Green Diesel Production From Vegetable Oil

FINAL YEAR PROJECT
GREEN DIESEL PRODUCTION FROM

VEGETABLE OIL USING ECOFINING
PROCESS
Project Supervisor:
Dr. Asif Nadeem Tabish
Project Co-Supervisor
Qazi Muhammad Umer
Submitted By:
Samiullah Ansari 2016-CH-269
Muhammad Hammad 2016-CH-295
Umar Shehrooz 2016-CH-257
Session 2016-2020
Department of Chemical, Polymer and Composite Material Engineering and

Technology U.E.T (New Campus)
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UNIVERSITY OF ENGINEERING AND TECHNOLOGY

LAHORE, NEW CAMPUS-54890, PAKISTAN
DEPARTMENT OF CHEMICAL, POLYMER AND COMPOSITE MATERIALS
ENGINEERING
This thesis is written by
1) Sami Ullah Ansari
2) Muhammad Hammad
3) Umar Shehrooz
Under the direction of their thesis advisor, has been presented and accepted, in partial
fulfillment of the requirements of the degree of Bachelor of Science in Chemical
Engineering.
__________________________ __________________________
Dr. Tanveer Iqbal Dr. Asif Nadeem Tabish
Department Chairman (Supervisor)
__________________________
Dr.
(Internal Examiner)
Date: _____________________
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Dedication
“This work is dedicated
To our beloved parents and
Our kind teachers”
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Acknowledgement
Thanks to ALLAH ALMIGHTY who gave us the strength to achieve this
project. And all respects for Our Holy Prophet (PBUH), whose teachings are
absolute source of guidance and knowledge for all man kind.
Beforehand of anyone else we are thanks full to our parents, as their moral
support helped us in difficult time. And they are the driving force behind what
we achieved. Further we are very grateful to our supervisor Dr Asif Nadeem
Tabish and co-supervisor Qazi Muhammad Umer for their helpful discussion,
inspiring guidance, and the way they guide us to the right pathway to solve the
problem. Without their remarkable suggestion we could not be able to complete
this report
We are very thankful to our faculty for their management, guidance and full
support.
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PREFACE
Rapid advancement in industrial activities and increasing growth of population,
cause excessive use of fossil fuels particularly petroleum and its derivatives as
fuel and industrial application and specially in transport. Which has caused
serious environmental, economical and social issues. Therefore, some different
more sustainable energy source is required. This report encircles the basic
mechanism behind green diesel production from vegetable oil using Eco-fining
process. This report is the result of our zealous efforts. We have in this report
concentrated on quality rather then blacking sheets with worthless or irrelevant
details.
All the basic equipment’s have been designed with the help of data and design
procedures from authentic source sited in the reference. However we selected to
design furnace, distillation column and reactor in order to minimize the number
of equipment designed and to devote full concentration on the core.
The design of any equipment is by definition a process that has extensive,
professional hands on experience in its background; that forms the fibre with
which to weave the fabric of design. However, this is the only drawback in our
work. Yet we hope that whoever examines this projects keeps this factor in
consideration. We do hope in favourable anticipation that this project will be
appreciated keeping in view all the inherent discrepancies in its generation.
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Table of Contents
Chapter 1 Introduction..................................................................................................................... 14
1.1 GREEN DIESEL...............................................................................................................................................14
1.1.1 Benefits of Green Diesel ....................................................................................................................14
1.1.2 Green Diesel Feedstocks ...................................................................................................................14
1.1.2.1 Jatropha Curcus ................................................................................................................................15
1.1.2.2 Cotton Seed Oil ................................................................................................................................16
1.1.2.3 Rapeseed Oil......................................................................................................................................16
1.1.2.4 Crude Tall Oil .....................................................................................................................................17
1.1.3 Specifications of Green diesel.............................................................................................................18
1.1.4 Cetane .....................................................................................................................................................18
1.1.5 Density ....................................................................................................................................................18
1.1.6 Sulphur ....................................................................................................................................................19
1.2 Process Description ....................................................................................................................................19
1.3 Difference between Petroleum and Green diesel .............................................................................20
1.4 Difference between biodiesel and green diesel ................................................................................20
1.5 Conclusion .....................................................................................................................................................21
Chapter 2 Process Description ........................................................................................................ 22
2.1 Process description .....................................................................................................................................22
2.2 Feed pretreatment ......................................................................................................................................22
2.2.1 Acidic value............................................................................................................................................22
2.2.2 Phosphors content ..............................................................................................................................22
2.2.3 Particles (contamination) ..................................................................................................................22
2.2.4 Water .......................................................................................................................................................23
2.3 Equipment’s used in process ...................................................................................................................23
2.3.1 Furnace ...................................................................................................................................................23
2.3.1.4 Furnaces in petroleum industry ...................................................................................................25
2.3.1.5 Combustion .......................................................................................................................................26
2.3.1.6 Selection of fuel ................................................................................................................................26
2.3.1.7 Replacement of fuel ........................................................................................................................26
2.3.1.8 Natural gas as a fuel .......................................................................................................................26
2.3.2 Reactor ........................................................................................................................................................27
2.3.2.1 Reactor details...................................................................................................................................27
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2.3.3 Separator: ...................................................................................................................................................29

2.3.4 Distillation column. ..................................................................................................................................29
2.3.4.1 Purpose of this unit .........................................................................................................................29
2.3.4.2 Choice between plate and packed column: ............................................................................29
2.3.4.3 Choice of tray: ...................................................................................................................................30
2.4 Process Flow Diagram................................................................................................................................31
Chapter 3 Material balance .......................................................................................................................... 32
3.1 Overall Material balance ...........................................................................................................................32
3.1.1 For Hydrogen ............................................................................................................................................32
3.1.2 For Other Products ..................................................................................................................................33
3.1.3 Further products formed during isomerization reaction ............................................................33
3.1.4 View of overall Balance ..........................................................................................................................34
Chapter 4 Energy Balance ............................................................................................................................. 35
4.1 Energy Balance Around Distillation Column ......................................................................................35
4.1.1 Specific heat of Feed ..........................................................................................................................35
4.1.2 Specific heat of top product ............................................................................................................35
4.1.3 Specific heat of bottom product ....................................................................................................36
4.1.4 Latent heat of vaporization of top product (Aspen HYSYS)..................................................36
4.1.5 Condenser Balance .............................................................................................................................36
4.1.6 Reboiler Balance ..................................................................................................................................37
4.2 Energy balance on furnace.......................................................................................................................39
4.2.1 Energy balance on furnace ...................................................................................................................39
4.2.1.1 Heat duty of Inlet stream of furnace .........................................................................................39
4.2.1.2 Heat duty of outlet stream of furnace ......................................................................................39
4.2.1.3 Heat supplied ....................................................................................................................................39
4.2.2 Energy balance on scale up furnace ..................................................................................................40
4.2.1 Heat duty of inlet stream of furnace .............................................................................................40
4.2.2 Heat duty of outlet stream of furnace ..........................................................................................40
4.2.3 Heat supplied........................................................................................................................................40
4.3 Energy balance across reactor ................................................................................................................41
4.3.1 For Reaction 01 ....................................................................................................................................41
4.3.2 For Reaction 02 ....................................................................................................................................42
Chapter 5 Equipment Design ....................................................................................................................... 45
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5.1 Distillation Column ......................................................................................................................................45

5.1.1 Material Balance...................................................................................................................................45
5.1.2 Procedure for plate column-design:.............................................................................................45
5.1.3 Identification of key component on basis of relative volatilities ..........................................46
5.1.4 Calculations of top and bottom temperature ............................................................................46
5.1.5 Calculation of Feed Conditions .......................................................................................................48
5.1.6 Design Steps .........................................................................................................................................48
5.1.7 Specification sheet: .............................................................................................................................58
5.2 REACTOR DESIGN .......................................................................................................................................59
5.2.1 INTRODUCTION...................................................................................................................................59
5.2.2 ALGORITHM FOR DESIGN OF REACTOR ....................................................................................60
5.2.3 Kinetic and thermodynamic data ...................................................................................................61
5.2.4 ....................................................................................................................................................................61
5.2.5 Reaction kinetics ..................................................................................................................................61
5.2.6 Reactor selection .................................................................................................................................62
5.2.7 Comparison and selection of reactor ...........................................................................................63
5.2.8 Reaction conditions for desired conversion: ..............................................................................64
5.2.15 Comparison for the selection:.......................................................................................................66
5.2.17 Specification sheet: ...........................................................................................................................67
5.3 Furnace Design.............................................................................................................................................68
5.3.1 Methods of Designing .......................................................................................................................68
5.3.2 Design Steps .........................................................................................................................................68
5.3.3 Design calculations .............................................................................................................................68
Chapter 6 HAZOP Study................................................................................................................................ 74
6.1 INTRODUCTION...........................................................................................................................................74
6.1.1 HAZARDS ...............................................................................................................................................74
6.1.2OPERATIBILITY .......................................................................................................................................74
6.1.3 WHEN HAZOP IS PRFORMED .........................................................................................................74
6.1.4 HAZOP SUCCESS AND FAILURE.....................................................................................................74
6.1.5 Study Notes: ..........................................................................................................................................75
6.1.6 Intention: ................................................................................................................................................75
6.1.7 Deviations: .............................................................................................................................................75
6.1.8 Causes: ....................................................................................................................................................75
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6.1.9 Consequences: .....................................................................................................................................75

6.1.10 Guide words:.......................................................................................................................................75
6.1.11 Guide words according to parameters: .....................................................................................76
6.1.12 Types of HAZOP: ...............................................................................................................................76
6.1.13 PROCESS HAZOP: .............................................................................................................................76
6.1.14 CONCLUSIONS ..................................................................................................................................77
6.2 Hazop Study of Distillation Column ......................................................................................................78
6.2.1 Distillation Column Diagram............................................................................................................78
6.2.2 HAZOP OPERATABILITY TABLE: .....................................................................................................78
6.3 HAZOP STUDY OF REACTOR ..................................................................................................................81
6.3.1 Reactor Diagram ..................................................................................................................................81
6.4 HAZOP STUDY OF FURNACE ..................................................................................................................83
6.4.1 Furnace Diagram .................................................................................................................................83
Chapter 7 INSTRUMENTATION AND PROCESS CONTROL.................................................................. 85
7.1 INTRODUCTION...........................................................................................................................................85
7.2 INSTRUMENTATION AND CONTROL OBJEVTIVES ..........................................................................85
7.2.1SAFER PLANT OPERATION ................................................................................................................85
7.2.2 Production Cost: ..................................................................................................................................85
7.2.3 Product Quality: ...................................................................................................................................85
7.2.4 Production Rate: ..................................................................................................................................85
7.3 CONTROL SYSTEM COMPONENTS: .....................................................................................................86
7.3.1 Process: ...................................................................................................................................................86
7.3.2 Measuring Means: ...............................................................................................................................86
7.3.3 MEASURABLE VARIABLES .................................................................................................................86
7.3.4Controller:................................................................................................................................................86
7.3.5 FINAL CONTROL ELEMENT ..............................................................................................................86
7.4 CLASSIFICATION OF THE CONTROLLERS ...........................................................................................86
7.5 MODES OF CONTROL ...............................................................................................................................87
7.6 ALARMS, SAFTEY TRIPS AND INTERLOCKS ........................................................................................87
7.6.1 Alarms: ....................................................................................................................................................87
7.6.2 Interlocks: ...............................................................................................................................................88
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7.7 DIFFERENT TYPES OF CONTROLLERS ..................................................................................................88

7.7.1 Flow Controller .....................................................................................................................................88
7.7.2 Temperature Controller .....................................................................................................................88
7.7.3 Pressure Controller .............................................................................................................................88
7.7.4 LEVEL CONTROLLER...........................................................................................................................88
7.7.5 Transmitter.............................................................................................................................................88
7.7.6 Control Valve ........................................................................................................................................88
7.8 CONTROL SCHEME ACROSS REACTOR ..............................................................................................89
7.8.1 INPUT & OUTPUT STREAMS ...........................................................................................................89
7.8.2 OPERATING CONDITIONS AND PROCESS PARAMETERS.....................................................89
7.9 Analysis of Measurement..........................................................................................................................89
7.9.3 Operation Scheme ..............................................................................................................................90
Instrumentation and control on distillation column ...............................................................................90
Chapter 8 Process Simulation and Analysis .............................................................................................. 93
8.1 Introduction ...................................................................................................................................................93
8.1.1 Benefits of simulation .........................................................................................................................93
8.2 Process Flow Diagram................................................................................................................................93
8.3 Process Simulation ......................................................................................................................................94
8.3.1 Selection of components ..................................................................................................................94
8.3.2 Selection of Thermodynamic model .............................................................................................95
8.3.3 Operating Conditions for Main Process Equipment’s .............................................................96
8.3.4 Drawing of the process flow diagram ..........................................................................................96
8.3.5 Simulation of Process Flow Diagram ............................................................................................97
8.3.6 Material balance using Aspen HYSYS ...........................................................................................98
8.4 Comparison between manual calculation and Aspen HYSYS calculation ................................99
8.4.1 Distillation column ..............................................................................................................................99
8.4.2 Furnace ................................................................................................................................................ 100
8.4.3 Reactor ................................................................................................................................................. 100
Chapter 9 COST ESTIMATION ................................................................................................................... 102
9.1 Introduction ................................................................................................................................................ 102
9.2 METHODS OF COST ESTIMATION ................................................................................................. 102
9.3 TOTAL CAPITAL INVESTMENT ........................................................................................................ 102
9.3.3 TOTAL CAPITAL INVESTMENT ..................................................................................................... 104
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9.4 TOTAL PRODUCT COST .................................................................................................................... 104

9.5 Product price and Profitability ......................................................................................................... 106
Chapter 10 ENVIORMENTAL IMPACTS OF BIOFUEL............................................................................ 107
10.1 Introduction ............................................................................................................................................. 107
10.2 HOW BIOFUELS HELPS TO MITIGATE THE CLIMATE CHANGE .............................................. 107
10.2.1 GREEN HOUSE GASES .................................................................................................................. 107
10.3 Effects of biofuel production .............................................................................................................. 109
10.4 Impacts on available water ................................................................................................................. 110
10.5 Effect of pesticides on environment ................................................................................................ 110
10.6 Practices for sustainable biofuel production................................................................................. 111
10.7 Standards and sustainable criteria ................................................................................................... 111
List of Symbols ................................................................................................................................................. 112
References....................................................................................................................................................... 113
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Table of Figures
figure 1-1:Jatropha caracus shrub [4] ..............................................................................................................15
figure 1-2: Composition of jatropha oil [7] ....................................................................................................15
Figure 1-3:Cotton seed oil plant ........................................................................................................................16
Figure 1-4:Rape seed oil plant ...........................................................................................................................17
Figure 1-5:Examples of resins and fatty acids prominent in CTO [10] ..................................................17
Figure 1-6:Simplified flow diagram [11] ..........................................................................................................20
figure 2-1:process inside furnace [19] .............................................................................................................23
figure 2-2:refractory alignment inside furnace [19] ....................................................................................24
figure 2-3:monolithic lining picture [19] .........................................................................................................24
figure 2-4:Ceramic fiber linings [19] .................................................................................................................25
figure 2-5:burner alignment [19] .......................................................................................................................25
figure 2-6:photos of industrial furnace [19] ...................................................................................................25
figure 2-7:fire triangle [20]...................................................................................................................................26
Figure 2-8:schematic diagram of a structured packing bubble column reactor [16] ......................27
Figure 2-9: horizontal longitudinal HLF separator [19] ..............................................................................29
Figure 2-10: Plate and packed column [63] ...................................................................................................30
Figure 2-11:bubble tray ........................................................................................................................................30
Figure 2-12:Sieve tray............................................................................................................................................30
Figure 2-13; valve tray...........................................................................................................................................30
figure 2-14: Process flow diagram for green diesel production from vegetable oil [21] ...............31
figure 5-1: Conversion Graph .............................................................................................................................62
figure 6-1: Distillation column diagram for HAZOP Analysis ...................................................................78
figure 6-2: Reactor diagram for HAZOP Analysis ........................................................................................81
figure 6-3: Furnace diagram for HAZOP Analysis ........................................................................................83
figure 7-1:: instrumentation and control scheme for reactor. .................................................................90
figure 7-2: Simple distillation column layout [41] ........................................................................................91
figure 7-3: instrumentation and control scheme on distillation column ..............................................92
figure 8-1: Process flow diagram for green diesel production from vegetable oil [21] ..................93
figure 8-2: Aspen HYSYS component list .......................................................................................................94
figure 8-3: Thermodynamic model (Aspen HYSYS) ...................................................................................95
figure 8-4: reaction 1 condition and stoichiometry Aspen HYSYS .........................................................95
figure 8-5: reaction 2 conditions and stoichiometry Aspen HYSYS .......................................................96
figure 8-6: Simulation of process flow diagram ...........................................................................................97
figure 8-7: Outlet streams and compositions of distillation column, Aspen HYSYS ........................99
figure 8-8: Heat duty of furnace, Aspen HYSYS ........................................................................................ 100
figure 8-9: outlet stream temperature of reactor, Aspen HYSYS......................................................... 101
Figure 9-1: Cash flow over the life span of plant ...................................................................................... 106
Figure 10-1 LCA for green fuel [47] ................................................................................................................. 108
Figure 10-2:greenhouse gas balances [6] ......................................................................................................... 108
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List of Tables
Table 1-1:Composition of cotton seed oil [8] ...............................................................................................16
Table 1-2: Composition of Rapeseed Oil [6] .................................................................................................17
Table 1-3:Specifications of ultra-low Sulphur Green diesel fuel [11] ....................................................19
Table 4-1: specific heat values of feed components along with compositions .................................35
Table 4-2: specific heat values of top components along with compositions ...................................35
Table 4-3: specific heat values of bottom product components along with compositions...........36
Table 4-4: latent heat of vaporization of top components along with compositions .....................36
Table 4-5: Heat Capacity of components at inlet and outlet stream of furnace ...............................39
Table 4-6: Heat Capacity of components at inlet and outlet stream of furnace ...............................40
Table 5-1: Material balance across distillation column ..............................................................................45
Table 5-2: Dew point Calculation for top temperature..............................................................................47
Table 5-3: Bubble point Calculation for bottom temperature .................................................................47
Table 5-4: bubble point calculation for feed temperature .......................................................................48
Table 5-5: Calculation of optimum R value....................................................................................................49
Table 5-6: Table for Calculation of Average Viscosity ................................................................................50
Table 5-7: specification sheet for distillation column .................................................................................58
Table 5-8: physical properties table for reactor ...........................................................................................61
Table 5-9: Selection among the PFRs is on the following basis ..............................................................63
Table 5-10: specification sheet for reactor .....................................................................................................67
Table 5-11: composition for natural gas [31] ................................................................................................69
Table 5-12: products formed due to buring of natural gas .....................................................................69
Table 5-13: Table for calculations for flue gases ..........................................................................................70
Table 5-14: flue gases composition ..................................................................................................................72
Table 6-1: guide words for HAZOP Analysis .................................................................................................75
Table 6-2:Guide words according to parameters ........................................................................................76
Table 6-3: HAZOP Analysis for Distillation Column ....................................................................................78
Table 6-4: HAZOP Analysis for Reactor...........................................................................................................81
Table 7-1: input and output streams of reactor ...........................................................................................89
Table 7-2: operating conditions for reactor...................................................................................................89
Table 8-1: feed components and compositions [42] ..................................................................................94
Table 8-2: Operating conditions for main equipment’s used in process .............................................96
Table 8-3: Condition and compositions of inlet and outlet streams of process................................98
Table 8-4; manually calculated composition of outlet streams of distillation column ................. 100
Table 9-1: Table for Equipment Cost ............................................................................................................ 103
Table 9-2: Table for calculation of direct cost ............................................................................................ 103
Table 9-3: Table for calculation of indirect cost ........................................................................................ 104
Table 9-4: Table for fixed charges calculation ........................................................................................... 105
Table 9-5: Table for direct production cost calculation .......................................................................... 105
Table 9-6: table for General Expense ............................................................................................................ 106
Table 10-1:water requirement for biofuel crops [53] .............................................................................. 110
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Chapter 1 Introduction
1.1 GREEN DIESEL

As there are adverse things connected with the used of petroleum products as they are going to
be end one day so their reserves are depleting and the secondly, they have worse effects on the
environment so there should be an alternative for that petroleum products like green diesel or
biodiesel. Green diesel which is renewable and produced from agriculturally based products
would be a better alternative because it is environmentally friendly and secondly its raw
material can be grown every where because of diverse range of agricultural products can be
used. In this regard several researches have took place for green diesel production from
different agricultural products like vegetable oil or seeds oils. Green diesel is second generation
biofuel and non-petroleum based it is alternative of diesel fuel derived from plant oils and
animal fats those consisting of paraffins. To produce green diesel from these feedstocks their
fatty acids and triglycerides undergoes hydrotreatment for oxygen removal.
Presently major source and raw product used for green diesel production is derived from
vegetable oil containing triglycerides having less free fatty acids. Major part of the total green
diesel production cost is directly connected to the refined vegetable oils of cotton seed,
jatropha, rapeseed or soybean. Recently some other cheap feedstocks are used for green diesel
production to better compete conventional petroleum products.
1.1.1 Benefits of Green Diesel

Green diesel have market potential due to its benefits in comparison with petroleum fuels
because petroleum fuels are toxic to some extent, they produce carbon mono oxide and they
are non-renewable while green diesel don’t along with high cetane number and local production
capability of green diesel [1]. Other advantages over petroleum fuels are solvent properties,
superior lubricant, lower emissions, ease of storage and their adoption to already in apparatus
infrastructure. It will not only decrease the foreign oil imports but also increase the
opportunities for locals in job sectors as Pakistan’s economy is agriculturally based economy.
One of the major benefit is the adoptability of feedstock for green diesel production like it don’t
only depends on specific vegetable oils but mixture and even the algae can be used.
Their environmentally friendly nature includes their biodegradability and renewability.
The cetane index is an important property of a diesel fuel which is a measure of the tendency
for it to auto ignite with respect to a reference fuel, cetane value (index of 100). Since the diesel
engine doesn’t rely on a spark plug in gasoline engines, it relies on the auto-ignition of the fuel
at high pressures to operate. Therefore, for green diesel to be an effective fuel for diesel engine
(compression ignition), its cetane index must resemble that the petroleum diesel. The cetane
number of green diesel is 50 [2].
1.1.2 Green Diesel Feedstocks

Major feed for the green diesel production is derived from vegetable oil though it has high
market demand but still it is not given global consideration as much it should be given. The
feedstocks recently in use are rape seed oil, jatropha, palm oil, animal fats and tall oil [3]
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1.1.2.1 Jatropha Curcus

Jatropha curcus (shrub) can be a good feed stock which can help many to eliminate green
diesel supply side issues.
figure 1-1:Jatropha caracus shrub [4]
Jatropha is a shrub that can face adverse weather conditions, can survive in tropics and semi
arid tropics. it grows wild in many areas of Asia and even thrives on infertile soil. So for green
diesel this makes it an ideal feed stock. So water efficiency of this plant and its huge plantation
for feed stock purpose required for the green diesel industry would cause the waste lands
regeneration.
The jatropha has a high yield per hector ranging from 1 to 5 tonnes dependent on the rain fall
and soil condition and period of yield [4]. Second year to onwards oil can be extracted from
seeds. It will also cause the elimination of poverty in the locals by employing them in industry
and agriculture. Huge amount of CO2per hectare jatorpha planation can absorb [5].
1.1.2.1.1 Composition of Jatropha

The composition of Jatropha is as follow:
figure 1-2: Composition of jatropha oil [7]
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1.1.2.2 Cotton Seed Oil

Cotton is widely grown crop in the fields of Asia so it can be a good source for the green diesel
production and as it is being used in the developing and under developed countries after the
WHO report of cotton seed oil harmfulness on women fertility so to use this oil in green diesel
production is excellently feasible.
Figure 1-3:Cotton seed oil plant
1.1.2.2.1 Composition of cotton seed oil
Fatty Acid No. of Carbon Weight (%)
Myristic Acid 14 1.5

Palmitic Acid 16 14.77
Stearic Acid 17 6.05

Oleic Acid 18 75.56
Linoleic Acid 18 2.12

Total unsaturated fatty acid = 77.68 Total unsaturated fatty acid = 22.32
Table 1-1:Composition of cotton seed oil [8]
1.1.2.3 Rapeseed Oil

Brassicaceae family plant grown mainly for its oil. erucic acid content of it was the reason of
its less cultivation in the past but in the sector of green diesel production it can be a good
source. Different fatty acids profiles of rape seed shows their triglyceride content that can be
used for green diesel production
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Figure 1-4:Rape seed oil plant
Table 1-2: Composition of Rapeseed Oil [6]
The composition varies a bit with the area of growth.
1.1.2.4 Crude Tall Oil

Major by-product of the Kraft pulping process are Crude Tall Oil (CTO). As it consists mostly
of resin and free fatty acids so CTO can be an important source of raw chemical materials.
Figure 1-5:Examples of resins and fatty acids prominent in CTO [10]
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Wood chips (commonly pine) are cooked during pulping in an alkaline solution (white liquor)
to saponify naturally occurring resin acids and fatty acids in the wood.
The spent solution (black liquor) containing salts, or soaps of the resin and fatty acid along
with some other neutral compounds of after the cooking process, the liquor is evaporated for
efficiently reuse of the pulping chemicals, the soaps after concentration float to the top and are
easily collected. The top skimming can then easily be converted to crude tall oil by the process
of acidification with sulfuric acid.
1.1.3 Specifications of Green diesel
A variety of blending components from different hydrocarbon types from which diesel fuel is
composed. To balance the key specifications refiners use blending components that produces
optimum diesel fuel for specified applications and operations.
In the primary distillation process some blending components are straight-run streams they
come directly from the crude oil. Hydrocracked streams produced from heavy gas oils are other
blending components. From the delayed coking of the refinery residual stream thermally
cracked distillates typically produced, and they are also produced from fluid catalytic cracker
(FCC) units . Desulphurization may be required depending on the sulphur content of the crude
oil, before addition into the final diesel-fuel blend the straight-run and processed streams may
be required.
1.1.4 Cetane
In the combination chamber diesel fuels ignites upon injection, for optimal power and
performance , engine ignition must occur without minimum possible delay or lag in ignition.
40 is specified minimum cetane number for diesel fuels in the United States and minimum
cetane number 50 in Europe , and in that range of 40-50 in most other parts of the world. Higher
cetane numbers provide optimum operations and also causes less particulate matter (PM)
emissions and that higher cetane number is 50 or above [1]. Cetane number of Green diesel is
greater than 74 that is higher than all current standards for diesel fuel, those established by the
Worldwide Fuel Charter also don’t matched by them.
1.1.5 Density
Higher the fuel density, higher will be the power output of a diesel engine per unit volume of
the fuel consumed. Lessening the fuel density lessens the nitrogen oxide (NOx) and PM
emissions.
It is shown by researches that reducing the density as small as 5% reduces PM emissions by

almost 20% in older engines, modern engines shows further PM reduction. it is observed that
lower peak pressure and temperatures associated with burning low-density fuels causes lower
NOx emissions [2]. That’s why current diesel engine engineering is focused on how to weigh
positive (emission reductions) factors linked with lower fuel densities between performances
while higher power fuels are those with higher fuel densities.
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1.1.6 Sulphur
Green diesel produced from vegetable oil removes all the traces of sulphur during feed
preparation process that is one of the reason green diesel fuel contains no measurable sulphur
content. Since it matches all other American Society for Testing and Materials (ASTM) D-
975 diesel fuel standards, green diesel is the cleanest diesel fuel available presently.
Other specification of green diesel in comparison with biodiesel and petroleum diesels are as
shown below:
Petroleum FAME
Components Green diesel
Diesel Biodiesel
Oxygen, % 0 11 0
Cetane 40-55 50-65 75-90
Energy Density, MJ/Kg 43 38 44
Sulpur, ppm less than 10 less than 2 less than 2
Cold Flow Baseline Poor Excellent
Oxidative Stability Baseline Poor Excellent
Table 1-3:Specifications of ultra-low Sulphur Green diesel fuel [11]
1.2 Process Description

In the Eco fining process the feedstock of primary interest is vegetable oil like palm, jatropha,
soybean and rapeseed oil. As these materials contains significant amount of oxygen so
processing of biologically derived feed stocks is complicated. Plant oil contains some
percentage of oxygen up to 11% [7] and triglycerides with a bit free fatty acid content. Others
such as tall oil, tallow oil, fish oil, and waste greases lower cost materials can also be used as
feedstocks. sometimes to remove contaminants such as solids or salts pre-treatment may be
required.
Simplified block flow diagram of the process is shown in the figure 1-6 . Feedstock is sent to
the catalytic reactor where it is reacts with hydrogen brought to elevated reaction temperature
and then converted to a branched paraffin rich diesel fuel by a series of optimized
decarboxylation, hydro-de-oxygenation, and hydro isomerization reactions. From the
decarboxylation reaction CO2 produce and from hydrodeoxygenation reaction H2O is produced
along with the hydrocarbon product. To maintain a minimum required hydrogen partial
pressure the excess hydrogen provided to the reactor is recovered and recycled back to the
reactor. To balance both chemical consumption and solution losses make-up hydrogen is added
to the process.
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Figure 1-6:Simplified flow diagram [11]
Catalytic reaction with hydrogen in the Eco finning process removes the oxygen by, producing
a paraffin-rich product. Fatty acids and triglycerides both contain relatively long linear aliphatic
hydrocarbon chains. Partially unsaturated aliphatic hydrocarbon chain have a carbon number
range and molecular weight comparable to the molecules fond in diesel fuels. The volumetric
yield of hydrocarbon products is greater than 99% and conversion of feed is 99% [8] .The
diesel boiling range selectively is too high. water and carbon oxides are the by-products of
deoxygenation reaction. Saturated fats rich feedstock such as palm and tallow oil requires less
hydrogen than feedstock which is higher in olefin content such as soybean or rapeseed oil [9].
Triglyceride + H2 Paraffin + Propane + Naphtha + H2O + CO2
Reaction 1-1
1.3 Difference between Petroleum and Green diesel

Oxygen contents is the biggest difference between petroleum and green diesel. petroleum has
essentially no oxygen content while bio renewables have oxygen level from 10-40%. Making
the chemical properties of bio renewable very different from petroleum. These bio- renewable
feed stocks are more polar and can be acidic in nature. They have very low organic sulphur and
nitrogen levels. Due to some properties like pre-treatment before feed entering to the refinery
and their acidic and alkali nature are incompatible with the present refinery operations.
Sulphur contents in green diesel are very low in comparison to petroleum diesel as shown in
above table 1-3.
1.4 Difference between biodiesel and green diesel

Biodiesel is produced via transesterification with methanol in the presence of caustic to produce
Fatty Acid Methyl Ester while (FAME)and glycerol are by-products [1]. The glycerol produced
from the three-carbon backbone and has less market value, particularly in unrefined raw form.
The chemistry is used in biodiesel or FAME route is difficult to substantiate, the reaction is as
follows [9]
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Triglyceride +Methanol FAME + Glycerol

Reaction 1-2
On the other hand side, green diesel is produced by using hydro processing route to remove
oxygen from triglyceride molecules. The oxygen is removed via two competing reaction:
i- Decarboxylation
ii- Hydrodeoxygenation
As a by-product propane is produced which can easily be recovered and can be a valuable
renewable LPG product.
1.5 Conclusion
As refiners are well settled recently to play a role in renewable fuel production in the near
future. Ecofining a new process to produce green diesel is a sustainable process to convert
vegetable oil into good-quality diesel fuel and can possibly be the first step for providing
technology to enable already settled refiners to participate in the production of renewable fuels.
Green diesel is a superior biodiesel alternative having significant better diesel product
properties and it is substitute to the conventional mineral diesel production.
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Chapter 2 Process Description
2.1 Process description

The feed stock for Ecofining process is vegetable oil. Selected vegetable oils are jatropha,
cotton seed and rape seed oils. Processing of such feed stocks is difficult because they have
high oxygen content 10-12 % [10] oxygen is present in a plant oil. Basic content of typical
plant oil is triglycerides with 1 - 2 percent free fatty acid. Oils such as fish oils, tall oil, animal
fats oil, tallow oil and waste grease are low in prices so they can be used as a feed stock.
Sometimes solids and salts are present in feed stocks, so pretreatment needed before processing.
Block flow diagram of the Ecofining process is shown in figure 1.6. Heated feed stock is
entered to the catalytic reactor where it reacts with the hydrogen, reached the required
temperature and then hydrodeoxygenation, decarboxylation and hydro isomerization reactions
occur in a series as a result diesel oil produced.
Deoxygenation reactions produces the water and carbon dioxide which are separated from the
product. [11] Light fuel byproducts are separated from the product. Basic equipment’s used in
producing green diesel are furnace, reactor and distillation column. Hydrogen partial pressures
maintained by adding excess hydrogen.
2.2 Feed pretreatment

There may be some problems occur with the feed oil and so we must pretreat the oil. Various
components present in the oil have distorting effects on engines. Some related terms are
discussed which define the quality of oil.
2.2.1 Acidic value

The acidic value shows the quality of oil related with present amount of fatty acids. High acid
value means high fatty acids and high acid value effect the engine working as it may damage
the metal components present in the injection system. So acid value must be low The pH of
neat vegetable oi used as feed varied between 7.38 and 8.63 [12]. RK standard gives a safe
limit which is 2 [13]. Above 2 damage of engine is possible.
2.2.2 Phosphors content

RK standard value compared with jatropha oil and comparison shows that phosphors may cause
problems. Presence of phosphorus is in the form of phospholipids and phospholipids are
pressed out of the cell walls. Such materials are slimy(plugging of filters). Abrasive scaling
may occur by phosphorus in the combustion chamber which is not good for engine life.
2.2.3 Particles (contamination)

It may be possible that abrasive effect occurs on the injectors and walls of the combustion
chamber due to large size particles. Large particles can also plug filters which is not dangerous
but annoying. Sediment removal is significant.5 micron is considered as a good mesh size for
filtering [14].
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2.2.4 Water
Corrosion in the injector system may occur by water so amount of water should be kept low as
possible. Amount of water is very low in but still it is not in a safe limit. In cold areas it may
also possible that water freezes.
2.3 Equipment’s used in process

2.3.1 Furnace
Contacting a feed with a catalyst in the presence of hydrogen requires a high temperature
therefore feed is heated to a temperature of 300C – 380C by passing through a furnace.
2.3.1.1 Furnace Detail.

Furnace is a type of heat exchanger which is used to heat the material and this energy is supplied
by combustion of fuel or by electricity.
Furnaces may be used for heating a material for physical processes or it may provide a help for
different chemical reactions. Furnaces use high fuel for operation, and they have low
efficiencies. Controlling of furnace operation is also very difficult.
figure 2-1:process inside furnace [19]
2.3.1.2 Refractory
refractories are those materials which are resistant to heat decomposition and chemical attack.
A variety of such materials are available.
Refractory are of three types
1. Bricks lining
2. Monolithic lining
3. Ceramic refractory
2.3.1.2.1 Bricks lining

Conductivity of bricks is quite high, so ceramic fiber is used along with the bricks because
ceramic fiber is very less conductive which helps to reduce the heat loss by conduction.
Temperature is very high in furnace due to which bricks face stress. To avoid such stress
expansion joints are used at some intervals.
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figure 2-2:refractory alignment inside furnace [19]
2.3.1.2.2 Monolithic lining

Basically, monolithic lining is of two types.
Castable refractory
These refractories consist of a bonding agent and refractory material. Bonding material may be
high alumina cement, colloidal silica or hydratable alumina. These refractories are generating
by mixing water in it and after mixing water this material cast into the moguls. According to
requirement sometimes needles are added to refractory for reinforcement purpose.
2.3.1.2.3 Ceramic refractory
Where small irregular areas are present plastic refractories are used. These refractories have
special properties due to which their installation is easy. In such properties some of them are
soft plasticity(help in repairing) and softness(help to cover the small gaps)
figure 2-3:monolithic lining picture [19]
Ceramic fiber linings

Ceramic fiber linings are less in durability so these lining only used in low duty processes like
insulation in backing gas fired heaters or furnaces.
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figure 2-4:Ceramic fiber linings [19]
2.3.1.3 Burner
Burner is a device which is used to change the chemical energy of fuel to heat energy by
different chemical reactions in the presence of oxygen. These chemical reactions are generally
called combustion.
figure 2-5:burner alignment [19]
2.3.1.4 Furnaces in petroleum industry

In petrochemical industries heating of fluid occur at high temperature. For achieving this
temperature direct heating occur. In direct heaters tubes are directly under the exposure of
flame. Basically, fired heater are of two types i.e. cylindrical heaters and box or cabin heaters.
figure 2-6:photos of industrial furnace [19]
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2.3.1.5 Combustion
Burning of fuel in the presence of oxygen is called combustion. In combustion chemical
reactions take place which liberated heat energy. Fuel may be solid liquid or gas.
figure 2-7:fire triangle [20]
2.3.1.6 Selection of fuel

Selection of fuel depends upon the Properties of a fuel. [15]
1. Flammability limits(lean value and rich value).
2. Emissivity of present gases.
3. Availability
4. Density of fuel
5. Heating value
6. Chemical reaction of combustion and toxicity of product
7. Effect of combustion on the product.
8. Ash content
2.3.1.7 Replacement of fuel

If we need to replace the fuel, we can select the fuel by using wobbe number.
If Gases have same wobbe number, it means that heat release will be the same by using same
nozzle having the same pressure.
CV = Gross calorific value (MJ/m3 or Btu/ft3

SG = specific density relative to air
CV
W=
SG
2.3.1.8 Natural gas as a fuel

Refractory life of furnace increases by using the gaseous fuel. Composition of natural gas varies
by the area or by degree of treatment. Natural gas may contain CO2, H2O, N2 etc.
2.3.1.9 Material of Construction

Austenitic type of stainless steel is used.
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2.3.2 Reactor
Eco-fining process is basically a hydrofining process. Feed at pressure 4-6 MPa is pumped and
mixed with hydrogen and then sent to multistage catalytic hydrodeoxygenation reactor, first
saturation of oil take place then deoxygenation take place. Complete conversion of feed take
place and yield of process is greater than 99% [8, p. 432]. selectivity is high of Diesel boiling
range paraffins. Propane, water and carbon-dioxide are primary by products of deoxygenation
reaction
The reactor used for this purpose is structured fixed bed catalytic reactor.
2.3.2.1 Reactor details

PFR multiphase reactor whose design lies between trickle bed reactor and slurry reactor. Fired
wire gauze is used to enclose solid catalytic particles, and gauze is mounted along the column
height, gas phase moves into liquid phase where it disperse and then move to empty space
between two adjacent envelops. For liquid phases it operates in batch form or it circulate the
liquid in counter or co-current manner to gas flow. Some main advantages of this reactor over
slurry bubble reactor are following
• Separation catalyst from the liquid is Not a problem
• Due to liquid phase staging, selectivity and conversion is improved
• Problems related to scale up is low
Some main advantages over trickle bed are following:
• Pressure drop is low even for 1mm particles size

• Radial dispersion are excellent
• without flooding counter-current operation is possible. This different concept is
represented in fig
Figure 2-8:schematic diagram of a structured packing bubble column reactor [16]
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2.3.2.1.1 Catalyst.
For hydrocracking of VO for green diesel production Ni-Mo/ -Al2O3 or Pt- zeolite based
catalyst are used [17]. For liquid hydrocarbons hydrocracking on Ni-Mo/ -Al2O3 catalyst yield
high conversion. For hydrogenation and cracking reaction Pt-Zeolite is found to be very active
and helpful in order to get high conversion. Nut partial pressure of hydrogen is more required
than those for Ni-Mo/ -Al2O3 [11]. For both cracking and hydrogenation time of reaction was
limited while observing rate of reaction, which depend more on type of reaction.
Catalyst supported on precious metal such as platinum or palladium is thus preferable.
2.3.2.1.2 Process Chemistry

In ecofining process oxygen is removed with hydrogen using catalytic reaction, causing
product rich in paraffins. Fatty acid and triglyceride both have linear, long hydrocarbon chains.
These chains are partially unsaturated, and their molecular weight and carbon number are near
present in diesel fuels. Feed conversion is 99% [18, p. 13] and yield for hydrocarbon products
is high further, selectivity of paraffins of diesel boiling range is very high. The by-products of
deoxygenation reaction are carbon dioxide and water. Saturated fats rich oils like tallow and
palm oil require less hydrogen then feed having high content of olefin. Feed like soya-been,
rape seed and cotton seed have high olefin content
2.3.2.1.3 Chemistry of the Hydro-conversion of Vegetable oils

Many professionals have tried to drive the mechanism of hydrocracking of vegetable oil to
diesel. Generally, first triglyceride is saturated at C-O bond, that lead toward formation of
monoglyceride, diglyceride and waxes.
Then further they are converted into hydrocarbon by three different paths decarboxylation,
hydrodeoxygenation and dehydration [11]
Hydrogenation of unsaturated triglycerides
C₅₇H₁₀₄O₆ + 3H₂ C₅₇H₁₁₀O₆

Triolein (OOO) Tristearin (SSS)
Reaction 2-1
Hydro deoxygenation
C₅₇H₁₁₀O₆ +12H₂ 3C₁₈H₃₄ + C₃H₈ + 6H₂O

Tristearin (SSS) C18:0
Reaction 2-2
Hydro decarboxylation
C₅₇H₁₁₀O₆ +3H₂ 3C₁₇H₃₆+ C₃H₈ +3CO₂

Reaction 2-3
The major product is n-octadiene and n-heptane. Propane, carbon dioxide and water are by
products
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Liquid products obtained in the hydrotreatment reactor are mainly n-alkanes in the diesel
boiling range (270-320◦C), resulting in a product with high cetane number but poor cold-flow
properties. In order to improve the quality of the product, it is essential for the mixture to enter
a second reactor.
improving the cold-flow properties of the product comes at the expense of inevitable cracking
of the diesel, which yields variable quantities of lower boiling point mixtures such as jet fuel
and naphtha, depending on reactor conditions.
2.3.3 Separator:
The product coming out of reactor is sent to heat exchanger where it is cooled and then sent to
separator where water, organic products and gases are separated. A horizontal longitudinal flow
separator is used for this purpose.
In three phase separator the liquid is captured In

the retention section where time is given to the
liquid to settle down heavier liquid which include
water moves toward bottom of tank while lighter
liquids which include paraffins come at top of
heavier liquid and gases products are removed
from the top. Then the heavier and lighter liquid
is separated, and lighter liquid is sent to
isomerization take to improve its cold flow
properties [19]
Figure 2-9: horizontal longitudinal HLF separator [19]
2.3.4 Distillation column.
2.3.4.1 Purpose of this unit
The purpose of distillation column here is to separate naphtha and gaseous products as top
products while diesel as bottom product. This way, the process is flexible enough to yield
variable quantities of products different from green diesel, depending on the market demand.
2.3.4.2 Choice between plate and packed column:

To choose between packed or plate distillation column for any requirement can only be done
with detail cost estimation of each design. But this is not always necessary activity to
perform, choice is usually based on experience. By taking under consideration following
advantages and disadvantages of each type [20]:
1. Huge range of gases and liquids flowrates could be handled using plate column rather
than packed column
2. For low flowrate packed column is not appropriate.
3. We can predict the efficiency of plate column with more effective way than the
packed column which use equivalent term (HTU and NTU).
4. Design of plate column can be predicted with more accuracy than packed column
5. In packed column cooling can easily be made cooling coils at plates could be
installed.
6. Side stream withdraw can easily be made in plate column
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7. Periodic cleaning
8. Plate column cleaning is easier so for liquids that cause fouling, or contain solid
particles, plate column is usually used.
Figure 2-10: Plate and packed column [63]
9. For liquids that cause corrosion it is better to use packed column rather than plate
column as it would be cheaper.
10. In packed column rather than plate column, liquid holdup is significantly low.
11. For forming system more suitable column is packed column
12. For packed column pressure drop per equilibrium stage (HETP) is lower than
equivalent size plate column
13. Only for small diameter column packing could be used; maximum up to 0.6m, here
plates are difficult to install and therefore expensive.
2.3.4.3 Choice of tray:

Three main types of trays are usually used:
Figure 2-11:bubble tray Figure 2-12:Sieve tray Figure 2-13; valve tray
I selected sieve tray because of following reasons:

• Sieve tray are not expensive and lighter in weight. They are economical and easier
to install.
• As compare to bubble cap trays pressure drop is low.
• Huge variety of flow rates could be handled.
• Due to easy cleaning its maintenance cost is low.
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figure 2-14: Process flow diagram for green diesel production from vegetable oil [21]
Off Gases
Fresh
hydrogen
Green LPG
Condensor
E-5
Recycled Separator
hydrogen (Reflux drum)
Amine unit S-3
Pretreated oil
Top product
Pump Distillation column
Furnace P-1
T-1
F-1
2.4 Process Flow Diagram
Separator
Reactor
S-2
R-1 Reactor
R-2
3 phase
Separator
S-1
Bottom product
Heat exchanger
E-1 Heat exchanger
E-2 Heat exchanger Reboiler
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Chapter 3 Material balance
3.1 Overall Material balance

Basis: 1 hour
At steady state,
Total mass in = total mass out

From [11],
59 ton/day of diesel produce from = 74 ton/day of vegetable oil
1 ton/day of diesel produce from = 1.254 ton/day of vegetable oil
3 ton/day of diesel produce from = 3.763 tan/day of vegetable oil
125 kg/hr. of diesel produce from = 156.75 kg/hr. of vegetable oil
125 kg/hr. of diesel produce from = 0.180 glom/hr. of vegetable oil
As,
Molecular weight of vegetable oil = 870.83 kg/kgmol
Hence,
Amount of oil required = 0.180 kgmol/hr.
3.1.1 For Hydrogen
From balance chemical equation
Two reactions take place independent of one another [11].
C₅₇H₁04O₆ +15H₂ 3C₁₈H₃₄ + C₃H₈ + 6H₂O
Triolein C18:0
Reaction 3-1: Hydro deoxygenation
C₅₇H₁04O₆ + 6H₂ 3C₁₇H₃₆+ C₃H₈ +3CO₂

Triolein C17:0
Reaction 3-2: Hydro decarboxylation
Taking reactor efficiency = 99 % [8, p. 432]

0.180 kgmol oil react with = 1.819 kgmol of hydrogen
H2/oil ratios, 3 to 5 times the theoretical consumption is recommended in order to ensure

gas-to-liquid mass transfer resistance of hydrogen does not play a role of interference in the
process [11].
So, we use hydrogen 4 times the theoretical consumption
Hydrogen required = 7.33 kgmol/hr
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3.1.2 For Other Products

Using Reaction 3-1 and 3-2,
Products formed
Reaction 3-1
Reactants Products
Components Tri-olein H2 nC18 H2O propane
Stoichiometric coefficient 1.000 15.000 3.000 6.000 1.000
Amount kgmol 0.087 1.299 0.260 0.520 0.087
Reaction 3-2
Reactants Products
Components Tri-olein H2 nC17 CO2 propane
Stoichiometric coefficient 1.000 6.000 3.000 3.000 1.000
Amount kgmol 0.087 0.520 0.260 0.260 0.087
3.1.3 Further products formed during isomerization reaction

Enhancement of cold flow properties of green diesel come at cost of inevitable cracking diesel.
That produce variable quantities of lower boiling point mixture that include naphtha and
kerosene, depending on reactor conditions
Chemical reactions take place [11]
C₁₈H₃₄ + H₂ C₁3H28 + C5H12

C18:0 C13:0 n-pentane
Reaction 3-3: Hydrocracking
C17H36 + H₂ C9H20 + C8H18

C17:0 nonane octane
Reaction 3-4: Hydrocracking
Reaction 3-3
Components nC18 H2 nC13 n pentane
Stoichiometric coefficient 1 1 1 1
Amount Kgmol 0.078 0.078 0.078 0.078
Reaction 3-4
Components nC17 H2 n-nonane n-octane
Stoichiometric coefficient 1 1 1 1
Amount Kgmol 0.130 0.130 0.130 0.130
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3.1.4 View of overall Balance
C₁₈H₃₄ = 46.294 kg
C17 = 31.248 kg
Vegetable Oil H20 = 10.692 kg
155.04 kg Propane = 7.640 kg
Overall CO2 = 11.436 kg
Process n-C13 = 14.375 kg
Hydrogen H 2 n-Pentane = 5.62 kg
14.784 kg n-Nonane = 16.670 kg
n-Octane = 14.838 kg
H2 = 10.692 kg
Total Mass in = Total Mass out

169.824 kg = 169.505 kg
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Chapter 4 Energy Balance
4.1 Energy Balance Around Distillation Column

First, we calculate the specific heat for feed, top and bottom product
4.1.1 Specific heat of Feed

Temperature of feed = 326 K
Specific heat of components at T = 326K
Specific heat values of components are taken from Aspen HYSYS.
Table 4-1: specific heat values of feed components along with compositions
Specific heat Cp,

Components Composition
kJ/Kgmol.0C
Propane 80.57 0.0423
C17 552.5 0.133
C18 582.2 0.2513
n- pentane 131.4 0.1340
n- C13 428.0 0.1076
Nonane 298.1 0.1332
Octane 265.5 0.1983
average Specific Heat of Feed = Σ specific heat * composition (1)
= 379.213 kJ/kgmol.oC
4.1.2 Specific heat of top product
Temperature of top product = 409K
Specific heat values of components are taken from (Aspen HYSYS).
Table 4-2: specific heat values of top components along with compositions
Specific heat Cp,

kJ/Kgmol.0C
Nonane 342.3 0.3880
Octane 249.4 0.5830
Propane 95.71 0.0061
n- pentane 157.0 0.0197
n-C13 479.7 0.0020
Average Cp of top product = Σ specific heat * composition (2)

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4.1.3 Specific heat of bottom product

Temperature of top product = 556K
Specific heat values of components are taken from Aspen HYSYS.
Table 4-3: specific heat values of bottom product components along with compositions
Specific heat Cp,

kJ/Kgmol.0C
C18 785.5 0.510
C17 746.2 0.270
n-C13 496.1 0.217
Nonane 346.6 0.0018
Average Cp of bottom product = Σ specific heat * composition (3)
4.1.4 Latent heat of vaporization of top product (Aspen HYSYS).

Latent heat of vaporization values of components are taken from Aspen HYSYS.
Table 4-4: latent heat of vaporization of top components along with compositions
Latent heat of
Components vaporization, Composition
kJ/kgmol.0C
Nonane 37470 0.3880
Octane 34860 0.5830
Propane 18900 0.0061
n- pentane 26000 0.0197
n-C13 46570 0.0020
Latent heat of vaporization of top product = Σ ΔHvap * composition (4)
= 40,196.4 kJ/kgmol.0C
4.1.5 Condenser Balance

Latent heat of top product = 40196.4 kJ/kgmol.0C
Specific heat of top product = 282.848 kJ/kgmol.oC
Enthalpy of liquid product = Cp*ΔT (5)
hL = 282.848*(409-273)
hL = 38467.32 kJ/kgmol.oC
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Enthalpy of entering vapors
hv = 38467.32 + 40196.4
= 78663.8 kJ/kgmol.0C
Reflux ratio
R = 1.7008
Top product flow rate,
N = 0.2857 kJmol/hr
Apply heat balance around Condenser [22].

Using formula,
Qc = (R+1)*N*hv + (R+1)*N*hL (6)
= 31016.59 kJ/hr
4.1.6 Reboiler Balance
Temperature of feed = 326K
Specific Heat of feed = 379.213 kJ/kgmol0C
Enthalpy of feed
hx = Cp*ΔT (7)
= 379.213*(326-273)
= 20098.28 kJ/kgmol0C
Flow rate of feed = X = 0.8404 kgmol/hr
Flow rate of top product = N = 0.2857 kgmol/hr
Flow rate of bottom product = G = 0.4132 kgmol/hr
Temperature of bottom product = 556 K
Specific Heat of bottom Product = 710.50 kJ/kgmol.0C
Enthalpy of bottom product
hxL = Cp*ΔT (8)

= 710.50*(556-273)
= 201,074 kJ/kgmol0C
Flow rate of bottom = G = 0.41328 kgmol/hr
Apply heat balance around reboiler,
Using formula [22],
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Qx = (R+1)*N*hN(V) - R*N*hN(L) + G*hGL – X*hXL (9)

Or use formula [23]
Qx = DHd + WHw +Qc -FHf (10)

Where,
D = top product flow rate
Hd = enthalpy of top product
W = bottom product flow rate
Hw = enthalpy of bottom product
Qc = condenser duty
F = feed flow rate
Hf = enthalpy of feed
By solving we get
Qx = 108,216 kJ/hr
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4.2 Energy balance on furnace

4.2.1 Energy balance on furnace
Given Data,
Heat Capacity values of components are taken from Aspen HYSYS.
Table 4-5: Heat Capacity of components at inlet and outlet stream of furnace
Sr Component Mole % Mass (kg) Inlet stream of Outlet stream of

furnace Cp furnace Cp
1 Triolein 0.973 152.23 2724 2681
2 Oleic Acid 0.020 31.43 575.1 736.7
3 N-Hexane 0.001 1.56 200.2 255.6
4 N-C29 0.001 0.23 1209 1394
5 M-Salicylate 0.004 0.62 339.7 267
Total molar flow rate = 0.18 kgmol/hr

Flow rate = 156.4 kg/hr
4.2.1.1 Heat duty of Inlet stream of furnace

Tin = 30 oC
Tref = 25 oC
Using this formula,
Qin = mCp(Tin − Tref ) (11)

Qin = (0.18)(0.937)(2724)(30-25) +(0.02)(0.18)(575.1)(30-25) +(0.001)(0.18)(200.2)(30-25)
+(0.001)(0.18)(1209)(30-25) +(0.004)(0.18)(339.7)(30-25)
Calculated value,
Qin = 2400 kj/hr(kg)
4.2.1.2 Heat duty of outlet stream of furnace

Tin = 360 oC
Tref = 25 oC
Using this formula,
Qout = mCp(Tout − Tref ) (12)

Qout = (0.18)(0.937)(2681)(360-25) +(0.02)(0.18)(736.7)(360-25) +(0.001)(0.18)(255.6)(360-
25) +(0.001)(0.18)(1394)(360-25) +(0.004)(0.18)(267)(360-25)
Calculated value,
Qout = 159036
4.2.1.3 Heat supplied

Qout - Qin =156636 kj/hr(kg)
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4.2.2 Energy balance on scale up furnace

Given data,
Heat Capacity values of components are taken from Aspen HYSYS.
Table 4-6: Heat Capacity of components at inlet and outlet stream of furnace
Sr Component Mole % Mass(kg) Inlet Cp Outlet Cp

1 Triolein 0.9734 15223 2724 2681
2 Oleic Acid 0.0201 3143 575.1 736.7
3 N-Hexane 0.0010 156 200.2 255.6
4 N-C29 0.0015 23 1209 1394
5 M- 0.0040 62 339.7 267
Salicylate
Scaling up to 100 times of pilot plant

Total molar flow rate = 18 kgmol/hr
Flow rate = 15640 kg/hr
4.2.1 Heat duty of inlet stream of furnace

Tin = 30 oC
Tref = 25 oC
Using formula,
Qin = mCp(Tin − Tref ) (13)

Qin = (18)(0.9734)(2724)(30-25) +(0.0201)(18)(575.1)(30-25) +(0.001)(18)(200.2)(30-25)
+(0.0015)(18)(1209)(30-25) +(0.004)(18)(339.7)(30-25)
Qin = 240000 kj/kg
4.2.2 Heat duty of outlet stream of furnace

Tin = 360 oC
Tref = 25 oC
Using formula,
Qout = mCp(Tout − Tref ) (14)

Qout = (18)(0.9734)(2681)(360-25) +(0.0201)(18)(736.7)(360-25) +(0.001)(18)(255.6)(360-
25) +(0.0015)(18)(1394)(360-25) +(0.004)(18)(267)(360-25)
Qout = 15903600 kj/hr(kg)
4.2.3 Heat supplied

Qout - Qin =15663600 kj/hr(kg)
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4.3 Energy balance across reactor

Our porpose is to calculate output temperature
We could calculate output temperature using this formula [24]

[−𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑜). 𝑋]
𝑇 = 𝑇𝑜 + (15)
𝐶𝑝𝑠 + 𝛥𝐶𝑝. 𝑋
Where,
To = temperature of stream entering the reactor
𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑜) = heat of reaction at temperature To
X = conversion
Cps = Σ θ.Cpi (16)

𝛥Cp = Cp (product) – Cp (reactant)
As two reactions are taking place
[−𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑜). 𝑋] [−𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑜). 𝑋]
𝑇 = 𝑇𝑜 + + (17)
𝐶𝑝𝑠 + 𝛥𝐶𝑝. 𝑋 𝐶𝑝𝑠 + 𝛥𝐶𝑝. 𝑋
Reaction 01 Reaction 2
4.3.1 For Reaction 01

C₅₇H₁04O₆ +15H₂ 3C₁₈H₃₄ + C₃H₈ + 6H₂O
Triolein C18:0
Reaction 1
4.3.1.1 Parameters estimation
First,

Where,
𝐹𝑖𝑜
Θ= (19)
𝐹𝑎𝑜
For Triolein,
Θ= 1
For hydrogen,
7.33
Θ= = 83.67
0.0876
For other components like C18, propane and water
Θ=0 (as their initial composition is zero)
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Specific heat of components,

Cp of triolein = 2655 kJ/kgmol.0C
Cp of hydrogen = 28.6 kJ/kgmol.0C
Cp of n-C18 = 561 kJ/kgmol.0C
Cp of propane = 121.4 kJ/kgmol.0C
Cp of water = 77.54 kJ/kgmol.0C
So,
Cps = Σ θ. Cpi (20)
Cps = (1*2655) + (83.67*28.68)

= 5054kJ/kgmol0C
Calculation of 𝜟Cp
𝛥Cp = Cp (product) – Cp (reactant) (21)

𝛥Cp = -1924.09 kJ/kgmol.0C
Now,
𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑜) = 𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑟𝑒𝑓) + 𝛥Cp (To – 𝑇𝑟𝑒𝑓 ) (22)
𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑟𝑒𝑓) = -9.6 * 105 kJ/kgmol.(from Aspen HYSYS)

𝑇𝑟𝑒𝑓 = 25 0C or 298 K
𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑜) = -9.6 * 105 – 1924.09*(475 – 298)
𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑜) = -1.30*106 kJ/kgmol
4.3.2 For Reaction 02

Second reaction is as follows,
C₅₇H₁04O₆ + 6H₂ 3C₁₇H₃₆+ C₃H₈ +3CO₂

Triolein C17:0
Reaction 2
4.3.2.1 Parameters estimation

First,
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Where,
𝐹𝑖𝑜
Θ= (24)
𝐹𝑎𝑜
For Triolein,
Θ= 1
For hydrogen,
7.33
Θ= = 83.67
0.0876
For other components like C17, carbon-dioxide and propane
Θ=0 (as their initial composition is zero)

Specific heat of components,
Cp of triolein = 2655 kJ/kgmol.0C
Cp of hydrogen = 28.6 kJ/kgmol.0C
Cp of n-C18 = 561 kJ/kgmol.0C
Cp of propane = 121.4 kJ/kgmol.0C
Cp of water = 77.54 kJ/kgmol.0C
So,

Cps = (1*2655) + (83.67*28.68)
=5054
Calculation of 𝜟Cp
𝛥Cp = Cp (product) – Cp (reactant) (26)

𝛥Cp = -1989.4 kJ/kgmol.0C
Now,
𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑜) = 𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑟𝑒𝑓) + 𝛥Cp (To – 𝑇𝑟𝑒𝑓 ) (27)

𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑟𝑒𝑓) = -6.2 * 105 kJ/kgmol.(from Aspen HYSYS)
𝑇𝑟𝑒𝑓 = 25 0C or 298 K
𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑜) = -6.2 * 105 – 1989.4*(475 – 298)
𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑜) = -9.72*105 kJ/kgmol
Calculation of total temperature at outlet stream using equation 16.
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[−𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑜). 𝑋] [−𝛥 𝐻𝑟𝑥𝑛 (𝑇𝑜). 𝑋]

𝑇 = 𝑇𝑜 + +
𝐶𝑝𝑠 + 𝛥𝐶𝑝. 𝑋 𝐶𝑝𝑠 + 𝛥𝐶𝑝. 𝑋
Take conversion 50% for first reaction and 50% for second reaction in order to get final
conversion of 99%
So, temperature of the stream leaving out the reactor calculated is,
𝑇 = 426 0C
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Chapter 5 Equipment Design
5.1 Distillation Column

5.1.1 Material Balance
Material balance across distillation column is not quite easy task. As you know that separation
across distillation occur due to difference in relative volatilities of components. And these
volatilities change across the temperature and in distillation column at each stage there is some
change in temperature so to find these volatilities at each stage is not possible, so we take
average temperature between top and bottom temperature and calculate relative volatilities at
average temperature.
We only have knowledge of the feed composition and we must find the top and bottom
compositions; we could use Lewis-Matheson method to calculate top and bottom compositions
as in this method we must calculate compositions tray after tray until we reach our desire
composition. In this method we could start form feed plate, bottom plate or top plate depend
upon the data you know. But for multi-component this method is very difficult to apply as you
have many components and their volatilities change at each tray.
So therefore, we took help of computer and some article in order to find the material balance.
We used Aspen HYSYS to simulate the data we have. And matched that data from article they
were close, so we used that data. The component that split between top and bottom product
was nonane and n-C13
Table 5-1: Material balance across distillation column

Feed Bottom Top Off gases
Components
(kgmol/hr) (Kgmol/hr) (Kgmol/hr) (Kgmol/hr)
propane 0.0355 0.0017 0.0338
C17 0.1118 0.1117
C18 0.2112 0.2111
n-pentane 0.1126 0.0056 0.1069
n-C13 0.0904 0.0897 0.0006
n-nonane 0.1119 0.0008 0.1110
n-octane 0.1667 0.1660
total 0.8401 0.4133 0.2849 0.1407
Total input to the distillation column Is 0.8404 kgmol/hr and total output of the system is
obtained by adding bottom product, top product and off gases which is equal,
Total input = 0.8404 kgmol/hr.
Total output = 0.8389 kgmol/hr
Input = output
5.1.2 Procedure for plate column-design:

Rough plate layout is taken at start for design procedure and trial and error method is used to
get desire accurate design. Performance key factors are checked, and design is reversed as per
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requirement until an acceptable design is reached. Generally used procedure for distillation
column is given below [20].
Procedure
1. Minimum and maximum liquid and vapor flowrates are calculated in order to find
required turn down ratio.
2. Then system physical properties are estimated or collected.
3. Then random plate spacing is selected for trail.
4. Column diameter is evaluated, based of flooding value
5. Liquid flow arrangement is decided
6. Trail plate layout (Down comer area, hole area, active area, weir size, hole size) is made
7. Weeping rate is calculated and checked, if not acceptable go back to step 6.
8. Plate pressure drop is calculated and checked, if too high return to step 6.
9. Down-comer backup is calculated and checked, if it’s too high go back to step 6 or 3.
10. Then percentage flooding is checked again based on the diameter of column.
11. Entrainment is checked, if too high go back to step 4.
12. Design is then optimized, repeat step 3 to 12, to get minimum diameter and acceptable
able plate spacing.
13. Design is then finalized, draw the layout and plate specification.
Before applying these steps, we must specify some things
5.1.3 Identification of key component on basis of relative volatilities

C18 = heavy non key (H.N.K)
C17 = heavy non key (H.N.K)
n-C13 = heavy key (H.K) (recovery at bottom 99%)
Nonane = light key (L.K) (recovery at top 99.5%)
Octane = light non key (L.N.K)
Propane = light not key (L.N.K)
n-pentane = light non key (L.N.K)
5.1.4 Calculations of top and bottom temperature

We use dew point and bubble point calculations in order to find the column top and bottom
temperature. But for these calculations we need K-values, and for K-values we need to know
components saturation pressure Psat at desire temperatures. To calculate Psat we use Antoine
equation
But to use Antoine equation we must have Antoine parameters A,B,C. we use Aspen HYSYS
and book [25] and then by using this formula
Ln Psat = A + B/(T+C) (10)
So, from here we calculated Psat and then K-value using this formula
K = Psat/P (11)
Were,
P is total pressure
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5.1.4.1 Top temperature:

use dew point calculation to calculate the top temperature, here we know the top compositions
(Distillate, y) and we calculated liquid composition x using formula,
X = (Y/K) (12)
We use iteration method in order to calculate the top temperature, we changed the temperature
until we get ΣX = 1. Using Excel
At temperature 409K and pressure 100kPa

Table 5-2: Dew point Calculation for top temperature
Relative
Components at Top Column1 Y X
volatility
Nonane 0.1111 0.3888 0.5802 0.6701
Octane 0.1666 0.5831 0.4390 1.3281
Propane 0.0018 0.0062 0.0001 79.3645
Pentane 0.0056 0.0197 0.0016 12.3247
C13 0.0006 0.0022 0.0461 0.0478
Total 0.2857 1.0000 1.0670
5.1.4.2 Bottom Temperature:
use bubble point calculation to calculate the bottom temperature, here we know the bottom
compositions (bottom product, X) and we calculated vapor composition Y using formula ,
Y = (X*K) (13)
We use iteration method in order to calculate the bottom temperature, we changed the
temperature until we get ΣY = 1. Using Excel
At temperature 556K and pressure 100kPa

Table 5-3: Bubble point Calculation for bottom temperature
Relative
Composition at Bottom kgmol/hr X Y
volatilities
C18 0.2111 0.5107 0.2449 0.4796
C17 0.1117 0.2702 0.1793 0.6635
c13 0.0897 0.2170 0.5887 2.7124
Nonane 0.0007 0.0018 0.0254 13.4239
Total 0.4132 1 1.0130
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5.1.5 Calculation of Feed Conditions

To determine the nature of feed its boiling point must be found, that is where,
ΣK ∗ xf = 1 (14)
At temperature 326 K and pressure 100kPa

Table 5-4: bubble point calculation for feed temperature
Components x K = Psat/P Y = K*xf

C18 0.2513 0.0000 0.0000
C17 0.1330 0.0000 0.0000
C13 0.1076 0.0005 0.0001
Nonane 0.1332 0.0265 0.0035
Octane 0.1983 0.0733 0.0145
Propane 0.0423 18.2527 0.7721
Pentane 0.1340 1.7321 0.2321
Total 0.9997 1.0223
At 326 K and 100 KPa feed is at bubble point
5.1.6 Design Steps

In order to design multicomponent distillation, we use FUG method (Fenske’s, underwood and
Gilliland correlation) to calculate minimum number of stages, minimum reflux ratio and feed
plate.
5.1.6.1 Minimum reflux ratio

Rmin is calculated by using Underwood method, using underwood equation as follows,
𝛼𝐴 ∗ 𝑥𝑓𝐴 𝛼𝐵 ∗ 𝑥𝑓𝐵 (15)

1−𝑞 = + +⋯
𝑎𝐴 − 𝜃 𝑎𝐵 − 𝜃
As feed is at bubble point so q = 1, by iteration on Microsoft excel value of θ = 1.25
Then by using this equation we calculated minimum reflux ratio
𝛼𝐴 ∗ 𝑥𝐷𝐴 𝛼𝐵 ∗ 𝑥𝐷𝐵 (16)

𝑅𝑚𝑖𝑛 + 1 = + +⋯
𝑎𝐴 − 𝜃 𝑎𝐵 − 𝜃
By solving above equation, we get,
Rmin = 1.1338
For optimum reflux ratio use (1.2 – 1.5 Rmin)
5.1.6.2 Fenske’s method ( minimum number of stages)

Use Fenske’s equation to calculate Nmin
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𝑥𝐿𝐾 𝑥𝐻𝐾
ln [(𝑥𝐻𝐾 ) 𝐷 ( 𝑥𝐿𝐾 ) 𝐵]
𝑁𝑚𝑖𝑛 = (17)
𝑎𝐿𝐾
ln (𝑎𝐻𝐾 )𝑎𝑣𝑔
Calculated,
Nmin = 4.976 or 5
𝑅𝑚𝑖𝑛
To calculate actual number to trays first calculate
𝑅𝑚𝑖𝑛+1
𝑅𝑚𝑖𝑛 (18)
= 0.5313
𝑅𝑚𝑖𝑛+1
As we can use R form (1.2 – 1.5 Rmin) [20]
So,
Table 5-5: Calculation of optimum R value
Nmin/N
For R R/(R+1) from fig N
11.11
1.2 1.3606 0.5763 0.5 9.9536
1.3 1.4740 0.5958 0.54 9.2163
1.4 1.5874 0.6135 0.56 8.8871
1.5 1.7008 0.6297 0.6 8.2946
We use R = 1.7008 as at this there are minimum trays means minimum cost
5.1.6.3 Location of feed plate

Kirkbride method is used to determine the ratio of trays above and below feed point
2
(𝑁𝑟 𝐵 𝑥𝐻𝐾 (𝑥𝐿𝐾)𝐵 (19)
𝑙𝑜𝑔 ⁄𝑁𝑠) = 0.2061 ∗ log [( ) ∗ ( )∗( ) ]
𝐷 𝑥𝐿𝐾 (𝑥𝐻𝐾)𝐷
Using this,
Nr/Ns = 0.957
Nr = 0.957*Ns
Also
Nr+Ns = 7 (excluding reboiler and condenser)
Using above two equations to calculate Nr and Ns
Nr = 3
Ns = 4
Feed will enter at 4th stage from top
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5.1.6.4 Column efficiency

Column efficiency is calculated using following relation
Eo = 51 – 32.5[log(𝜇𝑎𝑣𝑔 ∗ 𝛼𝑎𝑣𝑔)] (20)
Where,
µavg = average viscosity
αavg = average volatility
For Average Viscosity
Table 5-6: Table for Calculation of Average Viscosity
Components Viscosities Compositions µ * composition

c18 0.4179 0.2513 0.1050
c17 0.3712 0.1330 0.0494
c13 0.2434 0.1076 0.0262
nonane 0.0079 0.1332 0.0011
octane 0.0085 0.1983 0.0017
propane 0.0135 0.0423 0.0006
pentane 0.0109 0.1340 0.0015
Average viscosity 0.1853
Also,
∝𝐿𝐾 (21)
αavg = ( )𝑎𝑣𝑔 = 7.34
∝𝐻𝐾
Putting values in above equation 37. we get following result.
Eo = 51 – 32.5[log(0.1853*7.34)]
Eo = 46.656%
Number of actual trays
N = (9/0.466) = 19.29 or 19
5.1.6.5 Column diameter

Some available data
Feed flow rate = 0.8404 kgmol/hr (from material balance)
Top product = 0.2865 kgmol/hr (from material balance)
Bottom product = 0.4133 kgmol/hr (from material balance)
Vapor flow rate in stripping section:
Vm’ = 0.7069 kgmol/hr (Vm’=Vn) (22)
Liquid flow rate in stripping section:
Lm’ = 0.12615 kgmol/hr (Lm’ = Ln+feed) (23)
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Liquid rate in rectifying section
Ln = 0.4212 kgmol/hr (Ln = R*D) (24)
Vapor rate in rectifying section
Vn = 0.7069 kgmol/hr (Vn = D*(R+1)) (25)
5.1.6.6 Some physical properties

These properties are taken from Aspen HYSYS
Ρvb = density of vapor at bottom = 4.8740 kg/m3
ΡLb = density of liquid at bottom = 575.60 kg/m3
Surface tension at bottom = 0.0078 N/m
Molecular weight at bottom = 235.200 kgmol
ΡVt = density of vapors at top = 3.638 kg/m3
ΡLt = density of liquid at top = 612.700 kg/m3
Surface tension at top = 0.0122 N/m
Molecular weight at top = 118.60 kgmol
5.1.6.7 Liquid Vapor flow rate

Liquid Vapor flow rate is calculated using this formula:
At bottom,
𝐿𝑚′ Ρvb (26)

FLV = ′
√
𝑉𝑚 ΡLb
FLV = 0.1642
At top,
𝐿𝑛 Ρvt (27)
FLV = √
𝑉𝑛 ΡLt
FLV = 0.0459
Using figure 11.27 of Coulson and Richardson’s volume 6, find K at top and bottom.
At bottom,
K1 = 0.730
At top,
K1 = 0.088
5.1.6.8 Corrected K1
Corrected K1 at bottom using correlation Surface tension.
At bottom,
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𝛿 0.2
(28)
K1’ = (( ) ∗ 𝐾1
0.02
Were 𝛿 is surface tension at bottom

K1’ = 0.0604
At top,
𝛿 0.2
(29)
K1’ = (( ) ∗ 𝐾1
0.02
Were 𝛿 is surface tension at top

K1’ = 0.0797
5.1.6.9 Flooding Velocity
Flooding Velocity is calculated using this formula.
At bottom,
𝜌𝐿𝐵 − 𝜌𝑉𝐵 (30)

𝜇𝑓 = 𝐾1 ∗ √
𝜌𝑉𝐵
𝑚
𝜇𝑓 = 0.6540
𝑠
At top,
𝜌𝐿𝑡 − 𝜌𝑉𝑡 (31)

𝜇𝑓 = 𝐾1 ∗ √
𝜌𝑉𝑡
𝑚
𝜇𝑓 = 1.0311
𝑠
Superficial vapor velocity at 85% flooding is recommended
At bottom,
𝜇𝑣 = 𝜇𝑓 ∗ 0.85
𝑚
𝜇𝑣 = 0.5559
𝑠
At top,
𝜇𝑣 = 𝜇𝑓 ∗ 0.85
𝑚
𝜇𝑣 = 0.8764
𝑠
5.1.6.10 Maximum volumetric flow rate

Maximum volumetric flow rate is calculated using this formula,
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At bottom,
𝑉𝑚’ ∗ 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 (32)

=
𝜌𝑉𝐵∗3600
= 0.0095 m3/s
At top,
𝑉𝑛 ∗ 𝑚𝑜𝑙𝑒𝑐
𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 (33)
=
𝜌𝑉𝑡∗3600
= 0.0064 m3/s
5.1.6.11 Net Area Required
Net Area Required is calculated using this formula,

At bottom,
𝑚𝑎𝑥𝑖𝑚𝑢𝑚 𝑣𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 (34)

=
𝜇𝑣(𝑏𝑜𝑡𝑡𝑜𝑚)
= 0.0170 m2
At top,

=
𝜇𝑣 (𝑡𝑜𝑝)
= 0.0073 m2
Take down-comer area 12% of total cross-sectional area (Assumption)
𝑁𝑒𝑡 𝑎𝑟𝑒𝑎 (𝑏𝑎𝑠𝑒) (36)

Bottom column cross-sectional area =
0.88
= 0.0194 m2
𝑁𝑒𝑡 𝑎𝑟𝑒𝑎 (𝑡𝑜𝑝) (37)

top column cross-sectional area =
0.88
= 0.0083 m2
5.1.6.12 Column diameter:
At bottom,
𝑛𝑒𝑡 𝑎𝑟𝑒𝑎∗4 (38)

Column diameter = √
3.14
= 0.1571 m
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At top,
𝑛𝑒𝑡 𝑎𝑟𝑒𝑎∗4 (39)

Column diameter = √
3.14
= 0.1028 m
So, the diameter of column is 0.1571 m
5.1.6.13 Provisional plate design

Given Data
Column diameter = 0.1571 m
AC = column area = 0.0194 m2
Ad = down-comer area = 0.12*0.0194 = 0.0023 m2
An = Net area = Ac – Ad = 0.0194 – 0.0023 = 0.0170 m2
Aa = Active area = Ac - 2Ad = 0.0194 – (2*0.0023) = 0.0147 m2
Ah = hole area = take 15% hole area = 0.0010
Weir length (from fig 11.31 Coulson and Richardson’s volume 6)

=0.85*0.1571
=0.1335 m
Take,
weir height = 50 mm
hole diameter = 5 mm
plate thickness = 5 mm
5.1.6.14 Check weeping

First, we must calculate maximum liquid rate using formula,
𝐿𝑚’ ∗ 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑎𝑡 𝑏𝑎𝑠𝑒 (40)

Maximum liquid rate =
3600
= 0.0824 kg/s
Minimum liquid flow rate at 70% turn down
Minimum liquid flow rate = 0.0824 * 0.70
= 0.0577 kg/s
Weir height crust,
Maximum,
𝐿𝑤 (max 𝑙𝑖𝑞𝑢𝑖𝑑 𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒) 2

how = 750 * [
𝜌𝐿𝐵∗𝐿𝑤
]^(3) (41)
0.0824
=750 * (
575.60∗0.1335
)
= 7.8578 mm
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Minimum,
𝐿𝑤 (min 𝑙𝑖𝑞𝑢𝑖𝑑 𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒) 2

how = 750 * [
𝜌𝐿𝐵∗𝐿𝑤
]^(3) (42)
= 6.1949 mm
At minimum rate,
hw + how = 50 + 6.1949
= 56.1949 mm
From figure 11.30
K2 = 31.00
5.1.6.15 Minimum Design Vapor Velocity
Minimum design vapor velocity,
𝐾2 – 0.90∗(25.4 − ℎ𝑜𝑙𝑒 𝑑𝑖𝑎) (43)

μh(min) = [ 1 ]
(𝜌𝑣)2
= 5.7254 m/s
5.1.6.16 Actual Minimum Vapor Velocity
𝑚𝑖𝑛𝑖𝑚𝑢𝑚 𝑣𝑎𝑝𝑜𝑟 𝑟𝑎𝑡𝑒 (44)
Actual Minimum Vapor Velocity =
𝐴ℎ
0.7 ∗ 0.0095
=
0.0010
= 6.758 m/s
So actual min operating rate is well above weep point
5.1.6.17 Plate pressure drop

First, we must calculate dry plate drop

Maximum vapor velocity =
ℎ𝑜𝑙𝑒 𝑎𝑟𝑒𝑎
= 9.6552 m/s
From figure 11.34 (Coulson and Richardson’s volume 6)
For,
𝑝𝑙𝑎𝑡𝑒 𝑡ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠
=1
ℎ𝑜𝑙𝑒 𝑎𝑟𝑒𝑎
and
Ah/Ap = 0.15
Orifice coefficient = Co = 0.84
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Now,
μh 𝜌𝑣
hd = 51*(
𝐶𝑜
)*(
𝜌𝐿
) (46)
= 57.056 mm
Residual Head,
hr = 12.5 ∗ 103/ρLB (47)
= 21.7165 mm
Total Drop
ht = hd + (hw + how) + hr (48)
ht = 136.6304 mm of water
5.1.6.18 Down comer liquid back up

Down comer pressure drops
Take
hap = hw -10 (range is from 5 to 10 mm) [20]
= 40 mm
Area under apron = Aap = 40*10-3 * weir height
=40 * 10-3 *0.1335
= 0.0053 m2
Down-comer height,
2
𝐿𝑤𝑑
hdc = 166 ∗ [( ) ] (49)
𝜌𝐿 ∗ 𝐴𝑚
where,
Lwd = liquid flow rate in down-comer at max rate
Am = down-comer area
hdc = 0.1193 mm
5.1.6. 19 Down-comer design (back up)

backup in down-comer
hb = (hw +how) + ht + hdc (50)
= 194.6075 mm
hb should be less than ½(plate spacing +weir height)
so,
1/2(plate spacing + weir height) = 275 mm
So, hb is less than ½(plate spacing +weir height)
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5.1.6.20 Check residence time

Residence time can be calculated using this formula
𝐴𝑑 ∗ ℎ𝑏 ∗ 𝜌𝑙𝑏 (51)
Tr =
max 𝑙𝑖𝑞𝑢𝑖𝑑 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒
= 3.1590 sec
Residence time should be greater than 3 sec so, therefore residence time is satisfactory.
5.1.6.21 Check entrainment

𝑚𝑎𝑥 𝑙𝑖𝑞𝑢𝑖𝑑 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒
Uv = ∗ 100 (52)
𝑈𝑓(𝑏𝑎𝑠𝑒 )
= 0.555
Percentage flooding = Uv/Uf (base)
= 0.85
From figure 11.29, [20]
At,
FLv = 0.16421
Ψ = 0.016 well below 0.1
5.1.6.22 Height of distillation column
Height of distillation column is calculated using this formula
Height Hc = (Nact -1)*Hs + ΔH +total plates thickness (53)
Were,
Hc = height of column
Nact = actual number of trays
Hs = tray spacing = 0.30m (0.3 - 0.5m range) [20]
ΔH = (1 – 1.5% of total height) [20] for liquid holdup and disengagement)
ΔH = 0.5 m
Total thickness of trays = 0.005*17
= 0.085
Total height of column = 17*0.30 + 0.55 +0.085
= 5.1 m
The length/diameter ratio of a tower should be no more than 30-35 [20] and preferable
below 20-25
= 5.1/0.1571
= 32.58
So, it is in acceptable range.
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5.1.7 Specification sheet:

Table 5-7: specification sheet for distillation column
Tray type Sieve trays

No. of trays 19
Height of column 5.1 m
Diameter of column 0.1571 m
Hole size 5 mm
Pressure drop per tray 136.630 mm of water
Tray thickness 5 mm
Weir height 50 mm
Weir length 0.1335 m
Reflux ratio 1.7008 m
Tray spacing 0.3 m
Column area 0.0194 m2
Flooding percentage 85 %
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5.2 REACTOR DESIGN

5.2.1 INTRODUCTION
Rector is the chemical equipment used for the conversion of reactants into products under
specified reaction conditions and catalyst. Industrial chemical processes are designed to
produce economically preferred products from different starting materials through a sequence
of treatment steps. The raw material after passing through a number of physical steps to put
them in the reactor where they can react chemically. Then it comes to the reactor. The product
from the reactor further undergoes physical treatment steps like separations and purifications
to get the final desired product.
T=335.6 C
P=4000KPa
Vapor outlet
Vegetable oil
Top product
=156.4kg/hr
Hydrogen =14.7kg/hr
kg/hr
Liquid outlet
Energy Input and Bottom product
cooling jackets
Here the reactor R-101 is used to react vegetable oil 156.4kg/hr with hydrogen 14.7kg/hr.
Feed mixture is passed through fixed bed reactor and oil is converted into green diesel in the
presence of the catalyst.
T=335.6 C
P=4000KPa
Green diesel is further separated from the by-products in further treatment steps while going
through
three phase separator and distillation columns we get Green Diesel, Naphtha, kerosene and
off gases.
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5.2.2 ALGORITHM FOR DESIGN OF REACTOR.

START
Step 1 Step 5
Collect the kinetic and thermodynamic Reaction condition for the desired
data of the desired reaction conversion and yield
Step 2 Step 6
Collect data of physical properties Estimate the size of the reactor

required for the design
Step 3 Step 7
Identify the rate controlling mechanism Estimate reactor performance
Step 4 Step 8
Based on experience Comparison for the selection
Chose a suitable reactor type
EXIT
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5.2.3 Kinetic and thermodynamic data

The desired reaction is the conversion of vegetable oil into green diesel and some other useful
products like naphtha and kerosene some undesired once also formed like off gases.
Reactions occurring in the reactor are [11]
Hydrogenation of unsaturated triglycerides
C₅₇H₁₀₄O₆ + 3H₂ C₅₇H₁₁₀O₆
Triolein (OOO) Tristearin (SSS)
Hydro deoxygenation
C₅₇H₁₁₀O₆ +12H₂ 3C₁₈H₃₄ + 6H₂O + C₃H₈
Hydro decarboxylation
C₅₇H₁₁₀O₆ +3H₂ 3C₁₇H₃₆ + 3CO₂ + C₃H₈

Reaction occurs in the presence of sulphide NiMo, CoMo catalyst, in order to match catalysts
typically used in the industry.
5.2.4 Physical property data

Table 5-8: physical properties table for reactor
Property Units Physical values

Density of feed = ρf Kg/m³ 721.5
Viscosity of feed Kg/m.sec 0.0002086
Density of catalyst Kg/m³ 878
Diameter of particle = dp Mm 2
Bed porosity = ϕ 0.4
5.2.5 Reaction kinetics

Kinetic data is taken form [18]
k₁ = 1 1.56 * 10‫ ־‬³ min‫־‬¹ bar‫ ־‬¹

k₂ = 1 7.83 * 10-4 min‫־‬¹ bar‫ ־‬¹
Ks= 1.36 * 10‫־‬² L/mol
KH= 1 1.58 * 10‫ ־‬² bar‫ ־‬¹
Caჿ=1.023 mol/ m³
2
PH = 40 bar
X=0-0.99
k₁CaჿPH₂(1 − X)
r₁ = (54)
(1 − 3(X)KsCɑჿ)(1 + KHPH₂)
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−3(X)k₂Caჿ
r₂ = (55)
(1 + KsCɑჿ(1 − X)) (1 + KHPH₂)
For catalytic reactor:

𝟎.𝟗𝟗
𝑾 𝒅𝑿
=∫ (56)
𝑭𝒐 𝟎 −𝒓𝒂
figure 5-1: Conversion Graph
-
0.99
𝑑𝑋
𝑊 = 𝐹𝑜 𝑋 ∫ (57)
0 −𝑟𝑎
W= 0.180*83.33
W=15.01Kgcat.
5.2.6 Reactor selection
Reactor selection for a given reaction is subjected to a number of considerations
• Pressure temperature and condition of the reaction
• Removal or addition of the reactants and products
• Pattern required for the product to be delivered
• Considerations are used for catalyst such as requirement for solid catalyst particle and
their contact with fluid reactants and products
• Relative reactor cost
Some guideline for the reactor selection is:
• For conversion up to 90% , the performance of five or more CSTRs connected in
series approaches to that of a single PFR.
• Batch reactors are best suited for the small-scale production, very slow reaction or
those requiring intensive monitoring and control. For large operations CSTRs or PFRs
are used.
• CSTRs are used for slow liquid phase or slurry reactions. For gas phase reaction PFR
is more preferable.
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• For exothermic and endothermic reactions with the temperature control at the reaction
temperature plug flow reactor is used. For exothermic reaction that has a large
temperature rise during the reaction, recycle reactors are the best choice.
• For the reactions where heterogenic catalyst is used plug flow reactor is good choice.
The type of the reactor used industrially for completion of heterogeneous catalytic
reactions can be further classified in relatively small number of categories. Simple
mean of classification term is based on relative motion of the catalyst particles and
reactants
✓ Those reactors in which the solid catalyst particles position remains
fixed comparative to one another (Fixed Bed, Trickle Bed and moving
bed reactors)
✓ Those Reactors in which in a given fluid the particles are suspended and
constantly moving about (fluidized bed and slurry reactors).
Table 5-9: Selection among the PFRs is on the following basis
Reactor type characteristics Typical application

Single Adiabatic Bed reasonably exothermic or Mild hydrogenation
endothermic non-
equilibrium condition
Radial flow Where low pressure drop is Tristearin to octadecane
vital and useful where large
change in moles
Adiabatic beds in series elevated conversion, Hydrodeoxygenation, Hydro
configuration with equilibrium limited reactions decarboxylation
intermediate cooling or
heating
Multi Tubular Non- Highly endo or exo-thermic Hydrogenations
Adiabatic reactions where close
temperature control is
required to ensure high
selectivity
Non-Adiabatic Reactions of highly Steam reforming
Direct fired endothermic and high
temperature behaviour
5.2.7 Comparison and selection of reactor

5.2.7.1 Selection of reactor
Reaction for the conversion of vegetable oil into green diesel at elevated temperature and
pressure in the presence of catalyst (heterogenic catalyst). In case temperature goes higher than
the reaction temperature then continuous heat removal is necessary other wise the chain growth
probability and linearity of hydrocarbons will decrease. As the temperature decreases from
the desired temperature then the small chian hydrocarbons are formed, while the required
products are straight long chain hydrocarbons. Small branched hydrocarbons have low value
of cetane number and hence the poor quality of green diesel. So, the temperature control is very
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necessary in the reactor at desired reaction temperature in order to assure the formation of long
straight chain hydrocarbons. Since the reaction occurs at elevated temperature and in
heterogeneous phase and the conversion is also greater than 90% so PFR (plug flow multi-
tubular) is the best option [24].
5.2.8 Reaction conditions for desired conversion:

When controlling deoxygenation, main reactor variables and conditions are temperature,
pressure, H2/oil ratio and liquid space hourly velocity (LSHV). typical operating conditions do
not vary considerably from one study to another. In one study, Bezergianni et al. concluded
that increasing reactor temperature above 360 C translated into an undesirable degree of
cracking. In another study, Srifa et al. experimented with a wide range of hydrotreating
conditions for palm oil over a sulphide NiMo/Al2O3 catalyst. Results supported the hypothesis
that, under 300_C, partial conversion of triglycerides took place, whereas cracking and
isomerization broke down diesel molecules above 360_C. Regarding H2/oil ratios, 3 to 5 times
the theoretical consumption is recommended in order to ensure gas-to-liquid mass transfer
resistance of hydrogen does not play a role of interference in the process. LSHV values, on the
other hand, may vary between 1 and 5 h, although higher values could affect the level of
conversion [11]
The reaction occurs at elevated temperature 320-400 . Higher temperature causes faster
reactions and higher conversion rates and also tend to favour production of methane. That’s
why temperature is usually maintained at middle part of the range. Hydrogen atmosphere
further increases the reaction efficiency.
Increase in pressure results in higher conversion rates and also causes production of long
chained alkanes these are desirable.
5.2.9 Size of reactor

For catalytic reactor
Density of bed is ρb = 878kg/m³

𝑊
Volume of catalyst V= ρ
15
=
878
Volume of the catalyst Vc= 0.017084m³
5.2.10 Volume of the reactor:
For fixed bed reactor void age = = 0.4
Volume of reactor = volume of catalyst ∗ (1 + ɸ) (58)

= 0.01708 *(1+0.4)
Volume of reactor Vr =0.023918 m³
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5.2.11 Length of reactor:

𝜋
V = 4 𝑋 𝐷² X L (59)
For fixed bed reactor taking L/D =4
L=4D (60)
Putting this value in the equation 76. we have
0.𝑂1913
D=[ ]^⅓
π
D= 0.19998m
As L=4D
L= 4 * 0.199983
L= 0.799931 m
Taking 20% extra for ceramic balls to support the catalyst:
L= 0.799931 * 1.20
L= 0.959917m
5.2.12 Reactor performance:

Reactor performance includes pressure drop estimation and comparison of area required for
heat transfer with actual area available for heat transfer.
5.2.13 Pressure drop calculation:

Methodology taken from [26]
Using Ergun‘s Equation
Δ𝑃 150 (1 − ɛ) μ (1 − ɛ) G
= ( + 1.75G) + × (61)
L Dp 3 Dp ∗ ρgc
ɛ
Data:
Δ𝑃
Pressure drop per unit length = L
Void age between the catalyst particle = 0.4
Catalyst particle diameter =0.002m
Superficial velocity =15.739
Viscosity of entering fluid =0.0002086
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Calculation: putting values in eq 78
Δ𝑃 150𝑋(1−0.4)∗0.0002086 1−0.4 15.739

=( + 1.75𝑋15.739) ( )( )
L 𝑜.𝑜𝑜2 0.43 0.002∗878∗9.8
=0.00221bar
As pressure drop is too less 0.00221bar, so it is acceptable pressure drop that take place in
reactor.
5.2.14 Wall thickness:

Operating pressure = 4 MPa
The design pressure should be greater than operating pressure at least 10% greater than the
operating pressure.
Design pressure = =1.1*4
= 4MPa
= 4.38N/mm
For high temperature and pressure carbon steel is used,
From table 11.5 [27]; for C-Steel;
f=75N/mm
Di= 0.199983m
Joint factor =1
The calculation of the thickness is done by the following given equation [28];
Pi ∗ Di
ꬲ= (62)
2jf + 1.2 ∗ Pi
Where
ꬲ =Thickness of vessel
Pi = Design pressure
Di = Internal Diameter
ꬲ = 5.6418mm
For corrosion allowance; 0.36mm extra added to present calculated thickness;
ꬲ = thickness= 6mm
ꬲ =6mm
5.2.15 Comparison for the selection:

Head calculation:
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There are different types of head can be used;

➢ Tori spherical head
➢ Ellipsoidal head
➢ Hemispherical head
Standard tori spherical heads are use up to 15 bar operating pressure. They can be used for high
pressure but above 10bar its cost is comparable with ellipsoidal heads.
Above 15 bar ellipsoidal is considered to be most economical than torispherical head.
Hemispherical head is the strongest shape; resist twice pressure than tori spherical head. It is
used for high pressure.
Hence hemispherical is best for this process.
5.2.16 For hemispherical head:

Pi ∗ Di
ꬲ= (63)
4jf + 0.4 ∗ Pi
ꬲ =5.019mm
5.2.17 Specification sheet:

Table 5-10: specification sheet for reactor
Reactor type Fixed bed reactor

Operation Continuous
Operating pressure 4MPa
Operating temperature 355 C
Catalyst CoMo/γ -Al2O3 Ni-mo/γ -Al203
Porosity of catalyst 0.4
Shape of catalyst Pallet
Weight of catalyst 15Kg
Volume of reactor 0.02391m³
Length of reactor 0.959917m
Diameter of reactor 0.199983m
Pressure drop 0.002216 bar
Wall thickness of reactor 6 mm
Head type Hemispherical
Head thickness 5.019mm
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5.3 Furnace Design

5.3.1 Methods of Designing
There are several methods
1. Method of Lobo and Evans.
2. Method of Wilson, Lobo and Hottel.
3. The Orrok-Hudson Equation.
4. Wohlenberg simplified Method.
5.3.2 Design Steps

1. Calculation of total heat required from fuel.
2. Calculation of fuel required and material balance.
3. Radiant section calculation
4. Heat duty
5. Number of tube
6. Radiation section area & volume
7. Convection section calculation
8. Heat duty
9. Number of tube required
5.3.3 Design calculations

5.3.3.1 Calculations of fuel required and material balance
Methodology used [29]
Heatduty = Qin − Qout

Heat duty = 15663600 kj/hr(kg)
To develop an 80% efficient furnace.
Heat released by fuel is Qf
So,
heatduty
Qf = (64)
efficiency
Qf = 15663600/.8
Qf = 19579500 kj/hr(kg)
Fuel value for natural gas is 47179 kj/hr(kg)
So
Qf
mf = (65)
fuelvalue
mf = 415 kg/hr
As air to fuel ratio for natural gas is 9-11 so we take 10 as average [30]
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Mass of air is
ma =
air
(mf ) (66)
fuel
ma = 10*(415)
ma = 4154kg/hr
The composition of natural gas is given in the table 5-11.
Table 5-11: composition for natural gas [31]
Sr Component Mole %
1 Methane 90.589
2 Ethane 4.9543
3 propane 1.1630
4 I-Butane 0.2466
5 N-Butane 0.2817
6 I-Pentane 0.0996
7 Nitrogen 0.5109
8 Carbon dioxide 2.0760
9 N-Pentane 0.700
Heating value of fuel = 47130kj/hr(kg)

Amount of fuel used = 415 kg/hr
Molecular weight of fuel = 19 kg/kgmol [32]
Molar flowrate of fuel = 21.84 kgmol/hr
5.3.3.2 Excess Air
Using 40 % excess air, we have assumed 100 % conversion of natural gas.
Following are the reactions.
CH 4 + 2O2 → CO2 + 2H 2O
C2 H 6 + 3.5O2 → 2CO2 + 3H 2 0
C3 H 8 + 5O2 → 3CO2 + 4H 2O
C4 H10 + 6.5O2 → 4CO2 + 5H 2O
C5 H12 + 8O2 → 5CO2 + 6 H 2O
Table 5-12: products formed due to buring of natural gas
CO2 H2O
Mole Kg/hr O2
Sr Component Kgmol/hr produced produced
fraction required
1 Methane 0.905 19.76 316.1 39.52 19.76 39.52
2 Ethane 0.049 1.07 32.1 3.74 2.14 3.21
3 propane 0.011 0.24 10.56 1.2 0.72 0.96
4 Butane 0.005 0.10 5.8 0.65 0.4 0.5
6 I-Pentane 0.0009 0.01 0.72 0.08 0.05 0.06
7 Nitrogen 0.0051 0.11 3.08 ------- ------- -------
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O2 required = 45.19kgmol/hr
% excess air used = 40%
O2 supplied = 63.26 kgmol/hr or 2024 kg/hr
Air supplied = 301.23 kgmol/hr or
N2 supplied = 237.97 kgmol/hr or 6663 kg/hr
Table 5-13: Table for calculations for flue gases
Components Kgmol/hr Kg/hr

CO2 23.07 1015
H2O 44.25 796.5
N2 237.97 6663
O2 20.24 647
∑ = 9121 Kg/hr
Material In = mass of fuel + mass of N2 and O2 in air
= 415 + 6663 + 2024
= 9102 kg/hr
Material Out = mass of flue gases
=9121 kg/hr
Hence
Material In = Material Out
5.3.3.3 Radiant section calculations

Assume the average flux 10000 btu/hr ft2
A relation is available as
= 2( AvgFlux)
Q (67)
a( ACP )
So,
Q/a(ACP) = 2(10000)
Q/a(ACP) = 20000
As f = 0.57 in case of natural convection
Q/a(ACP)(f) = 35087 btu/hr ft2
By using the value of Q/a(ACP)(f) we can get the value of TG and TS. Put various combination
of tg and ts to get the available value of Q/a(ACP)(f).
So,
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 TG  4  TS  4 
  + 7(TG − TS )
Q
= 0.173  −
a( ACP )( f )  100   100  
As TG and TS are in Rankine unit

So TG = 2208 R
Ts = 1578 R
By putting these temperatures we get
Q/a(ACP) (f) = 35087 btu/hr ft2
5.3.3.4 Tube specifications and calculations
OD = 3 in
ID = 2.83 in
Thickness = 0.083 in
CTC = 1.8(O.D )
CTC = 5.4 in
Total of one row of tubes is arranged. [33]
Assume the tube length for calculations
Generally in refinery 40 ft is most commonly used.
Length(l) selection is 36 ft as it is close to 40 ft.
ACP = (l )
(CTC )
(68)
12
2
Acp = 16.2 ft
CTC/OD is 1.8(OD)
CTC/OD = 1.8
By using CTC/OD ratio we get a(alpha) from graph.
 O.D 
A = (l )  
 12 
A =28.26 ft2
So,
Q
Nt =
( AvgFlux)( A)
Nt = 15663600/(10000)(28.26)
Nt = 55.4 = 56
a(Acp)/tube = 14.9 ft2
((a )ACP )
((a )ACP ) = (N t )
tube
a(Acp) = 834 ft2
therefore,
Q/a(ACP)(f) = 2 (Average flux) = 35087 btu/hr ft2
Check it by putting the value of Q, a(Acp) and f
15663600/834(0.57) = 32949 btu/hr ft2
Approximately relation satisfied the values
5.3.3.5 Dimension calculations of furnace
We select the rectangular furnace.
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One of the dimensions (length) is already assumed.

Length = 36 ft
Dimension combination depends upon the number of tubes, tubes diameter, clearance
between tubes and their dimension ratios.
Dimension ratios are in variety, so we select according to tubes arrangements.
We select the dimension ratios 4 : 1 : 1
Length = 36 ft
Width = 9.7 ft
Height = 9.7 ft
Dimension ratios are approximately equal 36 : 9.7 : 9.7 = 4 : 1 : 1
Bridge wall height = height (2/3) = 5.2 ft
By using number of tubes and clearance between the tubes we decide the dimension ratios
and actual values of height and width.
5.3.3.6 Refractory surfaces
End walls = 2(9.7)(9.7) = 188 ft2
Side wall = 9.7(36) =349 ft2
Bridge wall = 5.2(36) = 187.2 ft2
Floor and arch = 2(9.7)(36) = 698.4 ft2
AT = 1422.6 ft2
AR = AT − (a )( ACP )
AR = 588 ft2
AR/a(Acp) = 588/834 = 0.7
5.3.3.7 Mean beam length calculations.
Mean beam length depends upon the furnace type(rectangular or cylindrical) and dimension
ratios.
So for having 4 : 1 : 1-dimension ratios
L = 1( Smallest dimension)
So L = 9.7 ft
5.3.3.8 Calculations of emissivity
Table 5-14: flue gases composition
Sr Gases Mole Mole fraction

1 Carbon dioxide 23.07 0.07
2 Water 44.25 0.135
3 Oxygen 237.97 0.73
4 Nitrogen 20.24 0.06
Total 325.53 1
It is assumed that flue gases composition is same at exit and inside the furnace
5.3.3.9 By Dalton’s law of partial pressure
Number of moles are directly proportional to the partial pressure of that gas as furnace is
operated at atmospheric pressure so molar fraction is equal to partial pressure.
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PCO2 = 0.07
PH20 = 0.135
PCO2(L) = 0.68
PH20(L) = 1.3
At Tg = 1749 R
qc = 5500 btu/hr(ft2)
qw = 12000 btu/hr(ft2)
At, Ts = 1578 R
qc = 1800 btu/hr(ft2)
qw = 3500 btu/hr(ft2)
qb at Tg is 41118.9 btu/hr(ft2)
qb at Ts is 10726 btu/hr(ft2)
  100 − % 

eg = (qc + q w )T − (qc + q w )T 
G S
( 1 
)
 qb − qb  100 
 (69)
 TG TS
eg(emissivity) = 0.37
Calculation of f
as AR/Acp = 0.7
so f = 0.47
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Chapter 6 HAZOP Study
6.1 INTRODUCTION
A HAZOP study is held to check for hazards and operability problems. The concept is to
investigate who the plant deviates from the design parameters. In identifying problems during
a HAZOP study if a solution becomes apparent, it will be recorded as a part of HAZOP results,
but care must be taken to find such solutions which are not apparent because the main purpose
of HAZOP is problem identification. The HAZOP study was introduced to supplement
experiences-based practices when a new engineering design or technology is involved, it uses
several experts with different backgrounds who interact and identifies more problems working
in association than working individually and combining their results.
6.1.1 HAZARDS
Any operation that could result in release of toxic, flammable or explosive chemical product
either fluid or gas or any action that could cause injury to person or have harmful impact on
the environment.
6.1.2OPERATIBILITY
Any operation in the process design envelop which can cause a shutdown and can possibly led
to the violation of environmental, health and safety rules or can have negative impact on
profitability.
6.1.3 WHEN HAZOP IS PRFORMED

The HAZOP study should prioritize to be first carry out as in the design phase, to have safety
margin impact on the design . While to carry out a HAZOP we should have a complete design.
To compromise this situation the HAZOP is performed as a final check when the detailed
design is completed. A HAZOP study can also be performed on an existing facility to check
for modifications that can be implemented to reduce risks and operational problems [34]
HAZOP study can also be used more diversely, including:
• When design drawings are available than in initial conceptional stage.
• After the final piping and instrumentation diagram (P&ID) availability.
• To ensure recommendations are either implemented during construction and
installation.
• During the design commissioning
• While in operation to check that plant emergency and operating procedures are either
regularly reviewed or updated as they should be.
6.1.4 HAZOP SUCCESS AND FAILURE

The success or the failure of HAZOP is dependent on following factors:
• The team’s ability to cope with and to concentrate on more serious identified hazards
• The technical skills of the working team
• The completion and correctness of used drawings as a basis for study.
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• The team ability to use approaches as an addition to their imagination in checking

deviations, causes and adverse results
The process systematically defines and helps the terms used there:
6.1.5 Study Notes:

The design points (of piping and instrumentation drawings and procedures) where the HAZOP
parameters are investigated for deviations in results.
6.1.6 Intention:
The intention indicates that who the plant will operate expectedly in the absence of deviations
at study notes. This can be represented in a number of forms either descriptively or
diagrammatically like flow sheets, line diagrams and P&IDs.
6.1.7 Deviations:
These are fluctuations or changings from the intentions which are requisitely defined by
systematic application of the guide words (i.e. more pressure)
6.1.8 Causes:
Reasons that causes deviations or due to which deviations might occur. Once a deviation shows
a credible cause, it will be treated as an operational deviation, they may cause hardware failures,
human errors, an unanticipated process state(i.e., change of composition), external disturbances
(i.e., loss of power), etc.
6.1.9 Consequences:
When deviations occur consequences are their results like failure of wall can cause toxic
material emission or release serious and highly adverse consequences relative to the study
objective, are not considered.
6.1.10 Guide words:

These are words that are used for qualifying or quantify the intentions to provide guide and
stimulation for the brain storming process to discover deviations. The guide words in the table
are those used most commonly in a HAZOP. Some of the organizations and companies have
made HAZOP list specific to there operations, for quick guideless to the areas of previously
found problems. Each guide word is associated to process variables at the points in the plant
(study node) which are being examined [34].
Table 6-1: guide words for HAZOP Analysis
Guide words Meaning

No deviation from the design intent
Less Decrease Qualitatively
More Increase Quantitatively
Part of Decrease Qualitatively
As well as Increase Quantitatively
Reverse Logic 180 degrees of the intent
Other than Complete negation
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6.1.11 Guide words according to parameters:

Table 6-2:Guide words according to parameters
Parameter Guide words / Deviation

Time Too early, Quick or too late
Sequence incorrect sequence, omissions, incorrect action
Procedure unavailability, inapplicability, unfollowed
Measurement Instrument crash, inspection error
Organization Unclear tasks, unfit for purpose
Communication Equipment failure, insufficient / mistaken
information
Personal Lack of skills, too little, too many
Position mistaken position, movement exceeding
acceptable limits
Power total loss, incompletely loss
Weather Above limitations causes delayed operations
6.1.12 Types of HAZOP:

6.1.12.1 Process HAZOP:
The HAZOP technique was actually formed to access plant and process system.
6.1.12.2 Human HAZOP:

This family of specialized HAZOPs is focused on human errors then technical failures.
6.1.12.3 Procedure HAZOP:

Assessment of the operational or procedure sequences some time denotes SAFOP- Safe
Operation Study.
6.1.12.4 Software HAZOP:

Identifies possible software errors in the development.
6.1.13 PROCESS HAZOP:

6.1.13.1 Prerequisites:
As a basis for HAZOP following information should be available:
• PFDs (Process flow diagrams)
• P&IDs (Piping and instrumentation diagram)
• Layouts presented diagrammatically
• MSD Sheets (Material safety data)
• draft operating directives
• Material and energy balances
• Equipment data sheet Start-ups
• Emergency shut-down measures
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6.1.13.2 HAZOP Procedures:

• Divide the system into several operational parts (e.g.: reactor, storage)
• Select a predefined study node (i.e. line, vessel, pump or operating instructions).
• explain the design intents
• choose process parameters
• Application of guide words
• conclude causes
• estimate adverse results or problems
• advised actions: What? When? Who?
• Documentation of information
• Go over procedure (from step 2)
6.1.14 CONCLUSIONS
6.1.14.1 HAZOP RESULTS:
• System improvement or operations
✓ lessen risks and enhanced contingencies
✓ added efficiency to operations
• perfection of actions
✓ reasonable order
✓ comprehensiveness
• General awareness rising for parties involved
• Team construction and building
6.1.14.2 ADVANTAGES:
• Systematically examining
• Study held in multidiscipline
• Utilization of operational experiences
• Cover both safety and operational sides
• Solution to the identified problems may be indicated
• Operational procedures must be considered
• Encircles human mistakes and errors
• Independently held personal study
• Results are documented
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6.2 Hazop Study of Distillation Column

Following objectives are suggested while studying distillation column:
1. To maintain the product quality (composition) of either bottom or overhead product at
a specified value
2. Flow rates control to maintain column bottom and top inventories and holdup between
minimum and maximum limits
3. Maintain the constrains, like column should not flood, pressure should be enough to
maintain effective column operation and the difference in temperature of reboiler
should not surpass critical temperature difference
6.2.1 Distillation Column Diagram
Coolant out
Condenser
Coolant in
Reflux Drum
Stream P3
Top product
Stream P4
Distillation
Stream P1 Column
Stream P2
Re-boiler
Bottom product
figure 6-1: Distillation column diagram for HAZOP Analysis
6.2.2 HAZOP OPERATABILITY TABLE:

Table 6-3: HAZOP Analysis for Distillation Column
Stream P1:
For transmission the reactant of the Distillation column
Guide Deviation Cause Consequence Action

word
No Flow -failure in - distillation - low level alarm should be
pump column may dry installed
- blockage in out - maintenance process must be
pipe - no operation schedule and checked
- valve failure
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- Control - dangerous - emergency shut down of this

valve shut concentration area of plant
could achieve
Less Flow - pump failure - distillation - low level alarm should be
- tube leakage column may dry installed
and blocking out - maintenance process must be
- valve failure - product quality schedule and checked
- Control changes - emergency shut down of this
valve shut area of plant
- make bypass
More Flow -Control valve - flooding occur - high level alarm must be
is fully opened the column installed
-Increase - change in - maintenance process must be
pumping product quality schedule and checked
capacity - decrease in - good control system must be
- control valve temperature installed
failure occur
- liquid level at
bottom rises
- pressure in
column increase
Stream P2:
For transmission of boiling stream from reboiler to column
No Flow -pipe is broken -product -temperature sensor and alarm

or plugging specification must be installed
-steam line change -install minimum flow valve
blocked or -no distillation
closed
-pump control
failure
Less Flow -pipe partially -product -temperature sensor and alarm

plugged or specification must be installed
blocked change -install minimum flow valve
-pump control -less distillation -schedule maintenance
valve fault
More Flow -stream line -product -temperature sensor and alarm
control failure specification must be installed
-pump control change -install automatic steam line
valve fault -more and pump shut down and
distillation control
As well as Composition Reboiler -product -install composition monitoring

steam line specification device and alarm
leakage in to change
reboiler and
mix with
bottom
product
Stream P3:
For transmission of vapours condensed back to column
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No Flow -closed valve - temperature - flow sensor and alarm

or pipe burst and pressure - automatic shutdown and
control loss in control system
distillation
column
Less Flow -pipe leakage - product - flow sensor and alarm
or blockage specification - automatic shutdown and
-control change control system
system failure -- temperature
and pressure
control loss in
distillation
column
More Level -reflux drum - temperature - install excess flow valve
overfill and pressure - flow sensor and alarm
-pump control control loss in - automatic shutdown and
failure distillation control system
column
Line P4:
Intention: separate reflux and distillate streams
No Flow -control valve - temperature - flow sensor and alarm
is failed and pressure - automatic shutdown and
- pipe burst control loss in control system
distillation - install minimum flow valve
column
Less Flow -pipe blockage - product - flow sensor and alarm
or leakage specification - automatic shutdown and
- control change control system
system failure
More Flow -pipe blockage -- temperature - install alarm and burst disk
of reflux line and pressure - excess flow valve
or distillate control loss in
line distillation
- control column
system failure - reflux drum
overfill/ break
Reverse Flow -pipe blockage - back flow of - install alarm and burst disk
of reflux line liquid in reflux - install level sensor in reflux
or distillate drum drum
line - reflux drum - use check valve
- control may falling-out
system failure
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6.3 HAZOP STUDY OF REACTOR

6.3.1 Reactor Diagram
Compressor
P1
Vegetable oil P2
Pump CV-1 Hydrogen
CV-2
P5
Coolant out
CV-5
P4
Coolant in
CV-4
CV-3
P3
product
figure 6-2: Reactor diagram for HAZOP Analysis

Table 6-4: HAZOP Analysis for Reactor
Line P1:
Intention: To transfer the reactant to the reactor
Guide word Deviation Cause Consequence
No Flow -failure of pump Decrease in
-CV-1 closed or Reaction rates and
stucked conversions
Less Flow Partially closed valve Decrease in
Reaction rates and
conversions
More Flow System control Rate of reaction
failure increases
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Line P2:
Intention: To transfer the reactant to the reactor
No Flow - failure of Decrease in
compressor Reaction rates and
-CV-2 closed or conversions
stucked
Less Flow Partially closed valve Decrease in
Reaction rates and
conversions
More Flow System control Sudden Pressure
failure increase
Line P3:
Intention: To remove the product from the reactor
No Flow -CV-3 closed Increases in reactor
stucked pressure
Less Flow -CV-3 free to open Decrease in
Reaction rates and
conversions
More level -CV-3 closed
partially
Line P4:
Intention: Cooling water transfer to the reactor jacket
No Flow -CV-4 close struck Increases in
temperature by
product formation
Less Flow -CV-4 free to open Reaction
temperature will not
be maintained
Line P5:
Intention: Removing the steam from the jacket
No Flow -CV-5 struck closed Pressure inside the
jacket increased
Less Flow -CV-5 free to open Reaction
temperature will not
be maintainable
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6.4 HAZOP STUDY OF FURNACE

6.4.1 Furnace Diagram
figure 6-3: Furnace diagram for HAZOP Analysis

P-1
Guide Deviation Cause Consequence Action
No Flow -Failure in -No operation -Alarm should be
pump -No heating installed
-Blockage in -Scheduled
pipe maintenance applied
-Valve failure
-Control
valve shut
Less Flow -Pump failure -Less heating -Actuator is attached
-Tube with the flow meter
leakage and -Bypass is used
blocking -Scheduled
-Valve failure maintenance applied
More Flow -Control -Explosion -Control system is
valve failure -More heating used to control valve
-Incomplete -Alarm should
combustion connect for indication
P-2
No Flow -Valve failure -Feed for reactor -Define fuel to air
-Blocking of is not desirable ratio by using bypass
pipe -No combustion
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-No heating -Shut down the fuel

input
Less Flow Valve failure -Less heating -Bypass
-Blocking of -Feed for reactor -Decrease fuel flow
pipe is not prepared -Regular maintenance
-Explosion
More Flow - control -Less heating -Instrumentation is
valve failure -Complete applied to control
-Valve fully combustion valve
opened -Bypass
-Regular training to
avoid human errors
P-3
No Flow -Valve failure -No combustion -Regular maintenance
-Blocking of -No feed for -Bypass
pipe process
-Failure of -No heating
pump
-Shortage of
fuel by
leakage
Less Flow Valve failure -Less heating -Regular maintenance
-Blocking of -Bypass
pipe
-Leakage
More Flow - control -Explosion -Instrumentation is

valve failure -More heating applied
-Valve fully -Reaction takes -High temperature
opened place alarm is used
P-4
No Flow -Blocking of -Feed for reactor -Alarm for fluid flow
pipe will not prepared should be installed
-leakage -Damage of -Decrease the fuel
-Valve failure pipelines inside and air for
at input the furnace by combustion
stress
Less Flow -Blocking of -Heat stress on Decease flow rate of
pipe pipelines inside fuel
-Valve failure the furnace -Scheduled
at input -Explosion maintenance
-Leakage
More Flow -More input -Less heating -Recycle is applied
is used -No reaction -Steady state system
- occur in reactor will develop
Accumulation
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Chapter 7 INSTRUMENTATION AND PROCESS CONTROL

7.1 INTRODUCTION
One of the important feature of all the process is their dynamic behavior because they are not
in static equilibrium in true sense and that is because of continual disturbances occurring in the
process that’s why the process goes away from the desired equilibrium condition so the process
must be manipulated or corrected in the manner that there should only be transient effect in the
process behavior. These passes without re-occurrence. If the periodic or cyclic forces would be
applied, then the process will behave in the cyclic or periodic behavior. Most of the
disturbances are random in nature with respect to time without repetitive behavior. So, these
are expected disturbances either then the predicted once for specific time period. To operate a
process efficiently the process must be controlled.
During plant operation instruments monitors the key process variables. Either they are
incorporated with the manual or automatic control loops for process monitoring. Or either they
may be the part of computer data logging system. Those instrumentations which are monitoring
critical process variables they relate to automatic alarm systems to make aware of the hazardous
or critical operational situations. [35]
Process variables that should be monitored they should be measured directly however that is
not a practical approach and some other dependent variables that are easier to measure they are
measured instead. Like in distillation column temperature is measured as an indication of
compositions. The temperature instrument may form part of a control loop controlling say,
reflux flow; with frequent sampling of composition checking of overheads through laboratory
tests.
7.2 INSTRUMENTATION AND CONTROL OBJEVTIVES

The primary objective of the designer when specifying instrumentation and control schemes
are;
7.2.1SAFER PLANT OPERATION

• Keeping the process in safe variables operating limits
• Detecting the dangerous situations when developed and to indicate through alarm or
stimulate automatic shutdown system.
• To avoid dangerous operating procedures, provide alarms and interlocks.
7.2.2 Production Cost:

To operate at the minimal production cost commensuration with other objectives
7.2.3 Product Quality:

To maintain the product within specified quality standards through composition
7.2.4 Production Rate:

To achieve designed output of the product from production line
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All the above described objectives should be considered altogether. The way they are listed is
not meant to precedence of any objective over another, other than the safety considerations.
Product quality, production rate and cost of the product will be sales dependent. Like it would
be desirable to produce a better-quality product at a higher cost.
In a typical chemical processing plant these objectives are achieved by a combination of
automatic control, manual monitoring and laboratory analysis. [36]
7.3 CONTROL SYSTEM COMPONENTS:

7.3.1 Process:
To produce a desirable product through a series of operations is called a process. In this
discussion the process is conversion of vegetable oils into green diesel and other useful
fractions.
7.3.2 Measuring Means:

Among all the parts of the control systems measuring parts are the important once. If
measurements are not properly made the system cannot operate satisfactory. The measured
available variables represent the desired conditions in the process.
7.3.3 MEASURABLE VARIABLES

• Temperature measurement
• Pressure measurement
• Flow rate measurement
• Level measurement
7.3.4Controller:
The controller is mechanism for indicating any error in the detecting mechanism. The
controller’s output is the predetermined function of the error.
In the controller there is also an error detecting mechanism to compare measured variables with
the desired values of the measured variables and the difference between them is called error.
[37]
7.3.5 FINAL CONTROL ELEMENT

The final control element receives the signals from the controller and through predetermined
relationships changes the energy input of the process.
7.4 CLASSIFICATION OF THE CONTROLLERS

Generally, the process controllers can be classified as:
• Pneumatic controller
• Electronic controller
• Hydraulic controller
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In the green diesels production from the vegetable oil the final control element may be
pneumatically operated due to following reasons
• Their rugged and low or free of maintenance requirement nature. As the maintenance
workers have not enough electronics background so pneumatic equipment’s are easy to
operate.
• They are safer in potentially explosive industrial environment.
• Short transmission distances for pneumatic and electronic transmissions which are
generally equal up to 200-300 feet. Above this distance electronics systems offer
savings.
7.5 MODES OF CONTROL

Different types used for control are modes to determine types of obtained response. We can
also say that these describes the action of controller that represents the relation of output of
output signal to input or error signal. It is worth noting here that it is error that actuates the
controller. The four basic modes of control are
• On off control
• Integral control
• Proportional control
• Rate or derivative control
Industrially the above described don’t exists independently in the control system. Their
combinations are often used. [38]
The on-off controller is the controller with high gain. In this case the error signal at once off
the valve or any other parameter upon which it sits or completely sets the system.
7.6 ALARMS, SAFTEY TRIPS AND INTERLOCKS

7.6.1 Alarms:
Alarms are basically used to alert the operators from the serious or potentially hazardous
disturbance or deviation in the process operation. Key instruments are fitted with switches and
relays to operate audible and visual alarms on the control panels.
The basic components of the automatic trip systems are
• Sensor to monitor the control variable and when the preset value is exceeded it gives
an output signal
• The signal is transferred to the actuator through a link usually consisting of a system of
pneumatic or electric relays.
• An actuator for carrying out the required action it may be valve opening or closing or
motor switch off
A safety trip must be incorporated in control loop. In systems like described once a high
temperature alarm operates a solenoid valve by releasing the air on the pneumatic activator
closing the valve on high temperature. [39]
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7.6.2 Interlocks:
Somewhere in the operation there is necessity to follow the fixed sequence of operations for
example during start up and shut down of a plant, or particularly in batch operations-inter-
locks are added to prevent operators from the deportation from the required operational
sequence. They can also be incorporated in the control system design, either as electrical and
pneumatic relays or mechanical interlocks.
7.7 DIFFERENT TYPES OF CONTROLLERS

7.7.1 Flow Controller
Flow controllers are used to control the feed rate into the process unit. Orifice plate are by far
the most type of flow rate sensor. Normally these plates are designed to give the pressure drop
of the range of 20 to 200 inches of water. Venture tubes and turbine meters can also be
produced for that purpose.
7.7.2 Temperature Controller

Thermocouples are mostly used as a temperature sensor. The two wires of different material
of construction produces a milli volt emf that varies with the ‘hot junction’ temperature. Over
the temperature range of 0 – 1300 F iron constricting thermocouples are generally used.
7.7.3 Pressure Controller

To measure and sense the pressure and the pressure difference bourdon tubes, diaphragms and
bellows are used. For example, process pressure force of a mechanical system is balanced by
the movement of a spring. The spring position can be related to process pressure.
7.7.4 LEVEL CONTROLLER

There are various schemes to detect the liquid levels the common among those are as follows
• Float method: Checking the position of less dense (less dense than that of water) float
• Displacement meter: Measuring the apparent weight of the heavy cylinder as it buoyed
up by the liquid
• Differential pressure: measurement of the difference in the static pressure of fixed
elevations, one is of the vapor above liquid and the second is under the liquid surface.
The differential pressure between the two-level taps is related directly to the level of
liquid in the vessel. [40]
7.7.5 Transmitter
It is the interface between the control system and the process. The job of the transmitter is to
convert the sensor signal (milli volts, mechanical movement or pressure difference) into a
control 3-15 psig air pressure signal, 1-5 or 10-50 milliampere electrical signal.
7.7.6 Control Valve

At the other end of the control loop the interface with the process is made by the final control
element by an automatic control valve which throttles the flow of the stem that opens or closes
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the opening of the orifice as stem is either lowered or raised. The stem is attached to the
diaphragm that is operated by varying the diaphragm pressure less than the air pressure. The
spring opposes the force of the air pressure
7.8 CONTROL SCHEME ACROSS REACTOR

7.8.1 INPUT & OUTPUT STREAMS
Table 7-1: input and output streams of reactor
Stream no. Components
Feed stream Vegetable oil,

1
(Inlet) Hydrogen
Product Stream A range of

2 Hydrocarbons from
(outlet) C4-C19
7.8.2 OPERATING CONDITIONS AND PROCESS PARAMETERS

Table 7-2: operating conditions for reactor
Parameters Inlet Outlet
Stream 1 2
Temperature 335.6 C 335.6 C
Pressure 4000KPa 4000KPa
Flow rate 156.4kg/hr 14.7kg/hr
7.9 Analysis of Measurement

7.9.1 Variables to be measured
1. Temperature measurement
2. Pressure measurement
3. Flow rate measurement
7.9.2 Variables to be recorded
• Indicated temperature
• Indicated pressure
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7.9.3 Operation Scheme

The production rate of plug flow gas reactors can be inherently maximized by the temperature
controller manipulating reactant feed rates. Reaction stoichiometry for two phase continuous
reactors can be inherently maintained by pressure and level control when the product and
reactants are in different phases (e.g., gas reactant flow manipulated by pressure control for
liquid product flow and gas purge flow). When reactant is recycled, various control strategies
are offered depending upon the source and path of the recycle. Auctioneering control system
is installed over reactor to maintain the temperature of reactor. In PFR reaction occurs through
the length and temperature also changes w.r.t length of reactor. Multiple temperature measuring
sensors are installed on the different points on surface of tube bundle within the reactor which
sense highest deviated temperature and signal through auctioneering system will be sent to
controller. Controller will compare value with sent point and according to generated error it
will send signal to final control element to change the valve opening.
figure 7-1:: instrumentation and control scheme for reactor.
Instrumentation and control on distillation column

Distillation column is basically used for the separation of mixture of liquids or solution to their
individual components. Further many new techniques have been developed but distillation
remain the most useful method for separation and is applied in industries.
Simple distillation column layout has been shown in figure 7.2. single feed enters the
distillation column and two products are formed for partial condenser three products are
formed: bottom product, top product and off gases. Heavy products having low volatilities are
removed from the bottom and light products having high volatilities are removed from the top.
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Heat in order to vaporize the liquid is supplied to reboiler and heat is removed in order to
condense vapors in condenser.
W
Off gases
Vt
LI
Mr
TI R D, xd
PI
FI FI
FI
F, xf
TI
Vb
LI
Mb
S
B, xb
FI
figure 7-2: Simple distillation column layout [41]
Where,
V = vapor flow
F = feed flow
R = reflux flow
D = distillate flow
B = bottom flow
x = composition
M = mass holdup
W and S= cooling water and steam flow
If we want constant separation of components in distillation column it should be well
instrumented and controlled. As liquid and vapor having certain amount of energy are present
in the distillation column basic instrumentation involve the calculation and measurement of
liquid holdups which include reflux drum level and column bottom level, Vapor holdup
(pressure in column), and temperature along the column. Further the out and in flows are
measured as shown in figure 7.2
In our process the feed to the distillation column is fixed so no control is shown at feed. But
occasionally feed preheater control valve is used in order to control the amount of feed that is
to vaporize. This mean that we have five manipulatable flows and there is five degree of
freedom for control process. But the holdup of liquid and vapors are also to be controlled, so
that mean 5-3 = 2 degree of freedom remain.
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In order to control distillation column we have some difficulties like, the process is often high
nonlinear and secondly we have five control variables (composition at bottom, composition at
top, pressure inside column, level at bottom and level in the reflux drum) and five manipulated
variables (flow D,R,B,S and W). so how to couple these control and manipulated variables
with each other is very interesting and a lot of word has been done in order to get best
combination.
I am using feed backward approach for the instrumentation and control of the distillation
column as it simple and doesn’t require high instrumentation like sensors, transducers, final
control element, etc. the instrumentation and control scheme along the distillation column is
shown in the figure 7.3.
Coolant out
PT PC
Off gases
Coolant in
Vt
LT LC
TT TC
Top product
Reflux
Feed mixture
TT TC
LC LT
Steam for heating
Bottom product
figure 7-3: instrumentation and control scheme on distillation column
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Chapter 8 Process Simulation and Analysis

8.1 Introduction
The whole process is simulated using Aspen HYSYS V10. In order to check the manual
calculations either they are correct by cross checking or verifying with the simulation results.
In this chapter the simulations results and the manual results are shown. Further simulation was
used in order to check or test the fitness of the data and conditions found in the literature, either
it is suitable or not for our process. And to find process conditions at which the process is most
optimal and feasible. Final selected conditions for the main process equipment’s are shown in
table 8.2.
8.1.1 Benefits of simulation
To check the flexibility of process is one main advantage of simulation. It allows us to apply
the sensitivity analysis and to study the impacts of key parameters (design) on the quantity and
quality of the desire product
Secondly, process performance is evaluated at variable operating conditions proves the model
validity used for the simulation. While In the study of reactor, two variables were seen
important for the conversion of reactants.
• H2 concentration in the bulk liquid
• Temperature inside the reactor
The performance of the reactor has not affected in a significant way by changing the feed
composition and feed temperature. By simulation it can be said that hydrogenation reaction is
feasible.
8.2 Process Flow Diagram
Off Gases
Fresh
hydrogen
Green LPG
Condensor
E-5
Recycled Separator
hydrogen (Reflux drum)
Amine unit S-3
Pretreated oil
Top product
Pump Distillation column

Furnace P-1
T-1
F-1
Separator
Reactor
S-2
R-1 Reactor
R-2
3 phase
Separator
S-1
Bottom product
Heat exchanger
E-1 Heat exchanger
E-2 Heat exchanger Reboiler
E-3 E-4
figure 8-1: Process flow diagram for green diesel production from vegetable oil [21]
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8.3 Process Simulation

Simulation of green diesel production on HYSYS include following steps
• Selection of the components used in the process
• Selection of thermodynamic model
• Drawing of process flow diagram
• Simulate the process by setting operating condition and input conditions
8.3.1 Selection of components
Vegetable oil components and composition is taken from [42]. As shown in table 8.1
Table 8-1: feed components and compositions [42]
Components Mass Fraction(%)

Triolein 97.29
Oleic acid 2.00
n-Hexane 0.10
n-C29H60 0.15
Sterol 0.40
As triglyceride are major component in any vegetable oil, we use triolein as triglyceride and
other components as free fatty acids which are in minor quantities. The components selected
for simulation are following
figure 8-2: Aspen HYSYS component list
Component list further include n-Octane which is at last of fig 8.2
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8.3.2 Selection of Thermodynamic model

Equation of state model, in general and the Peng-Robinson one and its variants, are mostly
preferable models in many commercial simulators for hydrocarbon mixtures even in the
presence of water and over wide pressure and temperature range
In our process the property package selected is Peng-Robinson equations corrected with Twu
Alpha function which is used to take in account the excess free energy to predict more precise
vapor pressure [42].
Figure 8.3, shows the selection of thermodynamic fluid selection
figure 8-3: Thermodynamic model (Aspen HYSYS)
After the selection of the thermodynamic model reaction are defined as these reactions are to
be using later in simulation. Two reactions are taking place in reactor R-1, as shown in figure
8.4 and 8.5.
figure 8-4: reaction 1 condition and stoichiometry Aspen HYSYS
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figure 8-5: reaction 2 conditions and stoichiometry Aspen HYSYS
8.3.3 Operating Conditions for Main Process Equipment’s

The operating conditions of the major equipment’s are defined as shown in table 8.2
Table 8-2: Operating conditions for main equipment’s used in process
Unit Process conditions Comments

F-1 360 oC, 1 bar Preparation of Reactor feed
H-1 25 oC, 40 bar hydrogen feed to reactor
360 oC, 40 bar, H2/oil ratio (4 time the
R-1 NiMo/Al2O3 catalyst
theoretical needed)
R-2 360 oC, 40 bar Pt/Al2O3 catalyst
o
S-1 30 C, 40 bar Flash tank
o
S-2 30 C, 15 bar Flash tank
o
T-1 135-282 C, 1 bar Main column, 19 trays
8.3.4 Drawing of the process flow diagram

Process flow diagram as shown in figure 8.1, is then drawn on the Aspen HYSYS in order to
simulate the process the input conditions of feed and the operating conditions of the major
equipment’s as shown in table 8.2 and minor equipment’s are provided in order to run the
simulation in proper way. The result of output streams of the process are shown in table 8.3
The simulated flow diagram of the process is shown in figure 8.6
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8.3.5 Simulation of Process Flow Diagram
figure 8-6: Simulation of process flow diagram
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8.3.6 Material balance using Aspen HYSYS
Table 8.3 shows the input (in green) and output streams (in blue) of the process flow diagram
(figure 8.6). Their temperature, pressure, flow rates and molar compositions of components
present
Table 8-3: Condition and compositions of inlet and outlet streams of process
Feed Hydrogen Amine Water Water bottom of Top of CO2

Units H2 out
stream C-1 solution S-1 S-2 distillation distillation out
Temperature oC 25 25 50 30 30 269.1 89.54 49.24 25
Pressure (Kpa) 100 4000 100 4000 1500 100 100 100 4000
Mole flow
0.1800 7.33 400 0.8552 0.3139 0.4133 0.2849 398.9 6.270
(kmol/h)
Mass flow
156.4 14.78 19270 15.56 5.735 96.05 31.76 19250 40.97
(kg/hr)
Mole fractions
Triolein 0.973
Oleic acid 0.020 0.0087
n-hexane 0.001 0.0004
n-C29 0.0015 0.0007
M-Salicylate 0.004
H2O 0.3 0.9947 0.9937 0.0001 0.2979 0.0897
CO2 0.0011 0.0001 0.0063 0.0001 0.0313
Propane 0.0060 0.0001 0.0216
hydrogen 1 0.0005 0.0002 0.0001 0.8458
n-C17 0.3180
n-C18 0.4451
MEAmine 0.7 0.0036 0.0059 0.0454 0.7018 0.0026
n-Pentane 0.1129 0.0073
n-C13 0.1908
n-nonane 0.035 0.4002 0.0005
n-octane 0.4346 0.0012
These are the results of overall process
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8.4 Comparison between manual calculation and Aspen HYSYS calculation
In order to find out either our manual calculation is correct it was necessary to cross verify it
with simulated values calculated by Aspen HYSYS. So, we applied same conditions and
parameters as we used in manual calculations to the Aspen HYSYS and compared their results.
8.4.1 Distillation column
The same parameters as number of trays, Reflux ratio, condenser and reboiler pressure, top and
bottom temperature, feed conditions are provided to Aspen and the output streams
compositions are compared to check either the separation we are taking from the distillation
column manually is feasible or not. The results are following
figure 8-7: Outlet streams and compositions of distillation column, Aspen HYSYS
Manual calculated results

The output compositions we calculated are shown in table 8.4. here we can see that the same
components are going to top, bottom and off gases streams. And have composition near
calculated by Aspen HYSYS. This slight difference might be because of, we took pure
components and neglect the impurities and Inerts, while Aspen has taken in account of all these
things.
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Table 8-4; manually calculated composition of outlet streams of distillation column
Components Feed Bottom Top Off gases

(kgmol/hr) (kgmol/hr) (kgmol/hr) (kgmol/hr)
propane 0.0355 0.0017 0.0338
C17 0.1118 0.1117
C18 0.2112 0.2111
n-pentane 0.1126 0.0056 0.1069
n-C13 0.0904 0.0897 0.0006
n-nonane 0.1119 0.0008 0.1110
n-octane 0.1667 0.1660
total 0.8401 0.4133 0.2849 0.1407
8.4.2 Furnace
The same parameters as feed temperature, feed composition and outlet temperature are
provided to Aspen and heat duty calculated by Aspen and manually is compared to find either
the amount of heat we calculated to heat the feed is correct or not. So, Heat Duty is the
parameter for checking our calculations. Heat duty calculated by Aspen is as follows
figure 8-8: Heat duty of furnace, Aspen HYSYS
Heat duty calculated manually is, Qout - Qin =156636 kj/hr. There is slight difference in the
manual and Aspen calculated values. This difference might be because of, we assume ideal
solution that component has no effect on the other components present in solution. So, we don’t
account heat of mixing, heat of solution etc. while Aspen take account all these things.
8.4.3 Reactor
The same parameters as feed temperature, feed pressure, hydrogen temperature, hydrogen
pressure, reactor temperature and pressure, reaction stoichiometry, conversion are provided to
Aspen and the output streams temperature are compared to check either the calculated
temperature match the Aspen calculated temperature. As we use the conversion reactor, we
have defined conversion at start so we could not make conversion as a parameter for check.
Output temperature calculated by Aspen is shown in fig 8.9
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figure 8-9: outlet stream temperature of reactor, Aspen HYSYS.
The temperature manually calculated as shown in chapter 4 is,
𝑇 = 426 0C
So, there is slight difference in temperature calculation, but it could be neglected.
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Chapter 9 COST ESTIMATION

9.1 Introduction
First the capital cost of the plant is calculated for the economic evaluation of the project and
then variable cost is calculated using ranges of process plant component cost outlined in [43].
Total product cost is then calculated on basis of manufacturing cost and general expense.
Manufacturing cost some time called production or operating cost. Payback period is also
calculated
9.2 METHODS OF COST ESTIMATION

Here are some different methods for cost estimation,
• Detailed item Estimate

• Unit Cost Estimate
• Percentage of delivered equipment cost
• Lang factor for approximation of Capital Investment
• Power factor applied for plant
• Investment cost per unit of capacity
• Turnover ratio
We use percentage of delivered equipment cost in order to calculate the cost as this method
give good estimate and does not require a lot of requirements. The first two method give very
good results but requires a lot data to be done.
So, as in Percentage of delivered equipment cost method total capital investment is first
calculated. So, calculation for total capital investment is as follows
9.3 TOTAL CAPITAL INVESTMENT

Total capital investment includes,
• Fixed capital investment

o Direct cost
o Indirect cost
• Working capital
So, first we must calculate fixed capital and working capital investment.
9.3.1 Purchased Equipment Cost

Capacity and size for the main process equipment are obtained from the manual calculations
and simulation. Cost for theses equipment’s are calculated using curves for each process
equipment from [43], cost is then updated with the help of CEPCI index for 2018, which is
603.1.
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Table 9-1: Table for Equipment Cost
Equipment cost Cost ($)

Furnace [43] 4500
Reactor [43] 9836
Isomerization Reactor [44] 16500
Distillation column [43] (Fig 16-28) 8400
Separator [44] 8300
Total cost (2002) 47536
Total cost (2020) 73497.96
We use cost index in order to calculate present value. CEPCI value in 2002 is 390.4 so we just
need to multiply each value with (603.1/390.4). final calculated purchased equipment cost is
73497.96 $. And the delivered equipment cost is 80847.76 $, as delivered equipment cost is
1.1 times the equipment cost.
9.3.2 Estimation of Total Capital Investment

9.3.2.1 DIRECT COST
For fixed capital investment we need to calculate direct and indirect cost. We use ratio factors
based on delivered equipment cost for the estimation of direct and indirect cost. [43] (table 6-
9)
Table 9-2: Table for calculation of direct cost
Name % of purchased equipment Cost($)

cost
Purchased equipment cost 100% 80847.77
Installation cost 47% 37998.45
Instrumentation cost 36% 29105.20
Piping cost 68% 54976.48
Electrical cost 11% 8893.25
Building auxiliary 18% 14552.60
Yard improvements 10% 8084.78
Service facilities 17% 13744.12
Total Direct Cost 248202.64
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9.3.2.2 INDIRECT COST

Table 9-3: Table for calculation of indirect cost
Name Used % Cost($)

Engineering & Supervision 33%
26679.76
cost
Construction expenses 41% 33147.58
Legal expenses 4% 3233.91
Contractor’s fee 22% 17786.51
Contingency 44% 35573.02
Total indirect cost 116420.78
9.3.3 TOTAL CAPITAL INVESTMENT

FCI = direct cost + indirect cost
= 364623.42 $
WC = 15% of TCI
= 54693.51 $
TCI = 419316.93 $
9.4 TOTAL PRODUCT COST

Total product cost is calculated using table (6-19) [43], calculation of total product cost
includes following factors.
• Manufacturing cost
o Fixed charges
o Direct product cost
o Plant overhead cost
• General expenses
o Administration cost
o Distribution and marketing cost
o R&D cost
These factors are calculated as follows
9.4.1 FIXED CHARGES

Using table (6-19) [43].
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Table 9-4: Table for fixed charges calculation
Name % of FCI Amount ($)

Local taxes 4% 14584.94
Insurances 1% 3646.23
Description 20% 83863.39
Rent 12% 43754.81
Financing (interest) 10% 36462.34
Total Fixed Charges 47% FCI 182311.71
9.4.2 DIRECT PRODUCT COST

Using table (6-19) [43].
Table 9-5: Table for direct production cost calculation
Name %range Used % Amount ($)

Raw material - - 98894.27
Operating labor 10% -20% of TPC 10% 15214.50
Direct super 10% -20% of OPL 20%
visionary & electrical 3042.90
labor
Maintenance repairs 2% -10% of FCI 10% 36462.34
Operating supplies 0.5% -1% of FCI 1% 3646.23
Laboratory charges 10% -20% of OPL 20% 3042.90
Patents and royalties 0% -6% of TPC 6% 9128.70
Direct production 81% TPC + 40% OP +
cost 11% FCI 169431.85
9.4.3 PLANT OVERHEAD COST

Plant overhead cost = 15% of TPC
= 22821.75 $
10.4.4 Manufacturing cost
= 58% FCI + 96% TPC + 40% OP
= 374565.31 $
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9.4.5 GENERAL EXPANSES

Table 9-6: table for General Expense
Name %range Used % Amount ($)

Administrative cost 2% - 5% of TPC 5% 7607.25
Distribution and 2% - 20% of TPC 20%
30429.01
marketing cost
Research and 5% of TPC 5%
7607.25
development cost
General expenses 40% TPC 45643.51
TOTAL PRODUCT COST

TPC = manufacturing cost + general expenses
= 136% TPC + 4% TPC + 58% FCI
= 152145.03 $
9.5 Product price and Profitability
To find the profitability of our process plant, we need to calculate annual cash flow. Annual
cash flow is calculated on basis of assumptions that plant operate 300 days a year, and
according to current price of diesel which is taken 0.51 $/liter. And subtracting the taxation
cost which is 35% over profit. The annual cash flow calculated is 130357.87 $/year
Cash flow over life span of plant is as follows
1200000
1000000
800000
600000
Dollor $
400000
200000
0
-4 -2 0 2 4 6 8 10 12
-200000
-400000
Years
Figure 9-1: Cash flow over the life span of plant
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Chapter 10 ENVIORMENTAL IMPACTS OF

BIOFUEL
10.1 Introduction
In the context of energy demand and consumption biofuel contribution is small. In relation to
current level agriculture production it is significant. The protentional of its growth should be
recognized both in social and environmental implications. In this context like many policies
are there to reduce the greenhouse gas emissions this supports the production of green diesel.
In general, unintended adverse impacts on land water and biodiversity count among agricultural
production but they have connection with the biofuels. The extent of such impacts depends on
who biofuel feed stock are produced and processed, the scale on which it would be produced
particularly how they influence the usage of land, intensification and changing international
trade. This chapter will elaborate the environmental impacts of biofuels; this social implication
will be considered in the chapter.
10.2 HOW BIOFUELS HELPS TO MITIGATE THE CLIMATE

CHANGE
Recently many of the policy makers are concentrating on the less greenhouse emission fuel
sources and the fuels that are produced from the biomass best meets the demands and these
fuels can play a vital role to control the negative climate change. Greenhouse gas emission can
directly be reduced by removing the air carbon dioxide by bio energy crops as they grow and
storing it in crop biomass. Other than that production of biofuel these crops also produces co-
products like protein for animal’s fee, thus saving on energy that would have been used to make
feed by other means. Though there are many potential benefits, but the scientific studies show
that there are different emission ratios of different biofuels in comparison with the petrol
depending on the method used to produce the feed stock and process the fuels. For example
nitrous oxide one of the greenhouse gas whose global warming potential is around 265–298
times than that of carbon dioxide [45], and that is released from the nitrogen fertilizers.
However, the greenhouse gases are produced and emitted in the other stages of bioenergy crops
and biofuels; in producing fertilizers, pesticides and fuel which is consumed for farming, during
chemical processing, transportation and distribution up to final usage.
10.2.1 GREEN HOUSE GASES

Land use changes triggered by increased biofuel production can directly or indirectly be related
with the greenhouse gases emission. For instance, when the carbon that is stored in forest or
grass lands is released during land conversion to crop production. For example, 1.8 tonnes of
carbon dioxide per hectare per year is generated while maze is being produced to produce
ethanol. And 8.6 tonnes per hector per year can be generated from the possible second-
generation crop which is switch grass. 300 tones per hectare can be produced from the
conversion of grasslands to produce those crops, and the forest land conversion can release
600-1000 tonnes per hectare. [46]
The life cycle analysis tool is used for the calculation of greenhouse gas balance. The
greenhouse gas balance is the result of the comparison between sum of production of
greenhouse gases during the whole process of production phase and use of a biofuel and all the
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greenhouse gases emissions during producing the equivalent amount of fuel and using the
respective amount of fossil fuel. This complex and well-established method systematically
analysis each component of the value chain to estimate greenhouse gas emissions.
Figure 10-1 LCA for green fuel [47]
Figure 10-2:greenhouse gas balances [6]
The starting point in estimating the greenhouse gas balance is a well-defined set of boundaries
for a specific biofuel system that can be compared with the suitable conventional reference
system which is petrol in most of the cases. Co-products are also generated by different biofuel
feedstocks such as press cake or livestock feed. These are considered “avoided” greenhouse
emissions and these are assessed by comparing them with similar standalone products or by
allocation (e.g. by energy content or market value). As green diesel production can be carried
out by diversified methods of conversion and feed stocks and for crops production inputs such
as nitrogen fertilizer and type of electricity generation (e.g. may be either from coal, oil or
nuclear source) these are also used for conversion of feed stock into biofuel and that may result
in widely varying levels of greenhouse gas emissions and that is also dependent on the area of
cultivation and process.
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Most life cycle analysis of biofuels, to date, have been undertaken for cereal and oilseeds in
the EU and USA and in Brazil conducted for sugar cane ethanol. Till now limited studies are
there on vegetable oil, biodiesel oil from palm oil, cassava and jatropha and biomethane from
biogas. Given the wide range of biofuels feed stocks and production and conversion
technologies so we should also expect similarly a wide range of emission outcomes in term of
emission reductions and that is our concern here. According to most of the studies it is evident
that by producing the first generation biofuel from current feed stocks results the emission
reduction up to 20-60% in comparison with the fossil fuels, provided the most efficient systems
are used and the carbon release from the land use is not included. Figure shows estimated range
of reduction in greenhouse gas emissions taking a series of crops and locations land usage
effect is not considered here. Greater reductions are noticed in the brazil as they are producing
ethanol from the sugar cane.
Though at commercial level second generation fuels are still insignificant while they cause
emission reductions up to 70-90% in comparison with the fossil, diesel and petrol fuel, also
excluding carbon release related to land use change. However, on several occasions LCA have
disregarded the effect of LUCC on overall GHG emissions. For example, if LUCC effects are
not considered, then jatropha biodiesel in Brazil can emit 55% less GHG than conventional
diesel [48]. However, if LUCC effects are considered, then biodiesel from jatropha emits 59%
more GHG than conventional diesel [48]. According to several studies it is found that the most
markable differences in the results stem from allocation methods chosen for co-products, land
use related carbon emission changes and nitrous oxide emissions. presently different methods
are being used to conduct the life cycle analysis and as prescribed some of these do not consider
the complex topic of land usage change. The measured parameters and the quality of the data
used in the assessment need to comply with the set standards’ the development of a harmonized
methodology for assessing greenhouse gas balances efforts are being made with others the
Global bioenergy Partnership. There is also a similar need for the harmonization in assessing
the brooder environmental and social impacts of bio energy crops to ensure that the results are
transparent and consistent across a wide range of systems. In order to complete the resulting
picture with accuracy the date on emissions emanating from land use change are crucial
particularly in assessing the greenhouse gas emissions balances.in the bio fuel production cycle
such emissions will occur early and if sufficiently large may require many year before they are
compensated by emission saving obtained in subsequent stages of production and use.
10.3 Effects of biofuel production

Large-scale feedstock production in extensive monocultures can be particularly hostile to
biodiversity. For example, oil palm plantations host fewer species than rubber plantations,
disturbed forests, and primary forests [49]. Extensive sugarcane and corn monocultures are
also known to support a relatively limited number of species [50]. On the other hand,
knowledge about species occurrence in emerging biofuel feedstocks such as jatropha is
basically nonexistent [51].Biofuel production not only effect our environment but it also affect
our agricultural system. Biofuel production directly affect our crops and land which is also
responsible for many problems such as shortage of food and serious health problem by using
excess chemical usage. We are trying to fulfill our feed stock requirements on the expense of
various bad impacts on agriculture such as water depletion, nutrients depletion, soil degradation
and pollution etc. It also effects the wild habitat as a large area of forest is already converted
into cultivable land due to which many species of animals are going to extinct. Extent of these
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impact depends upon many factors some of them are as type of feed stock, management system
of land, location, processing methods, available land, type of fertilizer or agrochemical and
scale of production.
10.4 Impacts on available water

Water is critical input for agricultural production as without water it is not possible to cultivate
the land. Available water also take part in the production of feedstock as scarcity of water does
not allow any country to produce crops which are used as feed stock in biofuel production.
About 70% fresh water is used in agricultural cultivation [52] due to which it is expected that
fresh water will runoff soon in some regions such as South Asia and North Africa. It may be
possible that Pakistan face shortage of fresh water in future, so Pakistan is already taking some
measurements to save their fresh water. Agricultural methods for production are also trying to
improve as one of the best examples is hydroponic techniques. Hydroponics uses relatively less
water than the classic ways of agriculture. Many crops like oil palm, maize and sugar cane
consumes relatively more water for commercial production and these crops are also used for
biofuel production so we must use such crops as a feed stock which consumes less water. Feed
stock used for the production of bio fuel account 1 % of water loss by crops as transpired water
and 2 % water loss by irrigation of water world widely [53].
Sr Crop Annual Energy Evapotranspirati Potential crop

obtainable yield on equivalent evapotranspiratio
fuel yield n
(liters/ha) (gal/ha) (liters/liter fuel) (mm/ha)
1 Sugar 6000 120 2000 1400
cane
2 Maize 3500 70 1357 550
3 Oil palm 5500 193 2364 1500
4 Rapeseed 1200 42 3333 500
Table 10-1:water requirement for biofuel crops [53]
10.5 Effect of pesticides on environment

Many feed stocks are the remaining of edible crops. For more profitable crop such crops are
grown on large scale and for better yield fertilizers and pesticides are extensively used. Such
pesticides protect the crops from pests, but it also effects the health of consumers. It also effects
the heath of birds and animals. One of the best examples of pesticide effects is discussed below.
During world war 2 DDT(Dichlorodiphenyltrichloroethane)was used as a pesticide as it was
cheap and effective. During war period it did not seem to be harmful but later it was discovered
that DDT is stored in animal tissues and transferred from one living body to other. It moves
through the food chain. DDT also effects the wild habitat as many of the bird were extinct due
to DDT as it affects their calcium metabolism which effect the thickness of the shell of their
eggs. DDT was banned when it was discovered that it transfers from mother to infant by milk.
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10.6 Practices for sustainable biofuel production

We must apply the available knowledge on harvesting and processing for sustainable feed stock
production. Natural resources management issues must be considered such as soil, water and
life cycle analyses. Life cycle analysis is used to determine the greenhouse gas emission. Life
cycle analysis also check biofuel is more climate friendly than fossil fuel. In general, we must
protect soil, water, nutrients, crops and energy. For sustainable production we must improve
water management, agrochemical management, harvesting and processing techniques.
Agriculture cultivation must be conservative to make crops profitable for farmers by the
expense of minimum soil disturbance.
Conservation agriculture must not affect the crop rotation, moisture and fertility of soil.
Agrochemical and fertilizer must be applied in optimal range as it will not affect the biological
processes.
10.7 Standards and sustainable criteria

Different environmental impacts of bioenergy development relatively same to the other forms
of agriculture but our purpose is finding a way in which they are best to assessed in the field
activities. We can collect the technical knowledge from the development in agriculture. Bio
energy impacts analysis can also be used for future developments as environmental impacts
includes soil acidification, biodiversity loss, toxicity due to pesticides and air pollution [54].
We also need to work on environmental and social sustainability criteria such as soil erosion,
nutrient leaching, deforestation, adverse impacts on biodiversity and competition with food
production. [55]
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List of Symbols
Symbol Definition Units

0
T Temperature C, K
Cp Heat Capacity kJ/kgmol.0C
hL Enthalpy of liquid product kJ/kgmol.0C
hV Enthalpy of entering vapors kJ/kgmol.0C
QC Condenser duty kJ/hr
hx Enthalpy of feed kJ/kgmol.0C
Q Heat duty kJ/hr
m mass kg
𝛥 𝐻𝑟𝑥𝑛 Heat of reaction kJ/kgmol
X Conversion
Cps Heat capacity of solution kJ/kgmol.0C
𝛥𝐶𝑝 Overall change in heat capacity kJ/kgmol.0C
P Pressure Pa, N/m2
q Feed condition
R Reflux ratio
α Relative volatility
N Number of trays
B Bottom product flow rate Kgmol/hr
D Distillate flow rate Kgmol/hr
Eo Efficiency
μ Viscosity cP
ρ Density kg/m3
A Area m
t Time Sec
W Weight kg
f Thickness factor mm
D Diameter m
OD Outer diameter m, in
ID Inner diameter m, in
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References
[1 2. N. D. C. 1. K. N. P. 1. a. M. A. G. 1. Savvas L. Douvartzides 1, “Green Diesel: Biomass

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Green Diesel Production From Vegetable Oil

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Green Diesel Production From Vegetable Oil

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FINAL YEAR PROJECT

GREEN DIESEL PRODUCTION FROM

Department of Chemical, Polymer and Composite Material Engineering and

UNIVERSITY OF ENGINEERING AND TECHNOLOGY

This thesis is written by

1) Sami Ullah Ansari

fulfillment of the requirements of the degree of Bachelor of Science in Chemical

To our beloved parents and

Our kind teachers”

2.3.3 Separator: ...................................................................................................................................................29

5.1 Distillation Column ......................................................................................................................................45

6.1.9 Consequences: .....................................................................................................................................75

7.7 DIFFERENT TYPES OF CONTROLLERS ..................................................................................................88

9.4 TOTAL PRODUCT COST .................................................................................................................... 104

1.1 GREEN DIESEL

1.1.1 Benefits of Green Diesel

1.1.2 Green Diesel Feedstocks

1.1.2.1 Jatropha Curcus

figure 1-1:Jatropha caracus shrub [4]

1.1.2.1.1 Composition of Jatropha

figure 1-2: Composition of jatropha oil [7]

1.1.2.2 Cotton Seed Oil

Figure 1-3:Cotton seed oil plant

1.1.2.2.1 Composition of cotton seed oil

Fatty Acid No. of Carbon Weight (%)

Myristic Acid 14 1.5

Stearic Acid 17 6.05

Linoleic Acid 18 2.12

Table 1-1:Composition of cotton seed oil [8]

1.1.2.3 Rapeseed Oil

Figure 1-4:Rape seed oil plant

Table 1-2: Composition of Rapeseed Oil [6]

The composition varies a bit with the area of growth.

1.1.2.4 Crude Tall Oil

Figure 1-5:Examples of resins and fatty acids prominent in CTO [10]

1.1.3 Specifications of Green diesel

It is shown by researches that reducing the density as small as 5% reduces PM emissions by

Cetane 40-55 50-65 75-90

Energy Density, MJ/Kg 43 38 44

Sulpur, ppm less than 10 less than 2 less than 2

Cold Flow Baseline Poor Excellent

Oxidative Stability Baseline Poor Excellent

Table 1-3:Specifications of ultra-low Sulphur Green diesel fuel [11]

1.2 Process Description

Figure 1-6:Simplified flow diagram [11]

1.3 Difference between Petroleum and Green diesel

1.4 Difference between biodiesel and green diesel

Triglyceride +Methanol FAME + Glycerol

Chapter 2 Process Description

2.1 Process description

2.2 Feed pretreatment

2.2.1 Acidic value

2.2.2 Phosphors content

2.2.3 Particles (contamination)

2.3 Equipment’s used in process

2.3.1.1 Furnace Detail.

figure 2-1:process inside furnace [19]

2.3.1.2.1 Bricks lining

figure 2-2:refractory alignment inside furnace [19]

2.3.1.2.2 Monolithic lining

figure 2-3:monolithic lining picture [19]

Ceramic fiber linings

figure 2-4:Ceramic fiber linings [19]

figure 2-5:burner alignment [19]

Qx = (R+1)NhN(V) - RNhN(L) + GhGL – XhXL (9)