tank on site.
4.1.6 SAFETY CONSIDERATIONS

With the construction of any materials or operating equipment in industry, several safety
precautions must be considered. Especially when using ammonia at elevated temperatures,
particular caution must be taken. For the pressurised charging vessel, we must ensure that the
vessel does not have a ‘seamed’ construction. This style of construction is best avoided as the
high internal pressures could, over time, lead to faults or weakening of any constructed seams.
A ‘seamless’ charged vessel will have a much better safety rating and less likely to cause fault
or fracture.
General precautions of the handling of liquids, operating the reaction vessel and managing the
treated biomass will all have to be introduced and followed too.
Eoin Sheehan - 67 -
4.1.7 ADVANTAGES OF AFEX PRE-TREATMENT PROCESS
 Enhances the sugar yield of the biomass, making it more favourable for fermentation.
 Avoids degradation of the carbohydrate compounds within
 Lower moisture content
 100% recovery of the biomass being treated
4.1.8 SANITY CHECK

Having initially set out to design an AFEX system that had two separate operations for the pre-
treatment and the ammonia stripping, a sanity check was needed to really logic and costings of
the unit operations.
Having the single batch reactor for the biomass and ammonia would have meant a unit sizing
to nearly 330,000m3 (or several smaller ones in parallel) and then the biomass would need to
be transferred to a separate ammonia stripping column. Overall, much more effort and money
would be needed for the unnecessary design.
Having found the new design AFEX unit, both of the operation mentioned above can be
accomplished in the one unit. An ammonia storage tank will still be necessary; however the
main pressure vessel will only be scaled to the biomass sizing.
4.1.9 DETAILS OF THE SELECTED AFEX PROCEDURE

The selected ammonia fibre expansion unit will be undertaken in a packed bed reactor. Within
the reactor, several baskets containing the biomass will be stacked upon one another. The
reason for my change in process design is purely to simplify the process procedures. The
following rig will be capable of preforming all pre-treatment steps within the one vessel, as
opposed to removing and loading the biomass to a separate vessel for stripping.
There are primary procedures that must be followed to ensure correct pre-treatment of the corn-
stover.
Loading of the biomass: The feedstock is loaded into baskets and compressed to a density of
100kg/m3.[3] In a pilot plant scale this would be completed by operators on the floor. However,
at an industrial scale, a hopper and manual compression unit will be used to fill and compress
the baskets with the biomass. It will then be hoisted up via a pulley system into the packed bed
reactor. Depending on the sizing of the reactor, mentioned below, a number of baskets will fit
into each vessel.
Eoin Sheehan - 68 -
Pre-steam: Initial pre-steaming of the biomass serves for two reasons; to preheat the biomass
in the baskets and to remove any entrained air. Steam is passed through the beds at separate
times, as the first vessel will be treated first, with the second vessel awaiting the ammonia
stream from the first stream. Hence, the second bed will be pre-streamed just prior to the first
bed being charged with ammonia, to have the timings correct. The pre-steaming is run until the
bottom temperature of the beds is within 5oC of the top temperatures. At this point the steam
flow is stopped and valves will be closed.
Ammonia Charge: Immediately after the pre-steaming, the beds are charged with the
ammonia vapour. The ammonia is charged until a pressure of 1378kPa is maintained. Then bed
is then allowed to soak for a calculated residence time, calculated below. The outlet for the
ammonia is linked to the compressor, where it is used in the second packed bed rector, which
was initially pre-steam separately. [4]
Depressurize: At the end of the soak time, the exit valve is slowly opened to allow the release
of vapour from the beds. The vapour from depressurization is vented out until the beds reach
atmospheric pressure.
Steam Strip: To ensure that no ammonia is left in the biomass before the fermentation process,
a final charging of steam is used, similar to the initial steaming. The stripping was continued
until the bottom bed temperature reaches within 10oC of the top bed.
After these steps, the baskets are removed and loaded to the further stages of the processing.
Figure 4.3: Procedures for the AFEX process
Eoin Sheehan - 69 -
4.1.10 NOMENCLATURE
SYMBOL MEANING SYMBOL MEANING
C CORROSION ALLOWANCE MJ MEGA J OULES
SPECIFIC HEAT CAPACITY
CP MPA MEGA PASCAL’S
(J/G.OC)
CSA CURVED SURFACE AREA (M) N NUMBER OF REACTORS
O
C DEGREES CELSIUS P PRESSURE (PA)
D DIAMETER (M) PA PASCAL’S
DA DAMKOHLER NUMBER Q ENERGY (KW)
EXTERNAL RADIUS OF REACTOR
E WELD EFFICIENCY RB
(M)
HR HEIGHT OF REACTOR (M) RPM ROTATIONS PER MINUTE
HEIGHT OF CYLINDER VESSEL
HC S MAX ALLOWABLE STRESS
(M)
∆HC HEAT OF COMBUSTION (MJ) TW THICKNESS OF VESSEL (IN)
∆HRXN HEAT OF REACTION (MJ) Τ RESIDENCE TIME (S )
IN INCHES Ρ DENSITY (KG/M3)
J J OULES V VOLUME (M3)
K1 RATE CONSTANT (S-1) VR VOLUME OF REACTOR (M3)
K KELVIN VC VOLUME OF CYLINDER (M3)
KP A KILO PASCAL’S VE ELLIPSOIDAL VOLUME (M3)
KW KILO WATTS VT TOTAL VOLUME (M3)
MOL MOLES V VOLUME (M3)
M METRES XA CONVERSION FACTOR
M MASS (KG) R RADIUS OF REACTOR (M
M3 CUBIC METRES Π PI
Eoin Sheehan - 70 -
4.1.11 AFEX DESIGN
4.1.11.1 Determining the Residence Time
In an industrial scale manufacturing plant, there are certain limitations and set requirements for
the appropriate sizing of a reactor. I will need to determine the number of reactors and
associated residence times necessary for my operation; and then make a decision on the figures
calculated, keeping costings in mind.
The Damkohler number was used in this instance, giving me an estimate for the residence time
for the number of reactors installed.
ln(1 − 𝑋𝑎 )
𝐷𝑎𝑚. 𝑁𝑜. = 𝜏𝐾1 𝐸𝑞𝑛. 1 𝑛= 𝐸𝑞𝑛. 2
ln(1 + 𝐷𝑎)
Where:
τ = residence time (sec)
K1 = Rate constant (s-1) = 0.008076
Xa = Conversion factor = 0.95
n = number of reactors in series
Example:
By rearranging the equation 3:
If n = 1, Xa = 0.95;
ln(1−𝑋𝑎)
−1
𝐷𝑎 = 𝑒 𝑛
Da = e (ln (1-0.95) / 1) -1)

Da = 19
∴ using the Damkohler equation:

τ = Da / K = 19/0.008076 = 2352.65 sec = 39 minutes residence time.
Da n Total τ (sec) Total τ (min)
19 1 2352.65 39.21
3.47 2 429.93 7.17
1.71 3 212.29 3.54
1.11 4 138.03 2.30
0.82 5 101.61 1.69
0.65 6 80.18 1.34

Table 4.1: Table of residence times for multiple reactors
Eoin Sheehan - 71 -
From the table above, all the relevant residence times were calculated based on the number of
reactors present.
Residence Time vs. Number of Reactors

45
40
35
residence Time (min)
30
25
20
15
10
5
0
0 1 2 3 4 5 6 7
Number of Reactors
Figure 4.4: Graph if the relationship of residence time vs. the number of reactors
4.1.11.2 Sizing of the Reactor

To begin, my reactor will consist of a series of baskets stacked on top of each other that the
steam and ammonia will passed through vertically from top to bottom. In preparing for the
designing of this unit operation, I needed to find the sizing of the pressurised vessel, the
ammonia storage facility, the diameter and height of both the vessel itself and the baskets
within. The number of baskets will also need to be determined. From these, certain parameters
like the residence time can be calculated.
The main vessel will hold the biomass. From previous reports it was found that a mass flow
rate of 15.08 kg/s of biomass. For a residence time of 39 minutes, a total batch size of
35,288.4kg of biomass is needed.
Taking that the density of the biomass will be compressed to 100kg/m3 when loading the
baskets, a volumetric size of 352.88m3. Given our reactor will only contain the biomass, a 10%
headspace safety feature will be added; Giving us the final volume of 388.17m3 needed for the
vessel.
At a Pressure of 300kPa:
𝑚
Density ( 𝝆 ) of Ammonia: 0.86 kg/m3 𝜌= 𝐸𝑞𝑛. 3
𝑣
Density (𝝆 ) of Biomass: 100 kg/m3
Eoin Sheehan - 72 -
Mass per Batch (kg/batch) Volume (m3)
Biomass 35288 348.66
Ammonia 35288 41033.02
Water 20919.6 20.9196
Totals for reactor - 352.884
Incl. 10% Headspace - 388.172
Table 4.2: Table showing the volume calculations for the main vessel
From the above table, 383.526m3 is the final reactor vessel sizing needed for the unit operation.
4.1.11.3 Determining the Volumes of reactors

Previously the number of reactors was determined, and the resulting residence times were
given. Now I will determine the volume size that the reactors would have to scale to, if more
than one was necessary.
Taking the initial volume size of 388.17m3 into account, I simply divided this by the number
of potential reactors that would be in parallel.
Number of Reactors Volume (m3)

1 388.17
2 194.09
3 129.39
4 97.04
Table 4.3: Table of the number of reactors and resulting volumes
As seen above, for two reactors in our system, each would be 194m3 in volume.
However, I will be taking the initiative and using one reactor for my operation, as this will
make the process easier to operate and will not be a costly to install a second packed bed vessel.
Reactors vs. Volume Needed

450
400
350
300
Volume (m3)
250
200
150
100
50
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Number of Reactors
Figure 4.5: Graph representing the number of reactors vs the volume
Eoin Sheehan - 73 -
4.1.11.4 Diameter and Height of the Reactor
Once the reactor size has been determined, next is to specify the diameter and the height. The
following equation was used to determine both:
𝐷2 𝑎
𝑉𝑟: 𝜋. . (𝐻𝑟 − ) 𝐸𝑞𝑛. 4
4 3
Where:
Vr = volume of reactor (m3)
D = Diameter (m)
Hr = Height of Reactor (m)
a = D/4 (m)
Example:
Taking the reactor volume as 388m3 and a diameter of 3m;
4 ∗ 𝑉𝑟 𝐷/4
𝐻𝑟 = +
𝜋(𝐷2) 3
Hr = (4 – 388) / (3.14*32) + 3/4/3
Hr = 55.2m
Having calculated the heights from varying diameters, the following table was constructed
Diameter (m) Height (m)
3 55.2
4 31.2
5 20.2
6 14.2
Table 4.4: Table representing the diameter to height ratios for the reactor
Eoin Sheehan - 74 -
4.1.11.5 Determining the Biomass Container Size
Once the main reactor size is calculated, we must determine the size of the biomass containers
that will be within the reactor. As explained, the containers will passed from a conveyor belt
packed with the biomass and loaded into the reactor. The bottom compartment of the vessel
will need to be hinged to open and allow the reactors in, and closed after loading to ensure no
leak or rupture is exposed.
If we are to take the vessel volume (without the headspace) to be 352.88m3, and divide into 4
segments for the baskets, each segment would be allocated a volume of 88.22m3.
Furthermore, if we assume that one reactor will be used in the process, we can determine the
height of the individual baskets by rearranging equation 4,
4 − 𝑉𝑟 𝐷/4
𝐻𝑟 = +
𝜋(𝐷2 ) 3
Example:
Taking D = 4m
HBASKET = ((4 – 352.88) / (3.14(42)) + (1)/3 = 7.357m
∴ for a basket of diameter of 4m, the height would be 7.4m.

Further calculation shows the resulting diameter to height ratios.
Diameter (m) Number of containers Volume (m3) Height (m)
4 4 87.2 7.4
5 5 69.7 4
6 6 58.1 2.6
Table 4.5: Table representing the difference in diameter, volume and height for containers
Height to Diameter comparisons for biomass containers

8
6
Height of Reactor (m)
0
4 5 6
Diameter Length (m)
Figure 4.6: Chart showing the height differences with varying diameters
Eoin Sheehan - 75 -
Taking all of the above calculations into consideration, I have decided to opt for a single
pressurised vessel, with a diameter of 5m, height of 20m and containing 5 biomass containers
of 4m in height.
Figure 4.7: Visual representation of an individual container of biomass
Eoin Sheehan - 76 -
4.1.11.6 Cross-Reference Volume Calculations
We have found the minimum sizing for our vessel. To make sure our values are accurate, we
will find the cylinder volume, ellipsoidal volume and the wall thickness, so we can get an
accurate estimate for the vessel size and compare to our original results.
The cylindrical volume will give a more accurate way to estimation to the vessel size, taking
the geometry of the vessel into consideration. The equation is given below, along with an
equation for the height, using the diameter and estimated height to calculate an accurate figure.
𝑉𝑐 = 𝜋. 𝑟 2 . 𝐻𝑐 𝐸𝑞𝑛. 5 𝐻𝑐 = 𝐻𝑟 − 2. 𝑎 𝐸𝑞𝑛. 6
Example:
Using eqn. 5 and using a diameter of 5m:
Vc = 3.14 * 2.52 * (20.196– 2*5/4)
Vc = 347.46m3
The ellipsoidal ends of the reactor are the surfaces that are shaped similar to spheres. The
volume obtained by these ends can be calculated by the following equation:
4
𝑉𝑒 = . 𝜋. 𝑎. 𝑟 𝐸𝑞𝑛. 7
3
Example:
Ve = (4/3) * (3.14) * (5/4) * (2.5)
Ve = 6.54m3
Finally, the total volume will be retrived using equation 8. This is simply the cylindriacal
volume plus the ellipsoidial volume, multiplied by the number of reactors:
𝑉𝑡 = 𝑛(𝑉𝑐 + 𝑉𝑒) 𝐸𝑞𝑛. 8

n = number of reactors = 1
Example:
Vt = 1 * (347.46 + 6.54)
Vt = 354m3
Eoin Sheehan - 77 -
4.1.11.7 Vessel Size Comparisons
To compare both results, initially I found a value of 352.9m3 for the reactor vessel (before an
additional 10% headspace was added on).
In the latter, I found a vessel size of 354m3. These figures are nearly identical, so I am
confident to continue with my chosen measurements and design parameters.
4.1.11.8 Vessel Thickness

A parameter that needs to be identified is the thickness of the vessel. This will have an impact
on the heat transfer and costing of the materials. It was determined by the equation below.
𝑃𝐷
𝑇𝑊 =
2𝑆𝐸 + 0.8𝑃
For this calculation, several of the parameters needed to be researched for the relevant values.
According to the maximum allowable stress for my material (#316 stainless steel) is 97.7 MPa.
For the E value, this is linked to the weld efficiency. I will be assuming 100% efficiency in
this, as anything less would not be fit for purpose in an industrial environment, so E = 1
Likewise with the corrosion allowance will be negligible, as lignin will be present in the
process which acts as a corrosion inhibitor, so C = 0
My internal pressure, P, was found to be 2.06MPa within the vessel. This is from the ammonia
being compressed and passing through the vessel;
Example:
Tw = (2.06 * 5) / (2 * 97.7 * 1 + (0.8 * 2.06)
Tw = 0.052m
Changing the units: 0.052m = 52.27mm = 2.06in
Eoin Sheehan - 78 -
4.1.11.9 Final Dimensions of Unit Operation
The aim of this section was to calculate the exact dimensions for the vessel in operation. Having
calculated the height, diameter, internal container heights, thickness and volumes; the
schematic drawing would look like the following:
Figure 4.8: Visual schematic of the AFEX vessel
As well as this, the total CSA (curved surface area) of the tank can be determined by the
following equation:
1
2 1.6 1.6 1.6 1.6
(𝑟 ) + (𝑟𝑎) + (𝑟𝑎)
𝐶𝑆𝐴 = 2𝜋𝑟ℎ + 4𝜋 [ ] 𝐸𝑞𝑛. 10
3
Where:
r = radius = 2.5m
h = height = 19.97m
a = D/4 = 5/4 = 1.25m
Example:
1
2 1.6 5 5 1.6
(2.5 ) + (2.5 ∗ )1.6 + (2.5 ∗ )1.6
𝐶𝑆𝐴 = 2𝜋𝑟ℎ + 4𝜋 [ 4 4 ] = 394.87𝑚2
3
Eoin Sheehan - 79 -
4.1.11.10 Other working operations around the Unit Op
The ammonia used in this unit operation will be taken from a large storage facility on the
production site. Passed through a heat exchanger, the ammonia will be heated and directed into
the vessel.
The equation 𝑸 = 𝑴 ∗ 𝑪𝒑 ∗ 𝒅𝑻 was used to calculate the energy expended through entering
the vessel.
With a temperature difference of 410 K and a Cp of 4.184 kJ/kg.K and a mass flow rate of
13.6kg/s the energy required for the heat exchanger worked out at 427 kJ/s
When the ammonia is leaving the vessel after depressurization, it will be passed through a
condenser and recycled back to the ammonia storage facility to be reused. From report two, the
Q value of ammonia necessary for this is 5.43x103 kJ/s
4.1.11.11 Hoist System to load with biomass containers

The hoist system will be installed to allow the containers of biomass to be loaded into the
reactor. Originally, on a pilot scale, the containers would be manually packed and loaded into
the reactor.
For the industrial scale procedure, this method is not realistic. The corn stover will be placed
from the silo storage into a hopper, and the biomass containers will be packed. When the
container is packed, it will be moved into the reactor via a conveyor belt. This belt will bring
the container to the base of the vessel, where a hoist system will elevate the containers to 5
separate points in the vessel. The base is sealed shut, and the procedure is commenced.
After the process is completed, and the biomass has been steamed and finished pre-treatment,
the bottom of the vessel is reopened and the hoist system release the containers back to the
conveyor belt, which is then passed to the next stage; Enzymatic Hydrolysis.
Eoin Sheehan - 80 -
4.1.11.12 Cost Analysis
To determine the cost of the stainless steel used for the pre-treatment process, we must first
find the overall weight of steel used, and use a certain equation to determine the cost using
#316 stainless steel.
To find the volume of the AFEX container:
𝑉𝑠𝑡𝑒𝑒𝑙 = 𝑅 2 ℎ − 𝜋𝑟 2 ℎ,
where R= external radius, r= internal radius, h= height
𝑆𝑖𝑑𝑒𝑠 = ℎ(𝑅 2 − 𝑟 2 )
Top/Bottom 𝑉𝑠𝑡𝑒𝑒𝑙 = 2[𝜋𝑅 2 𝑇ℎ] where Th = thickness
Mass of Steel for tank: 𝑀𝑠𝑡𝑒𝑒𝑙 = (𝜋ℎ(𝑅 2 − 𝑟 2 ) + 2𝜋[𝜋𝑅 2 𝑇ℎ]) ∗ 𝜌
= (π*20(2.5522 – 2.52) + 2[π*2.5522*0.052]) x 8000 = 148996kg
Mass of the Steel containers: 𝑀𝑠𝑡𝑒𝑒𝑙 = (𝜋ℎ𝑐 (𝑅𝑐2 − 𝑟𝑐2 ) + [𝜋𝑅𝑐2 𝑇ℎ]) ∗ 𝜌
= (π*3.96*(2.5522 – 2.52) + [π*2.5522*0.052]) x 8000 = 8510.4kg
For Five Containers: 8510.4 * 5 = 42552.1kg
Using the calculated weights of the steel used, we can use the cost formula [12] to calculate the
total costing of the steel:
AFEX Vessel: $3,084,373 [6]
Biomass Containers: $309007 per basket ($1,545,035)
4.1.11.13 Cost summary
The following figures were calculated using figures researched for the costing of the ammonia,
Corn Stover and water.
Ammonia: $0.509 * 34,866 kg/batch = $17,746.7 per batch
Corn Stover: $0.0487 * 34,866 kg/batch = $1700.87 per batch
Water = $4.9 water/tonne * 1000kg/tonne * 20919.6kg = $102.51 per batch
Item Cost ($) / Batch
Stainless Steel 4,629,408 (once off)
Corn Stover (Biomass) 1700.9 [7]
Ammonia 17,746.7 [8]
Water 102.5
Table 4.6: Overall cost analysis for the AFEX system
Eoin Sheehan - 81 -
4.1.12 ENZYMATIC HYDROLYSIS
After the pre-treatment process is complete and the biomass is removed from the containers, it
will then be fed into an enzymatic hydrolysis reactor. The aim of this process is to convert the
glucan and xylan in the pre-treated corn stover into glucose and xylose. These are then used in
the fermentation process to eventually be used to produce succinic acid 1,4-butanediol. [9]
The conversions of glucan to glucose and xylan to xylose are shown below:
 Glucan to Glucose: 90.67%
 Xylan to Xylose: 75.93%
Working from these percentages, the following outlet mass balances were acquired.
Biomass Inlet Outlet (solid) Outlet (liquid)

(kg/hr) (kg/hr) (kg/hr)
Glucan 15725 1431.3 -
Xylan 4881.2 1174.9 -
Lignin 14643.7 11888.6 2755.1
Glucose & Xylose - - 18000
Totals 35249.9 14494.8 20755.1
Table 4.7: Enzymatic Hydrolysis Mass Balance
Based from the table above, the total amount of converted biomass into the fermentation
process will be 20,755kg of liquid biomass stream per hour.
Enzymes in use:
Two enzymes will be used in the hydrolysis reaction:
1. Cellic CTec3
2. Cellic HTec3
The purpose of these enzymes is to eventually breakdown the cellulose in the biomass, and
converts the glucan and xylan in the feedstock into glucose and xylose. These two will later be
used in the fermentation process. These particular enzymes allow the most cost effective
conversion of pre-treated lignocellulosic to fermentable sugars.
A total amount of 4323.4kg of the enzyme feed is needed. The process is run at fed-batch, at a
temperature of 50oC and an agitation of 200rpm. Initially, 18% of the enzyme feed is loaded
into the tank, with citrate buffer to ensure 0.05M is kept constant. After the initial three hours,
the rest of the enzyme feed is fed for a total agitation time of 72 hours.
Using the mass flow rates, and a biomass density [10] 50kg/m3 the volumetric flow of inlet
was found to be 705m3 /batch. Calculating a volumetric flow rate of 3.759m3/batch of
enzymes loaded (using a density of 1150kg/m3) [11] Taking all of this into consideration, an
estimated volume of 780m3.
Eoin Sheehan - 82 -
4.1.12.1 Energy Balance
The enzymatic hydrolysis is to be kept at 50oC, and with the addition of the contents a certain
amount of energy will be generated. Using the heat of reaction,
∆𝐻𝑟𝑥𝑛 = (𝑛 ∗ ∆𝐻𝑐)𝑏𝑖𝑜𝑚𝑎𝑠𝑠 − ((𝑛 ∗ ∆𝐻𝑐)𝑠𝑢𝑔𝑎𝑟𝑠 − (𝑛 ∗ ∆𝐻𝑐)𝑙𝑖𝑔𝑛𝑖𝑛)
∆𝐻𝑟𝑥𝑛 = −772984 𝑀𝐽 − (−329948.45 𝑀𝐽)
∆𝑯𝒓𝒙𝒏 = −𝟒𝟒𝟑𝟎𝟑𝟓. 𝟓𝟓 𝑴𝑱
Using the calculated heat of reaction;
𝑄 = 𝑚 ∗ 𝐶𝑝 ∗ ∆𝑇 = −∆𝐻𝑟𝑥𝑛
443035 𝑀𝐽
𝑄=
72 ℎ𝑟 ∗ 3600 𝑠
𝑸 = 𝟏. 𝟕 𝒌𝑾
Incorporating the time to complete the batch, I can determine that the amount of heat generated
in the vessel is 1.7kW. To counteract this, a cooling water source will be provided to reduce
the temperature and keep it at 50oC.
Eoin Sheehan - 83 -
4.1.13 CONCLUSIONS
 After going through the analytics, costings and a sanity check, the second AFEX pre-
treatment was chosen as the most realistic and acceptable process to continue with.
 This procedure will combine both the biomass treated with the vapour ammonia stream
and also the stripping process in the one vessel.
 The biomass will be packed to 100kg/m3 in particular containers, and will be hoisted
into the reactor each batch.
 Based on the above findings, a single reactor of height 20m and dimeter of 5m will be
adequate to achieve the pre-treatment process.
 The calculated residence time worked out to be 39 minutes for the ammonia stage of
the process.
 Five containers will be installed into the vessel, all of a diameter of 5m and height of
4m.
 A cooler will be installed to retrieve the ammonia after the depressurisation and
recycled to majorly reduce operational costs.
 To construct the reactor and the containers within, using 316 stainless steel, a total of
$1,115,657 will be spent. This is purely for the material, so additional costs will be
implied for the construction and installation of the vessel.
 After the pre-treatment, the biomass will be removed and passed onto the next stage of
processing.
Eoin Sheehan - 84 -
4.1.14 APPENDIXES:
Figure 4.9: Excel spreadsheet of reactor size calculations
Figure 4.10: Aspen HYSYS file of the AFEX system with heat exchanger and condenser
Eoin Sheehan - 85 -
Figure 4.11: Microsoft Excel Spreadsheet of biomass container vessel sizing
Eoin Sheehan - 86 -
4.1.15 References
[1] B. B. S. C. D. M. B. E. D. Venkatesh Balan, “Lignocellulosic Biomass Pretreatment
Using AFEX,” August 2009. [Online]. Available:
https://www.researchgate.net/publication/26826040_Lignocellulosic_Biomass_Pretrea
tment_Using_AFEX.
[2] C. E. Wyman, Aqueous Pretreatment of Plant Biomass for Biological and Chemical
Conversion.
[3] F. Teymouri, “Process Improvement to Biomass Pretreatment for,” 2015.
[4] V. B. E. S. B. D. Chris Wedding, “Evaluating the impact of ammonia fiber expansion

(AFEX) pretreatment conditions on the cost of ethanol production,” 03 February 2010.
[Online]. Available:
https://www.sciencedirect.com/science/article/pii/S0960852410014185#tblfn2.
[5] “asme code calculation allowable stresses high alloy,” [Online]. Available:
http://www.cis-inspector.com/asme-code-calculation-allowable-stresses-high-
alloy.html.
[6] “MEPS - WORLD STAINLESS STEEL PRICES - $US/metric ton,” [Online].

Available: http://www.meps.co.uk/Stainless%20Prices.htm.
[7] W. Edwards, “Estimating a Value for Corn Stover,” [Online]. Available:

https://www.extension.iastate.edu/agdm/crops/html/a1-70.html.
[8] G. Schnitkey, “Fertilizer Costs in 2017 and 2018,” farmdoc daily, Illinois, 2017.
[9] “Lignocellulosic hydrolysis,” [Online]. Available:

http://thinkbioenergy.com/about/our-solutions/cellulosic-ethanol/lignocellulosic-
hydrolysis/.
[10] R. C. G. G. F. T. Capucine Dupont, “Heat capacity measurements of various biomass

types and pyrolysis residues,” 2013. [Online]. Available:
https://www.researchgate.net/publication/255721989_Heat_capacity_measurements_o
f_various_biomass_types_and_pyrolysis_residues.
[11] Sigma-aldrich, “Cellulase, enzyme blend,” [Online]. Available:

https://www.sigmaaldrich.com/catalog/product/sigma/sae0020?lang=en&region=IE&
gclid=EAIaIQobChMIgsn2xO3J2gIVAhbTCh3yLgseEAAYASAAEgJQz_D_Bw.
[12] R. K. Sinnott, Coulson & Richardson's Chemical Engineering Series: Vol 6. Chemical
Engineering Design, Oxford: Elsevier Butterworth Heinemann, 2005.
Eoin Sheehan - 87 -
Chapter 4.2 Design of a Semi-Batch Fermenter for
the Fermentation of Succinic Acid
Author: Hamed Al Jabri
4.2.1 Introduction ................................................................................................................. 90
4.2.2. Aims ................................................................................................................................ 90
4.2.3 Selecting Type of Batch Bioreactor .................................................................... 91
4.2.3.1 Stirred tank Bioreactor ............................................................................................. 91
4.3.2.2 Air-Lift Fermenter .................................................................................................... 91
4.3.2.3 Fluidised Bed bioreactor .......................................................................................... 91
4.2.5 Bioreactor Design ...................................................................................................... 92
4.2.4.1 Rushton turbine ........................................................................................................ 92
4.2.4.2 Pitched-Blade turbine ............................................................................................... 92
4.2.4.3 Marine-blade propeller ............................................................................................. 92
4.2.5 Nomenclature .............................................................................................................. 93
4.2.6 Assumptions ................................................................................................................ 93
4.2.7 Calculations .................................................................................................................. 94
4.2.7.1 Feed conditions ........................................................................................................ 94
4.2.7.2 Feed density.............................................................................................................. 94
4.2.8 Required working Volume ..................................................................................... 95
4.2.9 Bioreactor dimensions ............................................................................................ 95
4.2.10 Wall thickness .......................................................................................................... 96
4.2.11 Mixing requirement ............................................................................................... 96
4. .2.12 Power requirement .............................................................................................. 97
4.2.13 Gassed Fluids power requirement .................................................................. 97
4.2.14 Gas-liquid mass transfer rate ............................................................................. 98
4.2.15 Energy Requirements............................................................................................ 99
4.2.16 Results ...................................................................................................................... 100
4.2.17 Conclusion ............................................................................................................... 102
4.2.18 References ............................................................................................................... 103
Hamed Al Jabri - 89 -
4.2.1 Introduction
Succinic acid is produced by microbial fermentation process via corn Stover. The process
converts glucose sugars into simpler sugars and other by-products in a bioreactor equipped
with mixing requirements. In this part of design, the fermentation is a gas-liquid system, and
will be carried on a batch mode to ensure well mixing and obtain complete achievable
conversion of glucose.
4.2.2. Aims
- To design the working volume required for Fermentation, unite.
- To obtain dimensions of the bioreactor.
- To find out the minimum mixing requirement to achieve the production requirement.
- To calculate the cooling duty for the Fermentation, unite.
- To calculate the power requirements for operation.
- To design a bioreactor that meets the minimum required oxygen mass transfer rate
4.2.3 Selecting Type of Batch Bioreactor.
4.2.3.1 Stirred tank Bioreactor
Stirred tank reactor is a closed vessel equipped with an agitation
system. Stirred tank bioreactors are usually used for
Homogenization, suspension of solids, dispersion of gas-liquid
mixtures, aeration of liquid and heat exchange. A typical stirred
tank is equipped with the following: Agitator, baffles, aeration,
either internal or external heat exchange system as shown in Fig.
stirred bioreactors are often used for batch operations, because they
are simply designed and operated compared to other bioreactors. In
Addition, stirred tank bioreactors offers better mixing requirements
and reasonable mass transfer rates. Generally, stirred tank Figure 4.12: Stirred tank
bioreactors offer low volumetric productivity. [1]
4.2.3.2 Air-Lift Fermenter

Air-lift bioreactor is pneumatic reactor has no mechanical agitation
arrangements for mixing. Fig.2. show the flow direction inside the air-
lift bioreactor. The minimum turbulent flow is caused by the fluid flow
to achieve adequate mixing. A draft tube is equipped centrally inside the
bioreactor for internal loop to provide a fluid air/liquid upward motion
and a circulatory flow. Usually, energy consumption is low in air-lift
bioreactors due to the low air/liquid velocities resulted from fluid
air/liquid upward motion. It is very applicable for aerobic cultivation
because they offer very high oxygen mass transfer rate compared to the
stirred bioreactor [1]. In contrast, A-L-bioreactors has higher air
throughout and requires higher pressure. Since they are not provided
with mechanical agitation, they are not very efficient for foam break,
Figure 4.13: Air-Lift fermenter
and they don’t have a bubble breaker. [1]
4.2.3.3 Fluidised Bed bioreactor

Recently, Fluidised Bed bioreactors are more used than other
bioreactors due to its advantages over the other Bioreactors. Fluidised
Bed Bioreactors involving cells as biocatalyst typically has three phase
systems, solid, gas and phase. Usually, fluidisation is achieved either
externally by a liquid of gas fed into the reactor as shown in Fig.3. The
volumetric productivity achieved in FB-bioreactor is higher than that
in the stirred tank bioreactor as well as they offer higher mass transfer
rates and better mixing [1]. Usually, fluidised bed bioreactors requires
very high power due to requiring very high fluid velocity to suspend
solid materials. In addition, the understanding of the actual behaviour Figure 4.14: Fluidised bed bioreactor
of FB-bioreactor is limited, therefore difficult to scale up. [6]

Stirred tank bioreactor is selected because it has a simpler design criterion and offers all the
required applications for complete of conversion of glucose to produce the highest achievable
yield productivity of succinic acid.
4.2.4 Selecting type of impeller
For microbial growing, it is very important to select the suitable impeller for the bioreactor to
ensure optimum performance of mixing. There are three common types of impellers are used
in bioprocessing.
4.2.4.1 Rushton turbine

Flat-bladed turbine set vertically along the agitation shaft to generate
radial flow. Figure 4.15 shows the typical Rushton turbine with six
blades. Rushton turbine are commonly used in bioreactors that
involves two phases mixing gas/liquid due to its capability in offering
Figure 4.15: Rushton impeller
intense mixing. [1]
4.2.4.2 Pitched-Blade turbine

Flat Blades set at 450 angels, generate axial and radial flow
simultaneously. Pitched bladed-turbines are used for gently mixing
of a culture. Usually, they are used in fermentations that involves
very high viscous cultures because of their mixing design. [1]
Figure 4.16: Pitched Blade
4.2.4.3 Marine-blade propeller
The blades can be flat or concave while the backsides are convex as
shown in Figure 4.17. They generate an axial flow. Usually, the
oxygen mass transfer rate is lower than the other discussed.
Propellers are usually used for fluid viscosity < 2 pa s. [1] Figure 4.17: Marine Blade
Rushton Turbine is selected for the bioreactor because it offers

better mixing compared between the other impellers. It is very suitable for two phase mixing.
Typically, stirred tank bioreactor has a guideline of dimensions with relative ratios based on
the impeller used.
The bioreactor will be equipped with Rushton Turbine and has the following dimension ratios
as shown in Figure 4.18.
Figure 4.18: Typical stirred tank dimensions with Rushton Turbine
4.2.5 Nomenclature
𝑺𝒚𝒎𝒃𝒐𝒍 𝑴𝒆𝒂𝒏𝒊𝒏𝒈
𝒑𝑭𝒆𝒆𝒅 𝐹𝑒𝑒𝑑 𝑑𝑒𝑛𝑠𝑖𝑡𝑦
𝑽𝒓 𝑉𝑒𝑠𝑠𝑒𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 (𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑣𝑜𝑙𝑢𝑚𝑒)
𝒕𝒃𝒂𝒕𝒄𝒉 𝐵𝑎𝑡𝑐ℎ 𝑡𝑖𝑚𝑒
𝑺𝒘𝒂𝒍𝒍 𝑊𝑎𝑙𝑙 𝑣𝑒𝑠𝑠𝑒𝑙 𝑡ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠
𝒏𝒊 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑖𝑚𝑝𝑒𝑙𝑙𝑒𝑟𝑠
𝝁𝒇𝒍𝒖𝒊𝒅 𝐹𝑙𝑢𝑖𝑑 𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦
𝑸 𝐹𝑒𝑒𝑑 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒
𝝁𝒎𝒊𝒙𝒕𝒖𝒓𝒆 𝑀𝑖𝑥𝑡𝑢𝑟𝑒 𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦
𝑺 𝐴𝑙𝑙𝑜𝑤𝑎𝑏𝑙𝑒 𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑡𝑒𝑛𝑠𝑖𝑙𝑒 𝑠𝑡𝑟𝑒𝑠𝑠
𝑬𝒊 𝐽𝑜𝑖𝑛𝑡 𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦
𝑷𝒕 𝑇𝑜𝑡𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑣𝑒𝑠𝑠𝑒𝑙
𝑵𝒊 𝑅𝑜𝑡𝑎𝑡𝑖𝑜𝑛𝑎𝑙 𝑖𝑚𝑝𝑒𝑙𝑙𝑒𝑟 𝑠𝑝𝑒𝑒𝑑
𝑵𝑷 𝑃𝑜𝑤𝑒𝑟 𝑛𝑢𝑚𝑏𝑒𝑟
𝑷𝒈 𝑃𝑜𝑤𝑒𝑟 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑓𝑜𝑟 𝑔𝑎𝑠 − 𝑙𝑖𝑞𝑢𝑖𝑑 𝑐𝑜𝑛𝑡𝑎𝑐𝑡𝑜𝑟𝑠
𝑷𝒐 𝑃𝑜𝑤𝑒𝑟 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑤𝑖𝑡ℎ𝑜𝑢𝑡 𝑎𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝑠𝑦𝑠𝑡𝑒𝑚
𝑭𝒈 𝑉𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑔𝑎𝑠 𝑓𝑙𝑜𝑤
𝑪𝒄 𝐶𝑜𝑟𝑟𝑜𝑠𝑖𝑜𝑛 𝑎𝑙𝑙𝑜𝑤𝑎𝑛𝑐𝑒
𝑽𝑳 𝐿𝑖𝑞𝑢𝑖𝑑 𝑣𝑜𝑙𝑢𝑚𝑒
𝒈 𝐺𝑟𝑎𝑣𝑖𝑡𝑎𝑡𝑖𝑜𝑛𝑎𝑙 𝑎𝑐𝑐𝑒𝑙𝑒𝑟𝑎𝑡𝑖𝑜𝑛
𝑲𝑳 𝒂 𝑀𝑎𝑠𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑐𝑜𝑒𝑓𝑓𝑒𝑐𝑡
𝒕𝒎 𝑀𝑖𝑥𝑖𝑛𝑔 𝑡𝑖𝑚𝑒
𝑽𝒆𝒔𝒔𝒆𝒍 𝑫𝒊𝒎𝒆𝒏𝒔𝒊𝒐𝒏𝒔
𝑺𝒚𝒎𝒃𝒐𝒍 𝑚𝑒𝑎𝑛𝑖𝑛𝑔
𝑫𝒕 𝑉𝑒𝑠𝑠𝑒𝑙 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟
𝑯𝒕 𝑉𝑒𝑠𝑠𝑒𝑙 𝐻𝑖𝑔ℎ𝑡
𝑯𝑳 𝐿𝑖𝑞𝑢𝑖𝑑 𝐻𝑖𝑔ℎ𝑡
𝑫𝒊 𝐼𝑚𝑝𝑒𝑙𝑙𝑒𝑟 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟
𝑫𝒃 𝐵𝑎𝑓𝑓𝑙𝑒 𝑤𝑖𝑑𝑡ℎ
𝑾 𝐼𝑚𝑝𝑒𝑙𝑙𝑒𝑟 𝑏𝑙𝑎𝑑𝑒 𝑤𝑖𝑑𝑡ℎ
𝑳 𝐼𝑚𝑝𝑒𝑙𝑙𝑒𝑟 𝑏𝑙𝑎𝑑𝑒 𝑙𝑒𝑛𝑔𝑡ℎ
𝑬 𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑡𝑎𝑛𝑘 𝑏𝑜𝑡𝑡𝑜𝑚 𝑎𝑛𝑑 𝑡ℎ𝑒 𝑙𝑜𝑤𝑒𝑠𝑡 𝑖𝑚𝑝𝑒𝑙𝑙𝑒𝑟
4.2.6 Assumptions
 Well mixing is achieved.
 Complete conversion of 70% of glucose is achieved.
 No heat loss, the system is isolated.
4.2.7 Calculations
4.2.7.1 Feed conditions.
𝐈𝐧𝐩𝐮𝐭𝐬𝐭𝐫𝐞𝐚𝐦𝐬
𝐈𝐧 𝐆𝐥𝐮𝐜𝐨𝐬𝐞 𝐖𝐚𝐭𝐞𝐫 𝐀𝐦𝐦𝐨𝐧𝐢𝐚 𝐂𝐨𝟐 𝐓𝐨𝐭𝐚𝐥
𝑚𝑎𝑠𝑠 𝑘𝑔 1290126 3808924 243916 316000 5658966
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑔/𝑚𝑜𝑙 180.156 18.0153 17.031 44.01
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 7161160.328 2.11𝐸 14321883.62 7180186 2.4𝐸
+ 08 + 08
𝑚𝑎𝑠𝑠, 𝑔 1290126000 3.81𝐸 243916000 3.16𝐸 5.66𝐸
+ 09 + 08 + 09
𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 0.029826932 0.880615 0.059652045 0.029906
𝐾𝑚𝑜𝑙𝑒𝑠 7161.160328 211427.2 14321.88362 7180.186 240090.4
4.2.7.2 Feed density

Feed Density was calculated using the following equation:
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑝𝐹𝑒𝑒𝑑 = 𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 +
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
Density of water at different temperatures is obtained as shown in the following figures.
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 (0
− 100°𝐶 𝑎𝑡 1 𝑎𝑡𝑚,
> 100 °𝐶 𝑎𝑡 𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑖𝑜𝑛 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒) Density, Kg/m3
𝑇𝑒𝑚𝑝, 𝐶 𝐷𝑒𝑛𝑠𝑖𝑡𝑦, 𝐾𝑔 1010
/𝑚3
1000
0.1 999.85
1 999.9 990
4 999.97
980
10 999.7
15 999.1 970
20 998.21
25 997.05 960
y = -0.4148x + 1005.3
30 995.65 950
35 994.03 0 20 40 60 80 100 120
40 992.22
Figure 4.19: Water Density at diff temps
Using line-equation: y = -0.4148x + 1005.3, therefore Density of water at 25 C =994.93 kg/m3

1534042
𝑝𝑓𝑒𝑒𝑑 = 994.93 + = 1397.67 𝑘𝑔/𝑚3
3808.924
4.2.8 Required Working Volume
The total working volume was calculated based on the feed flowrate. The relationship is
express as the following equation:
𝑡𝑏𝑎𝑡𝑐ℎ
𝑉𝑟 = 𝑄. 𝑒𝑞(1)
𝑝𝑓𝑒𝑒𝑑
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑠𝑡𝑟𝑒𝑎𝑚𝑠 𝑘𝑔
𝑄= = 117895.125 𝑘𝑔/ℎ𝑟
𝑏𝑎𝑡𝑐ℎ 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑡𝑖𝑚𝑒 ℎ𝑟
Therefore:
𝑉𝑟 = 4048.82 𝑚3
This value is relatively large, which was decided to have multiple bioreactors. This volume is
distributed into 5 reactors. Then, each reactor volume will have a volume equal to 809.76m3.
Therefore the calculation will be applied for one bioreactor.
4.2.9 Bioreactor dimensions.

Since the bioreactor is a cylindrical vessel, therefore total height of the bioreactor is obtained
from the following equation based on the ration of total height to total diameter is 1.5:
𝐷𝑇2
𝑉𝑟 = ᴨ. ( ) . (1.5𝐷𝑇 )
4
𝐷𝑇 = 8.83 𝑚
The rest of dimensions are obtained based on the constant ratios shown in Figure 4.18. The
headspace was accounted for 15% of the total volume.
The number of impellers required is obtained based on the dimensions and using the following
equation:
𝐻𝐿 − 𝐷𝑎 𝐻𝐿 − 2𝐷𝑎
> 𝑛𝑖 >
𝐷𝑎 2𝐷𝑎
𝑡ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒, 𝑛𝑖 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑖𝑚𝑝𝑒𝑙𝑙𝑒𝑟𝑠 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 2
Two impellers are installed with spacing between them about 1.𝐷𝑎 = 2.91 m
Since the reactants has relatively small values of viscosity, therefore 4 Baffles will be installed
in the bioreactor with 0.883 m width to prevent formation of vortexes during agitation. Table
4.1 obtained reactor dimensions
4.2.10 Wall thickness
The vessel wall thickness is calculated using the following equation:
𝑃𝑡 . 𝐷𝑖
𝑆𝑤𝑎𝑙𝑙 = + 𝐶𝑐
𝑆. 𝐸𝑖 − 0.6𝑃𝑡
𝑃: 𝑡𝑜𝑡𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑖𝑛 𝑣𝑒𝑠𝑠𝑒𝑙
= 𝑆𝑡𝑎𝑡𝑖𝑐 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 (𝑝𝑓𝑒𝑒𝑑 . 𝑔. ℎ) + 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑎𝑡 𝑏𝑎𝑠𝑒 (101.325 𝑘𝑝𝑎)
= 282.86𝑘𝑝𝑎
Therefore, using the calculated results from the table.
𝑆𝑡𝑎𝑡𝑖𝑐 𝑝𝑟𝑢𝑠𝑠𝑒𝑢𝑟𝑒 181.53𝑘𝑝𝑎

𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑎𝑡 𝑏𝑎𝑠𝑒 101.325𝑘𝑝𝑎
𝐽𝑜𝑖𝑛𝑡 𝐸𝑓𝑓𝑒𝑐𝑖𝑒𝑛𝑐𝑦, 𝐸𝑖 1
𝑤𝑜𝑠𝑘𝑖𝑛𝑔 𝑠𝑡𝑟𝑒𝑠𝑠, 𝑆 94500𝑘𝑝𝑎
𝐶𝑜𝑟𝑟𝑜𝑠𝑖𝑜𝑛 𝐴𝑙𝑙𝑜𝑤𝑎𝑛𝑐𝑒, 𝑚 0.002
Therefore:
𝑆𝑤𝑎𝑙𝑙 = 0.024468201𝑚
𝑂𝑢𝑡𝑠𝑖𝑑𝑒 𝐷𝑡 = 𝐷𝑡 + 𝑆𝑤𝑎𝑙𝑙 = 8.851191845𝑚
𝑚𝑎𝑠𝑠𝑉𝑒𝑠𝑠𝑒𝑙 𝑎𝑝𝑝𝑟𝑜𝑥𝑖𝑚𝑎𝑡𝑖𝑜𝑛 𝑏𝑦 𝑤𝑒𝑖𝑔ℎ𝑡 = 6382379𝑘𝑔
4.2.11 Mixing requirement

The system is turbulent for Re>10000. Mixing can be achieved unless turbulent flow inside
the tank [2]. Therefore, the minimum required rotational speed is obtained from the following
equation:
𝑅𝑒. 𝜇𝑓𝑙𝑢𝑖𝑑
𝑁𝑖 =
𝜌𝑓𝑒𝑒𝑑 . 𝐷𝑖2
The viscosity of the mixture fluid is calculated based on mole fraction of reactants expressed
as follow:
ln 𝜇𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = 𝑋𝑎 . 𝜇𝑎 + 𝑋𝑏 . 𝜇𝑏
Then, the minimum required impeller rotational speed is 𝑁𝑖 = 0.84 𝑟𝑝𝑠 =

50.64515587 𝑟𝑝𝑚
4.2.12 Power requirement
The minimum required power to achieve the minimum required speed is calculated from the
following equation:
3 5
𝑃 = 𝑁𝑃 . 𝑝𝑓𝑒𝑒𝑑 . 𝑁𝑖𝑚𝑝𝑒𝑙𝑙𝑒𝑟 . 𝐷𝑖𝑚𝑝𝑒𝑙𝑙𝑒𝑟 𝑒𝑞(2)
Power number is independent of Reynold number in turbulent flow. For Rushton turbine, the
power number is typically 6. [1]
Therefore:
𝑃 = 1057514.08 𝑤𝑎𝑡𝑡 = 1057.51 𝑘𝑊
4.2.13 Gassed Fluids power requirement

A gas is introduced through a sparger into the bioreactor to provide air to the culture. This will
cause a decrease on the density of the fluid. Equation.2 can’t explain the power required if gas
is sparged. Usually, the power required in gassing systems is obtained by the following
expression ratio:
−0.20
−0.25
𝑃𝑔 𝐹𝑔 𝑁𝑖2 𝐷𝑖4
= 0.10 ( ) ( 2)
𝑃𝑜 𝑁𝑖 𝑉𝐿
𝑔𝑊𝑖 𝑉𝐿3
Where: 𝑃𝑔 , 𝑃𝑜 𝑎𝑟𝑒 𝑡ℎ𝑒 𝑝𝑜𝑤𝑒𝑟 𝑤𝑖𝑡ℎ 𝑔𝑎𝑠𝑠𝑖𝑛𝑔, 𝑝𝑜𝑤𝑒𝑟 𝑤𝑖𝑡ℎ𝑜𝑢𝑡 𝑔𝑎𝑠𝑠𝑖𝑛𝑔 𝑟𝑒𝑠𝑝𝑒𝑐𝑡𝑖𝑣𝑒𝑙𝑦
𝐹𝑔 = 𝑔𝑎𝑠 𝑣𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤 𝑚3 /𝑠

𝑉𝐿 = 𝑙𝑖𝑞𝑢𝑖𝑑 𝑣𝑜𝑙𝑢𝑚𝑒
Required gas volumetric flow.

A sparger drilled with holes is located under the agitator for
oxygen introduction into the reactor as shown in Figure 4.20.
The sparger diameter is ¾ impeller diameter with a hole size
should not exceed 6mm. The area of sparger was calculated
from the ratio of sparger Diameter to impeller Diameter using Figure 4.20: Sparger installation
position
the following expression:
𝑁𝑜. ℎ𝑜𝑙𝑒𝑠 ∗ 𝐴𝑟𝑒𝑎 𝑜𝑓 𝑎 ℎ𝑜𝑙𝑒 = 𝐴𝑟𝑒𝑎 𝑜𝑓 𝑠𝑝𝑎𝑟𝑔𝑒𝑟
2 2
𝐷ℎ𝑜𝑙𝑒 𝐷𝑖𝑚𝑝𝑒𝑙𝑙𝑒𝑟
𝑁𝑜. ℎ𝑜𝑙𝑒𝑠 ∗ ᴨ ∗ ( ) = ᴨ ∗ 3/4( )
4 4
Usually super facial aeration velocities don’t exceed 0.05 m/s. [1]
𝑆𝑝𝑎𝑟𝑔𝑒𝑟 𝐷𝑖𝑎𝑚𝑒𝑡𝑒𝑟, 𝑚 2.18
𝑁𝑜. 𝐻𝑜𝑙𝑒𝑠 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 92222.97
𝑚𝑖𝑛𝑖𝑚𝑢𝑚, 𝐷𝑖𝑎𝑚𝑒𝑡𝑒𝑟 ℎ𝑜𝑙𝑒 0.006
𝐴𝑟𝑒𝑎 𝑜𝑓 𝑎 ℎ𝑜𝑙𝑒, 𝑚2 2.82743𝐸 − 05

𝐴𝑟𝑒𝑎 𝑜𝑓 𝑠𝑝𝑎𝑟𝑔𝑒𝑟 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑚2 2.61
𝑎𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦, 𝑚/𝑠 0.05
Therefore:
𝐹𝑔 = 0.13 𝑚3 /𝑠
Hence:
𝑃𝑔
= 0.1698
𝑃𝑜
Solving for:
𝑃𝑔 = 179.65 𝑘𝑤𝑎𝑡𝑡
It is noticed that the power required during gassing is very small compared to the power without
gassing. The reason of that, the volumetric gas flow rate is slightly high.
4.2.14 Gas-liquid mass transfer rate

Generally, there are two methods to evaluate the mass transfer coefficient, calculating the
𝐾𝐿 𝑎 using empirical equations or using experimental method. 𝐾𝐿 𝑎 was measured using an
empirical correlation for gas-liquid mass transfer which expressed as follow:
𝑃𝑔 0.4 0.5
𝐾𝐿 𝑎 = 0.026 ( ) . 𝐹𝐺
𝑉𝐿
Therefore, 𝐾𝐿 𝑎 = 0.053841743 𝑠 −1
The value of 𝐾𝐿 𝑎 obtained is found to be within the range of (0.02 to 0.25s-1) of 𝐾𝐿 𝑎 as a
typical value for large scale fermentation [2]. The 𝐾𝐿 𝑎 value provides an evidence that the
minimum mixing requirement is achieved.
Mixing time.
Defined as the time required for the tracer concentration to reach 10% from the final
concentration [1]. An acid or alkali solution is used to trace the mixing time. The mixing time
is obtained using the correlation for Reynold above 5000, expressed as follows [2]:
3
𝑁𝑖 𝑡𝑚 = (1.54𝑉𝐿𝑖𝑞𝑢𝑖𝑑 )/𝐷𝑖𝑚𝑝𝑒𝑙𝑙𝑒𝑟
𝑁𝑖 𝑡𝑚 𝑟𝑒𝑎𝑐ℎ𝑒𝑠 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑣𝑎𝑙𝑢𝑒 𝑎𝑡 𝑅𝑒 > 5 ∗ 103
Therefore
𝑡𝑚 = 50.81 𝑠
The shorter mixing time, represents more intense mixing in the batch.
4.2.15 Energy Requirements
From Energy Balance
𝑄 = 9.434𝑀𝑊 𝑝𝑒𝑟 𝑓𝑒𝑟𝑚𝑒𝑛𝑡𝑒𝑟
From
𝑄 = 𝑚. 𝑐𝑝. 𝛥𝑇
The system is cooled to 5°C, So𝛥𝑇 = (35 − 5). The heat capacity of the coolant agent
(propylene glycol) is 2.5 kJ/kg.
Hence flowrate/batch = 125.3980007𝐾𝑔/𝑠 𝑝𝑒𝑟 𝑏𝑎𝑡𝑐ℎ

Finding the required Heat transfer area from the following equation:
𝑄𝑟 = 𝑈. 𝐴. 𝛥𝑇𝐴
Arithmetic mean temperature was calculated based on raising up one temperature profile.
Which states that, for steam, where the temperature of the primary fluid (steam) remains
constant, then the following expression is applied:
𝑇1 + 𝑇2
𝛥𝑇𝐴𝑚 = 𝑇𝑠𝑡𝑒𝑎𝑚 −
2
35 + 5
= 37 − = 17𝐶 𝑜
2
The overall heat coefficient was calculated using Checalc online estimator [9] of heat
coefficient, based on the operation conditions,
𝑈 = 604.374 𝑊/𝑚2 𝐾
Total heat transfer required for the cooling duty/Fermentation, 𝑄 = 4576.85534 𝑚2
Therefore, the required Heat transfer area, 𝑄 = 915.371068 𝑚2/batch
4.2.16 Results
𝑅𝑒𝑠𝑢𝑙𝑡𝑠 𝑓𝑜𝑟 𝑜𝑛𝑒 𝑏𝑖𝑜𝑟𝑒𝑎𝑐𝑡𝑜𝑟
𝑺𝒚𝒎𝒃𝒐𝒍 𝒗𝒂𝒍𝒖𝒆 𝑼𝒏𝒊𝒕
𝒑𝑭𝒆𝒆𝒅 1397.67 𝑘𝑔/𝑚3
𝑽𝒓 809.76 𝑚3
𝒕𝒃𝒂𝒕𝒄𝒉 48 hr
𝑺𝒘𝒂𝒍𝒍 0.02 m
𝒏𝒊 2 −
𝝁𝒇𝒍𝒖𝒊𝒅 1.0009 𝑃𝑎. 𝑠
𝑸 117895.12 𝑘𝑔/ℎ𝑟
𝝁𝒎𝒊𝒙𝒕𝒖𝒓𝒆 1.0009 𝑃𝑎. 𝑠
𝑺 94500 𝑘𝑝𝑎
𝑬𝒊 1
𝑷𝒕 282.86 𝑘𝑝𝑎
𝑵𝒊 50.64 𝑟𝑝𝑚
𝑵𝑷 6
𝑷𝒈 179.65 𝑘𝑤𝑎𝑡𝑡
𝑷𝒐 1057514.08 𝑘𝑤𝑎𝑡𝑡
𝑭𝒈 0.13 𝑚3/𝑠
𝑪𝒄 0.002 𝑚
𝑽𝑳 688.30 𝑚3
𝒈 9.81 𝑚/𝑠2
𝑲𝑳 𝒂 0.05 𝑠−1
𝒕𝒎 50.81 𝑠
𝑉𝑒𝑠𝑠𝑒𝑙 𝐷𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛𝑠
𝑺𝒚𝒎𝒃𝒐𝒍 𝑉𝑎𝑙𝑢𝑒, 𝑚
𝑫𝒕 8.826
𝑯𝒕 13.24
𝑯𝑳 11.25
𝑫𝒊 2.91
𝑫𝒃 0.88
𝑾 1.94
𝑳 0.73
𝑬 1.94
𝑈𝑛𝑖𝑡 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑓𝑒𝑟𝑚𝑒𝑛𝑡𝑎𝑡𝑖𝑜𝑛 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑚𝑒𝑛𝑡
𝑷𝒈 898.25 kw
𝑽𝒓 4048.83 m3
Table 4.8: Reactor dimensions
A vertical Carbon steel vessel was selected to be the equipment for the fermentation batch due
to the large volume of a bioreactor. Carbon steel over better anti corrosion than stainless steel
vessel.

4.2.17 Conclusion
A bioreactor was designed to be able to convert glucose into succinic acid and other by-
products. The reactors will have 13m height with 8.26m diameter. The reaction will be operated
at 37°C and 1 atm with minimum agitation speed set to 50 rpm. Each bioreactor will have
809.76 m3, equipped with two impellers. Before harvesting the broth, the batch is cooled to
5°C using a propylene glycol as a coolant agent. Kla value showed that the mixing requirement
are achieved.

4.2.18 References
[1] Sinnott, R. K., and J. M. Coulson. Coulson & Richardson's Chemical Engineering.
Volume 6, Chemical Engineering Design. Butterworth-Heinemann, 2005.
[2] Doran. “Bioprocess Engineering Principles.” Bioprocess Engineering Principles - ScienceDirect, May
1995, Pdf.
[3]Shomu B., (2013, November 19). Fed batch fermentation. Retrieved from
https://www.youtube.com/watch?v=GZOjahApNAs
[4] [𝟑] Davis, R. Z. (2010, June). Design and Scale-Up of Production Scale Stirred. Retrieved
February 15, 2018, from
https://digitalcommons.usu.edu/cgi/viewcontent.cgi?article=1533&context=etd
[5] Scale-up Design of A Multiple Impeller. (n.d.). Retrieved February 6, 2018,
fromhttp://www.resi.com.tw/mixing/09doc.pdf
[6] Howard, J. R. (1989). Fluidized Bed Technology: Principles and Applications. New York, NY: Adam Higler.
[7] Academic site, bioprocessing, retrieved from: https://bioprocessing.weebly.com/fermentation-technology.html
[8] Steam Engineering Principles & Heat Transfer, arithmetic mean temperature difference
(AMTD). arithmetic mean temperature difference (AMTD). Retrieved From: arithmetic mean
temperature difference (AMTD)/Resources/Pages/Steam-Engineering-Tutorials/steam-
engineering-principles-and-heat-transfer/heat-transfer.aspx
[9] CheCalc. 2018. Chemical Engineering Calculations. [ONLINE] Available
at: https://www.checalc.com/. [Accessed 18 April 2018].

Chapter 4.3 Design of a Batch Cooling Crystallizer for
the Purification of Succinic Acid
Author: Ryan Kiernan
4.3.1 Introduction .............................................................................................................. 106
4.3.2 Aims .............................................................................................................................. 106
4.3.3 Theory ......................................................................................................................... 107
4.3.3.1 Cooling Crystallization .......................................................................................... 107
4.3.3.2 Evaporative Crystallization .................................................................................... 108
4.3.4 Crystallizers .............................................................................................................. 109
4.3.4.1 Oslo Crystallizer ..................................................................................................... 109
4.3.4.2 Forced Circulation Crystallizer .............................................................................. 109
4.3.4.3 Stirred Tank Reactor .............................................................................................. 109
4.3.5 Nomenclature ........................................................................................................... 110
4.3.6 Assumptions ............................................................................................................. 111
4.3.7 Feed Conditions ....................................................................................................... 111
4.3.8 Crystallizer Design ................................................................................................. 112
4.3.8.1 Feed Density........................................................................................................... 112
4.3.8.2 Crystallizer Volume ............................................................................................... 113
4.3.8.3 Materials ................................................................................................................. 117
4.3.8.4 Agitation Requirements.......................................................................................... 119
4.3.8.5 Cooling Requirements ............................................................................................ 121
4.3.8.6 Additional Calculations .......................................................................................... 121
4.3.9 Results ......................................................................................................................... 122
4.3.10 Appendix .................................................................................................................. 124
4.3.11 References ............................................................................................................... 125
Ryan Kiernan - 105 -

4.3.1 Introduction
The aim of this unit operation is to design a crystallizer that is able to purify succinic acid from
the fermentation broth, which will be used to produce 1,4-Butanediol, our desired product. To
crystallize the succinic acid (Figure 4.21) a batch cooling crystalliser was chosen as the design.
The crystallizer is designed as a Stirred Tank Reactor that is cooled via a cooling jacket
supplied with Propylene Glycol. The crystallizer is operated at atmospheric pressure and has a
ΔT = 32°C. The crystallizer is designed to grow crystals with a diameter of 1mm and operates
at a 93.5% efficiency.
Figure 4.21: Crystalline Succinic Acid [1]
4.3.2 Aims
 To find Crystallization growth data and use this information to calculate the Crystallizer
Volume.
 To define the other physical dimensions of the Crystallize e.g. Wall Thickness, Agitator
Diameter, Agitator RPM, Baffle Thickness etc.
 To calculate the cooling requirements of the crystallizer.
 To evaluate different materials for the construction of the Crystallizer.
 To Calculate the Capital Cost of the Crystallizer.

4.3.3 Theory
Crystallization is the conversion of a substance from a liquid state, gaseous state, or amorphous
solid to a crystalline solid. A key production step, crystallization is both a separation process
and a purification technique. Crystallization is one of the oldest chemical engineering unit
operations and remains in use today producing high quality chemicals and pharmaceuticals. It
is used in many of the largest processes in the world such as in sodium chloride and sucrose,
in fertilizer components such as urea, ammonium nitrate, potassium chloride, and ammonium
phosphates, and in platinum group metals and organic fine chemicals. [2]
Figure 4.22: Solubility Curve of Succinic Acid [1]
For crystals to form supersaturation must be achieved. This is the driving force for the process.
Take the Solubility curve of Succinic Acid (Figure 4.22), the solution is undersaturated below
the line on the graph, the line represents saturation, and above the line is supersaturation. The
feed enters the crystallizer as an undersaturated solution and is brought to supersaturation. The
two main methods for achieving supersaturation are by cooling the feed or by evaporation the
solvent.
4.3.3.1 Cooling Crystallization

Cooling Crystallization is the preferred method for crystallization when the solubility of a
substance increases with temperature. The solution can be cooled either by the use of an internal
jacket or by an external heat exchanger. This process aims at obtaining and optimum
supersaturation where the rate of nucleation remains low for a coarse crystal product to be
formed whilst maintaining a high growth rate. A simple method in theory for Cooling

Crystallization is to set the rate of cooling to a constant rate, however this has its own problems.
Due to a lack of seeding at the beginning of crystallization a very high degree of supersaturation
can be created as well as a high degree of nucleation. Thus, the rate of cooling is set so that the
supersaturation remains constant during cooling. Well mixed contents and uniform heat
withdrawal give optimum supersaturation and crystal size distribution throughout the
crystalliser. [3]
4.3.3.2 Evaporative Crystallization

Evaporative crystallization is employed when the solubility of a substance only increases
slightly, remains constant, or even decreases with temperature. The solvent in the solution is
heated to its boiling point in the crystallizer at which point it begins to boil off, leading to the
solution becoming supersaturated. For continuous crystallisers, supersaturation depends on the
rate of evaporation. For evaporative batch crystallisers a high supersaturation at the beginning
becomes uneconomically low at the end. Thus, the rate of evaporation is set so that
supersaturation remains constant though time. [3]

4.3.4 Crystallizers
4.3.4.1 Oslo Crystallizer
The Oslo Crystallizer is a type of
fluidized bed continuous crystalliser.
The feed solution is circulated through
the Heat Exchanger before entering the
fluidized bed where the crystal can
grow without any mechanical
agitations. This allows for the growth
of large crystals subject to its residence
time in the fluidized bed. The slurry is
then removed to the centrifuge for Figure 4.23: Oslo-Krystal Crystallizer [21]
liquor removal. [4]
4.3.4.2 Forced Circulation Crystallizer

Forced Circulation Crystallizers are the most commonly
used Crystallizer, operating as a Mixed Suspension-Mixed
Product Removal (MSMPR) Crystallizer. The upper body
has a chamber large enough to allow for vaporisation of the
solvent. The liquor is removed from the lower part of the
body via suction and passed through the heat exchanger to
generate supersaturation before being returned to the upper
body. The Heat Exchanger is designed to give a low
temperature rise, prevent boiling or scaling in the pipes. The
forced Circulation Crystallizer can be operated in a batch
mode however it is most common to use it in a contiuous
mode. [5]
Figure 4.24: Forced Circulation Crystallizer [22]
4.3.4.3 Stirred Tank Reactor

Batch Crystallizers can be modelled similar to that of a stirred
tank reactor with minor changes in calculating the agitator
diameter and speed. The slurry enters the crystallizer
undersaturated where supersaturation is then generated.
Batch crystallizer generally employ cooling crystallization
techniques as evaporative crystallization generally require a
large vapour head, leading to large investment costs. Batch
Crystallizers are advantageous due to their simplicity and the
possibility for incrustation is avoided due to cleaning after
every cycle. [2]
Figure 4.25: Stirred Tank Crystallizer [23]

4.3.5 Nomenclature
Symbol Meaning Symbol Meaning
a Ellipsoid depth, m ṁPG Mass flow of Coolant, Kg/s
B System Constant Ns Impeller Rotational Speed, s-1
C Cost per unit Mass, $/kg Np Power Number
Feed Specific Heat Capacity,
Cp0 P Power, Watts
KJ/KmoleK
Coolant Specific Heat Capacity,
CpPG Pi Pressure inside Crystallizer, Nm-2
KJ/KgK
Di Impeller Diameter, m Q Heat, KJ/Kg
Dt Tank Diameter, m Re Reynolds Number
eelip Ellipsoid Thickness, m t1 Experiment 1 time, s
g/n Relative Kinetic Order t2 Experiment 2 time, s

Enthalpy of Crystallisation,
hc tf Crystallizer load time, s
KJ/Kmole
hf Fluid Height, m T0 Initial Temperature
J Welded Joint Factor Tf Final Temperature

Experiment 1 Mean Crystal Size,
L1 Vf Volume of Crystalliser Load, m3
m
Experiment 2 Mean Crystal Size,
L2 σd Yield Strength, Nm-2
m
Ratio of Log(Crystal Growth) to
LN Initial Crystal Size, m η
Log(time)
Molar Mass of anhydrous
Manh ρfeed Crystalliser Feed Density
Succinic Acid
Molar Mass of dissolved Succinic
Mhyd ρmaterial Material Density, Kg/m3
Acid
Succinic Acid Solubility at initial
mc Mass of Crystals, Kg ω0
Temperature, Kg/Kg water
mc/ Succinic Acid Solubility at final
Yield of Crystals per Kg of feed ωf
Vfρfeed Temperature, Kg/Kg water
Table 4.9: Nomenclature used

4.3.6 Assumptions
1. Inlet Feed is perfectly mixed entering the Crystallizer.
2. The viscosity of the feed can be modelled as 1 component containing all the solute
mass.
3. Internal Pressure, Pi, can be modelled on the surface area of the ellipsoid.
4. Each Crystallizer Cycle has the same mass & proportions.
4.3.7 Feed Conditions

Moles, Mole xi*Molar xiCp
Mass, Kg Cp, KJ/
Component Kmole Fraction, Mass KJ/
x103 KmoleK
x103 xi Kg/Kmole KmoleK
Water 4368 242.461 0.936 16.866 75.47 70.654
Succinic
873.6 7.398 0.029 3.373 153.6 4.388
Acid
Acetic Acid 202.734 3.376 0.013 0.783 122.11 1.592
Lactic Acid 62.663 0.696 0.003 0.242 213.47 0.573
Formic
49.762 1.081 0.004 0.192 100.35 0.419
Acid
HCl 145.152 3.977 0.015 0.707 75.47 1.159
258.989
Total 5701.9 Kg 1 22.162 78.784
Kmoles
Table 4.10: Feed to be purified per batch

4.3.8 Crystalliser Design
4.3.8.1 Feed Density
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑜𝑙𝑢𝑡𝑒
𝜌𝑓𝑒𝑒𝑑 = 𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑆𝑜𝑙𝑣𝑒𝑛𝑡 + 𝐸𝑞𝑛. 1
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑆𝑜𝑙𝑣𝑒𝑛𝑡
Temperature, °C Density, Kg/m3
45 990.21
50 988.04
55 985.69
Table 4.11: Density of Water at Different Temperatures [6]
991
990
989
Density, Kg/m3
y = -0.452x + 1010.6
988
987
986
985
0 10 20 30 40 50 60
Temperature, °C
Figure 4.26: Density of Water at different Temperatures
Density of Water @ 52°C = -0.452(52) + 1010.6 = 987.1Kg/m3

1333911.3 𝐾𝑔
𝜌𝑓𝑒𝑒𝑑 = 987.1 + = 1288.538 3
4368000 𝑚
987.1

4.3.8.2 Crystallizer Volume
The Batch Agitated Crystalliser designed in this chapter will be scaled up from lab-scale
experiments using the method described By Nyvlt & Mullin. The experimental data required
used was retrieved from the research paper Nucleation and Growth of Succinic Acid in a Batch
Cooling Crystalliser by Qui & Rasmuson. Experiment runs 4 & 11 were chose due to both runs
having the same:
 Temperature Drop
 Agitation Rate
 Initial Crystal Size [7,8]
First, the yield of crystals must be determined by Eqn. 2.
𝑚𝑐 𝜔0 − 𝜔𝑓
= 𝐸𝑞𝑛. 2
𝑉𝑓 𝜌𝑓𝑒𝑒𝑑 𝑀𝑎𝑛ℎ − 𝜔
𝑀ℎ𝑦𝑑 𝑓
Figure 4.27: Succinic Acid Solubility Curve [1]
The value for ω0 is the initial saturation concentration of the feed and ωf being the saturation
concentration at the final temperature. The final temperature has been chosen to be 20°C to
keep in line with experimental data.
𝑚𝑐 0.2 − 0.067 𝐾𝑔
= = 0.143
𝑉𝑓 𝜌𝑓𝑒𝑒𝑑 118.0878 − 0.067 𝐾𝑔 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛
118.0878

Nucleation & Growth rates of Crystals are normally expressed by the relations:
𝑚̇𝑁 = 𝑘𝑁 𝑉𝜌𝑓𝑒𝑒𝑑 ∆𝜔𝑛 𝑎𝑛𝑑 𝑚̇𝐺 = 𝑘𝐺 𝐴∆𝜔 𝑔
These two equations can be related by the Relative Kinetic Order g/n, which is an important
design parameter. Determination of these two values can be completed in a laboratory however
values for n can be unreliable. An alternate method is by performing batch experiments and
applying the growth data to Eqn. 3 & Eqn. 4.
𝐿̅ − 𝐿𝑁
log ̅1
𝑔 1−𝜂 𝐿2 − 𝐿𝑁
= 𝐸𝑞𝑛. 3 𝑤ℎ𝑒𝑟𝑒 𝜂= 𝑡 𝐸𝑞𝑛. 4
𝑛 1 + 3𝜂 log 𝑡1
2
Experiment Number Time, s LN x10-6m L x10-6m

E2 7200 250 755
E5 5400 250 657
Table 4.12: Experimental Data used [9]
(789 − 250)𝑥10−6
log
(657 − 250)𝑥10−6
𝜂= = 0.976
7200
log
5400
𝑔 1 − 0.976
= = 0.006
𝑛 1 + 3(0.976)
The System Constant, B, is calculated by Eqn. 5. This figure quantifies the influence of
nucleation and growth kinetics on crystalliser design. The value for L and tf can be used from
either experiment above.
𝑔
(𝐿̅ − 𝐿𝑁 )1+3𝑛
𝐵= 𝑔 𝑔 𝐸𝑞𝑛. 5
𝑚
(𝑉 𝜌 𝑐 )𝑛 𝑡1−𝑛
𝑓 𝑓𝑒𝑒𝑑
[(789 − 250)𝑥10−6 ]1+3(0.006)

𝐵= = 6.977𝑥10−8
(0.143)0.006 72001−(0.006)
By selecting a value of L and solving for tf in Eqn. 6, using the values previously calculated,
we can determine the time required to produce crystals of our selected size. The size of crystals
selected to be produced is 1mm.
𝑔 −1
(1− )
𝑔 𝑛
1+3
(𝐿̅ − 𝐿𝑁 ) 𝑛
𝑡𝑓 = ⌈ 𝑔 ⌉ 𝐸𝑞𝑛. 6
𝑚
𝐵(𝑉 𝜌 𝑐 )𝑛
𝑓 𝑓𝑒𝑒𝑑
−1
(1−(0.006))
([1000 − 250]𝑥10−6 )1+3(0.006)
𝑡𝑓 = [ ] = 10098.753𝑠
6.977𝑥10−6 (0.143)0.006

This calculated time is approximately 2.81 hrs. To account for time to load the crystalliser and
post processing extra downtime has to be applied. An extra 2.19 hours will be added giving a
time per load of 5 hours assumed. As there is 72 hours between the end of each fermenter batch
and only 5 hours is required for the crystalliser we are able to reduce the size of the crystallizer
by crystallizing smaller loads.
72
𝑁𝑜. 𝑜𝑓 𝐿𝑜𝑎𝑑𝑠 𝑝𝑒𝑟 𝐹𝑒𝑟𝑚𝑒𝑛𝑡𝑒𝑟 𝐵𝑎𝑡𝑐ℎ = = 14.4 𝐿𝑜𝑎𝑑𝑠
5
We are mathematically able to run the crystalliser 14.4 times between each fermenter batch.
As we cannot actually run 0.4 of a load, we are able to run 14 loads between each fermenter
batch. Assuming an ideal mixture each load will have a mass & Volume of:
5701911
𝑀𝑎𝑠𝑠 𝑜𝑓 𝐶𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 𝐿𝑜𝑎𝑑 = = 407279.379𝐾𝑔
14
407279.379
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐶𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 𝐿𝑜𝑎𝑑 𝑉𝑓 = = 316.079𝑚3
1288.538
Component Mass, Kg
Water 312000
Succinic Acid 62400
Acetic Acid 14481
Lactic Acid 4475.95
Formic Acid 3554.429
HCl 10368
Total 407279.4
Table 4.13: Mass of each component inside the crystallizer each cycle
The normal design of an agitated Crystallizer is a cylindrical vessel with an ellipsoidal bottom.
The Volume of the cylinder and ellipsoid bottom is given by Eqn. 7. [9] Most commonly, the
value of a, the depth of the ellipsoid, is one quarter the Crystallizer diameter. [10]
𝜋𝐷𝑡2 𝑎 𝐷𝑡
𝑉𝑓 = (ℎ𝑓 − ) 𝑤ℎ𝑒𝑟𝑒 𝑎 = 𝐸𝑞𝑛. 7
4 3 4
Rearranging the equation gives:
4𝑉𝑓 𝐷
ℎ𝑓 = 2
+
𝜋𝐷 12
Diameter of 5m was chosen for the Crystallizer:
4(316.079) 5
ℎ𝑓 = + = 16.51𝑚
𝜋52 12
The height of the crystallizer was chosen to be 20m giving a height to diameter ration of 4:1.
This figure was chosen to maximise the Surface Area whilst maintain a stable ratio. The volume
of such a crystalliser is calculated via Eqn. 7.
𝜋52 5
𝑉𝑐 = 𝑉𝑓 + (3.49 − ) = 376.34𝑚3
4 12

The available headspace in the crystallizer is 60.26m3 which is greater than the recommended
minimum of 15%.
Surface Area of the Crystallizer in contact with the liquid is given by Eqn. 8, where r is the
radius of cylinder, h is the height of the cylinder and a is equals to Dt/4. The value of p is and
approximation equal to 1.6075, Knud Thomsen’s Formula, which yields an error of 1.061%.
As I am only calculating the Area of half an Ellipsoid, the area is multiplied by 2π instead of
4π found in the reference. [11]
(𝑟 2 )𝑝 + (𝑟𝑎)𝑝 + (𝑟𝑎)𝑝 1
𝑆𝐴 𝑐𝑜𝑛𝑡𝑎𝑐𝑡𝑖𝑛𝑔 𝑙𝑖𝑞𝑢𝑖𝑑 = 2𝜋𝑟ℎ + 2𝜋( )𝑝 𝐸𝑞𝑛. 8
3
1
5 (2. 52 )1.6075 + (2.5 ∗ 1.25)1.6075 + (2.5 ∗ 1.25)1.6075 1.6075
𝑆𝐴 = 2𝜋(2.5) (16.514 − ) + 2𝜋 ( )
4 3
𝑆𝐴 = 239.773 + 27.138
𝑆𝐴 = 266.911 𝑚2
𝑇𝑜𝑡𝑎𝑙 𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝐴𝑟𝑒𝑎 = 2𝜋(2.5)(3.49 − 1.25) + 27.138 + 266.911
𝑇𝑜𝑡𝑎𝑙 𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝐴𝑟𝑒𝑎 = 329.165𝑚2

4.3.8.3 Materials
The choice of material that will be used in the design of this crystallizer mainly depends on the
properties of the solution that it is containing. The feed solution is a highly acidic and thus will
require a good corrosion resistant material for a long life.
 Low Carbon (Mild) Steel is the most commonly used material in unit operation design
however due to the solutions acidity this will be a poor material.
 Type 304 is the general form of Stainless Steel containing the minimum amount of
Chromium & Nickel to give its structure. This is a poor version of stainless steel having
a low corrosion resistance, thus it shouldn’t be selected.
 Type 316 Stainless Steel is an improved form containing added Molybdenum to
improve corrosion resistance and would be a suitable material.
 The family of Hastelloy alloys contain high amounts of Nickel, Chromium,
Molybdenum and Iron alloys and were developed for their corrosion resistance to
strong acids. The two main grades of Hastelloy are Hastelloy B & Hastelloy C.
 A glass lined vessel has a superior corrosion resistance compared to the other materials
and its cost will be reduced as a low carbon steel can be used to reinforce the glass.
The cost rating of a material is given by Eqn. 9 and compared in the Table below: [12]
𝐶𝜌𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙
𝐶𝑜𝑠𝑡 𝑅𝑎𝑡𝑖𝑛𝑔 = 𝐸𝑞𝑛. 9
𝜎𝑑
Material Cost, $/Kg ρmaterial, Kg/m3 σd, Nmm-2 Cost Rating
Stainless Steel 3.3333 8000 290 91.945
316
Hastelloy C 26 8890 365 633.26
Carbon Steel 0.738 7850 250 23.17
Table 4.14: Cost Ratings of Possible Materials [13-16]
The proposed material for the crystallizer is Stainless Steel 316. This provides excellent
corrosion resistance against both Organic Acids, Hydrochloric Acid, and Water, & will prove
to be economical for the process. The glass lined vessel manufactured with carbon steel was
rejected due to the added cost of forming the glass lining. This would have to be manufactured
in one single piece which would have a high cost. The wall thickness of the cylinder & Ellipsoid
is given by Eqn. 9 & 10 respectively. [12]
𝑃𝑖 𝐷𝑡
𝑒𝑐𝑦𝑙 = 𝐸𝑞𝑛. 9
2𝜎𝑑 − 𝑃𝑖
𝑃𝑖 𝐷𝑡
𝑒𝑒𝑙𝑖𝑝 = 𝐸𝑞𝑛. 10
2𝐽𝜎𝑓 − 0.2𝑃𝑖
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑙𝑜𝑎𝑑 𝑖𝑛 𝐶𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟 𝑥 𝑔
𝑃𝑖 =
𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑟𝑒𝑎 𝑜𝑓 𝐿𝑖𝑞𝑢𝑖𝑑 𝑖𝑛 𝑐𝑜𝑛𝑡𝑎𝑐𝑡 𝑤𝑖𝑡ℎ 𝐶𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑟
The pressure is calculated for the surface area of the ellipsoidal as this is the area that
experiences the most down force.

407279.379 ∗ 9.81
𝑃𝑖 = = 147225.412𝑁𝑚−2
27.138
The crystallizer is ran at atmospheric pressure, therefore including this gives a Pressure of
248525.412 Nm-2 For calculating the required thickness an additional 20% is added to the
Pressure value for safety. Therefore Pi is 298230.494 Nm-2. The value for J, the welded joint
factor, is assumed to be 1. This value accounts for the efficiency of welds in the vessel for
which a high value is required.
300000 ∗ 5
𝑒𝑒𝑙𝑖𝑝 = = 0.003𝑚 = 3𝑚𝑚
2(1)(250𝑥106 ) − 0.2(300000)
The diameter of the ellipsoid and therefore the cylindrical section has been calculated to be
3mm. I do not feel this is realistic as it would leave the wall to be weak. For safe protection
against corrosion and to strengthen the wall I will set the diameter to be 10mm.
The quantity of steel required for the crystallizer can be calculated by:
𝑉𝑠𝑡𝑒𝑒𝑙 = 329.165 ∗ 0.01 = 3.29 𝑚3
3.29 ∗ 8000 = 25827𝐾𝑔

4.3.8.4 Agitation Requirements
Diameter
The chosen agitator diameter is 2/5th the diameter of the Crystallizer. In this case that would be
2m.
Position
Due to the large fluid height to diameter ratio two impellers are required for the crystalliser to
ensure good mixing. These are located at 1/5th and at 3/5th the fluid height. Thus the heights are
3.303m ≈ 3.5m and at 9.908m ≈ 10m
Baffles
Baffles are added to the crystalliser to lower the threshold for turbulence & prevent vortexes
forming when low-viscosity liquids are agitated. The recommended size for baffles is 1/10th
the diameter of the crystallizer. Baffles will also only be place along the cylindrical portion of
the crystallizer. The width of each Baffle is 0.5m and the height is 15m. [17]
Agitator Speed
The minimum agitator speed that generates turbulence must be calculated as turbulence is
required to ensure good mixing, and suspension of solid particles. Due to the presence of
Baffles the Reynolds Number for turbulence is 10000, which is reduced from 50000 for an
unbaffled Crystallizer.
𝜌𝑓𝑒𝑒𝑑 𝑁𝑠 𝐷𝑖2
𝑅𝑒 = 𝐸𝑞𝑛. 11
𝜇
To calculate the viscosity of the feed it was assumed that the feed was an aqueous Succinic
acid solution as this is the most important component in the mixture. A plot of the Viscosity vs
Temperature for the Succinic Acid solution was generated and the viscosity at 52°C was
determined to be 0.532Pa s [18]
1.18
1.16
1.14
1.12
Viscosity, Pa s
1.1
1.08 y = -0.0187x + 1.5044
1.06
1.04
1.02
1
0.98
0 5 10 15 20 25 30
Temperature, C
μ, Pa s
Figure 4.28: Chart of Viscosity vs Temperature

10000(0.532)
𝑁𝑠 = = 1.03𝑠 −1
1288.538(2)2
𝑁𝑠 = 0.002(60) = 61.93𝑟𝑝𝑚
The agitator speed will be set to 62rpm.
Choice of Agitator
The choice of agitator is determined by the rotational speed and by the viscosity of the fluid.
[19]
 Propeller: <2 Pa s
 Turbine: <50 Pa s
 Paddle: <1000 Pa s
A pitched blade propeller is the most suitable agitator for this crystallizer. From Figure 4.29 a
pitched blade propeller (Curve 6) has a Power Number, Np, of 1.4. The power required by the
agitator can be calculated via Eqn. 12.
𝑃 = 𝑁𝑝 𝜌𝑓𝑒𝑒𝑑 𝑁𝑠3 𝐷𝑖5 𝐸𝑞𝑛. 12
623
𝑃 = 1.4(1288.538) ( ) (25 ) = 63.7𝑘𝑊
60
63693
𝑃/𝑉𝑓 = = 201𝑊 𝑚−3
316.079
Figure 4.29: Graph of Power Number vs Reynolds Number [19]

4.3.8.5 Cooling Requirements
The amount of heat to be removed from the crystalliser is defined by Eqn. 13. [7]
−𝑄 𝑚𝑐
=( ) ℎ + 𝐶𝑝0 (𝑇0 − 𝑇𝑓 ) 𝐸𝑞𝑛. 13
𝑉𝜌𝑓𝑒𝑒𝑑 𝑉𝜌𝑓𝑒𝑒𝑑 𝑐
−𝑄 −29061 78.784
= 0.143 ( )+ (52 − 20) = 78.675 𝐾𝐽/𝐾𝑔
𝑉𝜌𝑓𝑒𝑒𝑑 118.0878 22.162
The chosen coolant to be used is Propylene Glycol. This Glycol was chosen over Ethylene
Glycol as it is less, and because Ethylene Glycol is used to reduce temperature below 0°C
whereas Propylene Glycol is used as a coolant for temperature just above 0°C.
𝐾𝐽
78.678 = 32042687.38𝐾𝐽 = 3172.94𝐾𝑊
𝐾𝑔
The Temperature change was selected to be 10°C with the inlet glycol temperature being 5°C
and outlet temperature being 15°C. The mass flow of glycol is calculated by Eqn. 14
𝑄 = 𝑚𝑃𝐺
̇ 𝐶𝑝𝑃𝐺 ∆𝑇 𝐸𝑞𝑛. 14
3172.94
𝑚̇𝑃𝐺 = = 94.15𝐾𝑔/𝑠
10(3.37)
The maximum amount of coolant required to generate the temperature change calculated above
is:
94.15 ∗ 10098.753 = 950797𝐾𝑔
For cost saving purposes the coolant will be recycled through the Chiller and make three passes
of the crystallizer. The figure can be reduced from 950 tonnes to 300 tonnes.
4.3.8.6 Additional Calculations

The yield of crystals can be calculated by Eqn. 2.
𝑚𝑐 𝐾𝑔
= 0.143
𝑉𝜌𝑓𝑒𝑒𝑑 𝐾𝑔 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑚𝑐 = 1288.538(316.079)(0.143)
𝑚𝑐 = 58058.047 𝐾𝑔 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠/𝑐𝑦𝑐𝑙𝑒
Literature determines that the crystals collected are 99.99% pure. [20] Therefore we will
assume pure crystals here. The yield of Succinic Acid Crystals from the crystalliser is 93.04%

4.3.9 Results
Dimension Value Dimension Value
Feed Density, ρfeed 1288.538 Kg/m3 tf 10098.753s
Crystallizer Load
Cycle time 5 hrs, 18000s 407279 kg
Mass
Crystallizer Load
316.079 m3 Crystallizer Volume 384.518 m3
Volume
Crystallizer
5m Liquid Height 16.514 m
Diameter
Crystallizer Height 20 m Liquid Surface Area 266.911 m2
Crystallizer Surface Hastelloy C Cost
329.165 m2 633.26
Area Rating
Carbon Steel Cost
23.17 Internal Pressure Pi 300000 Nm-2
Rating
eelip Theoretical 2.57mm eelip Actual 10mm
Agitator Diameter,
2m Agitator Locations 3.5m & 10m
Di
Baffle Thickness 0.5m Baffle Height 15m
Minimum Agitator
61.93 RPM Agitator Speed 62 RPM
Speed
Agitator Power per
Agitator Power 63.7kW 0.2kW/m3
unit volume
Required Heat
78.675 KJ/Kg Mass of Coolant 300 tonnes
Removal
Crystal Yield 58058.047 Kg

Figure 4.30: Visio Diagram of Crystallizer (Not to Scale)

4.3.10 Appendix
Figure 4.31: Excel Spreadsheet of some calculations performed
Figure 4.32: Excel spreadsheet of values calculated

4.3.11 References
[1] Q. Li, D. Wang, Y. Wu, W. Li, Y. Zhang, J. Xing and Z. Su, “One Step Recovery of
Succinic Acid from Fermentation Broths by Crystallization,” Separation and
Purification Technology, vol. 72, no. 3, pp. 294-300, 2010.
[2] A. Lewis, M. Seckler, H. Kramer and G. V. Rosmalen, “Industrial Crystallization:

Fundamentals and Applications,” Cambridge, Cambridge Univeristy Press, 2015, pp.
xxiii, 56.
[3] A. Mersman, “Crystallization Technology Handbook,” New York, Marcel Dekker, Inc,
1995, pp. 56-57.
[4] “Crystallization Technology: Oslo Crystallizers,” GEA , 2018. [Online]. Available:

https://www.gea.com/en/products/oslo-crystallizer.jsp. [Accessed 14 February 2018].
[5] D. Neville, “Whiting Equipment Canada Inc. Swenson Crystallization Equipment,”

http://crystallisation.pbworks.com/f/Swenson+Crystallization+Equipment.pdf.
[Accessed 15 February 2018].
[6] “Water - Density, Specific Weight and Thermal Expantion Coefficient,” Engineering
Toolbox, [Online]. Available: https://www.engineeringtoolbox.com/water-density-
specific-weight-d_595.html. [Accessed 10 February 2018].
[7] J. Nyvlt and J. W. Mullin, “Design of Batch Agitated Crystallisers,” Crystal Research
& Technology, vol. 12, no. 12, pp. 1243-1249, 1977.
[8] Y. Qiu and Å. C. Rasmuson, “Growth and dissolution of succinic acid crystals in a
batch stirred crystallizer,” AIChE Journal, vol. 36, no. 5, pp. 665-676, 1990.
[9] D. Jones and Ph.D, “Calculating Tank Volume,” 02 06 2003. [Online]. Available:
http://www.webcalc.com.br/blog/Tank_Volume.PDF. [Accessed 10 02 2018].
[10] A. V. Barderas and S. G. Rodea, “HOW TO CALCULATE THE VOLUMES OF

PARTIALLY FULL TANKS,” [Online]. Available:
http://esatjournals.net/ijret/2016v05/i04/IJRET20160504001.pdf. [Accessed 10
February 2018].
[11] W. Formulas, “Surface Area of an Ellipsoid,” [Online]. Available: http://www.web-

formulas.com/Math_Formulas/Geometry_Surface_of_Ellipsoid.aspx. [Accessed 11
February 2018].

[13] “World Stainless Steel Prices,” MEPS, [Online]. Available:

http://www.meps.co.uk/Stainless%20Prices.htm. [Accessed 15 February 2018].
[14] “AISI Type 316 Stainless Steel,” ASM Aerospace Specification Materials Inc.,
http://asm.matweb.com/search/SpecificMaterial.asp?bassnum=mq316a. [Accessed 15
February 2018].
[15] “Hastelloy C276 Sheet Suppliers,” TM Corporation, [Online]. Available:

http://www.technicalmetalcorp.com/hastelloy-sheet-hastelloy-sheets/astm-b575-uns-
n10276-hastelloy-c276-sheet-suppliers-in-united-states-of-america-usa.html. [Accessed
15 February 2018].
[16] “HASTELLOY C-276 TECHNICAL DATA,” High Temp Metals, [Online]. Available:
http://www.hightempmetals.com/techdata/hitempHastC276data.php. [Accessed 15
February 2018].
[17] N. Harnby, M. F. Edwars and A. W. Nienow, “Butterworths Series in Chemical

Engineering,” in Mixing in the Process Industries, Oxford, Butterworth Heinemann, p.
115.
[18] J. W. Mullin and M. J. L. Whiting, “Succinic Acid Growth Rates in Aqueous

Solutions,” Industrial & Engineering Chemistry Fundamentals, vol. 19, no. 1, pp. 117-
121, 1980.
[19] R. L. Bates, P. L. Fondy and R. Corpstein, “Examination of Some Geometric

Parameters of Impeller Power,” Industrial & Engineering Chemistry Process Design &
Development, vol. 2, no. 4, pp. 310-314, 1963.
[20] W. H. Hong, S. Y. Lee, Y. K. Hong, J. W. Won, Y. S. Huh, H. Song and E. Z. Lee,

“Method for purifying succinic acid by crystallization of culture broth”. United Nations
Patent WO 20009082050 A1, 02 July 2009.
[21] “Crystallizers,” Thermopedia, [Online]. Available:

http://www.thermopedia.com/content/680/. [Accessed 14 February 2018].
[22] W. Genck, “Crystallization Design: It's Clear,” Chemical Processing, 23 October 2003.
[Online]. Available: https://www.chemicalprocessing.com/articles/2003/381/.
[Accessed 23 February 2018].

[23] “Batch Crystallization,” VRI Custom, [Online]. Available: http://www.vri-
custom.org/Research_Batch_crystallization_Kirti.html. [Accessed 15 February 2018].

Chapter 4.4 Design of a Catalytic Fixed Bed Reactor
for the Esterification of Succinic Acid to Dimethyl
Succinate
Author: Diarmaid Beecher
4.4.1 Introduction .............................................................................................................. 130
4.4.1.1 Unit Overview ........................................................................................................ 130
4.4.1.2 Aims ....................................................................................................................... 130
4.4.1.3 Assumptions ........................................................................................................... 130
4.4.1.4 Nomenclature ......................................................................................................... 131
4.4.1.5 Feed Conditions...................................................................................................... 131
4.4.2 Mass Transfer ........................................................................................................... 132
4.4.2.1 External Mass Transfer .......................................................................................... 132
4.4.2.1.1 Diffusivity ....................................................................................................... 133
4.4.2.1.2 Reaction Rate .................................................................................................. 133
4.4.2.1.3 External Mass Transfer Coefficient ................................................................ 134
4.4.2.1.4 Results of External Mass Transfer Analysis ................................................... 134
4.4.2.2 Internal Mass Transfer ........................................................................................... 135
4.4.3 Reactor Design ......................................................................................................... 136
4.4.3.1 Enthalpy of Reaction .............................................................................................. 136
4.4.3.2 Design Equations.................................................................................................... 137
4.4.3.3 Materials ................................................................................................................. 138
4.4.3.4 Wall Thickness ....................................................................................................... 138
4.4.4 Conclusion ................................................................................................................. 138
4.4.5 Appendix .................................................................................................................... 139
4.4.6 References ................................................................................................................. 142

4.4.1 Introduction
4.4.1.1 Unit Overview
The purpose of the selected unit is to convert succinic acid to dimethyl succinate by
esterification over a solid catalyst. The reaction scheme is as follows:
Reaction step 1: 𝑆𝐴 + 𝑀𝑒𝑂𝐻 → 𝑀𝑀𝑆 + 𝐻2 𝑂
Reaction step 2: 𝑀𝑀𝑆 + 𝑀𝑒𝑂𝐻 → 𝐷𝑀𝑆 + 𝐻2 𝑂
This process, as outlined by [1], operates adiabatically at 90°C and 300kPa in a fixed bed
reactor. The target outflow is 3.868 kg/s of DMS. The conversions expected are 99% for
succinic acid and 92% for monomethyl succinate.
The catalyst used for this reaction is DOWEX DR-2030, a styrenic plastic bead which functions
as an acidic ion exchange resin [2]. There is no degradation of catalyst mentioned so it can be
assumed that this is unimportant for the reactor design.
4.4.1.2 Aims
1. Quantify the effects of external and internal mass transfer
2. Outline the equations used in this reactor design
3. Determine the catalyst weight and therefore the reactor volume
4. Identify suitable materials of construction for the reactor
4.4.1.3 Assumptions
1. Plug flow assumed in the reactor
2. Pressure drop is assumed to be negligible
3. No degradation of catalyst
4. Methanol is assumed to be the most abundant chemical for estimating density and
viscosity
5. No change in heat capacity

4.4.1.4 Nomenclature
CAb Bulk Concentration of A t Wall Thickness, m
Surface Concentration of A,
CAs T Temperature, K
mol/L
Molar Heat Capacity of i,
Cp,i u Linear Velocity
J/(mol.K)
Molecular Volume of A,
DAB Diffusivity of A in B, m2/s VA
m3/mol
E Activation Energy, J/mol w Catalyst Loading, kg/kg
Molar Flow of component i,
Fi W Catalyst Weight, g
mol/s
k Reaction Rate Constant, s-1 xi Mole Fraction of component i
ks Mass transfer coefficient, m/s Xi Fractional conversion of i
Kc Equilibrium Constant ΔHrxn Enthalpy of Reaction, J/mol
MT Molecular Mass, g/mol ε Void Fraction
P Pressure, kPa μ Viscosity, Pa.s
R Gas Constant, J/(mol.K) ρ Density kg/m3
Observed Rate of Reaction of Catalyst Bulk Density, g
rA, Obs ρb
A, mol/s catalyst / litre solution
Rp Particle Radius ø Association Factor
Rep Reynolds Particle Number Φ Observable Thiele Modulus
Observable External Mass
S Yield Strength Ω
Transfer Modulus
Reaction Rate per Mass
Sc Schmidt Number -r’
Catalyst, mol/(kgcat.s)
Sh Sherwood Number
4.4.1.5 Feed Conditions

Component Mole Fraction, Moles, mol/s Mass, kg/s Cp, J/mol.K
xi
Succinic Acid 0.1635 26.74 3.158 153
Methanol 0.8174 133.7 4.284 81
Water 0.0050 0.816 0.015 75.47
MMS 0.0141 2.302 0.304 265.78
DMS 0 0 0 255.9
Total 1 163.6 7.761

4.4.2 Mass Transfer
In reactor bulk fluid, reactants are rapidly carried by convective currents. As these reactant
molecules approach the solid catalyst, they must be transported from the bulk fluid across the
relatively stagnant boundary layer to the solid surface.
Reactant concentrations can vary in solid catalysts thus local rates of reaction also vary
depending on their position in the catalyst. The catalyst molecules responds to the reactant
concentration at its location with a rate of reaction determined by the kinetic parameters of the
catalyst. This local rate of reaction is known as the true/intrinsic rate of reaction. Without
changing the reaction conditions, it is very hard to measure these true local reaction rates, so
the observed rate is instead calculated over the entire catalyst. [7]
For heterogeneous catalytic reactions it’s important to know if mass transfer, or reaction rate
is the controlling step.
4.4.2.1 External Mass Transfer

External mass transfer concerns the transport of materials in the bulk fluid phase surrounding
the reacting entity (i.e. acts outside the catalyst particle). To determine the significance of
external mass transfer, the observable mass transfer modulus (Ω) for a spherical particle was
calculated, where the criteria for external mass transfer to be negligible is Ω < 0.05 [7]:
𝑅𝑝 𝑟𝐴,𝑂𝑏𝑠
Ω= 𝐸𝑞𝑛. 1
3 𝑘𝑠 𝐶𝐴𝑏
For 1st Order Reaction Kinetics, the observed reaction rate is [7]:
𝑟𝐴,𝑂𝑏𝑠 = 4𝜋𝑅𝑝 𝐷𝐴𝐵 𝐶𝐴𝑠 ((𝑅𝑝 √𝑘1 ⁄𝐷𝐴𝐵 ) 𝐶𝑜𝑡ℎ (𝑅𝑝 √𝑘1 ⁄𝐷𝐴𝐵 ) − 1) 𝐸𝑞𝑛. 2
The effect of external mass transfer needs to be known to evaluate the surface concentration,
CAs, however CAs also needs to be known to calculate the effect of external mass transfer. To
overcome this, Eqn. 2 can be substituted into Eqn. 1, and rearranged so that CAs is divided by
CAb. From the subsequent Eqn. 3, Ω can be evaluated to be equal to Ω*·(CAs/CAb) such that if
Ω* is << 0.05 then external mass transfer is insignificant.
𝑅𝑝 4𝜋𝑅𝑝 𝐷𝐴𝐵 ((𝑅𝑝 √𝑘1 ⁄𝐷𝐴𝐵 )𝐶𝑜𝑡ℎ(𝑅𝑝 √𝑘1 ⁄𝐷𝐴𝐵 ) − 1) 𝐶𝐴𝑠

Ω= 𝐸𝑞𝑛. 3
3 𝑘𝑠 𝐶𝐴𝑏
𝐶𝐴𝑠
𝛺 = 𝛺∗ 𝐸𝑞𝑛. 4
𝐶𝐴𝑏
𝑅𝑝 4𝜋𝑅𝑝 𝐷𝐴𝐵 ∙ [(𝑅𝑝 √𝑘1 ⁄𝐷𝐴𝐵 ∙ coth(𝑅𝑝 √𝑘1 ⁄𝐷𝐴𝐵 )) − 1]

𝛺∗ = 𝐸𝑞. 5
3 𝑘𝑆
The catalyst used has a diameter of 0.42 – 1.19 mm [2]. The reactor is operated adiabatically
as the reaction enthalpies are low, because of this it can be assumed for quantifying mass

transfer that there is no temperature change so the rate constant, diffusivity, and external mass
transfer coefficient will remain constant.
4.4.2.1.1 Diffusivity
To determine the diffusivity, the Chang-Wilke Equation [8] was used:
1 𝑇
𝐷𝐴𝐵 = 1.173 ∗ 10−16 (𝜙𝑀𝑟,𝐵 )2 𝐸𝑞𝑛. 4
𝜇𝐵 𝑉𝐴0.6
Where 𝜙 = association factor, Mr,B = solvent molecular mass, T = temperature, μB = solvent
viscosity, and VA = molar volume of solute.
Referenced values are:
 𝜙 = 1.9 for methanol [8]
 Mr,B = 18 g/mol
 T = 363 K.
VA is estimated using atomic diffusion volumes [8]:
4(0.0148) + 6(0.0037) + 4(0.0091) = 0.1178 𝐿/𝑚𝑜𝑙
To estimate μB, a range of values were taken from [8] for the viscosity at varying temperatures
for 90% methanol and 40% methanol.
Viscosity vs. Temperature for Methanol

0.0014
y = 0.9415e-0.022x 90% MeOH
0.0012 R² = 0.998
40% MeOH
0.001
Viscosity (Pa.s)
0.0008
0.0006
0.0004
y = 0.0287e-0.012x
0.0002 R² = 0.9978
0
300 310 320 330 340 350 360 370 380 390 400 410 420 430
Temperature (K)
Figure 4.33: Viscosity at varying temperatures for methanol solutions
It is likely the values taken were for a methanol-water solution, in the reactor feed methanol is
roughly 50% of the weight so it’s possible the viscosities could be higher in a solution with
succinic acid. Therefore, for the purpose of this estimation, the higher value of 3.682 x 10-4
Pa∙s is taken from the 40% methanol solution as μB.
4.4.2.1.2 Reaction Rate

As there are two reaction steps external mass transfer must be assessed separately for each
reaction rate. Reference reaction rate constants and activation energies are taken from [1] and
the eqn. 5 is used to calculate the reaction rate constant, k1 at 363 K.
𝐸
𝑘1 = 𝑘𝑟𝑒𝑓 exp (− ) 𝐸𝑞𝑛. 7
𝑅𝑇
Where E = activation energy, and R = gas constant.
Reaction 1 Reaction 2
kref 1.186 x 1010 mol/L.s kref 4.741 x 1010 mol/L.s
E 72855 J/mol E 78646 J/mol
Table 4.15: Reference Reaction Rate Constants and activation energies
4.4.2.1.3 External Mass Transfer Coefficient

To determine the external mass transfer coefficient the following equation for the Sherwood
number was used, rearranged to obtain ks:
𝑘𝑠 𝐷𝑝
𝑆ℎ = 𝐸𝑞𝑛. 8
𝐷𝐴𝐵
For this process liquid-solid mass transfer takes place in a packed bed at low Reynolds number
(Re < 10), therefore the Sherwood number must be found with the following equation [9]:
1.13
𝑆ℎ = 𝑅𝑒𝑝1/3 𝑆𝑐 1/3 𝐸𝑞𝑛. 9
𝜖
Where ε = void fraction (0.26 ≤ ε ≤ 0.48), Rep = Particle Reynold number, Sc = Schmidt number
𝐷𝑝 𝑢𝑝𝐿 𝜌𝐿 𝜇𝐿
𝑅𝑒𝑝 = 𝐸𝑞𝑛. 10 𝑆𝑐 = 𝐸𝑞𝑛. 11
𝜇𝐿 𝜌𝐿 𝐷𝐴𝐵
upL = linear velocity of the particle relative to the bulk liquid, ρL = liquid density, and μL =
liquid viscosity
Porosity is taken from [2] as 0.33. The total volumetric flow into the reactor is 7.677 x 10-3
m3/s, using a 1.5 m diameter as a guide, upL is calculated as 4.344 x 10-3 m/s. Methanol density
is taken as 724 kg/m3 at 363 K.
4.4.2.1.4 Results of External Mass Transfer Analysis

From the above equations, Ω* for reactions 1 and 2 emerges as 2.493 x 10-10 and 1.804 x 10-10
respectively. These values are small enough that CAs/CAb will not cause the result of Ω to be
more than 0.05, therefore external mass transfer is insignificant.

4.4.2.2 Internal Mass Transfer
Internal mass transfer concerns the movement of substrate and products within particles (i.e.
acts inside the catalyst particle). Internal mass transfer can be evaluated, similarly to external
mass transfer, by using the observable Thiele Modulus where the criteria for internal mass
transfer to be negligible is Φ < 0.3.
𝑅𝑝 2 𝑟𝐴,𝑂𝑏𝑠
𝜙=( ) 𝐸𝑞𝑛. 12
3 𝐷𝐴𝐵 𝐶𝐴𝑠
In this case CAs appears in the numerator of eqn. 2 and the denominator of eqn. 10, this will
cancel out CAs.
Φ is determined to be 1.62 x 10-9, therefore internal mass transfer is insignificant.

4.4.3 Reactor Design
4.4.3.1 Enthalpy of Reaction
The enthalpy of reaction at 90 °C can be calculated using:
363𝐾
∆𝐻𝑟𝑥𝑛,363𝐾 = ∆𝐻𝑟𝑥𝑛,298𝐾 + ∫ ∆𝐶𝑝 𝑑𝑇 𝐸𝑞𝑛. 13
298𝐾
Reaction enthalpies at 298 K are provided by [1] as -8.43 kJ/mol and 9.78 kJ/mol respectively
for each reaction.
Its assumed heat capacity doesn’t change with temperature. Heat capacities for monomethyl
succinate and dimethyl succinate were not available, so it was required to estimate the heat
capacities as the sum of the liquid heat capacities of the group contribution [5].
Monomethyl Succinate Dimethyl Succinate
No. of Group Value No. of Group Value

1 CH3 36.84 2 CH3 2(36.84)
2 -CH2- 2(30.4) 2 -CH2- 2(30.4)
1 O- 35.17
1 O= 53
1 79.97 2 2(60.71)
265.78 kJ/kmol °C 255.9 kJ/kmol °C
Inputting the terms, the following equation can be obtained:

∆𝐻𝑟𝑥𝑛,𝑇 = (−0.00843 + 106.65∆𝑇) + (0.00978 − 15.41∆𝑇) 𝐸𝑞𝑛. 14

4.4.3.2 Design Equations
Packed bed reactors are designed in a similar fashion to plug flow reactor except instead of
being sized by volume they are sized by the catalyst weight, W. The reactor volume can then
be obtained by dividing the resulting catalyst weight by the catalyst bulk density, ρb. Sizing of
the catalyst weight can be performed using the design equations outlined by [3]:
𝑑𝑊 𝐹𝑖,0
= 𝐸𝑞𝑛. 15
𝑑𝑋𝑖 −𝑟′𝑖
𝑑𝑇 ∑ 𝑟𝑖 ∆𝐻𝑟𝑥𝑛
= 𝐸𝑞𝑛. 16
𝑑𝑊 ∑ 𝐹𝑖 𝐶𝑝𝑖
Rate of reaction equations are provided by [1]:

𝐸1 𝑥𝑀𝑀𝑆 𝑥𝐻20
𝑟1 = 𝑤𝑘1 exp (− ) (𝑥𝑆𝐴 𝑥𝑀𝑒𝑂𝐻 − ) 𝐸𝑞𝑛. 17
𝑅𝑇 𝐾𝐶1
𝐸2 𝑥𝐷𝑀𝑆 𝑥𝐻20
𝑟2 = 𝑤𝑘2 exp (− ) (𝑥𝑀𝑀𝑆 𝑥𝑀𝑒𝑂𝐻 − ) 𝐸𝑞𝑛. 18
𝑅𝑇 𝐾𝐶2
Where w = catalyst loading, ki = reaction rate constant, xi = molar fraction of component i, and
Kci = equilibrium constant.
However, to find -r’i, the rate of reaction per weight of catalyst, the reaction rate constant, k,
must be divided by the catalyst bulk density, ρb.
As polymath can only calculate for one variable in a differential equation, the chain rule was
used to allow for the calculation of dT/dXSA and dXMMS/dXSA:
𝑑𝑇 𝑑𝑇 𝑑𝑊 (𝑟 ′𝑆𝐴 + 𝑟 ′ 𝑀𝑀𝑆 )(∆𝐻𝑟𝑥𝑛 ) 𝐹𝑆𝐴,0
= = ∙ 𝐸𝑞𝑛. 19
𝑑𝑋𝑆𝐴 𝑑𝑊 𝑑𝑋𝑆𝐴 𝐹𝑇 𝐶𝑝𝑇 −𝑟′𝑆𝐴
𝑑𝑋𝑀𝑀𝑆 𝑑𝑋𝑀𝑀𝑆 𝑑𝑊 −𝑟′𝑀𝑀𝑆 𝐹𝑆𝐴,0
= = ∙ 𝐸𝑞𝑛. 20
𝑑𝑋𝑆𝐴 𝑑𝑊 𝑑𝑋𝑆𝐴 𝐹𝑀𝑀𝑆,0 −𝑟 ′𝑆𝐴
The complete input file and results are attached in the appendix. Given a catalyst weight of 340
kg, this gives a reactor volume of approximately 1.3 m3. A height/diameter ratio of 0.5
appropriate for ion exchange resins [4] was used to calculate a height of 0.75 m and diameter
of 1.5 m.

4.4.3.3 Materials
Some of the criterion in material selection are as follows:
 Corrosion resistance
 Suitable mechanical properties
 Economically suitable
Carbon steel was explored as material of construction. Its advantages include being relatively
cheap in comparison to stainless steel and being capable of withstanding pressures up to 90
MPa [5], however its main drawback is its susceptibility to corrosion. For this reason, it was
decided to use 304 stainless steel.
4.4.3.4 Wall Thickness

The calculation of minimum thickness required to resist internal pressure is outlined by [5]:
𝑃𝑖 𝐷𝑖
𝑡= 𝐸𝑞𝑛. 21
2𝑆 − 𝑃𝑖
Where t = wall thickness, Pi = internal pressure, Di = internal diameter, and S = yield strength.
Pi is 300 kPa, Di is 1.5 m, and the value given for S is 205000 kPa. [6] This gives a thickness
of 0.0011 m, this is below the minimum thickness of 0.007 m required for a vessel to withstand
its own weight [5].
Using a major and minor axis ratio of 2:1 for the ellipsoidal head, the shell mass can be
calculated to be 560 kg.
4.4.4 Conclusion
In conclusion, a fixed bed reactor has been designed to convert succinic acid to dimethyl
succinate by esterification over a solid catalyst. The reactor is kinetically controlled and is to
be operated adiabatically with temperature at 90 °C and pressure at 300 kPa. The reactor will
be manufactured with 304 stainless steel with the walls 0.007 m thick. Total reactor volume
should be approximately 1.3 m3 with 340 kg of catalyst required. The dimensions are 1.5 inner
diameter with a 0.75 m height.

4.4.5 Appendix
Figure 4.34: Polymath Input File

Figure 4.35: Polymath Results File

4.4.6 References
[1] J. Dudas and e. al., “Design consideration of dimethyl succinate production process,”
Chemical Papers, vol. 68, no. 12, pp. 1667-1677, 2014.
[2] “Product Information: DOWEX DR-2030 Catalysts,” Dow Chemical Company, 2002.
http://msdssearch.dow.com/PublishedLiteratureDOWCOM/dh_003c/0901b8038003cd6c
.pdf?filepath=liquidseps/pdfs/noreg/177-01815.pdf&fromPage=GetDoc.
[3] H. S. Fogler, Elements of Chemical Reaction Engineering, Pearson Education Inc., 2006.
[4] D. R. Woods, Rules of Thumb in Engineering Practice, WILEY-VCH Verlag GmbH &
Co. KGaA, 2007.
[5] R. Sinnott and G. Towler, Chemical Engineering Design, Elsevier Ltd., 2009.
[6] “Online Design Tools, Allowable Stresses,” CIS GmbH, [Online]. Available:
http://www.cis-inspector.com/asme-code-calculation-allowable-stresses-high-alloy.html.
[7] P. M. Doran, Bioprocess Engineering Principles, Elsevier Ltd., 1995.
[8] J. R. J. Coulson, Fluid Flow, Heat Transfer, and Mass Transfer, Elsevier Ltd., 1999.
[9] e. a. D. Seguin, “Liquid-solid mass transfer in packed beds of variously shaped particles
at low Reynolds numbers: experiments and model,” The Chemical Engineering Journal
and the Biochemical Engineering Journal, vol. 63, no. 1, pp. 1-9, 1996.

Chapter 4.5 Design of a Continuous Plug Flow
Reactor for the Hydrogenolysis of
Dimethyl Succinate to 1,4-Butanediol
Author: Mark Fitzpatrick
4.5.1 Unit Overview........................................................................................................... 145
4.5.2 Reactor Selection .................................................................................................... 145
4.5.3 Aims .............................................................................................................................. 145
4.5.3 Assumptions ............................................................................................................. 145
4.5.4 Nomenclature ........................................................................................................... 146
4.5.5 Catalyst Selection .................................................................................................... 147
4.5.6 Kinetics Overview................................................................................................... 147
4.5.7 Mass Transfer Analysis ........................................................................................ 148
4.5.7.1 External Mass Transfer .......................................................................................... 148
4.5.7.2 Determination of Diffusivity .................................................................................. 148
4.5.7.3 External Mass Transfer Coefficient ....................................................................... 149
4.5.7.4 Internal Mass Transfer ........................................................................................... 149
4.5.8 Reactor Sizing ........................................................................................................... 150
4.5.8.1 Design Equations.................................................................................................... 150
4.5.8.2 Mole Balance.......................................................................................................... 150
4.5.8.3 Energy Balance ...................................................................................................... 150
4.5.8.4 Momentum Balance (Ergun Equation) .................................................................. 151
4.5.8.5 Tube Geometries .................................................................................................... 152
4.5.9 Selected Reactor ...................................................................................................... 154
4.5.10 Reactor Material of Construction .................................................................. 156
4.5.11 Reactor Material of Construction .................................................................. 157
4.5.12 Reactor Costs ......................................................................................................... 158
4.5.13 Conclusion ............................................................................................................... 158
4.5.14 Appendix .................................................................................................................. 159
4.5.15 References ............................................................................................................... 163

4.5.1 Unit Overview
Reactor R302, is the final reaction step in the conversion of raw corn stover to 1,4-butanediol.
The requirement for this reactor is the production of 75,200 tonnes a year (2.56kg/s) of 1,4-
butanediol from the intermediary dimethyl succinate produced upstream in R301.
4.5.2 Reactor Selection

From literature the two step conversion of dimethyl succinate (DMS) to 1,4-butanediol (BDO)
via the intermediary methyl-4-hydroxybutanoate (MHB) in an excess of hydrogen, producing
methanol (MeOH) as a by-product [1] is known to be a hydrogenolysis (a primary substitution
reaction process where hydrogen replaces the alkyl group) reaction as follows:
Reaction step 1: 𝐷𝑀𝑆+2𝐻2→𝑀𝐻𝐵+𝑀𝑒𝑂𝐻
Reaction step 2: 𝑀𝐻𝐵+2𝐻2→𝐵𝐷𝑂+𝑀𝑒𝑂𝐻
This is a vapour phase reaction, well described by Langmuir-Hinshelwood-type kinetics. Due
to the production requirements and gaseous state of this reaction, continuous reactors such as
packed bed, moving bed and fluidised bed were considered. As regeneration of the catalyst is
not required, moving bed reactor was ruled out. Due to the further processing and dust proofing
required down stream of fluidised bed reactors, and lacking knowledge of the catalyst’s
resistance to attrition, fluidized bed was similarly disregarded. Thus a plug flow packed bed
tubular reactor will be modelled in this report. [2] The conditions required for the reaction are
270°C (543K) and 5 bar pressure.
4.5.3 Aims
 Provide an overview on the kinetics for use in the reactor design.
 Quantify the effects of internal and external mass transfer.
 Construct a model using plug flow reactor design equations for this reaction.
 Determine the required mass of catalyst, optimum reactor size and pressure drop
through the reactor.
 Identify suitable materials of construction for the unit.
4.5.3 Assumptions
 Inlet feed is perfectly mixed by sparging hydrogen into the gaseous reactant feed.
 Plug flow is assumed in this reactor.
 All catalyst sites are active.
 No deactivation of catalyst or side reactions occur.
 Uniform temperature in reactor tubes and coolant fluid.
 Viscosity is assumed to be equivalent to that of hydrogen as molecularly it’s the most
abundant chemical, and limited viscosity data is available for the other reactants and
products.
 The thermodynamic properties of hexanoic acid are used in place of methyl-4-
hydroxybutanoate (MHB), due to insufficient information on this rarely used chemical.

4.5.4 Nomenclature
Observed reaction rate of species
Ac Cross-sectional area of tubes, m2 ri,obs
i, mol s-1
Bulk Concentration of DMS, Reynolds number of catalyst
CDMSb Rep
mol L-1 particles
Surface Concentration of DMS,
CDMSs Rp Catalyst particle radius, m
mol L-1
Cp Heat capacity, J mol-1 K-1 Sc Schmidt number
Db Reactor shell diameter, m Sh Sherwood number
Diffusivity of DMS in
DDMSH T Temperature in reactor
Hydrogen,
Dp Catalyst particle diameter, m2 s-1 T0 Temperature at reactor inlet
Flow rate of coolant around
Fcoolant Ta Temperature of coolant
each tube, kg s-1
Molar flow rate of DMS per
FDMS0t U Overall heat transfer coefficient
tube at inlet, mol s-1
Superficial mass velocity per
G u Superficial linear velocity
tube, kg m-2 s-1
Enthalpy of reaction at
Hrxn,T Vi Molecular volume of species i
temperature T, J mol-1
ID Inner diameter of tubes, m vi Stoichiometric coefficient of i
Reaction rate constant, mol cm-3
k1 W Weight of catalyst
s-1
Coefficient for calculation of
KD1 X Conversion
shell diameter
Adsorption constant of species i,
Ki z Reactor length
Pa-1
Mass Transfer Coefficient for Fraction change in volume per
kG ε
gas, m s-1 mole
Ratio of moles of i initially
Molecular weight of species i,
Mi Θ entering reactor to the number of
kg/mol
moles of A
Coefficient for calculation of
n1 μ Viscosity, Pa.s
shell diameter
Nt Number of tubes ρo Density of the inlet gas, kg m-3
Bulk density of the catalyst in the
OD Outer diameter of tubes, m ρb
packed bed, kg m-3
Density of the catalyst particles,
P Pressure in reactor, Pa ρc
kg m-3
P0 Pressure at inlet, Pa φn Observable Thiele Modulus
Pi Partial pressure of species i, Pa φ Void fraction of catalyst
Rate of consumption of DMS, Observable External Mass
-rDMS Ω
mol s-1 Transfer Modulus

4.5.5 Catalyst Selection
Kohler et al. 1986[3] and Kohler et al. 1987[4]
studied the hydrogenolysis of dimethyl succinate
over a range of copper-based catalysts. Figure 4.36
illustrates the results of this study showing the
conversion and selectivity of each catalyst they
investigated. It can be seen that catalyst D (Raney
copper promoted with chromium) shows the highest
conversion and selectivity to 1,4-butanediol. It is
prepared by the selective dissolution of aluminium
from CuCrAl7 using aqueous caustic solutions. The
copper remaining after this caustic leaching
rearranges to form a new morphology without itself
dissolving. [3] This rearrangement results in a highly
porous copper catalyst, with a large surface area Figure 4.36: Plot of 1,4-butanedoil selectivity versus
for adsorption. Therefore Raney copper promoted conversion at 543K for various catalysts
with chromium will be used in this reactor.
4.5.6 Kinetics Overview

As described above, the conversion of DMS to BDO occurs linearly via two steps in series.
The kinetics for both steps in this reaction follow Langmuir-Hinshelwood models and are
described by: [1]
𝑘1 (𝐾𝐷𝑀𝑆 𝑃𝐷𝑀𝑆 )1⁄2 𝐾𝐻 𝑃𝐻
𝑆𝑡𝑒𝑝 1: 𝑟𝐷𝑀𝑆 = 𝐸𝑞𝑛. 1
(1 + (𝐾𝐷𝑀𝑆 𝑃𝐷𝑀𝑆 )1⁄2 + 𝐾𝐻 𝑃𝐻 )2
𝑘2 (𝐾𝑀𝐻𝐵 𝑃𝑀𝐻𝐵 )1⁄2 𝐾𝐻 𝑃𝐻

𝑆𝑡𝑒𝑝 2: 𝑟𝑀𝐻𝐵 = 𝐸𝑞𝑛. 2
(1 + (𝐾𝑀𝐻𝐵 𝑃𝑀𝐻𝐵 )1⁄2 + 𝐾𝐻 𝑃𝐻 )2
Where KDMS, KMHB and KH are the adsorption constants, and k1, k2 are the rate constants.
The reaction rate constants for reaction steps 1 and 2 using Raney copper catalyst promoted
with chromium, are shown in Table 4.16. The ratio of k2/k1, shows that the conversion of DMS
to MHB occurs slower than the subsequent conversion of MHB to BDO. Reaction step 1 is the
limiting step and so this will be used for modelling this reactor. Subsequent conversion of 93%
of MHB to BDO will be assumed to occur as fast as the MHB is created, in agreement with the
selectivity of the Raney copper-chromium catalyst.[1]
Reaction k k2/k1 KDMS KMHB KH

Step s-1 Pa-1 Pa-1 Pa-1
1 5.2E-05 2.5E-03 - 7.2 E-06
0.8
2 4.8 E-05 - 2.4 E-03 7.2 E-06
Table 4.16: Reaction Kinetics

4.5.7 Mass Transfer Analysis
As described in Chapter 4.4, it must be determined if mass transfer rate or rate of reaction is
the controlling step in this hydrogenolysis reaction, before design of the reactor can be
attempted.
4.5.7.1 External Mass Transfer

Due to the gas phase of this reaction, literature suggests external mass transfer will not be
limiting, however its effects will still be quantified. The same method as described in Chapter
4.4 will be utilised, where Ω’ (Eqn. 1) will be evaluated in place of observable mass transfer
modulus (Ω) (Eqn. 2) which cannot be determined without knowing the concentration of
reactants on the surface of the catalyst. If Ω’ is determined to be much less than 0.05 then it
can be confidently said that Ω is much less than 0.05, and that external mass transfer is
insignificant.
𝑅𝑝 4𝜋𝑅𝑝 𝐷𝐷𝑀𝑆𝐻 ∙ [(𝑅𝑝 √𝑘1 ⁄𝐷𝐷𝑀𝑆𝐻 ∙ coth(𝑅𝑝 √𝑘1 ⁄𝐷𝐷𝑀𝑆𝐻 )) − 1]

𝛺′ = 𝐸𝑞𝑛. 3
3 𝑘𝐺
𝐶𝐷𝑀𝑆𝑠
𝛺 = 𝛺′ 𝐸𝑞𝑛. 4
𝐶𝐷𝑀𝑆𝑏
In Eqn. 3, Rp is the radius of catalyst particles (4.25mm), k1 is the reaction rate constant of the
limiting reaction step 1 and DDMSH is the diffusivity of gaseous DMS in hydrogen, which will
be calculated below.
4.5.7.2 Determination of Diffusivity

Due to the lack of literature data on the diffusivity of dimethyl succinate in hydrogen, a
predictive method must be used. The method chosen is thanks to Gilliland [3], and is based on
the “Stefan-Maxwell” hard sphere model.
4.3 × 10−4 𝑇 1.5 √(1⁄𝑀𝐷𝑀𝑆 ) + (1⁄𝑀𝐻 )

𝐷𝐷𝑀𝑆𝐻 = 1/3 1/3
𝐸𝑞𝑛. 5
𝑃(𝑉𝐷𝑀𝑆 + 𝑉𝐻 )
Where MDMS and MH are the molecular weights of dimethyl succinate and hydrogen
respectively, and VDMS and VH are the molecular volumes calculated using Kopp’s law of
additive volumes, and Table 6 in the appendix.

4.5.7.3 External Mass Transfer Coefficient
Using the dimensionless number correlations between Reynolds Particle Number (Rep),
Schmidt Number (Sc) and Sherwood Number (Sh), the external mass transfer coefficient for
gases (kG) can be calculated.
Based on published data by WAKAO and FUNAZKRI, for gas phase fluid through a fixed bed
of spherical pellets, with Reynolds numbers in the range of 3<Re<104, the Sherwood number
can be calculated by: [4]
𝑆ℎ = 2.0 + 1.1𝑆𝑐1/3 𝑅𝑒𝑝0.6 𝐸𝑞𝑛. 6
Where:
𝑘𝐺 𝐷𝑝 𝜇 𝐷𝑝 𝑢𝜌0
𝑆ℎ = 𝐸𝑞𝑛. 7 𝑆𝑐 = 𝐸𝑞𝑛. 8 𝑅𝑒𝑝 = 𝐸𝑞𝑛. 9
𝐷𝐷𝑀𝑆𝐻 𝜌0 𝐷𝐷𝑀𝑆𝐻 𝜇
Taking the superficial velocity (u) of the fluid to be 1 m/s, the mass transfer coefficient kG is
calculated and reported below.
Temp Density Viscosity Diffusivity Rep Sc Sh k1 KG Ω’
K Kg/m3 Pa.s m2/s s-1 m/s
243 2.117 1.37E-05 8.503E-06 1500 0.761 82.800 60 0.1656 8.626E-10
Table 4.17: Results of external mass transfer analysis
Ω’ is much less than 1, thus CDMSs ≈ CDMSb and external mass transfer effects are insignificant.
4.5.7.4 Internal Mass Transfer

Internal mass transfer can calculated in a similar way to external mass transfer. Doran [5]
defines the observable Thiele modulus (𝛷𝑛 ) as:
𝑅𝑝 2 𝑟𝐷𝑀𝑆𝑜𝑏𝑠
𝛷𝑛 = ( ) 𝐸𝑞𝑛. 10
3 𝐷𝐷𝑀𝑆𝐻 𝐶𝐷𝑀𝑆𝑠
𝑅𝑝 2 4𝜋𝑅𝑝 𝐷𝐷𝑀𝑆𝐻 ∙ [(𝑅𝑝 √𝑘1 ⁄𝐷𝐷𝑀𝑆𝐻 ∙ coth(𝑅𝑝 √𝑘1 ⁄𝐷𝐷𝑀𝑆𝐻 )) − 1] 𝐶𝐷𝑀𝑆𝑠

𝛷𝑛 = ( ) 𝐸𝑞𝑛. 11
3 𝐷𝐷𝑀𝑆𝐻 𝐶𝐷𝑀𝑆𝑠
When rDMSobs is substituted into Eq.10, the unknown CDMSs cancels, allowing the Observable
Thiele Modulus to be calculated.
Temperature Density Rp Viscosity Diffusivity k1 Φ
K kg/m3 m Pa.s m2/s s-1
243 2.117 2.125E-03 1.37E-05 8.503E-06 60 1.19E-08
Table 4.18: Results of internal mass transfer analysis
As the Observable Thiele Modulus is so small (<0.3[5]) the effects of internal mass transfer of
dimethyl succinate are insignificant.
As shown, both internal and external mass transfer have a negligible effect on the reaction rate
in this gas phase reactor, thus reaction rate is the limiting factor.

4.5.8 Reactor Sizing
The sizing of tubular plug flow reactors is based on the mass of solid catalyst particles (W)
required to achieve the conversion (X) of the reactants to products under the conditions in the
individual reactor tubes. However, as the reaction progresses, the reactant partial pressure
(PDMS), temperature (T) and pressure (P) change. It is very difficult to numerically solve these
three differential equations, so Polymath Ordinary Differential Equation solver was used.
However this solver can only solve for one variable (conversion, X), so all design equations
are rearranged using the chain rule so they can be solved with respect to conversion.
4.5.8.1 Design Equations

The limiting reactant in this reaction is dimethyl succinate, and thus the reaction will be
modelled using the rate of consumption of DMS (−𝑟𝐷𝑀𝑆 , 𝐸𝑞. 1), where k is the rate constant,
KDMS/KH are the adsorption constants and PDMS (Eq.12), PH (Eq.13) are the partial pressures of
DMS and hydrogen respectively. 𝑃𝐷𝑀𝑆0 represents the partial pressure of DMS at the reactor
inlet, while 𝛩𝐻 is the ratio of number of moles of H entering the reactor, to the number of moles
of DMS entering. Finally 𝑣𝐷𝑀𝑆 /𝑣𝐻 are the stoichiometric coefficients of DMS and hydrogen,
and ε is the fraction change in volume per mole.
𝑘(𝐾𝐷𝑀𝑆 𝑃𝐷𝑀𝑆 )1⁄2 𝐾𝐻 𝑃𝐻

−𝑟𝐷𝑀𝑆 = 𝐸𝑞𝑛. 1
(1 + (𝐾𝐷𝑀𝑆 𝑃𝐷𝑀𝑆 )1⁄2 + 𝐾𝐻 𝑃𝐻 )2
𝑃 𝑃
𝑃𝐷𝑀𝑆0 (𝑃 ) (1 − 𝑣𝐷𝑀𝑆 𝑋) 𝑃𝐷𝑀𝑆0 (𝑃 ) (𝛩𝐻 − 𝑣𝐻 𝑋)
0 0
𝑃𝐷𝑀𝑆 = 𝐸𝑞𝑛. 12 𝑃𝐻 = 𝐸𝑞𝑛. 13
(1 + 𝜀𝑋) (1 + 𝜀𝑋)
4.5.8.2 Mole Balance

The mass of solid catalyst particles (W) required to achieve the conversion (X) of the reactants
to products in each reactor tube is shown in Eq 14, where 𝐹𝐷𝑀𝑆0𝑡 is the inlet molar flow of
DMS per tube, and 𝜌𝑏 is the bulk density of the catalyst in the tubes. This bulk catalyst density
is calculated based on the density of the catalyst particles (𝜌𝑐 ) and the void fraction in the tube
(𝛷). For this reactor, a value of 0.4 was selected. [6]
𝑑𝑊 𝜌𝑏 𝐹𝐷𝑀𝑆0𝑡
= 𝐸𝑞𝑛. 14 𝜌𝑏 = 𝜌𝑐 (1 − 𝛷) 𝐸𝑞𝑛. 15
𝑑𝑋 −𝑟𝐷𝑀𝑆
4.5.8.3 Energy Balance

To prevent side-reactions and to achieve the desired 99.9% conversion of DMS, this
exothermic reaction is operated isothermally, maintaining the reactants at a temperature (T) of
270°C/543K, by cooling using Dowtherm A coolant entering the shell side of the reactor at
267°C/540K (Ta). [6] Using equations 16 and 17, to model the change in temperature of the
reaction fluid and coolant fluid as the reaction conversion progresses, the necessary coolant
flow rate per tube (𝐹𝐶𝑜𝑜𝑙𝑎𝑛𝑡 𝑝𝑒𝑟 𝑡𝑢𝑏𝑒 ) to ensure isothermal operation, can be calculated using a
trial and error method.

4𝑈 −𝑟𝐷𝑀𝑆
𝑑𝑇 𝑑𝑇 𝑑𝑊 (𝜌𝑏 𝐼𝐷) (𝑇𝑎 − 𝑇) + ( 𝜌𝑏 ) [−∆𝐻𝑟𝑥𝑛, 𝑇 ] 𝐹𝐷𝑀𝑆𝑂 𝜌𝑏
= ∙ = ∙ 𝐸𝑞𝑛. 16
𝑑𝑋 𝑑𝑊 𝑑𝑋 𝐹𝐷𝑀𝑆𝑂𝑡 (∑ 𝛩𝑖 𝐶𝑝𝑖 + 𝑋∆𝐶𝑝 ) −𝑟𝐷𝑀𝑆
4𝑈
𝑑𝑇𝑎 𝑑𝑇𝑎 𝑑𝑊 (𝜌 𝑂𝐷) (𝑇𝑎 − 𝑇) 𝐹𝐷𝑀𝑆𝑂𝑡 𝜌𝑏
𝑏
= ∙ = ∙ 𝐸𝑞. 17
𝑑𝑋 𝑑𝑊 𝑑𝑋 𝐹𝐶𝑜𝑜𝑙𝑎𝑛𝑡 𝑝𝑒𝑟 𝑡𝑢𝑏𝑒 𝐶𝑝,𝑐𝑜𝑜𝑙𝑎𝑛𝑡 −𝑟𝐷𝑀𝑆
Where ∑ 𝛩𝑖 𝐶𝑝𝑖 is the heat capacity of the reaction fluid entering the reactor, and 𝑋∆𝐶𝑝 accounts
for the change in heat capacity of the reaction mixture as the reaction progresses.
Although operating isothermally, Kirchhoff’s Law was used to account for the enthalpy of the
reaction if temperature variances were to occur:
𝑇
∆𝐻𝑟𝑥𝑛, 𝑇 = ∆𝐻𝑟𝑥𝑛,298 + ∫ ∆𝐶𝑝 𝑑𝑇 𝐸𝑞𝑛. 18
298
∆𝛽 2 ∆𝛾 3
∆𝐻𝑟𝑥𝑛, 𝑇 = ∆𝐻𝑟𝑥𝑛,298 + ∆𝛼(𝑇 − 298) + (𝑇 − 2982 ) + (𝑇 − 2983 ) 𝐸𝑞𝑛. 19
2 3
An approximation for the overall heat transfer coefficient (U) from the reaction mixture
through the tube walls to the coolant fluid on the shell side of the reactor was used. [7] It is
dependent on the Reynolds number (Re) of the reaction fluid through the tube, and the size of
the catalyst particles in the tube.
0.6885 × 10−3
𝑈 = 15.45 + ( 𝑅𝑒) 𝐸𝑞𝑛. 20
𝐷𝑃
4.5.8.4 Momentum Balance (Ergun Equation)
The flow of gas-phase reactants through a packed-bed reactor causes a loss of pressure as it
passes through the reactor. This loss of pressure has to be modelled, as the rate of reaction is
dependent on the partial pressure of DMS and hydrogen (Eqn. 12/13). ε is the fractional change
in volume, Ac is the cross-sectional area of the tubes and G is the superficial mass velocity per
tube[6]:
𝑑𝑃 𝑑𝑃 𝑑𝑊 −𝛼𝑇𝑃0 (1 − 𝛷)(1 − 𝜀𝑋) 𝐹𝐷𝑀𝑆𝑂𝑡 𝜌𝑏

= ∙ = ∙ 𝐸𝑞. 21
𝑑𝑋 𝑑𝑊 𝑑𝑋 2𝑇0 𝑃 −𝑟𝐷𝑀𝑆
Where:
2𝛽0 𝐺(1 − 𝛷) 150(1 − 𝛷)𝜇
𝛼= 𝐸𝑞. 22 𝑎𝑛𝑑 𝛽0 = [ + 1.75𝐺] 𝐸𝑞. 23
𝜌𝑏 𝐴𝑐 𝑃0 𝜌0 𝛷 3 𝐷𝑝 𝐷𝑝
∑ 𝐹𝑖0 𝑀𝑖
𝐺= 𝐸𝑞. 24
𝐴𝑐
After solving for the mass of catalyst per tube (W) required for 99.9% reactant conversion, the
length (z) of the reactor is calculated based on the internal tube volume needed to hold that
mass of catalyst.
4𝑊
𝑧= 𝐸𝑞. 25
𝐼𝐷2 𝜋𝜌𝑏

Diameter of the shell required to surround all the tubes in the reactor is called the bundle
diameter. Towler [2] defines it as in eq. 26 where KD1 is 0.319 and n1 is 2.142 for a single pass
heat exchanger using triangular pitch, and Nt is the number of tubes.
𝑁𝑡 1⁄𝑛1
𝐷𝑏 = 𝑂𝐷 ( ) 𝐸𝑞. 26
𝐾1
4.5.8.5 Tube Geometries

The number and diameter of the reactor tubes impacts the required cooling flow, reactor
manufacturing cost and catalyst mass needed. Therefore, 23 reactor geometries were trialled to
find the optimum tube diameter and number of tubes. To reduce manufacturing cost, only
industrial standard pipe sizes were used. [8] The tested geometries are shown as the yellow
boxes in Table 4 below, some reactor geometries caused a pressure drop that was greater than
the inlet pressure of the reactant feed thus these were removed from selection and are
represented by the red boxes.
Nominal Internal Number of tubes

Diameter (inch) Diameter (cm) 300 400 500 600 700 800 900 1000
1.25 3.51 Y Y Y
1.5 4.09 Y Y Y Y Y
2 5.25 Y Y Y Y Y Y Y
2.5 6.27 Y Y Y Y Y Y Y Y
Table 4.19: Plan of reactor geometries that were trialled
From the results in Figure 4.47 of the appendix, it can be said that the higher the number of
tubes, the lower the pressure drop as the superficial mass velocity per tube is lower. However,
this comes at the cost of a lower Reynolds number, although still above the turbulent range.
This is also in agreement with literature[9], which says that the wider the diameter the shorter
the reactor length. The major drawback of an increased number of tubes is the increased
diameter of the reactor shell (Db) to accommodate the bundle of tubes. In the case of this
reactor, the optimum reactor configuration (1000 x 6.25cm diameter tubes) that requires the
least mass of catalyst and has the least pressure drop is an unconventional design where the
bundle diameter is 3.5 times the length of the reactor. For this reason a common sense approach
must be taken to identify the most suitable tube size and number.
As shown in Figure 4.37 below, the pressure drop for each of the 23 reactor configurations
considered in this design scope was plotted against the corresponding reactor length minus the
shell diameter. The orange points, represent the reactor configurations where the reactor
diameter is greater than the length, which is an unfeasible reactor shape. The blue points, show
reactor configurations with a feasible length to diameter ratio, however the pressure drop in the
reactors is too great resulting in a greater catalyst mass required. Finally the three green points
are the reactor configurations with both feasible length to diameter ratios and feasible pressure
drop across the tubes, these are compared in Table 4.20.

3
2
Length/diameter
Pressure drop too high

Pressure drop is satisfactory
Diameter is greater than length
0
0 1 2 3
Pressure drop (bar)
Figure 4.37: Plot of pressure drop through reactor against reactor length minus diameter
Tubes Tube Pressure Reactor Shell Catalyst Reynolds Coolant

Diameter drop Length Diameter Mass flow rate
- cm bar m m kg - lpm
1000 4.09 0.41 2.59 2.21 2834 1709 286
600 5.25 0.42 2.62 2.20 2835 13570 289
400 6.27 0.50 2.76 2.21 2842 17050 293
Table 4.20: Comparison of three reactors suitable for selection
Of these three reactors, the second configuration with 600x5.25cm tubes is selected as it has
less of a pressure drop than the 400x6.27cm tube configuration (and therefore less catalyst
mass), yet it has 8 times the Reynolds number of the 1000x4.09cm configuration. This
Reynolds number is important as the reactant flow should be in the turbulent phase entering
the reactor to ensure all reactants are well mixed entering the tubes before plug flow begins.
The difference in required cooling flow rate is negligible.

4.5.9 Selected Reactor
The selected reactor configuration of 600x5.25cm diameter tubes, with a length of 2.62m is the
most suitable configuration to meet the production requirements of this reactor. As shown in
Table 4.21 and Figure 4.38 below, 99.9% of DMS is converted to Methyl 4-Hydroxybutanoate,
in the rate limiting first reaction step and 93% of this MHB is subsequently converted to 1,4-
butanediol in a faster second reaction step.
Inlet
Dimethyl Succinate Hydrogen Methanol Methyl 4-HB 1,4-Butanediol Total
kg/s 3.871 0.481 0.011 0.210 0.024 4.597
mol/s 26.49 238.42 0.35 1.78 0.27 267.31
Outlet
Dimethyl Succinate Hydrogen Methanol Methyl 4-HB 1,4-Butanediol Total
kg/s 0.004 0.268 1.700 0.234 2.391 4.597
mol/s 0.03 133.01 53.05 1.98 26.53 214.60
Table 4.21: Mass balance across reactor
4
Dimethyl Succinate
1,4-Butanediol
Hydrogen
3
Methanol
Methyl 4-Hydroxybutanoate
Mass flow (Kg/s)
0
0 1 2 3
Reactor Length (m)
Figure 4.38: Illustration of the conversion of DMS and hydrogen to BDO and methanol

Figure 4.39 shows the percentage conversion of DMS increasing linearly with reactor length.
The rate of reaction of DMS is also shown in Figure 4.40, where it initially decreases as the
reactant feed is cooled when introduced to the coolant, increases as the reaction progresses
before decreasing rapidly as the DMS available for reaction becomes scarce. The residence
time in the reactor is only 1.43 seconds.
100 10
Rate of reaction (mol m-3 s-1)

8
75
Conversion %
6
50
25
2
0 Rate of conversion to MHB

0
0 1 2 3 0 1 2 3
Reactor length (m) Reactor length (m)
Figure 4.39: Conversion over reactor length Figure 4.40: Rate of reaction along the reactor
546
5
545
Reactor Pressure (bar)
4 544
Temperature (K)
543
3
542
2
541
1 Reactor temperature
540
Coolant fluid temperature
0 539
0 1 2 3 0 1 2 3
Reactor length (m) Reactor length (m)
Figure 4.41: Pressure drop over reactor length Figure 4.42: Temperatures over reactor length
The pressure drop due to gas flow through the packed bed is linear along the reactor as shown
in Figure 4.41, with the pressure dropping down to 4.58 bar. Figure 4.42 shows the balancing
of the reactor temperature with the coolant temperature as they both enter the reactor at the
same point. After this the reactor temperature is maintained at 543K.

Figure 4.43: Reactor dimensions
The dimensions of reactor R302 are shown in Figure

4.43. The tube pitch (pt) is used to describe the shorted
centre to centre distance between the tubes. It is
calculated as 1.25 times the outer tube diameter, which
for this reactor means there’s 9.1cm between each tube.
Two configurations are used; triangular and square as
shown in Figure 4.44. Square pitch tubes are
recommended when fouling on the coolant side of the
tubes is an issue, and regular cleaning is required.
Triangular pitch was instead selected for this reactor,
Figure 4.44: Tube configurations
to minimise the shell diameter. The minimum wall
thickness to support a shell this size’s own weight
and to meet British standards for heat exchangers (BS3274)
is 9.5mm. This size of shell, would be rolled from steel plate. [2]
4.5.10 Reactor Material of Construction

None of the reactants or products in this reactor are known to be corrosive, so non-corrosion
inhibited carbon steel could be used. High-temperature hydrogen attack (HTHA) however is
a concern. Over time, equipment exposed to hydrogen at elevated temperatures can decarbonise
and degrade, which can result in catastrophic brittle failure of the reactor, releasing flammable
chemicals into the environment. [10]
The American Petroleum Institute created a ‘Nelson curve’ to determine what steel properties
are required to combat HTHA at different temperatures and hydrogen partial pressures. The
maximum partial pressure of hydrogen in R302 is at the inlet and is 0.45MPa, and 270°C. This
is marked with the green dot on Nelson curve plot in Figure 4.45. It can be seen that this reactor
is operating at a relatively safe temperature and hydrogen partial pressure, where carbon steel
would be a satisfactory Material of Construction (MoC). Due to the exothermic reaction taking
place in this reactor, large increase in temperature is a potential hazard, therefore 304 stainless
steel with added chromium and molybdenum, was selected as the material of construction of
R302.

Figure 4.45: Nelson curve of the operating limits for steels in hydrogen service to avoid decarbonisation and fissuring [11]
4.5.11 Selection of Coolant

Due to the exothermic reaction taking place within the tubes of R302, an effectual cooling fluid
must be selected to provide effective cooling on the shell side of the reactor.
Boiling of water to steam at 54bar and 270°C was considered, however this presented safety
issues if too must steam was boiled off, resulting in the 275°C tubes not being covered by
cooling water, resulting in tube damage and possible reactor failure. A method of corrosion
and fouling control would also be needed.
Dow Chemical Company produces many cooling fluids for all process operating conditions
under their Dowtherm brand name. Dowtherm A (biphenyl and diphenyl oxide) was selected
as the best coolant for use as it remains liquid at R302’s operating temperatures, does not
decompose readily at operating temperatures and is noncorrosive to stainless steel. It has an
autoignition temperature of 600°C, much higher than that of the reaction fluid, so if the coolant
leaks into the reactor tubes it will not ignite. [2]

4.5.12 Reactor Costs
Tubular reactors are effectively shell and tube heat exchangers with the tubes packed with
catalyst particles. Therefore the cost of manufacturing this reactor is similar to that of a shell
and tube heat exchanger where by the manufacturing cost is based on the heat transfer surface
area of the tubes.[2] The heat transfer surface area of this reactor is calculated in Eqn. 27, where
z is the tube length and OD is the outer diameter of a single tube. This was then used as the
sizing parameter for the calculation of the reactor manufacturing cost ($) using carbon steel
based on the costing formula shown in Eqn. 28.[2] As described earlier, 304 stainless steel was
selected as a safety precaution, but this comes with a relative cost rating of twice that of carbon
steel. The cost of manufacturing R302 is $248,000, excluding delivery and installation costs
which will be covered in Chapter 7: Economics.
𝑆𝐴 = 𝜋 ∙ 𝑧 ∙ 𝑂𝐷 ∙ 𝑛𝑜. 𝑡𝑢𝑏𝑒𝑠 𝐸𝑞𝑛. 27
𝐶𝑎𝑟𝑏𝑜𝑛 𝑆𝑡𝑒𝑒𝑙 𝑀𝑎𝑛𝑢𝑓𝑎𝑐𝑡𝑢𝑟𝑖𝑛𝑔 𝐶𝑜𝑠𝑡 = 24000 + (46 ∙ 𝑆𝐴1.2 ) 𝐸𝑞𝑛. 28
𝑆𝑡𝑎𝑖𝑛𝑙𝑒𝑠𝑠 𝑆𝑡𝑒𝑒𝑙 𝑀𝑎𝑛𝑢𝑓𝑎𝑐𝑡𝑢𝑟𝑖𝑛𝑔 𝐶𝑜𝑠𝑡 = 𝐶𝑎𝑟𝑏𝑜𝑛 𝑆𝑡𝑒𝑒𝑙 𝐶𝑜𝑠𝑡 × 2 𝐸𝑞. 29
R302 requires 2835kg of Raney copper-chromium catalyst. Although manufactured by
W.R.Grace Cataysts, no price was publically available. Instead a price for the similarly
processed Raney nickel catalyst will be used. This is available for purchase at $150/kg, or
$425,000, again excluding delivery & installation charges. [12]
4.5.13 Conclusion
In conclusion, a plug flow fixed bed tubular reactor has been designed to convert gaseous
dimethyl succinate and hydrogen to 1,4-butanediol via hydrogenolysis. The reaction is
kinetically controlled and operated isothermally at 270°C, with shell side cooling. The reactor
pressure is to be 5 bar with a 0.5 bar loss across the reactor. The reactor is to be made from 304
stainless steel, containing 600x2.62m long tubes, with a tube diameter of 5.25cm and thickness
3.9mm. The total volume for reaction in the tubes is 3.4m3, containing 2834kg of
catalyst. These tubes are surrounded by a constant flow of 259Lpm Dowtherm A coolant
contained in a 2.21m diameter shell, allowing 5.5m3 of coolant around the reactor at all times.
Total cost of manufacture is $675,000.

4.5.14 Appendix
Molar Volume Calculation
Figure 4.46: Atomic and structural diffusion volume increments (m3/kmol) [4]
Reactor Sizing Results

Tubes Tube Pressure Reactor Shell Catalyst Reynolds
Diameter drop Length Diameter Mass
- m bar m m kg -
800 0.0351 2.96 4.86 1.75 3136 15230
900 0.0351 1.67 4.09 1.85 2969 13540
1000 0.0351 1.12 3.60 1.94 2907 12180
600 0.0409 2.65 4.71 1.76 3094 2838
700 0.0409 1.35 3.82 1.88 2932 2435
800 0.0409 0.84 3.28 2.00 2877 2132
900 0.0409 0.57 2.89 2.11 2850 1897
1000 0.0409 0.41 2.59 2.21 2834 1709
400 0.0525 1.71 4.12 1.83 2974 20360
500 0.0525 0.76 3.18 2.02 2869 16290
600 0.0525 0.42 2.62 2.20 2835 13570
700 0.0525 0.26 2.23 2.36 2819 11630
800 0.0525 0.17 1.95 2.50 2811 10180
900 0.0525 0.12 1.73 2.64 2806 9049
1000 0.0525 0.09 1.55 2.77 2803 8144
300 0.0627 1.31 3.79 1.94 2928 22730
400 0.0627 0.50 2.76 2.21 2842 17050
500 0.0627 0.25 2.19 2.45 2818 13640
600 0.0627 0.14 1.82 2.66 2808 11370
700 0.0627 0.09 1.56 2.85 2803 9742
800 0.0627 0.06 1.36 3.03 2800 8524
900 0.0627 0.04 1.21 3.20 2799 7577
1000 0.0627 0.03 1.09 3.35 2798 6819
Figure 4.47: Results of reactor sizing

Polymath Input File for Mass Transfer Calculations
Polymath Results for Mass Transfer

Polymath Input File for Reactor Sizing Calculations

Polymath Results

4.5.15 References
[1] M. A. Kohler, “Reaction Kinetics and Selectivity of Dimethyl Succinate
Hydrogenolysis over Copper-Based Catalysts,” Industrial Engineering Chemistry, vol.
26, no. 4, pp. 652-656, 1987.
[3] R. a. V. S. Chhabra, Coulson and Richardson's Chemical Engineering: Volume 1: Fluid

Flow, Heat Transfer and Mass Transfer: Fundamentals and Applications., Elsevier
Science & Technology Books, 2017.
[4] J. e. a. Backhurst, Coulson & Richardson's Chemical Engineering: Solutions to the

Problems in Chemical Engineering, Volume 2 and Volume 3, Butterworth-Heinemann,
2002.
[5] P. Doran, Bioprocess Engineering Principles, Elsevier Science & Technology Books,
1995.
[6] H. Fogler, Elements of chemical reaction engineering., Prentice-Hall, 1986.
[7] W. Luyben, Chemical Reactor Design and Control, John Wiley and Sons Inc., 2007.
[8] Antec, “Steel pipe sizing catalogue,” 2003. [Online]. Available:

http://antec.com.au/media/downloads/pipe_steel_pipe_catalogue.pdf. [Accessed 3
March 2018].
[9] P. Harriott, Chemical Reactor Design, CRC Press, 2002.
[10] D. &. M. P. J. Benac, “Reducing the Risk of High Temperature Hydrogen Attack
(HTHA) Failures,” Journal of Failure Analysis and Prevention., no. 10.1007/s11668-
012-9605-x. , 2012.
[11] American Petroleum Institute, “Steels for Hydrogen Service at Elevated Temperatures
and Pressures in Petroleum Refineries and Petrochemical Plants,” API Publishing
Services, Washington DC, 2004.
[12] Oakwood Catalysts, “Raney Nickel Catalyst,” Oakwood Products, [Online]. Available:
http://oakwoodchemical.com/ProductsList.aspx?CategoryID=-
2&txtSearch=38562&ExtHyperLink=1. [Accessed 3 March 2018].

Chapter 5 Process Control
Author: Mark Fitzpatrick
5.1 Objectives of Process Control................................................................................ 166
5.2 Types of Controllers .................................................................................................. 166
5.3 Chosen System ............................................................................................................. 166
5.4 Types of Instrumentation ....................................................................................... 167
5.5 Final Control Elements............................................................................................. 167
5.6 Temperature Control ................................................................................................ 169
5.7 Pressure.......................................................................................................................... 173
5.8 Flow .................................................................................................................................. 175
5.9 Level ................................................................................................................................. 176
5.10 References .................................................................................................................. 177

5.1 Objectives of Process Control
The purpose of a good industrial process control strategy is to:
1. Prevent injury to plant personnel, protect the environment by preventing emissions and
minimizing waste, and prevent damage to the process equipment.
2. Maintain and protect quality (composition, purity, colour, etc.) on a continuous basis
and with minimum cost.
3. Maintain plant production rate at minimum cost. [1]
To ensure all of these requirements are met, Layers of Protection are built into the control
strategy to mitigate the effects of any process disturbances.
5.2 Types of Controllers

The two standard control types are feedforward and feedback. A feedforward controller
measures the disturbance variable and sends this value to a controller which adjusts the
manipulated variable, before the disturbance affects the process. A feedback control system
waits until the disturbance propagates through the system before it measures the output
variable, compares that value with the desired output value and uses this information to adjust
the manipulated variable. Feedforward control is more expensive as its configurations assume
disturbances are known in advance and requires sensors associated to them, and assumes no
undetected disturbances will occur. Feedback control however can compensate for all
disturbances, irrespective of what causes the disturbance. Both feedforward and feedback
control are used in this control strategy. [1]
Cascade control
A disadvantage of feedback controllers is the delay in reacting to disturbances in the system,
which can lead to cycling of the controlled variable. Using cascade control, two control loops
are created inside each other, with the first (master) controller keeping the primary variable at
the set point, by creating a remote set point for the second (slave) controller, which then
controls a different manipulated variable based on this remote set point. The most important
consideration when designing a cascade control strategy is that the slave variable must respond
faster to the disturbance than the master controller. Cascade control will be used in this control
strategy to improve reactions times to disturbances with relatively slow dynamics such as
temperature. [1]
5.3 Chosen System

Due to the safety hazards associated with all reactants and products of the Dimethyl Succinate
hydrogenolysis reaction, R302 as described in Chapter 4.5 was selected to be controlled. In this
reactor, 3.87kg/s DMS reacts exothermically with 0.21kg/s hydrogen to produce 2.39kg/s of
1,4-Butanediol. This reaction occurs at 5 bar gauge in a packed bed tubular reactor made of
600x5.25cm diameter tubes, cooled by passing Dowtherm A through the reactor shell. The
reaction mixture is to be fed into the reactor at 272°C/545K, and maintained at 270°C /543K
using 289 litres per minute of Dowtherm A coolant supplied at 267°C/540K.

5.4 Types of Instrumentation
The most crucial step in controlling a process, is measurement of process variables such as
temperature, pressure, flow and level. Sensors such as temperature probes, flowmeters and
diaphragms are used to allow the process controller to “see” the process, by transmitting the
measured parameter back to the controller. Unsuitable process sensors can lead to bad process
control as the controller is calculating base on inaccurate or incorrect data. [2]
The instrumentation used in this design strategy are as follows;
Temperature – thermocouple in thermowell
Pressure – pneumatic differential force balance
Flow – ultrasonic flowmeters
Level – radar level device
5.5 Final Control Elements

The final control elements receive the controllers output, and convert it into a change to the
process. In this control strategy, compressed air actuated diaphragm control valves is the
most practical and used FCE, however the three compressors CM301/2/3 and PU305 are also
used as FCEs. A table listing the control valves used in the process, as well as their fail state
are listed below in Table 5.1.
Control Valve Stream Number Parameter being controlled Fail State
CV301 S316 DMS Inlet Flow Fail Close
CV302 S336 Fresh Hydrogen Inlet Flow Fail Close
CV303 S409 Furnace Fuel Flow Fail Close
CV304 S343 Furnace By-pass Fail Open
CV305 S406 Coolant Cooling water flow Fail Open
CV306/CV307 S408 Back-up cold coolant flow Fail Open
CV308 S346 Heat exchanger X306 by-pass Fail Open
Table 5.1: Fail State of Control Valves

5.6 Temperature Control
Temperature is the most significant parameter to be controlled in this hydrogenolysis reactor.
All reactants & products are a flammability and combustion hazard. The reaction product, 1,4-
butanediol has the lowest autoignition temperature of 350°C. Despite the reaction being highly
exothermic, for optimum operation and desired product conversion, the reactor is run
isothermally at 270°C (543K). Liquid coolant (Dowtherm A, at 267°C /540K) is pumped into
the shell side of this tubular reactor for temperature regulation. Reaction simulations show that
if complete coolant failure was to occur the reactor temperature would increase to >500°C
within the first meter of the reactor.
Temperature at reactor inlet:
The inlet temperature of the reactor feed (S323) has a set point of 272°C/545K.
TC1 uses both feedforward (TT2) and feedback control (TT1) to maintain the inlet temperature
at the required temperature as shown in Figure 5.1. If the reactor feed pre-furnace (S322) is
below the set point of 272°C, TC1 outputs a set point for the furnace fuel flow rate and cascades
this down to the furnace fuel flow controller (FC1). FC1 calculates the required change to
control valve CV303’s position based on the current fuel flow rate (FT1) in order to meet this
new set point.
TT2 is used to close TC1’s control loop. It provides a response to the change in fuel flow rate
(FT1) in the form of an increased/decreased furnace outlet temperature. If the reactor feed
exiting the furnace (S323) is above 272°C, TC1 will calculate lower set point outlet for FC1.
TC1 is a reverse acting controller so that an increase in temperature at TT1/2 necessitates a
reduction in furnace fuel flow (S409). Correspondingly, a temperature below the set point at
TT1/2 requires an increase in fuel flow rate.
If the reactor feed pre-furnace (S322) is already at the set point of 272°C, TC1 will open CV304
to allow this stream by-pass the furnace via S343. The output of this controller is split ranged
so TC1 cannot simultaneous by-pass the furnace and request an increase in furnace heating.
CV303 is a fail closed valve, to stop fuel flow to the furnace in the event of
electrical/compressed air failure. Conversely, CV304 is fail open, so that any gases remaining
in the piping, are not excessively heated in the furnace.
To Stack S4gb
S343
CV304 S323
S322
Furnace TT1
TT2 TC1
CV303 FT1
Fuel & Air
S409
FC1
Figure 5.1: Furnace Control Loop

Temperature in reactor:
Seven temperature transmitters (TT4-10) are located axially along reactor R302 to due to the
temperature increase along the vessel. [3] This exothermic reaction is not self-regulating, in
that if a temperature increase occurs it will not correct itself and will lead to thermal runaway
if a control system is not implemented to regulate the temperature. [1]
In this project three layers of protection are utilised for temperature control.
Primary Layer:
A high value selector (HS1) receives the seven temperature transmitter readings and forwards
the highest signal to the reactor temperature controller (TC3) as shown below in Figure 5.2.
TC3 compares this peak reactor temperature to its set point of 267°C.
Initially TC3 uses feedback control to maintain the peak reactor temperature by controlling the
coolant pump (PU305) power. If an error is calculated by TC3 that is greater than its set point,
it outputs an increased pump power signal (direct acting), there-by increasing the mass flow of
coolant through the reactor. On the other hand, if the error between the peak reactor temperature
and the set point is negative, TC3 ramps down PU305’s power to the minimum flow rate to
maintain reactor temperature - 5L/s.
Activate
Interlock
S306
Burst Disk & PRV for
X309 tubes to Incinerator
PU305 TC3
S401 S402
S345
HS1
To Drain
S407
TT4 TT5 TT6 TT7 TT8 TT9 TT10
S323
S324
S403
Figure 5.2: Reactor Temperature Control Loop

Secondary Layer:
The reactor coolant loop also has its own cooling system, as shown below in Figure 5.3. TT3
measures the temperature of the coolant before entering the reactor. If this is greater than
267°C, TC3 can set a new flow set point for its slave controller FC2. FC2 compares the flow
rate of cooling water through FT2 to this new set point to calculate an appropriate CV305
position. This is a direct acting control system as if the temperature recorded by TT3 is high,
the flow rate of cooling water must therefore increase.
CV305
Cooling water
FT2
FC2
S3cf
TC2
Warm
Coolant X309 TT3
Storage
Tank PU305
ST301
S401 S402
S405
To Drain
S407
Figure 5.3: Coolant Cooler Control Loop
Under normal operation, any heat gained by the coolant system in the reactor is integrated back
into the system by preheating the reactant feed in heat exchanger X306. This returns the coolant
from 272°C to the desired 267°C without the need for cooling in X309. However, if the reactor
temperature becomes excessive, there-by increasing the heat gained by the coolant in the
reactor this excess energy is would be passed to the reactor inlet feed, accentuating the excess
heat. To resolve this, TC4 is used to control the by-passing of X306 (Figure 5.4). If the
temperature of coolant leaving the reactor (S403) as measured by TT11, is at or below the set
point of 272°C, CV308 remains closed. However, if TC4 calculates an error greater than the
set point, CV308 is opened using proportional control.
S404
S322
X306
S403
CV308
TC1 T11
S321
Figure 5.4: X306 By-pass

Ternary Layer:
If the reactor peak temperature (from HS1) reaches the critical temperature of 290°C (20°C
deviation from its set point), reactor shutdown is initiated. By this stage, both the maximal
increase in coolant flowrate, and increase in coolant cooling (X309) have been unsuccessful in
returning the reactor to 270°C/543K. TC3 sends an “Open” signal to CV306, to dump the 25°C
cold back-up coolant tank (ST302) contents into the reactor’s cooling shell. This cold coolant
results in a greater temperature difference within the reactor allowing more heat to be removed
rapidly. Simultaneously, TC3 activates the inlet flow and compressor interlock. Hydrogen inlet
flow (CV302) and DMS inlet flow (CV301) as well as their corresponding double isolation, is
set to their fail close position. Power to all three inlet compressors (CM301/2/3) is also reduced
to zero.
For added redundancy, operators in the control room can remotely open (CV307) to empty the
back-up cold coolant tank into the reactor. Both CV306/7 are fail open valves by default.
Emergency
remote activation
from control
room
Back-Up
Activate
Cold Interlock
Coolant
Tank
ST302
TC3
CV307 CV306
HS1
S408
TT4 TT5 TT6 TT7 TT8 TT9 TT10
S323
S324
S403
Figure 5.5: Back-up Cold Coolant Tank

5.7 Pressure
The inlet pressure of the reactor is a very important parameter. The concentration of reactants
in this gas phase reactor is dependent on the reactor pressure. If the pressure is too low, the
concentration of the reactants is low and this slows the reaction rate, resulting in lost
productivity and lower product purity. A higher pressure in the reactor results in a faster
reaction rate, increasing the heat generation and possibly resulting in reactor runaway. Gas
phase packed bed reactors also have a fundamental pressure drop along the reactor. This reactor
has been designed to minimise that pressure drop to less than 0.4 bar. The pressure at the reactor
inlet has a set point of 5 bar gauge.
Pressure transmitter 1 (PT1) measures the pressure of the fluid flow in S323. This signal is sent
to PC1, which compares it to the set point value of 5 bar. If PC1 calculates an error between
the set point and actual pressure, the inlet compressors (CM301/2/3) are given a reverse action
feedback signal. If the pressure at PT1 is above the set point, the compressor power is reduced,
while if the pressure in PT1 is below the set point, the compressors are ramped up appropriately.
S323
S324
PT1 S403
PC1 Interlock
Activated
S333 CM302 FT6 Recycled
S332 Reactants
FT5 Recycled
X307 CM303 S336 Hydrogen
S321 S341 S340 S339 S337 Interlock

Activated
S325 CV302 FT4 Fresh
S320 S338
Purification Hydrogen In
CM301
FC3
FT3 CV301 Reactants Ratio

S316 from R301 Interlock
Interlock
Activated
Activated
Figure 5.6: Reactor Pressure Control Loop

Reactor R302 is designed with Pressure Relief Valves and Burst disks on both the tubes and
coolant shell side. These are to prevent reactor over pressurisation releasing hot flammable
gases. The tube side gas PRV is rated to lift at a pressure of 5.25 bar. The burst disk acts as
back up, rated for 5.3 bar, and sized to rapidly vent the excess reactor pressure. Due to the
flammable and combustible nature of all components of this reaction, the gas is to be piped
directly to the on-site incinerator via S243 and burnt immediately. Similarly for the coolant
side of R302 (normally pressurised to 3 bar), the liquid coolant could undergo thermal
expansion around the tubes at heightened temperatures. The PRV is rated for 3.25 bar, and
Burst disk for 3.3bar, and both vent to the coolant containment tank ST303 via S344.
Relief via tube side/shell side PRV or burst disk with activate the inlet flow control valve
interlocks and power down the compressors.
Burst Disk &

PRV for
Coolant to
Containment
Activate Tank ST303
Interlock LT1
S344
Burst Disk & PRV for
tubes to Incinerator
S345
Activate
Interlock
Burst Disk & PRV
for Coolant
S323
S324
PT1 S403
Figure 5.7: Pressure Relief Valves & Burst Disks on Reactor

5.8 Flow
The reactor feed is a mixture of reactants from four sources. Only one of these feeds can be
controlled. Both recycle streams - recycled reactants (S332) and recycled hydrogen (S336) and
the DMS feed stream from R301 (S316) are considered “wild streams” which cannot be
controlled by this reactor control system. Thus the fresh hydrogen inlet (S338) is the sole
control variable. For optimum reactor productivity and desired reaction, the molar ratio of
hydrogen to DMS is to be maintained at a 9:1 ratio.
A ratio controller is utilised to calculate the require hydrogen inlet flow. FT3 and FT6 measures
the flow of reactants from R301 and the recycled reactants respectively. The ratio controller
calculates the excess of hydrogen required to maintain the 9:1 ratio and subtracts the current
flow of hydrogen being recycled (FT5) to produce a flow set point of fresh hydrogen In. FC3
compares the current recycle flow rate of hydrogen (FT4) to its set point created by the ratio
controller and determines the necessary valve position of CV302.
S333 CM302 FT6 Recycled

S332 Reactants
S324
FT5 Recycled
X307 CM303 S336 Hydrogen
S321 S341 S340 S339 S337
S326 CV302 FT4 Fresh

S321 S338
Purification Hydrogen In
CM301
FC3
FT3 CV301 Reactants Ratio

S316 from R301 Interlock
Interlock
Activated
Activated
Figure 5.8: Flow Control

5.9 Level
The reactor coolant containment tank (ST303) is designed to contain any hot coolant relieved
from the reactors cooling shell by the shell side PRV or Burst Disk. As described above, if over
pressurisation of the coolant occurs, coolant needs to be removed to prevent structural damage
to the vessel. Activation of the coolant PRV/Burst disk should activate the inlet flow &
compressor interlocks to shut-down the reactor & bring it to a safe park state.
As a redundancy for the activation of the inlet flow & compressor interlocks, ST303 is fitted
with a Level Transmitter (LT1) which detects the coolant filling the tank and activates the
interlocks independently to make the reactor safe.
Burst Disk &

PRV for
Coolant to
Containment
S344
Activate Tank ST303
Interlock LT1
Burst Disk & PRV

for Coolant
Figure 5.9: Level Transmitter on Coolant over Pressurisation Containment Tank

5.10 References
[1] C. A. Smith, Automated Continuous Process Control, Florida, USA: John Wiley & Sons
Inc., 2002.
[2] A. M. Seal, Practical Process Control, London, UK: John wiley & Sons Inc, 1998.
[3] W. L. Luyben, Essentials of Process Control, New York, USA: McGraw-Hill Companies
Inc, 1997.

Chapter 6 Health & Safety and EIA
Authors: Eoin Sheehan & Ryan Kiernan
6.1 Health & Safety ............................................................................................................ 180
6.1.1 Training of Staff ........................................................................................................ 180
6.1.2 Personal Protective Clothing ..................................................................................... 180
6.1.3 Hierarchy of Hazard Controls ................................................................................... 180
6.1.4 Hazards Analysis ....................................................................................................... 181
6.1.5 List of Chemicals ...................................................................................................... 182
6.1.6 Potential Hazards associated with Chemicals Onsite................................................ 182
6.1.7 ATEX Zones ............................................................................................................. 183
6.1.8 HAZOP...................................................................................................................... 184
6.1.9 Process under Inspection ........................................................................................... 184
6.2 Plant Layout .................................................................................................................. 193
6.3 EIA Environmental Impact Assessment ........................................................... 195
6.3.1 Process Feedstocks .................................................................................................... 195
6.3.2 Process Emissions ..................................................................................................... 195
6.3.3 IChemE Sustainability Metrics ................................................................................. 196
6.3.4 Environmental Burdens for Emissions to Air ........................................................... 196
6.3.5 Aquatic Impacts......................................................................................................... 197
6.3.6 Secondary Hazards & Pollution ................................................................................ 197
6.3.7 Environmental Protection & Emission Mitigation .................................................... 197
6.4 References ..................................................................................................................... 199
- 179 -
6.1 Health & Safety
General Health and Safety guidelines need to be established and understood throughout a
working industrial plant to ensure the health and wellbeing of the employees and all personal
in the area. Several areas need to be addressed when discussing health and safety.
6.1.1 Training of Staff

The first step in ensuring a safe workplace is to have the staff fully trained and up to date with
procedures and operations in the workplace. Depending on the role and position of the
employee, certain procedures will apply to them.
For operators, being able to identify what normal operating parameters look like, as opposed
to abnormal or hazardous process parameters are is critical for the safety of the plant and staff
onsite. Things like temperature, flow or pressure fluctuations can be easily adjusted by having
the working knowledge of the process system, relief valves and adequate training from
Standard Operating Procedures (SOP’s).
All other staff within the workplace must have knowledge of safety procedures when alarms
sound and potential evacuation is needed. Knowing exit routes, allocated stations on the
premises for staff counts and guidelines for safe exit are essential for everyone to evacuate
safely and be accounted for. Other necessary programs may include safe lifting courses or first
aid etc.
6.1.2 Personal Protective Clothing

Another critical element in health and safety comes from the clothing that is worn. By
definition, personal protective clothing, helmets, goggles or other garments or equipment
designed to protect the wearer’s body from injury or infection. Essentially, a failure to adhere
to these guidelines could potentially result in an injury or hazard as the person could be exposed
to hazardous chemicals or zones containing hazardous materials.
6.1.3 Hierarchy of Hazard Controls

When designing a large scale operating process, potential unforeseen hazards must be noted
and identified, and the potential hazards or effects should be minimised. The Hierarchy of
Hazard control is an inverted triangle of sections of prevention techniques decreasing in
importance. From top down: [1]
 Elimination: Completing remove the hazard completely from the process

 Substitution: Substitute out the hazard with a safer option or one of less potential harm.
 Engineering Controls: Isolate people from the hazard
 Administrative Controls: Changing the way people work. Safe protocols, trainings etc.
 Personal Protective Equipment (PPE): Last resort to protect the operator from the
hazard
Eoin Sheehan - 180 -

6.1.4 Hazards Analysis
For the process at hand, several aspects needed to be further investigated and eventually
substituted or an engineering control put in place to elevate the potential hazard. Firstly, several
safety features were attached to the main reaction vessels in the purification stages, such as
relief valves and burst disks. If it is a case that these systems do not work, or the process
continues to get out of control, the contents will be sent to an incinerator to ensure no hazardous
explosions or leakages take place on site. This was an example of an engineering control that
was put in place.
A second hazard that needed attention was the product itself, 1,4-butanediol. BDO has been
known to be used as a recreational drug. For this reason, strict procedures must be put in place
to ensure no employees exploit the product being made. Administrative controls will be put in
place i.e. Standard Operating Procedures (SOP’s) to ensure all employees onsite are aware of
the effects and consequences of the product, and that a strict traceability system must be
followed to track all batches and outputs of 1,4-BDO.
Finally, the 1, 4-BDO products will dissolve most types of plastic over time. For this reason, it
is crucial that the product is stored in glass-lined storage containers. [3]
Figure 6.1: Hierarchy of Hazard Control

6.1.5 List of Chemicals
Chemicals Potential Danger
Corn Stover Not hazardous
Ammonia Corrosive, Toxic if inhaled
Water Not hazardous except potential to burn at high temperatures
Glucose Not hazardous
Carbon Dioxide Harmful if inhaled. May cause frostbite if on contact with
eyes/skin
Hydrochloric Acid Corrosive. Cause burns if in contact with skin/eyes
Tridodecylamine Acute toxicity (oral, dermal, inhalation), eye/skin irritation,
Skin sensitisation.
Acetic Acid Flammable liquid and vapour. Cause severe burns to skin/eyes.
Lactic Acid Corrosive. Combustible material May cause burns to skin/eyes
Formic Acid Can cause eye/skin burns. Vapours are irritating and painful to
breath.
Succinic Acid Exposure can cause irritation to eyes, skin & respiratory.
Methanol Highly flammable. Exposure to excessive vapour can cause
eye irritation, head-ache or drowsiness.
Monomethyl Succinate Irritant [2]
Dimethyl Succinate Combustible. May be harmful by inhalation, ingestion or skin
absorption.
Hydrogen Highly flammable. Exposure to excessive vapour can cause
eye irritation, head-ache or drowsiness.
Methyl 4- Skin/eye irritation. Harmful if inhaled [3]
Hydroxybutanoate
1,4-Butanediol Highly flammable. Combustion products are CO2 and CO.
Table 6.1: List of Chemicals within process
6.1.6 Potential Hazards associated with Chemicals Onsite

Materials [4] Explosive Toxic Irritant Carcinogen Flammable Corrosive
Corn Stover x x x x x x
Ammonia x ✓ ✓ x x ✓
Water x x x x x x
Glucose x x x x x x
Carbon Dioxide x x ✓ x x x
Hydrochloric x x ✓ x x ✓
Acid
Tri-dodecylamine x ✓ ✓ x x ✓
Acetic Acid ✓ x ✓ x ✓ x
Lactic Acid ✓ x ✓ x ✓ ✓
Formic Acid x x ✓ x x x
Succinic Acid x x ✓ x x x
Methanol ✓ ✓ ✓ x ✓ x
Monomethyl x x ✓ x x x
Succinate

Materials [4] Explosive Toxic Irritant Carcinogen Flammable Corrosive
Dimethyl ✓ ✓ x x ✓ x
Succinate
Hydrogen ✓ x ✓ x ✓ x
Methyl 4- x ✓ ✓ x x x
Hydroxybutanoate
1,4-Butanediol ✓ x x x ✓ x
Table 6.2: Potential Hazards associated with chemicals onsite
6.1.7 ATEX Zones

Certain areas in a processing plant will fall under certain zones, based on the level of safety
from exposure to hazardous gases. The three ATEX zones are listed in Table 6.3:
Zone Zone Classification for Gases

Zone 0 An area which an explosion mixture is continuously
present or for long periods
Zone 1 An area where an explosive mixture is likely to occur in
normal operation
Zone 2 Area where explosive material is unlikely to occur
Table 6.3: ATEX zoning for flammable gases
From our process, there are several areas where the chemicals present are highly flammable.
By the criteria above, the zone 1 is the most applicable for our process, as no areas will
continuously have hydrogen present and will be safety regulated. [5]
In zones where the flammable chemicals are present, certain requirements such as PPE, anti-
static shoes and protocols. For corrosive chemicals, acid resistant clothing must be worn by
operators. Full face Jupiter/respiratory masks must be worn in areas that could hold the
potential to have airborne chemical hazards.
Emergency procedures will be the final instalment to the processing plant. Protocols need to
be installed, including:
1. Wash stations for eyes and body in areas of potential containment
2. First Aid facilities
3. Fire hoses and fire blankets
4. Training for staff and operators for different scenarios
5. Alarms to indicate evacuation

6.1.8 HAZOP
A Hazard and Operability Analysis (HAZOP) is a structured and qualitatively risk assessment
tool used to asses' risk management and a preform a system examination. The most important
technique a HAZOP is used for is to find potential hazards that could occur in a processing
plant or procedure, and then the safeguards and procedures but in place to avoid these potential
hazards.
When assessing a process, four main points must be touched on. First, we must define the scope
and the objectives for the HAZOP in place. What outcomes are we looking for? Once this has
been established, we must prepare a schedule and roles for each team members. Dividing the
process into sections, everyone having a certain area that they will analysis and preform their
risk assessment on. In this, potential hazards must be identified, consequences and causes
identified, existing safeguards that have been put in place and then any future action to take to
prevent a certain hazard from occurring.
6.1.9 Process under Inspection

For the HAZOP, the reaction to form 1,4-butanediol was inspected and all potential health
hazards were identified, discussed and safety measure was described. Given that the reactants
are all highly flammable and nearing their auto-ignition point (see process control section),
extremely caution and attention must be given to ensure complete safety throughout the
operating site. The temperature, flow, pressure and reaction parameters were all investigated
and potential hazards identified.
Traditionally, all common safety equipment (such as sensors for Temperature and Pressure)
would be incorporated into the design of the process, with HAZOP being used to identify
potential hazards that may not be easily recognised. As this process is still being designed it
was decided to attempt to combat both obvious and hidden hazards simultaneously in the study.
During routine operation of the plant, it is often useful to perform additional HAZOP studies
to determine if any more potential hazards can be identified and dealt with accordingly.

Reviewer: Mark Fitzpatrick - 185 -
# Deviation
Guideword Parameter Cause Consequence Existing Safeguard Recommended Action
1.1 Malfunction in the 1.1.No flow resulting - All pumps, compressors - Regular PM checks on
compressors, resulting in in no reaction and flowmeters are all working equipment
no flow, indicated by the 1.2 Pressure builds up - doubled up in parallel so - Regular staff training for

Flow flow transmitters FT3 – Potential explosion can be swapped over to management of danger
1 No (reaction FT6 1.3 No reaction takes backup if needed events
Reviewer: Mark Fitzpatrick

stream) 1.2 Blocked/closed valve place - Temperature and -Flow transmitters will
on S316 or S338 1.4. Rupture in heat pressure transmitters will have alarms installed to
1.3 No input from R301 exchanger alarm if no flow is sound if flowrate is
1.4 Heat exchanger present. abnormal
blockage - Operators onsite to
monitor process
parameters
2.1 CM301/2/3 running 2.1 Increased flowrates - Alarm set on FT3 – FT6 -Regular PM checks on
too fast – pressure build up – and the compressors to transmitters
2.2 Incorrect ratio potential explosion alert if high flowrates
Flow controller set point 2.2 Imbalance of - All pumps, compressors
2 More (reaction materials in reactor. No and flowmeters are
stream) reaction doubled up in parallel
2.3. Excessive flowrate - Burst Disk on shell
into reactor – rise in coolant to containment
temperature & tank.
pressure. Potential - On the reactor tubes,
explosion burst disk to incinerator in
place
- 186 -
# Deviation
3.1 CM301/2/3 running 3.1 Reduced -Transmitters to indicate - Regular PM checks on

too slow flowrate into reactor abnormalities to compressors, flowmeters
3.2 Compressor – incomplete operators. and pump

Flow malfunction in reaction. - All pumps, compressors - Pressure and temperature
3 Less (reaction CM301/2/3 3.2 Incorrect and flowmeters are indicators fitted after the

stream) 3.3 Incorrect ratio composition, ratio or doubled up in parallel reactor to monitor output
controller set point reduced reaction - PT1 alarm for decreased - Valves locked in
3.4 Reduced flow of fresh conversion pressure due to reduced position
H2 in. 3.3 As per 3.2 flowrate - Admin needed to
change ratio controller
set point
4.1 Fault in PU305 4.1 Pressure build up at - FT2 will indicate a no - Operator checks on
4.2 Closed valve on cold S405 - potential flow. flowmeters, compressors
water tank ST302 explosion in pipe / no - All pumps, compressors and critical parameters
Flow 4.3 Leak in X306 or X309 reaction and flowmeters are - Regular PM checks on
4 No (coolant due to corrosion or lack of 4.2 No cooling for doubled up in parallel pump and heat
stream) maintenance. reaction – potential - TT4 to TT10 to alarm exchangers.
4.4. Line breakage thermal runaway the rise in temp of the - Test pipes for
4.3 Mixing of streams; reactor & activate back- corrosion/blockages
contamination or up cold coolant
reactants.
4.4 As per 4.2
- 187 -
# Deviation
5.1 Fault in PU305 5.1 Increase flowrate - All pumps, compressors -Flow transmitter on S402
5.2 Read invalid high through vessel – and flowmeters are to ensure correct flow rate
temperature in TT4 – reduced reaction rate doubled up in parallel - Regular PM checks on

Flow TT10 in tube transmitters 5.2 As per 5.1 all temperature
5 More (coolant 5.3 TT3 reads high 5.3 As per 5.1 transmitters and pump

stream) temperature 5.4 As per 5.1 PU305
5.4 Leak of cooling water 5.5 Flooding of coolant
into coolant in X3095.5 into reactor – reduced
Valve failed on back up reaction. Loss of safety
coolant tank layer
6.1 Excessive heating in 6.1 Pressure & -TT2 feedback to TC1 -Regular PM checks on
furnace, from excessive temperature increase to reduce flow of fuel safety equipment and
fuel flow in S409 within vessel – into furnace if reactor transmitters
Temperature 6.2 Reactants over heated potential explosion. feed is at/above desired - Adequate training for
6 More (reactor in X306 & X307 6.2 As per 6.1 temperature staff to know how to
feed) 6.3 Fault in temperature 6.3 As per 6.1 -TC2 can choose to react to potential
transmitters TT1 or TT2 6.4 Refer to #4 ‘No bypass the reactant feed shutdown
6.4 Decreased coolant Coolant Flow’ around the furnace if it - If the back-up storage
flow is at 545K measured by is used, and reaction is
TT2 not quenched, we could
-TC3 increases coolant add a level transmitter
flow when TT4 detects on ST302 in the event
high temp at inlet. of accidental discharge
- Back up cold storage into reactor
tank to flood the reactor
if temperature reaches
critical
- 188 -
# Deviation
7.1 Insufficient heating 7.1 Reduced Reaction - Regular PM checks on -Regular PM checks on
in X306 or furnace rate – no product, pumps and valves furnace
7.2 Errors in TT1 or gas condensing in - TT1 & TT2 to detect - Ensure all transmitters

Temperature TT2 7.3 Coolant piping/reactor leading any drop in temp which are correctly calibrated.
7 Less (reactor temperature too low to “Steam hammer” TC1, can control the fuel - Heat exchangers

feed) (S402) causing damage in input to FU301 regularly checked for
piping and fittings -TT3 can detect coolant fouling.
7.2 As per 7.1 temperature, and - Include a steam trap
7.3 As per 7.1 subsequently reduce the before reactor inlet
7.4 As per 7.1 and flow of coolant cooling
refer to #5 ‘More water to X309
Coolant Flow’
8.1 Insufficient cooling 8.1 Insufficient cooling - TC2 & TT3 ensure -Regular checks on
within the reactor; high within the reactor; high coolant at 540K by transmitters and
temperature – refer to 6 temperature – refer to 6 controlling cooling water temperature gauges
Temperature ‘More Temperature’ ‘More Temperature’ flow into X309 - Heat exchanger
8 More (coolant 8.2 As per 8.1 8.2 As per 8.1 - If pressure is increased validation checks
stream) 8.3 No quench. Potential 8.3 No quench. as a result of the reactor - Adequate training to
over pressurization. Potential over temp increase, burst discs ensure correct shutdown
X306 can be by-passed pressurization. X306 or the relief valves will in emergency
can be by-passed discard the inner reactants
and reactor
- Back up cold coolant
can flood into reactor to
decrease temperature
- 189 -
# Deviation
9.1 Fault in 9.1 Reduced flowrate -Compressors are doubled -Regular PM checks on
compressors into the reactor from in parallel so if failure pressure gauges,
CM301/2/3 lower product yield. occurs it can be swapped transmitters and

Less 9.2 Reduced 9.2 As per 9.1 over. compressors
9 Less Pressure flowrate of 9.3 As per 9.1 - Signal between PT1 to - Adequate training to

(reactor) reactants in. PC1 to increase ensure correct shutdown
9.3 Fault in PT1 compression in emergency
on S323 at reactor
inlet
10.1 Compressor 10.1 Increase pressure -PC1 controls pressure - Regular PM checks on
malfunction in may lead to rupture / using PT1 at the reactor pressure gauges,
CM301 – CM303 explosion with the inlet. transmitters and
Less 10.2 Malfunction in vessel - Burst disk or relief compressors
10 More Pressure flow transmitters 10.2 As per 10.1 valve will open to -Staff trained in the
(reactor) FT3 – FT6 10.3 As per 10.1 relieve the reactor scenario of shutdown
10.3 Fault in PT1 contents safely to the -Possibly a second
incinerator pressure gauge installed
- If bursting discs are before S322 to ensure
opened, the interlock adequate pressure
will automatically maintained
activate to shut down
the reactor.
- If reactor is shutdown,
PU305 will keep
operating to pump
coolant into the reactor
- 190 -
# Deviation
11.1 Malfunction in 11.1 Higher flow rate - If pressure does - Regular PM checks on
PU305 of coolant reactor increase, burst discs pump, transmitters
11.2 Thermal expansion cooling; refer to #7 will rupture to either -Staff trained in the

Pressure of coolant in reactor ‘Less temperature’. incinerate or contain scenario of shutdown
11 More (coolant) shell 11.2 Rupture of vessel the reactants, and -Pressure gauge to be

activated interlock will installed on the coolant
activate. line
12.1 Reduced 12.1 No reaction – No - Temperature - Regular PM checks on

temperature within the products transmitters TT4 – TT10 pressure gauges,
reactor. See #8. 12.2 See 12.1 will signal to the pump to transmitters and
12.2 No flow. See #1 reduce, allowing the compressors
12 No Reaction ‘No flow’ temperature to increase in -Ensure adequate signage
12.3 No Product. the reactor; refer to #1, for tank contents and feed
12.4 Incorrect feed tank #8, #10 times
connected instead of -Relevant S.O.P’s in place
hydrogen
- 191 -
## Deviation
1 Guideword Parameter Cause Consequence Existing Safeguard Recommended Action
13.1 Inadequate 13.1 Serious injury or - All operators must wear N/A
training to operators or death hydrogen gas monitors in
staff 13.2 As per 13.1 areas of potential danger

13.2 Faulty equipment 13.3 As per 13.1 - Staff training days and
13 No Safety onsite or not regularly operator assessments

checked - SOP’s in place
13.3 Hydrocarbon
monitors not worn in
an area of potential
hydrogen present
14.1 Any blockage that -Reverse flow may -Safeguards for this - Regular PM checks on
occurs in the reactant cause a build-up in hazard are the check pressure gauges,
stream may cause a pressure, leading to a valves in place along the transmitters and
reverse flow at T joints rupture and potential major/minor process flow compressors and check
14 Reverse Flow where reactants are explosion streams valves
mixed -No Reaction – refer to -PT1 will detect pressure - Possibly install a
14.2 Reverse flow at #12 drop pressure relief valve on
furnace by-pass S343 result feed lines to
incinerator
- 192 -
6.2 Plant Layout
The layout of the plant was designed to incorporate hazard reduction. First, the essential
requirements of a plant were determined, and then, specific rules for the location of each were
devised.
It was determined that the required facilities for our proposed development were:
 Facility for Pre-Treatment of Biomass.
 Facilities for Fermentation & Purification of Succinic Acid.
 Facilities for the conversion of Succinic Acid to 1,4-Butanediol, and purification of the
produced 1,4-Butanediol.
 An office block is required for plant managerial roles or any other departments not
directly involved in the manufacturing process, i.e. HR or Finance.
 A canteen is required for employees
 Laboratory Facilities for on-site testing & growth of cell cultures for fermentation.
 A Waste-Water treatment will reduce any ecological impact from plant waste.
 A facility for the supply of utilities i.e. steam or cooling
 A facility for maintenance equipment and personnel.
 A tank farm for any raw materials and storage for Corn Stover & Finished Product.
The rules defining the location of each unit are as follows:
 Car Park & Offices are to be located beside the road, providing quick & easy employee
access.
 Canteen and offices will be located together to accommodate employees
 Waste-water treatment plant will be placed next to the utilities providing clean water
for steam.
 Storage area & tank farm should be placed far away from the road and offices,
minimizing any hazards.
 The processing should be placed away from the offices and road but kept near the
storage are and tank farm.
 Maintenance will be placed near to utilities.
 The fermentation and purification step of the process was identified as the least
hazardous step of the process and out of the three process steps will be placed closest
to office areas.
The layout of the plant is shown below in Figure 6.2.

Figure 6.2: Plant Layout

6.3 EIA Environmental Impact Assessment
In this Environmental Impact Assessment, the impact of the proposed development on the local
environment has been evaluated.
The areas assessed are:
 Production of Hazardous Waste
 Effluents/Emissions
 Raw Materials
 Impact on the local environment
The IChemE sustainability metrics have been used in this section to assess the proposed
development. The metrics are able to quantify the sustainability, and environmental impact of
the proposed development. The metrics are divided into sections covering Environmental
Indicators, Economic Indicators, and Social Indicators. [6]
The process involves the following major steps:
 Pre-treatment of Corn Stover to extract Cellulose
 Acid Hydrolysis of Cellulose to Glucose
 Fermentation of Glucose to Succinic Acid
 Crystallisation of Succinic Acid
 Conversion of Succinic Acid to Dimethyl Succinate
 Conversion of Dimethyl Succinate to 1,4-Butanediol
The plant will in both batch and continuous modes for 24 hours, 340 days of the year. The
proposed development aims to produce 75,000 tonnes per year of 1,4-butanediol which
requires 284500 tonnes per annum of Corn Stover.
6.3.1 Process Feedstocks

The proposed raw material for this process is Corn Stover. This is a waste product that remains
in the field following the corn harvest and comprises corn stalks, leaves and cobs. This is a
non-hazardous material posing zero threat to the local environment in the event of an
emergency at the development.
6.3.2 Process Emissions

Process Emissions have been quantified from the Mass & Energy Balances. These relate to
emissions from the proposed development which have been removed without being recycled
back into the process or being reused.

6.3.3 IChemE Sustainability Metrics
IChemE sustainability metrics were applied to quantify the environmental burden of the
emissions of the proposed development. The environmental burden approach is used to
estimate potential impact.
The Environmental Burden (EB) caused by the emission of a range of substances, is calculated
by adding up the weighted emission of each substance. The weighting factor is known as the
“potency factor”. Because a single substance will contribute differently to different Burdens,
each substance will have a number of different potency factors.
The formula used to calculate the environmental burden is:
𝐸𝐵 = ∑ 𝑊𝑁 𝑥𝑃𝐹𝑁
Where:
 EB = Environmental Burden
 WN = Weight of Substance N emitted
 PFN = Potency Factor for Substance N
6.3.4 Environmental Burdens for Emissions to Air

Atmospheric Acidification Burden per unit value added
Emissions
Substance Potency Factor, PF
Tonnes W EB Value = W*PF
NO2 0.7 2654 1857.8
Total 1857.8
The potential of certain released gases to form acid rain and acids to water is the potency factor
for atmospheric acidification. The unit of Environmental Burden is te/y sulphur dioxide
equivalent. For this section NO was assumed to be the same as NO2 as upon contact with air
NO will form NO2. [7]
Global Warming burden per unit value added
Emissions
CO2 1 35553 35553
NOx 40 2654 106160
Total 141713
These potency factors are based on a 100-year integrated time horizon. The unit of
Environmental Burden is te/y carbon dioxide equivalent – the global warming potential.
Human Health Burden per unit value added
There are no emissions from the process likely to cause Human Health effects (Carcinogens)
Stratospheric Ozone Depletion Burden per unit value added
There are no Stratospheric Ozone depleting emissions from the process

Photochemical Ozone Burden per unit value added
Emissions
NO2 0.028 2654 74.312
Total 74.312
Potency factors for this category are obtained from the potential of substances to create ozone
photochemically. The unit of Environmental Burden is te/y ethylene equivalent.
6.3.5 Aquatic Impacts
Aquatic Acidification per unit value added
There are no emissions to water that would add to aquatic acidification.
Aquatic Oxygen Demand per unit value added
There are no emissions to water that would add to Aquatic Oxygen Demand.
6.3.6 Secondary Hazards & Pollution

The impact of noise and visual pollution on the local environment was also assessed. The
proposed development contains many large heat exchangers, condensers and pumps which
have a high energy requirements. These will increase the noise pollution and will be
unacceptable to any nearby residential areas. Thus, an industrial park with a pre-existing
presence of heavy industries is chosen as the most suitable location to locate the plant. This
area will reduce the visual impact of the development as it will blend in with other
developments there.
Due to the nature and temperatures of chemicals used in the process, potential leaks pose a
significant risk to people in the immediate vicinity of the process. There is a potential for leaks
and spills to occur during delivery, during waste disposal and during storage. There is also a
potential for there to be leaks in the pipework and process equipment leading to process liquid
being exposed to the environment resulting in adverse effects. Prevention and Mitigation
measures are discussed in the HAZOP section of this report.
6.3.7 Environmental Protection & Emission Mitigation

The proposed development follows waste management policies based on the US EPA Waste
Management Hierarchy, Figure 6.3. Plant output stream are being recycled back into the
process wherever possible, methanol that is produced in the hydrogenolysis is recycled back to
be used in the esterification. Lignin that is a waste product from the enzymatic hydrolysis is
sold on to be further processed and reused in manufacturing of polymers. Biomass cells from
the fermentation are incinerated instead of being disposed of in a landfill so that energy can be
recovered and reused onsite.

Figure 6.3: EPA Waste Management Hierarchy [8]
To prevent emissions of excess CO2 from the fermenter into the atmosphere a recycle stream
to a collection vessel can be implemented allowing the CO2 to be reused during another
fermentation. To prevent emissions of CO2 form the thermal oxidiser into the atmosphere a gas
adsorption tower should be added to the process. To combat NOx emissions a Selective Non-
Catalytic Reduction system is applied which can reduce emissions by up to 70%. The release
of organic acids, and HCl will be controlled by the Wastewater Treatment Plant onsite. [9]

6.4 References
[1] T. N. I. f. O. S. a. H. (NIOSH), “HIERARCHY OF CONTROLS,” The National Institute
for Occupational Safety and Health (NIOSH), [Online]. Available:
https://www.cdc.gov/niosh/topics/hierarchy/.
[2] ChemSpider, “YA2V724S0A,” ChemSpider, [Online]. Available:

http://www.chemspider.com/Chemical-Structure.69896.html.
[3] fluorochem, “403056 - Methyl 4-Hydroxybutanoate,” fluorochem, [Online]. Available:

http://www.fluorochem.co.uk/Products/Product?code=403056 .
[4] C. chemicals, “LACTIC ACID,” Cameo chemicals , [Online]. Available:

https://cameochemicals.noaa.gov/chemical/8774 .
[5] I. E. Starting, “ATEX Zone 0,” IPU , [Online]. Available: https://www.ipu.co.uk/what-

is-atex-directive/atex-zone-0/ .
[6] IChemE, “The Sustainability Metrics,” [Online]. Available:

http://www.icheme.org/communities/subject_groups/sustainability/resources//~/media/
Documents/Subject%20Groups/Sustainability/Newsletters/Sustainability%20Metrics.pdf
. [Accessed 27 February 2018].
[7] J. V. Caneghem, J. De Greef, C. Block and C. Vandecasteele, “NOx reduction in waste

incinerators by selective catalytic reduction (SCR) instead of selective non catalytic
reduction (SNCR) compared from a life cycle perspective: a case study,” Journal of
Cleaner Production, vol. 112, no. 5, pp. 4452-4460, 2016.
[8] US Environmental Protection Agency , “Toxics Release Inventory (TRI) 2016 National
Analysis EXECUTIVE SUMMARY,” 2016. [Online]. Available:
https://www.epa.gov/sites/production/files/2018-
01/documents/2016_tri_national_analysis_execsumm.pdf. [Accessed 07 March 2018].
[9] WORLD BANK GROUP, “Nitrogen Oxides: Pollution Prevention and Control,” July
1998. [Online]. Available:
https://www.ifc.org/wps/wcm/connect/60add78048855368aeecfe6a6515bb18/
HandbookNitrogenOxidesPollutionPreventionAndControl.pdf?MOD=AJPERES.
[Accessed 08 March 2018].

Chapter 7 Economics
Authors: Diarmaid Beecher & Hamed Al Jabri
7.1 Introduction .................................................................................................................. 202
7.2 Fixed-Capital Investment ........................................................................................ 202
7.3 Equipment cost............................................................................................................ 202
7.4 Manufacturing Costs ................................................................................................. 206
7.4.1 Variable Production Costs......................................................................................... 206
7.4.1.1 Cost of Raw Material ......................................................................................... 206
7.4.1.2 Operating & Administration Labour .................................................................. 207
7.4.1.3 Utilities............................................................................................................... 208
7.4.1.3 Utilities............................................................................................................... 208
7.4.1.5 Laboratory Charges ............................................................................................ 208
7.4.1.6 Patents & Royalties ............................................................................................ 209
7.4.2 Plant Overhead Costs ................................................................................................ 209
7.4.3 Fixed Charges ............................................................................................................ 209
7.4.3.1 Financing............................................................................................................ 209
7.4.3.2 Taxes .................................................................................................................. 210
7.4.3.3 Property Insurance ............................................................................................. 210
7.4.4 Total Manufacturing Costs ........................................................................................ 210
7.5 Analysis of Plant Economics .................................................................................. 211
7.5.1 Net Cash Flow & Corporation Tax ........................................................................... 211
7.5.2 Breakeven Point ........................................................................................................ 211
7.5.3 Cash Flow Diagram................................................................................................... 212
7.5.4 Rate of Return ........................................................................................................... 213
7.6 Discussion ...................................................................................................................... 213
7.7 References ..................................................................................................................... 214
- 201 -
7.1 Introduction
In this part, an analysis is presented to the plant to examine the capital needed to supply the
necessary manufacturing and plant facilities. This capital needed is taken as the sum of fixed
capital investment and working capital which is known as the total capital investment. [1]
7.2 Fixed-Capital Investment.

Fixed-capital investment split into direct costs and indirect costs as shown in the table below.
Direct Costs Indirect
Purchased equipment Engineering and supervision
Purchased equipment installation Construction expense
Instrumentation and controls (installed) Contingency
Piping (installed)
Electrical (installed)
Buildings (including services)
Yard improvements
Service facilities (installed)
Land
7.3 Equipment cost

The equipment cost is examined using index factor method of cost estimation. This method is
based on guide prices of chemical equipment obtained from [1]. The following equation is
used if there is a difficulty on accessing cost of a certain equipment, therefore the correlation
of equipment cost is expressed as follow:
𝐶𝑒2007 = 𝑎 + 𝑏. 𝑆 𝑛 𝑒𝑞𝑛. 1
𝐶𝑒2007 : 𝑚𝑎𝑛𝑢𝑓𝑎𝑐𝑡𝑢𝑟𝑖𝑛𝑔 𝑒𝑞𝑢𝑖𝑝𝑚𝑒𝑛𝑡 𝑐𝑜𝑠𝑡 𝑜𝑛 𝑎 𝑈𝑆 𝑔𝑢𝑙𝑓 𝑏𝑎𝑠𝑖𝑠 2007
𝑎, 𝑏: 𝑐𝑜𝑠𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑏𝑎𝑠𝑒𝑑 𝑜𝑛 𝑒𝑞𝑢𝑖𝑝𝑚𝑒𝑛𝑡 𝑡𝑦𝑝𝑒.
𝑛: 𝑒𝑥𝑝𝑜𝑛𝑒𝑛𝑡 𝑓𝑎𝑐𝑡𝑜𝑟 𝑓𝑜𝑟 𝑡ℎ𝑎𝑡 𝑒𝑞𝑢𝑖𝑝𝑚𝑒𝑛𝑡
𝑆: 𝑠𝑖𝑧𝑒 𝑝𝑎𝑟𝑎𝑚𝑒𝑡𝑒𝑟 𝑜𝑓 𝑒𝑞𝑢𝑖𝑝𝑚𝑒𝑛𝑡 𝑓𝑜𝑟 𝑎 𝑔𝑖𝑣𝑒𝑛 𝑢𝑛𝑖𝑡
This price has to be adjusted for inflation from 2007 prices to 2018 prices. The cumulative
inflation over this time was 20.10%. [3]
𝐶𝑒2018 = 𝐶𝑒2007 × 20.10% 𝑒𝑞𝑛. 2
Then, the rest of the direct costs and indirect costs, are calculated based on a percentage of
equipment cost. The installation cost percent of an equipment is obtained from [2] hence,
examining the installation equipment cost. The following table shows the price percent for each
component based on equipment cost;

Component % Of an equipment
Instrumentation and controls (installed) 13
Piping Cost 31
Component % of the total equipment Cost
Buildings Including Services Cost 47
Yard Improvements 15
Service facilities Cost 60
Land Cost 6
Engineering and Supervision cost 30
Construction Expense 10
Contractor’s Fee 5
Contingencies 8
The following tables show the cost of manufacturing, installing, and adding of piping and
instrumentation for all equipment in each section of the process. The material factor is used to
account for the relative increase in cost of using more expensive materials of construction.
Carbon steel is the standard with a factor of 1, with 304 stainless steel doubling the cost (2)
and finally 316 stainless steel having a factor of 3.5.
No. Equipment Name Size Sizing Units Material Factor Cost 1000$
R101 AFEX reactor 148996 kg steel 3.5 4441
B101 AFEX basket 1 8510 kg steel 3.5 445
R102 Hydrolysis reactor 780 m3 3.5 10063
CM101 Ammonia compressor 4355 kW 1 2513
X101 Ammonia inlet cooler 19 m2 1 44
X102 Ammonia outlet cooler 24 m2 1 45
CV101 Conveyer 20 m 1 109
ST101 Storage tank 1000 m3 1 313
19754
Table 7.1: Pre-treatment unit costings
No. Equipment Name Size Sizing Units Material Factor Cost 1000$
F201 Fermenter 1 900 m3 1 16908
F202 Fermenter 2 900 m3 1 16908
F203 Fermenter 3 900 m3 1 16908
F204 Fermenter 4 900 m3 1 16908
F205 Fermenter 5 900 m3 1 16908
X201 Glucose heat exchanger 1 24 m2 1 45
X202 Glucose heat exchanger 2 37 m3 1 48
X203 Carbon dioxide heater 27 m2 1 46
X204 Ammonia heater 20 m2 1 44
84723
Table 7.2: Fermentation unit costings

Material Cost
No. Equipment Name Size Sizing Units Factor 1000$
CR201 Crystallizer 376 m2 3.5 11315
MX201 Hydrochloric acid mixer 60 L/s 1 10
PU201 Crystallizer feed pump 5.9 kW 1 18
X204 Crystallizer inlet heater 70 m2 1 55
LLE201 Liquid-liquid extractor 70 m3/h 1 247
UF201 Fermentation broth filter 50 m2 2 677
UF202 Succinic acid crystals filter 50 m2 2 677
12997
Table 7.3: Purification unit costings
Material Cost
MX301 Mixer 9 L/s 1 5
R301 Esterification reactor 560 kg steel 1 28
PU301 Reactor inlet pump 7.7 L/s 1 18
PU302 Methanol and water pump 12 L/s 1 18
PU303 Methanol recycle pump 3.3 L/s 1 17
PU304 Succinic acid recycle pump 0.3 L/s 1 17
DC301 Distillation column 1 33 kg steel 1 18
Distillation column 1 trays x4 1 m 1 3
Distillation column 2 trays x13 1.2 m 1 14
Distillation column 3 trays x10 3.2 m 1 54
X301 Reactor inlet heat exchanger 65 m2 1 534
X302 Water recycle cooler 19 m2 1 442
X303 Methanol recycle cooler 3 m2 1 418
X304 DMS, MMS heater 14 m2 1 434
X305 SA recycle cooler 4 m2 1 419
2488
Table 7.4: Esterification unit costings

Material Cost
R302 Hydrogenolysis reactor 1000 m2 2 358
F301 Furnace 0.5 MW 1 211
PU305 Coolant pump 5.7 L/s 1 14
CM301 DMS compressor 283 kW 1 655
CM302 Recycled reactants comp. 17 kW 1 414
CM303 Recycled hydrogen comp. 803 kW 1 981
X306 Coolant heat exchanger 47 m2 1 50
X307 Reactor outlet cooler 125 m2 1 68
X308 Reactor outlet Condenser 330 m2 1 125
VLS301 Main VLS1 28260 kg steel 1 322
VLS302 Hydrogen/methanol VLS2 560 kg steel 1 28
DC304 Distillation column 487 kg steel 1 27
Distillation column trays x5 3.5 m 1 32
3284
Table 7.5: Hydrogenolysis unit costings
Material Cost
FU001 Biomass thermal oxidiser 7.9 MW 1 957
FU002 Furnace 9.5 MW 1 1092
BR001 Boiler 1 11503 kg/h steam 1 356
BR002 Boiler 2 13725 kg/h steam 1 390
2796
Table 7.6: Miscellaneous unit costings
The total cost of equipment to be purchased and installed is: $126,042,980.

From this total equipment cost, we can make estimations of the additional costs of starting off
our plant:
Expense name % of equipment cost Cost, 1000$
Equipment purchase and installation 126042
Buildings including services 0.47 59240
Yard improvements 0.15 18906
Service facilities 0.6 63021
Land 0.06 7562
Engineering and supervision 0.3 37812
Construction expense 0.1 12604
Contractor’s fee 0.05 6302
Contingencies 0.08 10083
341576
The fixed capital cost of building this plant is $341,576,000.

7.4 Manufacturing Costs
All costs directly associated with manufacturing of our product are contained in manufacturing
costs. These are divided into variable production costs, fixed charges, and plant overhead costs.
7.4.1 Variable Production Costs
Variable production costs consist of expenses directly associated with the manufacturing
operation. These costs are incurred only when the plant operates, however some costs such as
maintenance and repair still occur during shut down.
7.4.1.1 Cost of Raw Material
Once off costs
Once off costs are for raw materials that once bought will be continuously recycled or have a
lifespan long enough that they can be considered a once off.
Pre-T Ferm. Cryst. Ester. Hydro. Price Cost
Raw Materials
tonnes $/tonne $M
Ammonia 34.866 460 0.016
Hydrochloric Acid 13.161 85.43 0.001
Tridodecylamine 330 100000 33
Cellic CTec3/HTec3
4.3234 1619096 7
(Enzyme)
Propylene Glycol
3500 300 1080 4.104
(Coolant)
Dowex DR-2030
0.34 135700 0.046
(Catalyst)
Raney Copper
2.835 60000 0.17
(Catalyst)
Dowtherm A
16 4000 0.064
(Coolant)
Total 44.4
Annual Costs
Annual costs are for the total amount of raw materials that will need to be purchased throughout
the year. Factoring in recycling of methanol (125,663 tonnes/year) and carbon dioxide (95
tonnes/year), the yearly material requirements and costs are as follows:
Pre-T. Ferm. Cryst. Ester. Hydro. Price Cost
Raw Materials
tonnes/year $/tonne $M
Corn stover 284507 30 8.535
Water 170699 431678 0.6 0.345
A. Succinogenes
113a 228b 0.026
(Bacteria)
Ammonia 27644 460 12.716
Carbon Dioxide 35718 3 0.107
Hydrochloric 328 85.43 0.028
Acid
Methanol 183 2116 0.1
Hydrogen 6226 1380 8.592
Total 30.5
a. Live cultures required per batch.
b. Price per culture

7.4.1.2 Operating & Administration Labour
To estimate the operating labour the processes were grouped as follows:
1. Pre-treatment + Fermentation
2. Crystallisation + Waste Water Treatment
3. Esterification + Hydrogenolysis
Most plants require at least 3 shift positions; one operator in the control room, one outside, and
one in the feed/product shipping and receiving area. For this estimation we chose to have 5
shift positions for each process, with an extra 3 for waste water treatment. Almost all plants
typically have 5 operators per shift position, this gives us a total of 90 operators, and using a
standard ratio of 10 workers per manager, gives us 9 managers. Average salaries for each were
taken from the US Bureau of Labour Statistics [4, 5] and are assumed to include holiday pay,
insurance, pension contributions, etc.
Wages per employee Total wages
Position No. of
($/year) ($M/year)
Operator 90 46110 4.15
Manager 9 64890 0.584
Total 4.734
To calculate administration labour for the rest of the plant, it was assumed there is a total of
500 employees based on similarly sized plants, this leaves 401 employees to calculate wages
for. Again, a ratio of 10:1 was assumed for managers. Average wages for our location (O’Brien
county, Iowa) were used to give an estimate for non-management employees, and based off
operator wages managers were assumed to have 60% higher wages [6]. Calculations were
based off a 40-hour work week and roughly 48.6 weeks of operation.
Work Weekly Yearly Total for all
Wages
Position No. of week wage wage employees
($/h)
(h/week) ($/week) ($/year) ($M/year)
Non-management 361 16.95 40 678 32931 12
Managers 40 27.12 40 1085 52690 2
Total 14
The total wages for employees add up to 18.7 $M/year.

7.4.1.3 Utilities
For this section utilities will include the cost of electricity to run agitators, compressors, and
pumps, and the cost of natural gas for our boiler and furnace.
For electricity, a cost of 0.053 $/kWh is taken as the average industrial rate in Iowa [7], and
plant operation is 8160 h/year. Cost $ = kW * kW h.
Cost per Cost
ID kW Total kW
MW h / year $M
R102 667
Agitators F201 850 1581 12.9 0.683
CR201 64
CM101 4355
CM301 282
Compressors 5401 44.07 2.336
CM302 17
CM303 747
PU201 5
PU301 1.528
PU302 0.123
Pumps 8.29 0.068 0.003
PU303 0.036
PU304 0.003
PU305 1.6
Total 3.023
From the US Energy Information Administration, the price of natural gas in Iowa is 5.44
($/1000 ft3) [8], dividing by 28.3 (m3/1000 ft3) converts this to 0.192 $/Nm3.
Equipment g/s Nm3/year $M/year
Furnace 11.7 531778 0.102
Boiler 188 8516095 1.637
Total 1.74
The total cost of utilities adds up to 4.762 $M/year.
7.4.1.4 Maintenance & Repairs
Maintenance and repairs for the entire plant can be taken as 7% the fixed capital investment.
Total fixed capital investment 341.5 $M/year
x 7% 0.07
Maintenance cost 23.9 $M/year
7.4.1.5 Laboratory Charges
The cost of laboratory will cover product quality control, tests for control of operations, and
lab scale growth of bacteria and enzyme to production scale. These charges can be taken as
20% of the operating labour.
Operating labour 4.734 $M/year
x 20% 0.2
Laboratory cost 0.947 $M/year

7.4.1.6 Patents & Royalties
Can be roughly approximated as 6% of the total product cost.
Total product cost 64.8 $M/year
x 6% 0.06
Patent and royalties cost 3.89 $M/year
7.4.2 Plant Overhead Costs
The costs in the previous section concerned those directly related to the production operation,
however for the plant to function as a whole, there are also additional costs covering safety and
protection, canteen, packaging, etc. These costs are taken as 70% of the total cost of labour,
supervision, and maintenance.
Total labour costs 43.6 $M/year
x 70% 0.7
Plant Overheads 30.5 $M/year
7.4.3 Fixed Charges
Fixed charges are costs that change little or not at all with the amount of production. These
expenses are estimated from the fixed capital investment (capital required to set up the plant).
7.4.3.1 Financing
To fund the design, building, and running of plant operation until profit is earned, borrowed
capital (working capital) will be required. The Federal Reserve of America sets a base interest
of 2% for commercial banks, a further percentage is added by the bank providing the loan, for
this estimation it will be assumed as 3%. The repayment interest will therefore be 5% of the
total repayment, this is assumed to be spread out over 10 years.
Another method of raising capital is through equity financing, this is contributed by
stockholders. Though this method demands a higher interest rate (25-35%), it is common for
companies to use a balance of both debt and equity. For this estimation it will be assumed that
capital is raised through 60% debt (at 5% interest) and 40% equity (at 25% interest).
Total required capital 393 $M
Debt Equity
% 236 $M 157 $M
Interest 11.8 $M 39.3 $M
Total debt repayment 248 $M 197 $M
Total repayment over 10 years 445 $M
Repayment per year 44.5 $M

7.4.3.2 Taxes
For the production costs estimation, only property tax is considered. Property tax can be
assumed to be 1% of the fixed capital investment.
x 1% 0.01
Property tax 3.416 $M/year
7.4.3.3 Property Insurance

Property insurance depends on the type of process and the extent of protection facilities;
however, it can be assumed to be 1% of the fixed capital investment.
x 1% 0.01
Property insurance 3.416 $M/year
7.4.4 Total Manufacturing Costs

Once-off raw materials are included in fixed charges as they will be purchased with working
capital.
Direct production costs 64.8 $M/year
Administration labour 14 $M/year
Patent and royalties 3.9 $M/year
Fixed charges 51.3 $M/year
Plant overheads 30.5 $M/year
Total Manufacturing Costs 165 $M/year

7.5 Analysis of Plant Economics
7.5.1 Net Cash Flow & Corporation Tax
Net Cash Flow = Revenue (Sales) – Expenditure (Manufacturing Costs)
Corporation tax in the US is 21% (as of 20th Dec 2017)
Revenue 228 $M/year
Expenditure 165 $M/year
Gross Profit 63.8 $M/year
x 21% 0.21
Corporation tax 13.4 $M/year
Net Profit 50.4 $M/year
7.5.2 Breakeven Point
There is a close relationship between operating time, rate of production, and selling price. The
point where total product cost equals total income represents the breakeven point, the optimum
production must above the point corresponding to the breakeven point.
First direct production cost per kg is calculated:
𝐷𝑖𝑟𝑒𝑐𝑡 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝐶𝑜𝑠𝑡𝑠
𝐷𝑖𝑟𝑒𝑐𝑡 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝐶𝑜𝑠𝑡 𝑝𝑒𝑟 𝑘𝑔 = 𝐸𝑞𝑛. 3
𝑆𝑎𝑙𝑒𝑠 𝑅𝑒𝑣𝑒𝑛𝑢𝑒
𝑆𝑒𝑙𝑙𝑖𝑛𝑔 𝑃𝑟𝑖𝑐𝑒 𝑝𝑒𝑟 𝑘𝑔
The direct production cost per kg is 0.92 $/kg
The kg/year for a breakeven point is calculated as:
𝑘𝑔
(𝑇𝑜𝑡𝑎𝑙 𝑀𝑎𝑛𝑢𝑓𝑎𝑐𝑡𝑢𝑟𝑖𝑛𝑔 𝐶𝑜𝑠𝑡𝑠) + (𝐷𝑖𝑟𝑒𝑐𝑡 𝑃𝑟𝑜𝑑𝑢𝑐𝑡 𝐶𝑜𝑠𝑡 𝑝𝑒𝑟 𝑘𝑔) ( )
𝑦𝑟
𝑘𝑔
= (𝑆𝑒𝑙𝑙𝑖𝑛𝑔 𝑃𝑟𝑖𝑐𝑒 𝑝𝑒𝑟 𝑘𝑔) ( ) 𝐸𝑞𝑛. 4
𝑦𝑟
This is rearranged to find the kg/year:
𝑘𝑔 𝑇𝑜𝑡𝑎𝑙 𝑀𝑎𝑛𝑢𝑓𝑎𝑐𝑡𝑢𝑟𝑖𝑛𝑔 𝐶𝑜𝑠𝑡𝑠
= 𝐸𝑞𝑛. 𝑋
𝑦𝑟 𝑆𝑒𝑙𝑙𝑖𝑛𝑔 𝑃𝑟𝑖𝑐𝑒 𝑝𝑒𝑟 𝑘𝑔 − 𝐷𝑖𝑟𝑒𝑐𝑡 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝐶𝑜𝑠𝑡 𝑝𝑒𝑟 𝑘𝑔
The kg per year that needs to be achieved for a breakeven point is 51.6x106 kg/year.
The current capacity of the plant is 70.237x106 kg/year of BDO. The breakeven point is
calculated as follows:
𝑘𝑔
𝑃𝑟𝑜𝑑. 𝑅𝑎𝑡𝑒 𝑓𝑜𝑟 𝐵𝑟𝑒𝑎𝑘𝑒𝑣𝑒𝑛 𝑃𝑜𝑖𝑛𝑡 ( 𝑦𝑟 )
(100) = % 𝑜𝑓 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑓𝑜𝑟 𝑏𝑟𝑒𝑎𝑘𝑒𝑣𝑒𝑛 𝑝𝑜𝑖𝑛𝑡
𝑘𝑔
𝐶𝑢𝑟𝑟𝑒𝑛𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 ( 𝑦𝑟 )
𝐸𝑞𝑛. 6
This gives a percentage of 73%, indicating the plant breaks-even.

7.5.3 Cash Flow Diagram
Another method of finding the breakeven point is to construct a cash flow diagram.
The initial capital investment is required to design, build, and run the plant until profit can be
made from sales. Total operating time (from start to finish) is estimated at around 195 hrs, a
new batch is started every 72 hrs. Once the plant is built, capital is needed for 3 runs of the
process before profit from the first run is made, assuming the product is sold as soon as it is
purified.
Administration costs are calculated by dividing the 195 hrs operating time by 24 hrs to get 8
days of operation, so for administration labour working a 40-hour week capital will be required
to pay wages for 1 week before profits are earned.
Plant design and construction is assumed to take 1 year, and equipment installation is assumed
to take another year after that.
Figure 7.1: Cash flow diagram
A-B: Plant design and construction -215.5 $M

B-C: Equipment installation -126 $M
C-D: Working Capital -51.8 $M
Consists of once off raw materials, production costs for 3 runs of the process, and
administration costs for 1 week.
D-E: Breakeven +393.3 $M
Investment is paid off at this point at 6 and a half years.
E-F: Profit +467.6 $M
Project is earning a return on investment

7.5.4 Rate of Return
The ratio of investment to annual profit is used to determine the performance of the invested
capital. The life of the project is assumed to be 10 years, and the rate of return is calculated as:
𝑇𝑜𝑡𝑎𝑙 𝑁𝑒𝑡 𝐶𝑎𝑠ℎ 𝐹𝑙𝑜𝑤 𝑎𝑡 𝑡ℎ𝑒 𝐸𝑛𝑑 𝑜𝑓 𝑃𝑟𝑜𝑗𝑒𝑐𝑡
𝑅𝑂𝑅 = (100) 𝐸𝑞𝑛. 7
𝐿𝑖𝑓𝑒 𝑜𝑓 𝑃𝑟𝑜𝑗𝑒𝑐𝑡 ∗ 𝑂𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝐼𝑛𝑣𝑒𝑠𝑡𝑚𝑒𝑛𝑡
Total Net Cash Flow at the End of Project 468 $M

Life of Project 10 years
Original Investment 393 $M
Rate of Return 12 %
7.6 Discussion
From the analysis of Section 7.5 of this report, the production of BDO will breakeven at 73%
capacity, and at 100% capacity will breakeven after 6.5 years, the Rate of Return is also 12%.
These factors show the plant is economically viable and very profitable.
It should be noted that for accounting purposes the life time of the project is taken as 10 years,
though this isn’t the physical life time of the plant. This economic analysis is only a preliminary
estimate and that certain costs would have to be investigated in finer detail, however even
allowing for an overestimation shows the plant still achieves profitability over the lifetime of
the plant.

7.7 References
[1] R. Sinnott and G. Towler, Chemical Engineering Design, Elsevier Ltd., 2009.
[2] M. S. Peters, K. D. Timmerhaus and R. E. West, Plant Design and Economics for
Chemical Engineers, The McGraw-Hill Companies. Inc., 2003.
[3] “U.S Inflation Calculator,” Coinnews Media Group LLC, [Online]. Available:
http://www.usinflationcalculator.com/.
[4] “Occupational Employment and Wages, May 2017 - Chemical Plant and System
Operators,” Bureau of Labor Statistics, [Online]. Available:
https://www.bls.gov/oes/current/oes518091.htm.
[5] “Occupational Employment and Wages, May 2017 - General and Operations Managers,”
Bureau of Labor Statistics, [Online]. Available:
https://www.bls.gov/oes/CURRENT/oes111021.htm.
[6] “County Employment and Wages in Iowa — Second Quarter 2017,” Bureau of Labor
Statistics, [Online]. Available: https://www.bls.gov/regions/midwest/news-
release/CountyEmploymentAndWages_Iowa.htm.
[7] “Iowa Electricity Rates & Consumption,” Electricity Local, [Online]. Available:
https://www.electricitylocal.com/states/iowa/.
[8] “Natural Gas,” U.S. Energy Information Administration, [Online]. Available:

https://www.eia.gov/dnav/ng/ng_pri_sum_dcu_SIA_m.htm.

Chapter 8 Conclusion
Author: All Members
The large scale production of 1,4-butanediol has been designed for the final year design project
as part of the B.E. in Chemical and Biochemical Engineering. This is a project that incorporates
all the major skills taught over the course of this degree programme. There are numerous,
invaluable skills that are gained from this project also such as process design, engineering
skills, problem solving, teamwork, presentation and report writing skills.
The synthesis routes and operation units chosen were all evaluated and produce the most
efficient, cost effective design possible
Our plant is designed to convert 287,000 ton of corn stover per year into 70,227tn of 1, 4-
butanediol per year.
The plant is situated in Iowa, United States of America based off the market research and
availability of the biomass.
The process is partly self-sufficient, as several heat and energy streams were re-integrated back
into other processes to avoid unnecessary utilities. Both time and money will be saved from
these mass and energy integrations. As well as this, having a waste product of lignin gives us
the opportunity to dry and sell the biomass offsite. This again will be another source of revenue
for the processing plant.
A detailed HAZOP was produced on the hydrogenolysis of dimethyl succinate, and an in-depth
environmental analysis was undertaken on the whole processing plant.
After an economic analysis on the process, it was found that the production of BDO will
breakeven at 73% capacity, rate of return of 12% and at 100% capacity will breakeven after
6.5 years. It should be noted that for accounting purposes the life time of the project is taken
as 10 years, though this isn’t the physical life time of the plant.
A yearly net profit of $50.4 million per year is projected, given the cost of BDO of $3.25 per
kilogram.
- 216 -

Production of 1,4 - Butanediol From Renewable Resources

Uploaded by

Copyright:

Available Formats

You might also like

Production of 1,4 - Butanediol From Renewable Resources

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Production of 1,4 - Butanediol From Renewable Resources

Uploaded by

Copyright:

Available Formats

Production of 1,4-Butanediol from

Hamed Al-Jabri 12131822

Chemical & Biochemical Engineering, LM115

Figure 1.1: Uses of 1,4-Butanediol

Figure 1.2: Succinic Acid Derivatives [5]

Figure 1.3: Schematic of BDO synthesis routes

1.2.1 Current Industrial Standard

Figure 1.4: Hydrogenation of Butynediol [1]

Figure 1.5: BDO biosynthetic pathways introduced into E. coli

1.2.3 Fermentation via A. Succinogenes

1.2.4 Ruthenium Nanoparticles Catalysed Hydrogenation of Succinic Acid

1.2.5 Davy Method of Succinic Acid to 1,4-Butanediol:

1.3.3 Alkaline Hydrolysis (NaOH/Ca(OH)2/AFEX™):

1.4 Environmental Benefits of Bio-Based BDO

Figure 1.6: Types of Cereals produced in the E.U. [15]

1.5.3 Corn Stover

1.6 Plant Location

Figure 1.8: Iowa Location [24]

1.7.2 Corn Fermentation

1.7.3 Succinic Acid Purification

1.7.4 Succinic Acid Esterification

1.7.5 Hydrogenolysis of Dimethyl Succinate

Figure 1.11: Global Consumption of 1,4-Butanediol [29]

1.9 Plant Size

S214 S220 S223

Figure 2.1: Overall Plant layout

Gold Line Corn stover

CM101 Steam R102

Figure 2.2: Pre-treatment of corn stover

Figure 2.3: Fermentation of glucose to succinic acid & its Purification

Figure 2.4: Esterification reactor & DMS purification flow sheet

Figure 2.5: Hydrogenolysis reactor and 1,4-butanediol purification flow sheet

Figure 2.6: Scheduling of Batch Operations

𝑇𝑜𝑡𝑎𝑙 𝑀𝑎𝑠𝑠 𝐼𝑛 = 𝑇𝑜𝑡𝑎𝑙 𝑀𝑎𝑠𝑠 𝑂𝑢𝑡 𝐸𝑞𝑛. 1

For vapour-liquid separators and mixing vessels:

∆𝐻𝑟𝑥𝑛,298 = (∑ 𝑛∆𝐻𝑓,298 ) − (∑ 𝑛∆𝐻𝑓,298 ) 𝐸𝑞𝑛. 10

∆𝐻𝑟𝑥𝑛 = ∑(𝑛∆𝐻𝑐 )𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 − ∑(𝑛∆𝐻𝑐 )𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝐸𝑞𝑛. 12

𝑄𝑐𝑜𝑛𝑑 = −∆𝐻𝑐𝑜𝑛𝑑 𝐷(𝑅 + 1) 𝐸𝑞𝑛. 14

𝐹(𝐻𝑓𝑠 − 𝐻𝑓 ) = 𝑚̇𝐶𝑝 (𝑇𝑏 − 𝑇𝑓 ) 𝐸𝑞𝑛. 15

D Top product kmol/s

Figure 3.1: AFEX Reactor R101

This unit op is covered in greater detail in Chapter 4.1.

Figure 3.2: Enzymatic Hydrolysis R102

Figure 3.3: Fermenter F201

Refer to Chapter 4.2: Unit Operation for more information

∑(𝑛∆ℎ𝑐 )𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = − 4020893 − 1097909 = −5118802𝑀𝐽

∑(𝑛∆ℎ𝑐 )𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 = − 444084 − 2207691 − 591240 − 190537 − 55084 = 3488636𝑀𝐽

∆𝐻𝑟𝑥𝑛 = −5118802 − (−3488636) = −1630166𝑀𝐽

3.5.4 Filter UF201

Molar mass of solution is 21.79 Kg/Kmole

3.5.8 Liquid-Liquid Extractor LLE201

𝑀𝑎𝑠𝑠 = 406.7 ∗ 810 = 329428.19𝐾𝑔

𝐻𝐶𝑙𝑒𝑥𝑡𝑟𝑎𝑐𝑡 = 10368 ∗ 0.98 = 10160.64𝐾𝑔

𝐻𝐶𝑙𝑟𝑎𝑓𝑓 = 10368 ∗ 0.2 = 207.36 𝐾𝑔

3.5.11 Fixed Bed Reactor R301

Figure 3.4: Reactor R301

See Chapter 4.4: Unit Operation for further information

3.5.12 Distillation Column DC301