Production of Ammonia by Biomass Gasification

PRODUCTION OF HYDROGEN GAS BY
GASIFICATION OF BIOMASS
Session: 2008-2012
PROJECT ADVISOR
SIR M.ASIF AKHTAR
PROJECT MEMBERS
Anam Asghar (group leader)
2008-Chem-06
Arooba Arooj
2008 -Chem-44
Syed Tahir Ali Rizvi
2008 -Chem-58
Sidra Qadeer
2008 -Chem-73
DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY OF ENGINEERING AND TECHNOLOGY
LAHORE-PAKISTAN
Production Of Hydrogen Gas By Gasification Of Biomass
This project is being submitted to the Chemical Engineering Department,

University Of Engineering And Technology Lahore-Pakistan as the requisite
of the
Bachelors Degree
in
CHEMICAL ENGINEERING
Internal Examiner:
Sign: _____________________
Name: _____________________
External Examiner:
Sign: _______________________
Name: ______________________
DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY OF ENGINEERING AND TECHNOLOGY
LAHORE-PAKISTAN
All praises to Almighty Allah,

whose uniqueness, oneness and
wholeness is changeable. All
respects are for His Holy Prophet
Muhammad (PBUH) who enabled
us to recognize our Creater.
DEDICATED TO
Our loving parents,
Their unreturnable patience and
guidance to bring us to bring us to
this position.
ACKNOWLEDGEMENT
We express gratitude and praise to ALMIGHTY ALLAH ,the creater of universe, who is
beneficient and merciful, guided us in difficult and congeal circumstances, who endowed us to
the will to undertake this design project. Great respect our Holy Prophet Hazrat Muhammad
(PBUH), who taught us to learn till lap of grave.
We are highly thankful to Sir Asif (respected lecturer) for giving us a chance to work on such an
interesting topic.
His complete support and guidance in solving each problem was highly encouraging for us to
make this work done. His continuous guidance, scientific aptitude and a will to teach us
thoroughly and conclusively made a sea change in our aptitude for project. His light heartedness
was the brightest shine in the dark and dreary environment.
In the end we salute our parents for all the troubles they had to face in supporting our
expenditures and for their patience throughout our entire educational career.
We are thankful to our friends for their support and help in every way.
MOTIVATION
Pakistan is facing energy crises for about half a decade now. The bad impact state affair is that
despite having enormous renewable energy, Pakistan has to import a huge amount of
hydrocarbons from abroad to meet its energy needs. Industrial manufacturing constitutes the
second largest sector in Pakistans economy.
Natural gas accounts for almost half of all energy consumed, while coal consumption accounts
for approximately 25% (see fig 1 given in annexure A).
The total share of the fertilizer industry to the natural gas consumption is only 19% of the total
consumption (see fig 2 in annexure A). Now the resources of natural gas are depleting and
within 20 years all the natural resources would deplete. Because of this deficit, urea sector is
facing serious load shedding of natural gas and the prices of the urea are increasing and load is
shifting to consumers, which is indirectly affecting urea economy badly.
Urea industry meets its hydrogen demand by reforming the natural gas. Coal can also be used to
meet the industrial demands and it is also abundant in Pakistan. But CO 2 emissions in the case of
coal is high and it is very expensive because the downstream processing. Besides coal, the
renewable energy as biomass has solutions to our problems. Biomass, material from different
resources can be used to produce hydrogen from biomass gasification and it has advantage on
other processes as it is environment friendly.
Production Of Hydrogen Gas From Gasification Of Biomass
INTRODUCTION
1.1 BIOMASS
Biomass refers to any organic materials that are derived from plants or animals (LoppinetSerani et al., 2008).
A generally accepted definition is difficult to find. However, the one used by the United Nations
Framework Convention on Climate Change (UNFCCC, 2005) is relevant here:
Biomass is a Non-fossilized and biodegradable organic material originating from plants,
animals and micro-organisms. This shall also include products, by-products, residues and
waste from agriculture, forestry and related industries as well as the non-fossilized and
biodegradable organic fractions of industrial and municipal wastes.
Biomass is formed from living species like plants and animals that is why anything that is now
alive or was a short time ago. As a sustainable and renewable energy resource, biomass is
constantly being formed by the interaction of CO2, air, water, soil, and sunlight with plants and
animals. After an organism dies, microorganisms break down biomass into elementary
constituent parts like H2O, CO2, and its potential energy. Biomass covers a wide spectrum from
tiny grass to massive trees, from small insects to large animal wastes, and the products derived
from these. Fossil fuels do not reproduce whereas biomass does, and, for that reason, is
considered a renewable. This is one of the basic attractions as a source of energy.
1.2 PRODUCTS OF BIOMASS

Three types of primary fuel are produced from biomass:
Liquid (ethanol, bio-diesel, methanol, vegetable oil, and pyrolysis oil)

Gaseous (biogas (CH4, CO2), producer gas (CO, H2, CO2, CH4), syngas (CO, H2),
substitute natural gas (CH4)
Solid (charcoal)
From these come four major categories of product:
Chemical such as methanol, fertilizer and synthetic fiber

Energy such as heat
Electricity
Transportation fuel such as gasoline
1
The use of ethanol and bio-diesel as transport fuels reduces the emission of CO2 per unit of
energy production. It also lessens dependence on fossil fuel. Thus, biomass based energy not
only is renewable but is also clean from a greenhouse gas (GHG) emission standpoint, so it can
take the centre stage on the global energy scene.
Fig: 1.1. Uses of biomass
1.3 COMMON SOURCES OF BIOMASS

Common sources of biomass are:
Agriculture
Forest
Municipal
Biological (animal waste and biological waste)
1.4 MOTIVATION FOR BIOMASS CONVERSION

Gasification is almost ancient as combustion, but it is less developed because commercial
interest in it has not been as strong as combustion. However, there has been a recent surge of
interest in conversion of biomass into gas or liquid due to three motivation factors:
Renewability benefits
Environmental benefits
Sociopolitical benefits
1.5 BIOMASS GASIFICATION

1.5.1 OVERVIEW
Biomass largely contains cellulose, hemi-cellulose, and lignin having an average composition of
C6H10O5, with slight variations. For the complete combustion of biomass the theoretical amount
of air required (defined as the stoichiometric quantity) is 6 to 6.5 kg of air per kg of biomass. The
end products are CO2 and H2O.
In gasification, biomass is subjected to partial pyrolysis under sub-stoichiometric conditions with
the air quantity being limited to 1.5 to 1.8 kg of air per kg of biomass. The resultant mixture of
gases produced during gasification process is called biogas, which contains CO and H2 and is
combustible.
The raw biogas also contains tar and particulate matter, which have to be removed depending on
the application. The process is best thought of as a thermo-chemical conversion of solid biomass
into gaseous fuel.
The biogas produced has a low calorific value (1000 to 1200 kcal/Nm3); however, this product
can be combusted at a relatively high efficiency and with good degree of control without
emitting smoke. Typical conversion efficiencies of the gasification process are 60 to 70%.
1.5.2 TECHNOLOGY ADVANTAGES

By converting solid biomass into combustible gas the following advantages are captured:
The process may be considered a clean technology because of the reduction achieved in
CO2 emissions; the equipment has a relatively small footprint and is compact; there is a
high thermal efficiency and a good degree of combustion control; and in areas where
biomass sources are readily already available at low prices, gasifier systems offer
economic advantages over other energy generating technologies.
Biomass resources are a major component of strategies to mitigate global climate change.
Plant growth recycles CO2 from the atmosphere, and the use of biomass resources for
energy and chemicals results in low net emissions of carbon dioxide. Since the emissions
of NOx and SOx from biomass facilities are also typically low, it is a technology that
helps to reduce acid rain.
When applied in regions that favor agricultural and forestry products, the technology
helps to develop new markets and serves as a mechanism for rural economic
development.
When compared with combustion systems, the fuel gas produced by gasifiers is lower in
both volume and temperature than the fully combusted product from a combustor. These
characteristics provide an opportunity to clean and condition the fuel gas prior to use.
1.6 AVAILABILITY OF BIOMASS IN PAKISTAN

Approximately 50,000 tones of solid waste, 225000 tones of crop residue and over 1 million
tones of animal manure are produced daily. It is estimated that the potential production of biogas
from livestock residue is 8.8 to 17.2 billion cubic meters of gas per year. Still we can use the
biomass easily for the hydrogen production.
1.7 USE OF BIOMASS IN PAKISTAN

In Pakistan biomass is available in abundant form. But people are not aware of the actual
importance of biomass. The following table 1.1 shows that how biomass is utilized in Pakistan.
TABLE 1
WOOD
DUNG
ADR.RESIDUE
TOTAL
(Mtoes)
(Mtoes)
(Mtoes)
(Mtoes)
Cooking
46
12
64
Space heating
Water heating
Others
Total urban
59
13
URBAN
2
6
78
RURAL
Cooking
342
90
69
499
Space heating
32
32
Water heating
37
37
Others
Total rural
411
96
69
575
Total
470
108
75
653
(Reference: PAK-IEM, Final Report Volume 1; December 2010)
1.8 BIOMASS FOR HYDROGEN PRODUCTION

The biomass that can be used to produce hydrogen by gasification according to the analysis of
Oak Ridge National Laboratory, Department of energy U.S
Forest residue
Mill residue
Urban wood wastes
Agriculture residue
The biomass that cannot be used to produce hydrogen by gasification is
Oil and oil seeds

Pulp processing wastes
Animal wastes
Landfill gasses
Forest Residue
Forest residue include
logging residue
rough, rotten and salvageable trees
Mill Residue
Mill residue include
Barks
Coarse residue
Fine residue
Urban wood wastes

Urban wood wastes contains
Municipal solid waste landfill

Construction and demolition landfill
Yard trimming
Agricultural residue
Agriculture residue includes
Wheat straw
Corn Stover
Rice husk
Bagasse
REFERENCES
http://www.cepe.ethz.ch/education/termpapers/Yazdanie.pdf
http://www.pakistantoday.com.pk/2011/11/urea-shortage-to-affect-food-security/
Prabir Basu, Biomass Gasification and Pyrolysis Practical Design Elsevier Acedemic
Press, Amsterdam Boston London Oxford Paris San Diego San Fransisco Singapore
Sydney Tokyo, 2005.
Report: International Resource Book, PAK-IEM, Final Report, Volume 1; December

2010.
PROCESS AND CAPACITY SELECTION
2.1 HYDROGEN DEMAND IN THE WORLD

While it is not always the case that worldwide demand for the hydrogen is completely met,
hydrogen is a commodity industrial gas and is readily available in most places across the globe.
Petroleum refinery is the single largest demand items. Demand for the hydrogen in areas like fuel
cells is mere a fraction of the total worlds demand. The following graph is showing the basic
trend for the hydrogen demand worldwide (fig 2.1)
Fig: 2.1. Historical and Predicted hydrogen demand (Source: Business Communication
Companies, Inc.)
2.2 USES OF HYDROGEN

The uses of the hydrogen are as follows:
Ammonia production
Oil refinery
8
Fossil fuels
Oils and fats
Fuels for cars
Synthetic natural gas
Electricity
Fig: 2.2. Uses of hydrogen
2.3 METHODS FOR THE HYDROGEN PRODUCTION
2.3.1
Natural gas Steam reforming

Partial oxidation of natural gas
Coal gasification
Biomass gasification
STEAM REFORMING
Steam methane reforming or SMR, is the single most dominant hydrogen production
methodology used today. Methane also known as natural gas has one carbon and four hydrogen
atoms. Given high ratio of hydrogen to carbon, this feedstock is desirable in that it has the lowest
carbon emission profile of any fossil fuel.
SMR involves the catalytic conversion of methane with the water vapor. Steam reforming is a
two stage approach that has the following general chemical conversion.
CnHm + nH2O = nCO + (m/2+n) H2
G= 82.6 kJ
G= -20.1 kJ
CO + H2O = CO2 + H2
First a light CH4 (light hydrocarbon) is endothermically combined with steam to produce CO and
H2. The CO is itself exothermically combine with the steam to CO2 and additional hydrogen.
Neither of these reactions is spontaneous.
2.3.2 GASIFICATION OF HIGHER HYDROCARBONS

In this process, heavy hydrocarbons such as residual oil are partially oxidized with oxygen and
steam. This process is much like SMR, except that the feed stocks are heavier. Like SMR this
process is highly efficient and commercially proven.
2.3.3 COAL GASIFICATION

Like heavy hydrocarbon gasification, coal can also be used to produce hydrogen. An initial step
must be taken to convert the coal into suspension. In this step the coal is ground into powder and
then mixed with the water to create 50-70% solid content suspension. Once this step is complete,
the process is highly similar to heavy hydrocarbon gasification.
2.3.4 BIOMASS GASIFICATION

This is an advance method and is expected to hit the market within the next few years. Biomass
is subjected to high pressure steam and a subsequent reaction with air or pure oxygen or may be
steam.
Biomass + H2O + Air = 20% H2 + 20% CO + 10% CO 2 + 5% CH4 + 45% N2
Finally the process emits CO, CO2 and N2, the emissions are low. This is because these
emissions do not represent new carbon and nitrogen molecules. Furthermore CO can actually be
further shifted into CO2 and more hydrogen can be produced through water gas shift reaction.
10
2.4
PROCESS SELECTION
2.4.1 NATURAL GAS CONSUMPTION

Now days, Pakistan is facing an extreme shortage of the natural gas. Natural gas is being used
for many purposes as shown in pie charts (fig 2.2 & 2.3) and a few years back it was considered
the most suitable energy resource .
Fig: 2.2. Natural gas consumption by sector

(Reference: http://www.c2es.org/technology/factsheet/natural-gas)
Fig 2.2 shows that in Pakistan, industrial sector consumption of natural gas is only 28%. In the
industrial sector, natural gas consumption increased in 2010 and 2011, reversing a trend of
declining consumption that lasted from the mid-1990s to 2009. Natural gas is used in the
industrial sector and manufacturing subsector for process heating, steam generation, onsite
electricity generation, space heating, and petrochemical processing
11
Fig: 2.3. Industrial natural gas consumption

(Reference: http://www.c2es.org/technology/factsheet/natural-gas )
2.4.2 NATURAL GAS RESERVES IN PAKISTAN

TABLE: 2.1
190.2
YEARS
REMAINING
(MAXIMUM
RATE)
23.1
YEARS
REMAINING
(CURRENT
RATE)
23.1
55.7
27.7
12.5
20.5
12.5
25.6
415.9
13.9
20.8
689.5
15.6
20.4
COMMODITY
TYPE/REGION
RESERVES
(MTOES)
NATURAL GAS
BALO
NATURAL GAS KPK
NATURAL GAS
PUNJ
NATURAL GAS
SINDH
NATURAL GAS
TOTAL
(Reference: PAK-IEM, final report volume 1; December 2010)
At present, because of the natural gas deficit, Pakistans urea demand stands at approximately
6.2 million tons, whereas local production is approximately 5.2 million tons. To cover this
shortfall, the GOP annually imports an average of 500 million dollars worth of urea, in addition
to bearing the subsidy for imported urea.(Reference: Article, Worlds largest urea plant
begins operation by Azhar Shah, Magazine: Pk economist protocol).
12
2.4.3 COMPARISON
TABLE: 2.2
COMPARISON OF METHODS:
Processes
STEAM
REFORMING OF
NATURAL GAS
HEAVY OIL
GASIFICATION
OF COAL
GASIFICATION
OF BIOMASS
Feed
stock
Sulfur
content
42 % of
the total
cost
0.5% in
the feed
28% of
the total
cost
16% of
the total
cost
19% of
the total
cost
Varies
0.921.34% in
the feed
0.070.09% in
the feed
Production
cost
$5.06$11.13 per
gigajoule
per year
Fixed
capital cost
$14.2 per
gigajoule
per year
CO2
emissions
Conversion
efficiency
Extremely
large
78.5 %
based on
HHV
$7.07$14.02 per
gigajoule
per year
$12.03 per
gigajoule
per year
Extremely
large
-----
$10$16.82 per
gigajoule
per year
$10$16.82 per
gigajoule
per year
Double of
SMR
48 % based
on HHV
$8.77$17.29 per
gigajoule
per year
$38 per
gigajoule
per year
Less
emissions
57.8%
based on
HHV
(Reference: The Economics for biological Methods of Hydrogen Production, by Richard J.

Resnick; June 2004)
CONCLUSION
As Pakistan is facing natural gas shortage so steam reforming of the natural gas is not possible.
The prices of the heavy oils make it expensive to produce hydrogen gas. Coal and biomass are
easily available in Pakistan but the recovery of the CO2 from the flue gases is expensive process.
(use of coal has severe environmental constraints which adds cost to tits down stream
purification process As in the case of biomass the CO2 emissions are less so it is the optimum
method for the hydrogen production in the present scenario.
13
2.5 CAPACITY SELECTION

Because of the power crises Pakistans fertilizer industries are facing the shortage of natural gas
for their production. Day by day the requirement of the urea is increasing because of the
increased population. The graph shown in fig 2.4 indicates an increasing trend of urea
consumption.
Fig: 2.4. Trends for the urea production and consumption (Reference: PAK-IEM, Final Report
Volume 1 ; December 2010)
The following table (Table 2.3) shows the amount of hydrogen required to overcome this urea
deficit.
TABLE: 2.3
AMOUNT REQUIRED
1.6 million tons/ annum
12.48 tons/ annum
UREA DEFICIT
H2 REQUIRED
14
2.5.1 CAPACITY
By using the above calculated demand and the production capacity of the various industries we
have tried to set a capacity for our process. The details about the production capacity of urea
industries of Pakistan are given in the table 2.4
TABLE: 2.4
Industries
Fauji Fertilizer Company
Plant -1(FFC -1)
Plant-2 (FFBL, Fauji
Fertilizer Bin Qasim)
Plant-3 (Mirpur
Mathelo District
Ghotki Sindh)
Capacity (MT/DAY)
H2 required(MT/day)
2122
1913
215
197
1739
176
Engro Urea
2608
265
Pak Arab Fertilizer

(Multan)
1670
169
Fatima Fertilizer
1339
136
Dawood Hercules
1417
144
According to the availability of biomass in Pakistan, the selected capacity of the plant is 197
MT/day production of hydrogen.
15
REFERENCE
John Rezaiyan Nicholas P.Cheremisinoff, Gasification technology, CRC Press Taylor

and Francis Group, 2005.
http://www.efpe.org/theses/Joaquin_Reina.pdf
Richard J. Resnick The Economics for biological Methods of Hydrogen Production
June 2004
Klass, Donald L., Biomass for Renewable Energy, Fuels and Chemicals, Academia Press,
1998.
U.S. Department of Energy, http//www.netl.doe.gov/coalpower/gasification/models.
16
PROCESS DESCRIPTION
3.1 PROCESS DESCRIPTION

The process is divided into following sections:
Gasification and tar reforming

Gas clean up and compression
Reforming, shift and PSA
3.2 GASIFICATION SECTION

A gasification section consists of gasifier, chars combustor and associated cyclones. Pretreated
dried wood enters the gasifier which operates at 870 OC and 159 kPa and tar reforming section.
It enters in the gasifier and following reaction takes place:
2C3.2H5O3 + 5.9O2 = 6.4CO2 + 5H2O
H = +1708081KJ/Kgmol
2C3.2H5O3 + 0.4H2O = 6.4CO + 5.4H2
2C3.2H5O3 + CO2 = 7.4CO + 0.6H2O + 4.4H2
2C3.2H5O3 + 13.8H2 = 6.4CH4 + 6H2O
CO + 3H2 = CH4 + H2O
H = -118090 KJ/Kgmol
CO + H2O = H2 + CO2
H = -41123.7 KJ/Kgmol
The gasification process in actual is endothermic. Heat for the endothermic gasification reactions
is supplied by circulating a hot medium between the gasifier vessel and the char combustor. In
this case the medium is synthetic olvine, a calcined magnesium silicate (primarily Enstatite
MgSiO3) Forsterite (Mg2SiO3) and Hamatite (Fe2O3) used as sand for various applications.
A small amount of MgO must be added to the fresh olvine to avoid the formation of glass like
bed agglomerations that would result from the biomass potassium interacting with the silicate
compounds. The MgO titrates the potassium in the feed ash. Without MgO addition the
potassium will form glass, K2SiO4, with the silica in the system. K2SiO4 has a low melting point
and its formation will cause the bed media to become sticky, agglomerate and eventually defluidize. Adding MgO makes the potassium from a high melting ternary eutectic with the silica
17
and thus sequestering it. Potassium carry over in the gasification combustor cyclones is also
significantly reduced. The ash content of the feed is assumed to contain 0.2 % wt potassium. The
MgO flow rate is set at two times the molar flow rate of potassium.
3.2.1 GASIFICATION MEDIUM

The gasification medium is the steam which is supplied at 104 OC and 159 kPa. The steam to
wood ratio is 0.4 lb of steam / lb of the bone dry wood. Steam is used because it aids in the
increased formation of the H2 in the product gas as compared to the other gasification medium.
The char combustor temperature is set at 920OC and the gasifier temperature obtained from the
energy balance around the combustor and gasifier. The resulting gasifier temperature is 870 C.
the gasifier pressure is 150 kPa. The olvine circulating flow rate is 27 lb of olvine/ lb of the bone
dry wood. Fresh olvine is made up at rate of 0.11 % of the circulating rate to account for the
losses from the cyclones. The combustion air is varied from 5% - 20 % excess air until the heat
duty of the char combustor is zero.
Particulate removal is performed through cyclone separators. The majority of the olvine and char
is separated in the gasifier cyclone and sent to the char combustor.
The char that is formed in the gasifier is burnt in the combustor to reheat the olvine and
following reactions takes place in the combustor.
C + O2 = CO2
H = -393795KJ/Kgmol
2H + O2 = H2O
H = -242018KJ/Kgmol
N2 + 2O2 = 2NO2
H = -33200 KJ/Kgmol
S + O2 = SO2
H = -1242483KJ/Kgmol
The combustor cyclone separated the olvine from the combustion gases and olvine is sent back
to the gasifier.
3.3 TAR REFORMER

The gas from the gasifier cyclone is sent to the tar reformer. In this bubbling bed fluidized bed
reactor CH4, C2H6, C2H4, C6H6 and C10; while the NH3 is converted to N2 and H2. In tar
reformer, the following reactions take place:
18
CH4 + H2O = CO + 3H2
H = 205951.9 KJ/Kgmol
C2H6 + 2H2O = 2CO + 5H2
H = 346940.8 KJ/Kgmol
C2H4 + 2H2O = 2CO + 4H2
H = 210123.6 KJ/Kgmol
C10H8 + 10H2O = 10CO +14H2
H = 1767099 KJ/Kgmol
C6H6 + 6H2O = 6CO + 9H2
H = 1628707 KJ/Kgmol
C2H2 + 2H2O = 2CO + 2H2
H = 35824.27 KJ/Kgmol
H = 46147.2 KJ/Kgmol
2NH3 = N2 + 2H2
H = -41123.7 KJ/Kgmol
CO + H2O = CO2 + H2
3.4 GAS CLEAN UP AND COMPRESSION

3.4.1 QUENCH CHAMBER
After the direct cooling of the syngas to 150 OC, additional cooling is carried out via water
scrubbing. The scrubber also removes impurities such as particulates, ammonia, and any residual
tars. The scrubbing system consists of quench chamber and here water is used for the
recirculation. The syngas is then sent to the compression section as it is cooled down to 60 OC.
Here it is compressed using five section centrifugal compressor with inter-stage cooling.
3.4.2 SULFUR REMOVAL

Sulfur solids are the main poison of reforming catalysts. Low temperature shift catalysts are also
very sensitive to sulfur. Because the syngas exiting the gasifier contains about 400 ppmv of H 2S,
a ZnO by itself cannot be used for the sulfur removal. The normal sulfur concentration at the
inlet of the ZnO bed is typically 10-20 ppmv of H2S. The ZnO bed will reduce the sulfur to less
than 1 ppmv H2S. A very low concentration of less than 1 ppmv H2S is required for the steam
reforming and the LTS catalyst. Even at a concentration of 0.1 ppm the catalyst can start to
deactivate. Therefore, sulfur removal via liquid phase oxidation process followed by ZnO bed is
chosen. The LOCAT process will remove the bulk of the sulfur at 49 OC but it cannot reliably
reduce the sulfur but it can reduce the sulfur concentration to extremely low levels required by
the downstream conversion steps. Therefore, two ZnO beds in series follow the LOCAT process
because the H2S requirement is so low and ZnO bed is simple, relatively inexpensive piece of
equipment.
19
Additionally the ZnO bed contains a layer of hydrogenation catalyst to convert organic sulfur to
H2S. Elemental sulfur is produced and since there is such a small amount, it is stock piled for
eventual disposal rather than conditioned and sold. The LOCAT process removes the sulfur to
concentration of 10 ppm H2S and ZnO bed removes the remaining sulfur to concentration of less
than 1 ppm. The air flow rate for re-oxidizing of the LO-CAT solution is 2 mole O2 per mole
H2S. Before entering the LOCAT absorber the gas stream is superheated as the ZnO bed operates
at high temperature so that the reaction closely approaches equilibrium. The following reaction
takes place in the ZnO bed:
ZnO + H2S = ZnS + H2O
During operation over length of time, the reaction zone will gradually move down through the
ZnO bed until the bed material finally needs to be changed out.
3.5 REFORMING, SHIFT AND PSA

3.5.1 REFORMING
There is significant amount of CO, CH4 and other hydrocarbons in the biomass derived syngas
thus these compounds need to undergo conversion via reforming shift conversion reactions at
850 OC and 2790 kPa.
Reforming and water gas shift are the main reactions in the steam reformer.
CH4 + H2O = CO + 3H2
H = 205951.9 KJ/Kgmol
C2H6 + 2H2O = 2CO + 5H2
H = 346940.8 KJ/Kgmol
C2H4 + 2H2O = 2CO + 4H2
H = 210123.6 KJ/Kgmol
C2H2 + 2H2O = 2CO + 2H2
H = 35824.27 KJ/Kgmol
2NH3 = N2 + 2H2
H = 46147.2 KJ/Kgmol
CO + H2O = CO2 + H2
H = -41123.7 KJ/Kgmol
3.5.2 SHIFT REACTORS (LTS & HTS)

The reforming reactions are endothermic and favored at high temperatures and low pressures.
The steam reformer is comprised of catalyst filled tubes, surrounded by the fire box that provides
sufficient heat for the endothermic reaction. The main components of the reformer tube include
air/fuel combustion system, a radiant heat transfer section and convection section. The radiant
20
section provides the heat for the catalyst tubes. The reformer is fueled by the PSA off gas and a
small amount of the natural gas is also added for burner control.
Following the steam reformer, the gas exiting the reformer is first cooled and entered in LTS and
HTS. The LTS and HTS reactors convert the majority of the remaining CO when reacted with
H2O, into CO2 and H2 through water gas shift reaction.
H = -41123.7 KJ/Kgmol
CO + H2O = CO2 + H2
The gas exiting the HTS is first cooled prior to entering the LTS reactor. The HTS catalyst has
been the iron oxide, chromium oxide basis while the majority component in LTS is copper oxide,
most often in the mixture of zinc oxide.
3.5.3 PRESSURE SWING ADSORBER

For purification, a PSA unit is used to separate the hydrogen from the other components in the
shifted gas stream, mainly CO2 and un-reacted CO, CH4 and other hydrocarbons. The hydrogen
purity achieved from PSA unit can be greater than 99.99%. The shifted stream must contain 70
mole% hydrogen before it can be economically purified in PSA unit. The hydrogen obtained
from the PSA is final product and off gases from the PSA are sent to the reformer for burning
purposes.
REFERENCE
Report: Biomass to Hydrogen Production Detailed Design and Economics Utilizing the Battelle
Columbus Laboratory Indirectly Heated Gasifier, National Renewable Energy Laboratory.
21
MATERIAL BALANCE
Basis of Calculation= 2000 ton of biomass on dry basis/day=83333.33 biomass/hr
4.1 OVERALL MATERIAL BALANCE
4.2 MATERIAL BALANCE ACROSS GASIFIER
4.2.1
GASIFIER REACTIONS
2C3.2H5O3+5.9O26.4C 2+5H 2O
2C3.2H5O3+0.4H2O6.4CO+5.4H 2
2C3.2H5O3+CO27.4CO+0.6H 2O+4.4H 2
2C3.2H5O3+13.8H2 6.4CH4+6H2O
CO+3H2 CH4+H2O
23
4.2.2
CO+H2OH2+CO2
ELEMENTAL BALANCE
Source: Craig and Mann (1996)[1]
C in biomass
42437.98
H in biomass
5037.842
O in biomass
34272.34
N in biomass
141.7936
S in biomass
75.06717
Ash in biomass
767.3533
Total
83333.33
Source: Battelle Columbus Laboratory [1]
24
GASIFIER VARIABLES
VALUE
Temperature
870C
Pressure
151kPa
Steam/bone dry feed
0.4kg/kg
Gas yield
0.035kgmol/kg
Char yield
0.22kg/kg
H2:CO molar ratio
0.565
Source: Battelle Columbus Laboratory [1]
Carbon Balance
Carbon in char = carbon in biomass carbon in gaseous material
= 42438 - 29298
= 13140Kg/hr
Sulphur Balance
Sulphur in char = Sulphur in biomass Sulphur in gaseous material
= 75-69 = 6.27Kg/hr
Hydrogen Balance
Hydrogen in char = Hydrogen in biomass Hydrogen in gaseous material + Hydrogen in steam
+ Hydrogen in moisture
= 5038- 8851+ 3688+ 1264= 1139Kg/hr
Nitrogen Balance
Nitrogen in char = Nitrogen in biomass Nitrogen in gaseous material
= 142 132 = 9 Kg/hr
25
Ash Balance
Ash in char = Ash in biomass + Ash in recycle
= 767+40=807Kg/hr
Oxygene Balance
Oxygen in char = mass of char C,H,N ,O,S and Ash in char
= 18380 - 15102 = 3278Kg/hr
Free Oxygen = Oxygen in biomass Oxygen in gaseous material + Oxygene in steam +
Oxygene in moisture Oxygene in char
= 770.5Kg/hr
Components in Char
Carbon
Composition
71.49
Sulphur
0.03
Nitrogen
0.04
Hydrogen
6.19
Oxygen
17.83
Ash
4.39
4.2.3 Calculation of empirical formula of biomass after pyrolysis

Carbon in biomass after pyrolysis =Total Carbon in biomass- C in C2H6 - C in C2H2 C in
C2H4 - C in C2H6 - C in tar- Carbon in char
Hydrogen in biomass after pyrolysis=Total Hydrogen in biomass- H in C2H6 - H in C2H2 H in
C2H4 - H in C2H6 - H in tar -Hydrogen in char
Oxygen in biomass after pyrolysis=Total Oxygen in biomass- Oxygen in char
Carbon in biomass after pyrolysis = 24667kg/hr=2056Kgmol/hr = 2056/1937*3 = 3.2
Hydrogen in biomass after pyrolysis= 3206 kg/hr=3206 Kgmol/hr =3206/1937*3 = 5
Oxygen in biomass after pyrolysis =30994 kg/hr=1937 Kgmol/hr =1937/1937*3 = 3
26
C:H:O=3.2:5:3
So empirical formula of biomass
C3.2H5O3
COMPONENT
STREAM
STREAM2
STREAM7
STREAM
Kg/hr
1
Kg/hr
Kg/hr
Kg/hr
3
H2
1403
CO2
16427
CO
34471
H2O
11374
33093
44530
CH4
7189
C2H2
310
C2H4
3560
C2H6
256
C6H6
290
C10H8
870
NH3
161
H2S
73
Olvine
2243874
2243875
Ash
40
Char
18363
Biomass
83408
Total
94782
33093
2243914
2371777
27
4.3 MATERIAL BALANCE ACROSS GASIFIER CYCLONE
Separation efficiency= 99.9% [2]

COMPONENT
STREAM 3
STREAM 5
STREAM 4
Kg/hr
3
Kg/hr
5
Kg/hr
4
H2
1403
1403
CO2
16427
16427
CO
34471
34471
H2O
44530
44530
CH4
7189
7189
C2H2
310
310
C2H4
3560
3560
C2H6
256
256
C6H6
290
290
C10H8
870
870
NH3
161
161
H2S
73
73
Olvine
2243875
224
2243651
Char
18363
18361
Total
2371778
109766
2262012
28
4.4 MATERIAL BALANCE ACROSS CHAR COMBUSTOR
4.4.1
CHAR COMBUSTOR REACTIONS
C+O2=CO2
2H+O2=H2O
N2 +2O2=2NO2
S+O2=SO2
COMPONENTS
STREAM 4 STREAM 8 STREAM 9

Kg/hr
STREAM 6
Kg/hr
Kg/hr
Kg/hr
CO2
90
48222
H2O
5740
10858
N2
149242
149242
O2
45758
4903
Ar
2539
2539
SO2
12
NO2
30
MgO
Ash
807
Olvine
2243651
2470
2246122
Char
18361
Total
2262012
2470
203369
2467735
29
4.5 MATERIAL BALANCE ACROSS CHAR COMBUSTOR CYCLONE
Separation efficiency=99.99% [2]

COMPONENTS
STREAM 6
STREAM 7
STREAM 10
Kg/hr
Kg/hr
Kg/hr
CO2
48222
48222
H2O
10858
10858
N2
149242
149242
O2
4903
4904
Ar
2539
2539
SO2
12
12
NO2
30
30
MgO
Ash
807
40
766
Olvine
2246122
2243874
2248
Char
total
2462735
2243914
218821
30
4.6 MATERIAL BALANCE ACROSS TAR REFORMER
4.6.1 TAR REFORMER REACTIONS
CH4+H2O = CO+3H2
C2H6+2H2O =2CO+5H2
C2H4+2H2O =2CO+4H2
C10H8+10H2O =10CO+14H2
C6H6+6H2O = 6CO+9H2
C2H2+2H2O =2CO+2H2
2NH3 = N2+2H2
CO+H20 =CO2+H2
Tar reformer
variables
CH4 Conversion
Value
C2H6 conversion
90%
C2H4 Conversion
50%
Tar conversion
95%
C6H6 Conversion
70%
C2H2 conversion
50%
NH3 Conversion
70%
H2:CO molar ratio
2.08
20%
NRELs Thermochemical Pilot Process Development Unit (TCPDU) [1]
31
COMPONENT
STREAM 5
STREAM 10
STREAM 11
STREAM 12
Kg/hr
Kg/hr
Kg/hr
Kg/hr
H2
1403
3951
CO2
16427
41780
CO
34471
27471
H2O
44530
28318
CH4
7189
5751
C2H2
310
155
C2H4
3560
1780
C2H6
256
25
C6H6
290
87
C10H8
870
43
NH3
161
48
H2S
73
73
Olvine
224
27
27
Char
224
N2
92
Total
109766
27
27
109765
32
4.7 MATERIAL BALANCE ACROSS SYNGAS QUENCH CHAMBER
COMPONENTS
Solubility at 43C
kg of gas/ kg of water
H2
CO2
0.0009
CO
0.00002
CH4
0.000015
C2H2
0.0000868
C2H4
C2H6
C6H6
C10H8
NH3
0.3
H2S
N2
Olvine
Char
Annexure B [3]
33
COMPONENTS
Stream 15
Stream 19
Stream 20
Stream 21
Kg/hr
kg/hr
Kg/hr
Kg/hr
H2
3951
3951
CO2
41780
41756
24
CO
27471
27468
H2O
28318
887899
18767
897449
CH4
5751
5745
6.356
C2H2
155
154
0.454
C2H4
1780
1775
4.54
C2H6
25
26
C6H6
87
73
14
C10H8
43.5
41
NH3
48.3
38
10
H2S
73
73
N2
93
93
Olvine
224
224
Char
Total
109802
887899
99921
897780
34
4.8 COMPRESSION SECTION
4.8.1 MATERIAL BALANCE ACROSS PRE COMPRESSOR KNOCK-OUT DRUM
35
COMPONENTS
STREAM
20
STREAM
23
STREAM
24
Kg/hr
kg/hr
Kg/hr
H2
3951
3951
H2O
18767
14468
4299
CO
27468
27468
N2
93
93
CO2
41756
41756
H2S
73
73
NH3
38
38
CH4
5744
5744
C2H6
26
26
C2H4
1775
1775
C2H2
155
155
C6H6
73
73
C10H8
TOTAL
99920
95546
4374
36
4.8.2 MATERIAL BALANCE ACROSS COMPRESSOR
COMPONENTS
STREAM 23
STREAM 25
Kg/hr
Kg/hr
H2
3951
3951
H2O
14468
14468
CO
27468
27468
N2
93
93
CO2
41756
41756
H2S
73
73
NH3
38
38
CH4
5744
5744
C2H6
26
26
C2H4
1775
1775
C2H2
155
155
TOTAL
95546
95546
37
4.8.3 MATERIAL BALANCE ACROSS POST-COMPRESSOR KNOCK-OUT

DRUM
COMPONENTS
STREAM 26
STREAM 27
STREAM 28
Kg/hr
Kg/hr
Kg/hr
H2
3951
3951
H2O
14468
278
14190
CO
27468
27468
N2
93
93
CO2
41756
41684
72
H2S
73
73
NH3
38
12
25
CH4
5744
5744
C2H6
26
26
C2H4
1775
1775
C2H2
155
155
TOTAL
95546
81259
14287
38
4.9 MATERIAL BALANCE ACROSS LO-CAT ABSORBER
COMPONENTS
STREAM
29
Kg/hr
STREAM
30
Kg/hr
STREAM
37
Kg/hr
STREAM
33
Kg/hr
AIROUT
Kg/hr
STREAM
31
Kg/hr
H2
3951
3951
CO2
41684
41684
CO
27468
27468
O2
41
Fe+3L
1779
1743
Fe+2L
Ar
N2
93
93
137
135
H2S
73
H2O
278
278
59228
59228
CH4
5744
5744
C2H2
26
26
C2H4
1775
1775
C2H6
155
155
NH3
12
12
Total
81259
81187
61005
181
145
60971
39
4.10 MATERIAL BALANCE ACROSS ZnO SULFUR REMOVAL BEDS
ZnO bed required= 3.26 kg/hr & ZnS formation= 3.26 kg/hr
COMPONENTS
STREAM 41
STREAM 42
Kg/hr
Kg/hr
H2
3951
3951
H2O
278
278
CO
27468
27468
N2
93
93
CO2
41684
41684
H2S
NH3
12
12
CH4
5744
5744
C2H6
26
26
C2H4
1775
1775
C2H2
155
155
Total
81187
81186
40
4.11 MATERIAL BALANCE ACROSS REFORMER
4.11.1 REACTIONS OF REFORMER
CH4+H2O = CO+3H2
C2H6+2H2O = 2CO+5H2
C2H4+2H2O = 2CO+4H2
C2H2+2H2O = 2CO+2H2
2NH3 = N2+2H2
CO+H20 = CO2+H2
Conversion = 50% CH4 &NH3 and all other hydrocarbon are 100% converted [1]
COMPONENTS
STREAM 47
STREAM 43
Kg/hr
Kg/hr
H2
3951
6079
CO2
41868
51605
CO
27468
30253
H2O
79674
69920
CH4
5746
2872
C2H2
154
C2H4
1775
C2H6
26
NH3
12
N2
93
118
Total
160764
160775
41
4.12 MATERIAL BALANCE ACROSS HIGH TEMPERATURE SHIFT

REACTOR
4.12.1 HIGH TEMPERATURE SHIFT REACTOR REACTION

CO+H20 =CO2+H2 conversion =70% [1]
4.12.2 MATERIAL BALANCE

COMPONENTS
STREAM 44
STREAM 45
Kg/hr
Kg/hr
H2
6142
7626
CO2
52565
85228
CO
29693
8908
H2O
69516
56154
CH4
2866
2866
NH3
N2
118
118
TOTAL
160908.042
160912.63
42
4.13 MATERIAL BALANCE ACROSS LOW SHIFT REACTOR
CO+H20 =CO2+H2 conversion =89% [1]
COMPONENTS
STREAM 46
STREAM 47
Kg/hr
Kg/hr
H2
7626
8193
CO2
85228
97686
CO
8908
979
H2O
56154
51057
CH4
2866
2866
NH3
N2
118
118
TOTAL
160912
160908
43
4.14 MATERIAL BALANCE ACROSS PRE-PSA KNOCK OUT DRUM
COMPONENTS
STREAM 52
STREAM 53
STREAM 54
Kg/hr
Kg/hr
Kg/hr
H2
8193
8193
CO2
97686
97206
480
CO
979
979
H2O
51057
493
50564
CH4
2866
2866
NH3
N2
118
118
TOTAL
160908
109864
51044
44
4.15 MATERIAL BALANCE ACROSS PRESSURE SWING ADSORBER
COMPONENTS
STREAM
STREAM
STREAM
53
55
56
kg/hr
Kg/hr
Kg/hr
H2
8193
8185
others
101976
10
101966
total
110169
8195
101974
API Technical Data Book
45
REFERENCES
1. J. Jechura, P. Spath, A. Aden, T. Eggeman M. Ringer, B. Wallace,. "Biomass to
Hydrogen Production Detailed Design and Economics Utilizing the Battelle Columbus
Laboratory Indirectly-Heated Gasifier." NREL/TP-510-37408. N.p., May 2005. Web. 8
Oct. 2011
2. "Air construction permit application biomass gas & electric (bg&e) tallahassee
renewable energy center." .dep.state.fl.us. N.p., Apr. 2008. Web. 20 Nov. 2011.
3. "Solubility of Gases in Water." Engineeringtoolbox, n.d. Web. 11 Dec. 2012.
<http://www.engineeringtoolbox.com/gases-solubility-water-d_1148.html>.
4. API technical Data Book
5. Hougen, Olaf A., Kenneth M. Watson, and Roland A. Ragatz. Chemical Process
Principles. 1st ed. Vol. 1. New York [etc.: Wiley, 1959. Print
46
ENERGY BALANCE
5.1 REFERENCE CONDITION
P = 1 atm
T = 25 C
5.2 ENERGY BALANCE ACROSS GASIFIER
5.2.1
GASIFIER REACTIONS
1) 2C3.2H5O3+5.9O 26.4CO 2+5H2O
H=+1708081KJ/Kgmol
2) 2C3.2H5O3+0.4H 2O6.4CO+5.4H 2
H=+1711805KJ/Kgmol
3) 2C3.2H5O3+CO 27.4CO+0.6H 2O+4.4H 2
H=+1711805KJ/Kgmol
4) 2C3.2H5O3+13.8H 2=6.4CH4+6H2O
H=+1711905KJ/Kgmol
5) CO+3H2=CH4+H2O
H=-118090 KJ/Kgmol
6) CO+H2OH2+CO2
H=-41123.7 KJ/Kgmol
47
COMPONENT
STREAM
STREAM
STREAM
STREAM
KJ/hr
KJ/hr
KJ/hr
KJ/hr
H2
18234059
CO2
17588449
CO
35390362
H2O
4081022
5078978
89530288
CH4
29140966
C2H2
696568
C2H4
10795611
C2H6
932752
C6H6
696568
C10H8
2762998
NH3
473055
H2S
87088
Olvine
2901685499
4.13e +09
Char
84591206
Biomass
15155228.5
Total
19236251
5078978
2901685499
4422603918
H = H out Hin + HeatR where HR = Enthalpy of reaction

H = 4.953 e 3 - 4.422 e 3 - 5.52 e 2
H = 0 GJ/hr
48
5.3 ENERGY BALANCE ACROSS GASIFIER CYCLONE
COMPONENT
STREAM 3
STREAM 5
STREAM 4
KJ/hr
KJ/hr
KJ/hr
H2
18234059
18234059
CO2
17588449
17588449
CO
35390362
35390362
H2O
89530288
89530288
CH4
29140966
29140966
C2H2
696568
696568
C2H4
10795611
10795611
C2H6
932752
932752
C6H6
696568
696568
C10H8
2762998
2762998
NH3
473055
473055
H2S
87088
87088
Olvine
4.13e +09
257108
2370819745
49
Char
84591206
3839
38384564
Total
4422603918
201197052
2409204309
H = H out Hin
H = 4.422 e 3 - 4.422 e 3 = 0 GJ/hr
5.4
ENERGY BALANCE ACROSS CHAR COMBUSTOR
5.4.1
CHAR COMBUSTOR REACTIONS
C+O2=CO2
H=-393795KJ/Kgmol
2H+O2=H2O
H=-242018KJ/Kgmol
N2 +2O2=2NO2
H= -33200 KJ/Kgmol
S+O2=SO2
H= -1242483KJ/Kgmol
COMPONENTS
STREAM 4
STREAM 8
STREAM 9
STREAM 6
KJ/hr
KJ/hr
KJ/hr
KJ/hr
CO2
595
56670838
H2O
179207
24051517
N2
1131495
162912511
O2
307091
5004203
Ar
9534
1203295
SO2
9969
NO2
31007
50
MgO
Olvine
2570819745
2927791480
Char
38384564
1814177
total
2609204309
1627922
3179488997
H = H out Hin + HR
= 3.179 e3 - 2.609 e 3 +5.68 e 2 = 0
5.5 ENERGY BALANCE ACROSS CHAR COMBUSTOR CYCLONE
COMPONENTS
STREAM 6
STREAM 7
STREAM 10
KJ/hr
KJ/hr
KJ/hr
CO2
56670838
56670838
H2O
24051517
24051517
N2
162912511
162912511
O2
5004203
5004203
Ar
1203295
1203295
SO2
9969
9969
51
NO2
31007
31007
Olvine
2927791480
260979340
3506387
Char
1814177
81071
Total
3179488997
2609874911
226472232
H = H out Hin
= 2.840 e 4 - 2.840 e 4 = 0
5.6 ENERGY BALANCE ACROSS TAR REFORMER
5.6.1
TAR REFORMER REACTIONS
CH4+H2O = CO+3H2
H= 205951.9 KJ/Kgmol
C2H6+2H2O = 2CO+5H2
C2H4+2H2O = 2CO+4H2
C10H8+10H2O = 10CO+14H2
H= 1767099 KJ/Kgmol
C6H6+6H2O = 6CO+9H2
H= 1628707 KJ/Kgmol
C2H2+2H2O = 2CO+2H2
2NH3 = N2+2H2
H= 46147.2 KJ/Kgmol
CO+H2O = CO2+H2
H= -41123.7 KJ/Kgmol
52
COMPONENTS
STREAM 5 STREAM 10
STREAM 11
STREAM 12
KJ/hr
KJ/hr
KJ/hr
KJ/hr
H2
18209818
43968183
CO2
17573112
37781086
CO
35332258
24014862
H2O
88688842
47951630
CH4
29037090
19177733
C2H2
695477
293185
C2H4
10769356
4495735
C2H6
928878
77116
C6H6
694227
173438
C10H8
2786954
116796
NH3
471668
117630
H2S
86791
72818
Olvine
256664
24919
209302
Char
4181
3632
N2
Total
0
205535315
0
0
0
24919
79501
178532648
H = H out Hin + HR
=1.78 e 2 -2.05 e 2 + 0.27
= 0 GJ/hr
53
5.7 ENERGY BALANCE ACROSS POST TAR REFORMER COOLER/

STEAM GENERATOR
HOT STREAM
Tin =750 C
Tout= 537 C
Mass flow rate = 109802 kg/hr
Qin = 50624859 KJ/hr
COLD STREAM
Tin = 229 C
Cp = 5.65 KJ/Kg.C
Tout=?
Qin = 50624859 KJ/hr
Tout= 325 C
54
*Reference:http://www.engineeringtoolbox.com/water-thermal-properties-d_162.html
5.8 ENERGY BALANCE ACROSS POST TAR REFORMER COOLER/

BFW HEATER
HOT STREAM
Tin =537C
Tout= 149 C
Qin = 83440929 KJ/hr
COLD STREAM
Tin = 110 C
Tout=300 C
Qout= 83440929 KJ/hr
Cp= 4.54 KJ/Kg.C
55
*Reference:http://www.engineeringtoolbox.com/water-thermal-properties-d_162.html
5.9 ENERGY BALANCE ACROSS SYNGAS QUENCH CHAMBER
Total Heat of absorption = -0.46GJ/hr

Total Heat of liquefaction of water = -49GJ/hr
Total Heat input = 94GJ/hr
Total Heat output = 143.46 GJ/hr
56
H = Heat out Heatin + HeatA + HeatL

= 143.46 - 94-0.46-49
= 0 GJ/hr
COMPONENTS
Stream 15
Stream19
Stream 20
Stream 21
KJ/hr
KJ/hr
KJ/hr
KJ/hr
H2
7001014
1960881
CO2
5167250
1313266
757
CO
3586943
1001768.
99
H2O
68824067
69027035
2844207
136008463
CH4
1861254
469682
520
C2H2
37710
10612
31
C2H4
427976
103837
266
C2H6
7180
2025
C6H6
16387
4282
831
C10H8
13199
125
3018
NH3
13775
2895
755
H2S
9586
2616
N2
12212
3411
Olvine
23693
6193
Char
665
182
Total
25061251
69027035
7719611
136021115
57
5.10 COMPRESSION SECTION
58
5.10.1 ENERGY BALANCE ACROSS PRE COMPRESSOR KNOCK-OUT DRUM
COMPONENTS
STREAM 20
STREAM 23
STREAM 24
KJ/hr
KJ/hr
KJ/hr
H2
1955350
1955350
3.2 e-1
H2O
2917705
2249406
668299
CO
1001758
1001758
1.8 e-1
N2
3411
3411
2 e -3
CO2
1313414
1313394
20
H2S
2616
1.3 e-1
NH3
2873
2832
41
CH4
469629
469629
1.0 e -3
C2H6
1729
193607
247
59
C2H4
103873
5.4 e -2
1.9692 e-11
C2H2
9841
3.3 e -1
7.6107 e-10
C6H6
4423
4423
C10H8
134
134
TOTAL
7786757
7189393
673164
H = H out Hin
= 7.786 -7.786 =0 GJ/hr
5.10.2 ENERGY BALANCE ACROSS COMPRESSOR 1
COMPONENTS
STREAM 23
STREAM 25
KJ/hr
KJ/hr
H2
1955350
7595401
H2O
1313394
5391203
CO
1001758
3904713
N2
2249406
3785375
CO2
469629
2538791
H2S
3.4 e -1
60
NH3
5.37 e -2
2.4 e-1
CH4
193607
884334
C2H6
2832
11636
C2H4
18
C2H2
3411
13359
TOTAL
7189393
24124831
Power Requirement = H out Hin = 6.7-1.99

=4.7 MWatt
5.10.3 ENERGY BALANCE ACROSS WATER COOLED INTER COOLER 1
HOT STREAM
Tin =145 C
Tout= 60 C
Qin = 12434008 KJ/hr
COLD STREAM
61
Tin = 30 C
Tout=40 C
Qin = 12434008 KJ/hr
5.10.4 ENERGY BALANCE ACROSS KNOCK OUT DRUM 2
COMPONENTS
STREAM
STREAM
STREAM
Cold 1
(vapor)
(liquid)
KJ/hr
KJ/hr
KJ/hr
H2
1955350
1955349
1.5 e-1
CO2
1320555
1320504
51
62
CO
1003681
1003680
7.3 e-1
H2O
2249406
1166288
1083119
CH4
470836
470836
3.6 e-3
C2H2
3.4 e -1
3.3 e-1
2.86049E-09
C2H4
5.37 e -2
5.37 e -2
7.43893E-11
C2H6
194626
194106
521
NH3
2853
2719
134
H2S
4.6
6.8 e-4
N2
3418
3418
2.9 e-3
TOTAL
7200729
6116904
1083825
H=H out Hin

=7.2-7.2 = 0 GJ/hr
COMPONENTS
H2
STREAM 23
STREAM 25
KJ/hr
KJ/hr
1955349
6785225
63
H2O
1320504
4815954
CO
1003680
3488208
N2
1166288
1753316
CO2
470836
2267986
H2S
3.3 e-1
1.6
NH3
5.37 e-2
2.13e -1
CH4
194106
787892
C2H6
2719
9908
C2H4
4.6
16
C2H2
3418
11934
TOTAL
6116904
19920440
Power Requirement = H out Hin = 5.53 -1.69

=3.83 MWatt
5.10.6 ENERGY BALANCE ACROSS WATER COOLED AFTER COOLER 2
HOT STREAM
Tin = 145 C
64
Tout= 60 C
Qin = 11624 M J/hr
COLD STREAM
Tin = 30 C
Tout=40 C
Qin = 11624 M J/hr
65
COMPONENTS
STREAM
STREAM
STREAM
Cold 2
(vapor)
(liquid)
KJ/hr
KJ/hr
KJ/hr
H2
1956732
1956732
2.2 e -1
CO2
1339210
1339131
78
CO
1008487
1008486
H2O
1166288
490505
675783
CH4
473650
473650
5.45 e-3
C2H2
3.4 e-1
3.4 e-1
4.36586 e-09
C2H4
5.4 e -2
5.4 e -2
1.13393 e-10
C2H6
196646
196646
1.08 e-4
NH3
2776
2586
189
H2S
4.6
4.6
1.03 e-3
N2
3431
1033
2398
TOTAL
6147224
5468775
678449
66
H= H out Hin = 6.1-6.1

= 0 GJ/hr
COMPONENTS
STREAM
STREAM
KJ/hr
23
KJ/hr
25
H2
1956732
7938244
H2O
1339131
5858493
CO
1008486
4116885
N2
490505
2118588
CO2
473650
2206381
H2S
3.4 e -1
1.5
NH3
5.4 e-2
2.7 e-1
CH4
196646
989589
C2H6
2586
11386
C2H4
4.6
20
C2H2
1033
4244
TOTAL
5468775
23243830
67

= 3.72 MWatt
HOT STREAM
Tin = 146 C
Tout= 60 C
Qin = 11042 MJ/hr
HOT STREAM
Tin = 146 C
Tout= 60 C
Qin = 11042 MJ/hr
68
COMPONENTS
STREAM
STREAM
STREAM
in
KJ/hr
(vapor)
KJ/hr
(liquid)
KJ/hr
H2
1958115
1958115
2.5 e-1
CO2
1391007
1390921
86
CO
1020022
1020020
1.2
H2O
490284
202523
287761
CH4
481089
481089
5.9e-4
C2H2
3.5 e-1
3.54 e-1
4.84593E-09
C2H4
5.6 e-2
5.6e-2
1.25371E-10
C2H6
204268
204268
1.2 e-4
NH3
2744
2549
195
H2S
4.9
4.9
1.1 e-3
69
N2
1044
1043
1.41e-3
TOTAL
5548578
5260535
288043
H= H out Hin
H = 5.549 5.549
H = 0 GJ/hr
COMPONENTS
STREAM 23
STREAM 25
KJ/hr
KJ/hr
H2
1958115
7988930
H2O
1390921
6135058
CO
1020021
4191713
N2
202523
877464
CO2
481089
2253889
H2S
3.54 e-1
1.6
NH3
5.6 e-2
2.8 e-1
70
CH4
204268
1031031
C2H6
2549
11351
C2H4
4.9
21
C2H2
1044
4312
TOTAL
5260535
22493772

Power Requirement = 4.7 MWatt
HOT STREAM
Tin = 146 C
Tout= 60 C
Qin = 10763 M J/hr
COLD STREAM
Tin = 30 C
71
Tout=40 C
Qin = 10763 M J/hr
COMPONENTS
STREAM
STREAM
STREAM
H2
KJ/hr
in
1963646
KJ/hr
(vapor)
1963646
KJ/hr
(liquid)
2.67 e-1
CO2
1562028
1561931
97
CO
1048862
1048861
1.3
72
H2O
202387
86498
115889
CH4
1216091
1216091
1.5 e-2
C2H2
3.6 e-1
3.62 e-2
5.06005 e-09
C2H4
7.4 e-2
7.41 e-2
1.69076 e-10
C2H6
253049
253049
1.5 e-4
NH3
2549
2372
176
H2S
5.9
5.98
1.3 e-3
N2
1070
1070
1.51 e-3
TOTAL
6249689
6133525
116164
H= H out Hin
H = 6.249-6.249
H = 0 GJ/hr
COMPONENTS
H2
STREAM 23
STREAM 25
KJ/hr
KJ/hr
1958115
6807727
73
H2O
1390921
4831045
CO
1020021
3499765
N2
202523
130613
CO2
481089
2275508
H2S
3.54 e-1
NH3
5.6 e-2
2.1 e -1
CH4
204268
790505
C2H6
2549
8011
C2H4
4.9
16
C2H2
1044
3605
TOTAL
5260535
18346797

Power Requirement = 3.39 MWatt
74
HOT STREAM
Tin = 146 C
Tout= 60 C
Qin = 10753 MJ/hr
COLD STREAM
Tin = 30 C
Tout=40 C
Qin = 10753 MJ/hr
75
5.10.16 ENERGY BALANCE ACROSS WATER COOLED AFTER COOLER
HOT STREAM
Tin = 60 C
Tout= 49 C
Qin = 2972 MJ/hr
COLD STREAM
Tin = 30 C
Tout=40 C
Qin = 2972 MJ/hr
Mass flow rate =Q/cp( Tout Tin)
76
5.10.17 ENERGY BALANCE ACROSS POST-COMPRESSOR KNOCK-OUT DRUM
COMPONENTS
STREAM 20
STREAM 23
STREAM 24
KJ/hr
KJ/hr
KJ/hr
H2
1339385
1339385
5.01 e-2
CO2
1091063
1091026
36
CO
719204
719203
2.9 e -1
H2O
58948
26238
32710
CH4
338532
338532
7.95 e -4
C2H2
2.5 e -1
2.49 e -1
6.39498E-10
C2H4
4.3 e -2
4.33 e -2
1.4834E-11
C2H6
165094
165094
1.30716E-05
NH3
3817
3608
209
H2S
8.2
8.2
1.004 e-3
N2
732
732
4.6 e -4
TOTAL
3716781
3683826
32956
H= H out Hin
H= 37.16-37.16
77
H = 0 GJ/hr
5.11 ENERGY BALANCE ACROSS LO-CAT ABSORBER
PUMP POWER REQUIREMENT

=135 kWh
78
COMPONENTS
STREAM
29
KJ/hr
STREAM
30
KJ/hr
H2
2173505
1935161
H2O
28940.84
31739.48
CO
919409.7
1023099
N2
2915.403
3460.466
CO2
1308244
1552785
H2S
3963.215
65.42231
NH3
6860.621
6999.439
CH4
415048.2
487357.1
C2H6
1433.303
2041.176
C2H4
101022.1
120349.6
C2H2
9918.062
11815.58
STREAM
37
KJ/hr
10265657
STREAM
33
KJ/hr
AIR
OUT
KJ/hr
STREAM
31
KJ/hr
113.5332
288.561 10182644
1014.223
2589.702
S
Fe+2L
Fe+3L
171394
169865.9
O2
272.7751
126.6552
AR
8.612952
21.86221
79
STREAM
34
KJ/hr
S
TOTAL
1127.092
4971261
5174874
10437051
1409.144
3026.78 10352510
5.12 ENERGY BALANCE ACROSS Zn BED PREHEATER
COLD STREAM
Tin =49 C
Tout= 375 C
Qin = 5.3975 e 4MJ/hr
HOT STREAM
Tin = 639 C
Qout = 5.3975 e 4MJ/hr
80
1127.092

Tout = 466 C
5.13 ENERGY BALANCE ACROSS ZnO SULFUR REMOVAL BEDS
ZnO + H2S = ZnS + H20 H = 165753 KJ/Kgmole
COMPONENTS
STREAM 41
STREAM 42
KJ/hr
KJ/hr
H2
20497323
19670468
H2O
161845
155878
CO
10607289
10173196
N2
36086
34642
CO2
16233426
15582788
81
H2S
578
NH3
35295
33880
CH4
7000700
6719248
C2H6
28579
27430
C2H4
1645946
1580199
C2H2
124177
119209
Total
54103563
54096940
H= H out Hin HR
H =54-53.934 6.6 e -2
H = 0 GJ/hr
5.14 ENERGY BALANCE ACROSS REFORMER
COMPONENTS
STREAM 47
STREAM 43
Kg/hr
Kg/hr
H2
20407952
77324123
CO2
16847989
55377996
CO
10790301
29192660
82
H2O
61833239
102272368
CH4
7867577
11263229
C2H2
129427
C2H4
1869735
C2H6
31495
NH3
13303
N2
14125
90766
Total
119805141
275521142
Heat required =1.56 e 2 GJ/hr

Natural gas required =5746 NMCH
5.15 ENERGY BALANCE ACROSS REFORMED SYNGAS COOLER
HOT STREAM
Tin = 850 C
83
Tout= ?
Qin = 81301 MJ/hr
Tout= 487 C
COLD STREAM
Tin = 110 C
Tout= 300 C
Qout =?
Qout= 81301 MJ/hr
5.16 ENERGY BALANCE ACROSS REFORMED SYNGAS COOLER 2
HOT STREAM
84
Tin = 487 C
Tout= 350 C
Qin = 30109 MJ/hr
COLD STREAM
Tin = 300 C
Tout= ? C
Qout = 30109 MJ/hr
Tout = 356 C
85
5.17 ENERGY BALANCE ACROSS HIGH TEMPERATURE SHIFT

REACTOR
CO + H2O = CO2 + H2 H=-41123.7 KJ/Kgmol
COMPONENTS
STREAM 44
STREAM 45
KJ/hr
KJ/hr
H2
30831275
47345983
CO2
19713635
39827350
CO
11217878
4180494
H2O
52197760
52232049
CH4
3328180
4218855
NH3
4724
5849
N2
44854
55806
TOTAL
117338306
147866385
H= H out Hin HR
H= 147.8 - 117.3 -30.5
86
H= 0 MJ/hr
5.18 ENERGY BALANCE ACROSS LOW TEMPERATURE SHIFT

PRECOOLER
HOT STREAM
= 430 C
Qin = 43475040 MJ/hr
o t= 306 C
COLD STREAM
= 110 C
o t= 250 C
Qout = 43475040 MJ/hr
Tout = 356 C
87

PRECOOLER 2
HOT STREAM
= 306 C
o t= 200 C
Qin = 35808 MJ/hr
COLD STREAM
= 70 C
Qout = 35808 MJ/hr
Tout = 121 C
88

REACTOR
CO + H2O = CO2 + H2 H=-41123.7 KJ/Kgmol

COMPONENTS
STREAM 46
STREAM 47
KJ/hr
KJ/hr
H2
40485835
50861296
CO2
32380629
43757891
CH4
5326534
711016
CO
3529617
454139
H2O
74421923
48706874
NH3
4621
5550
N2
47235
55266
89
TOTAL
156196395
144552032
H= H out Hin HR
H= 1.561 e2 1.45 e2 -11.6
H= 0 GJ/hr
5.21 ENERGY BALANCE ACROSS PSA PRE COOLER
HOT STREAM
= 235 C
o t= 167.7 C
Qin = 22497053 KJ/hr
COLD STREAM
= 38 C
90

Qout = 22497053 KJ/hr
o t = 70 C
5.22 ENERGY BALANCE ACROSS PRE-PSA AIR COOLER
HOT STREAM
= 167 C
o t= 60 C
Qin = 40677281 KJ/hr
91
AIR
= 32 C
o t= 59 C
Qin = 40677281 KJ/hr
5.23 ENERGY BALANCE ACROSS PSA WATER COOLER
HOT STREAM
= 60 C
o t= 43 C
Qin = 7516650 KJ/hr
92
COLD STREAM
= 30 C
o t = 70 C
Qin = 7516650 KJ/hr
5.24 ENERGY BALANCE ACROSS PRE-PSA KNOCK OUT DRUM
93
COMPONENTS
STREAM 52
STREAM 53
STREAM 54
Kg/hr
Kg/hr
Kg/hr
H2
2129520
2122996
6524
CO2
1862208
1853057
9150
CO
19488
19488
H2O
4146861
40042
4106820
CH4
127710
127710
NH3
613
102
511
N2
2347
2347
TOTAL
8288747
4165742
4123005
H= H out Hin
H= 8.288 8.288
H= 0 GJ/hr
5.25 ENERGY BALANCE ACROSS PRESSURE SWING ADSORBER
COMPONENTS
STREAM
STREAM
STREAM
53
55
56
94
KJ/hr
KJ/hr
KJ/hr
H2
2129520
3049267
296
CO2
18423667
2293867
CO
19868
24713
H2O
40041
49806
CH4
127499
158591
NH3
102.
127
N2
2345
27
2891
Total
4161742
3049267
2530294
HEAT OF ADSORPSION (HAD)
CO2= -553.106 KJ/Kgmole
CO =-1228.13 KJ/Kgmole
H2O =-1681.7 KJ/Kgmole
CH4 =-569.87 KJ/Kgmole
NH3 =-1011.81 KJ/Kgmole
N2 =-318.662 KJ/Kgmole
95
H= H out Hin -HAD

H= 5.579 - 4.161-1.418
H= 0 MJ/hr
REFERENCES
1. Hougen, Olaf A., Kenneth M. Watson, and Roland A. Ragatz. Chemical Process
Principles. 1st ed. Vol. 1. New York [etc.: Wiley, 1959. Print
2. API Technical Data Book
96
DESIGN OF GASIFIER
6.1 GASIFICATION
Gasification is a process of converting carbonaceous materials to combustible or synthetic gas. in
general gasification involves the reaction of carbon with oxygen, steam, CO 2 or a mixture of
these gases at 700OC or higher temperature to produce gaseous product that can be used to
provide the electrical and heat or as raw material for the synthesis of chemicals, liquid fuels, or
other gaseous fuels such as hydrogen.
Gasification of biomass involves removal of oxygen from the fuel to increase the density.
Gasification or pyrolysis increases the relative hydrogen content (H/C ratio) in the product
through one the followings means:
Direct: Direct exposure to hydrogen at high pressure.

Indirect: Exposure to steam at high temperature and pressure, where hydrogen, an
intermediate product, is added to the product. This also includes steam reforming.
Pyrolysis: Reduction of carbon by rejecting it through solid char or CO 2 gas.
6.2 GASIFICATION REACTIONS

Three main types of chemical reactions occurring in gasifier include:
1. Pyrolysis reactions
2. Combustion reactions
3. Gasification reactions
6.2.1 PYROLYSIS REACTION

It is defined as thermal cracking/decomposition of coal involving following two processes;
1. Release of volatiles or gases (H2O, H2, N2, O2, CO2, CO, CH4, H2S, NH3, C2H6 and very
low levels of unsaturated hydrocarbons) and primary char
2. Thermal cracking of primary tars to produce gases, secondary tars (low molecular wt) &
carbonaceous residue.
97
Stages in Pyrolysis are:
Pyrolysis rate controlling mechanism depends on the type of gasifier selected. The 3
possible rate controlling mechanisms are:
1. Heat transfer to biomass particles.
2. Heat transfer across biomass particles.
3. Chemical reactions kinetics.
6.2.2 COMBUSTION REACTIONS

Combustion reaction involves the reaction of biomass with the oxygen to form CO 2 and H2O.
2C3.2H5O3+5.9O26.4CO2+5H2O
6.2.3 GASIFICATION REACTIONS

The principal gasification reaction is endothermic in nature and is known as water-gas reaction.
It is favored at high temperature and low pressure.
2C3.2H5O3+0.4H2O6.4CO+5.4H2
6.2.4 BOUDOURD REACTION

It is endothermic in nature and much slower than the combustion reaction at the same
temperature in the absence of catalyst.
98
2C3.2H5O3 + CO2 = 7.4CO + 0.6H2O + 4.4H2
H = + 1711805KJ/Kgmol
6.2.5 HYDRO-GASIFICATION REACTION:

Hydro-gasification reaction is very slow except at high temperature.
2C3.2H5O3 + 13.8H2 = 6.4CH4 + 6H2O
H=+1711905KJ/Kgmol
6.2.6 METHANATION REACTION

Methanation reaction proceeds very slowly at low temperature in the absence of catalyst.
H = -118090 KJ/Kgmol
CO + 3H2 = CH4 + H2O
6.2.7 WATER GAS SHIFT REACTION

Water-gas shift reaction can be important if the H2 production is desired. Optimum yield is
obtained at low temperature in the presence of catalyst and pressure has no effect on increasing
hydrogen yield.
H = -41123.7 KJ/Kgmol
CO + H2O = H2 + CO2
6.2.8 SIDE REACTIONS
Apart from these reactions sulfur in coal form H2S and nitrogen mainly released as elemental N2
and NH3 and traces of Hydrogen Cyanide is form.
H2 + S = H2S
N2 + 3H2 = 2NH3
6.3 TYPES OF GASIFIER

Gasification is carried out generally in one of the three major types of gasifier:
Moving bed (also called fixed bed)

Fluidized bed
Entrained flow
99
6.3.1 MOVING BED GASIFIER

In fixed bed gasifier the bed is supported on a grate. This type is also called moving bed because
the fuel moves down the gasifier as a plug. Fixed bed gasifier can be built inexpensively in small
sizes, which is one of their major attractions. Both mixing and heat transfer within the
moving(fixed ) bed are rather poor, which makes it difficult to achieve uniform distribution of
fuel, temperature and gas composition across the cross section of the gasifier. Thus, fuels that are
prone to agglomeration can potentially form agglomerates during gasification. This is why fixed
bed gasifier are not very effective for biomass fuels or coal with a high caking index in large
capacity units.
FIXED BED GASIFIER TYPES

Depending upon air injection fixed bed gasifier is categorized as:
1. Updraft
2. Down draft
3. Cross draft
1. UPDRAFT GASIFIER
An updraft gasifier is one of the oldest and simplest of all designs. Here, the gasification medium
(air, oxygen or steam) travels upward while the bed of fuel moves downward, and thus the gas
and solids are in counter-current mode (fig 6.1). The gasifying medium enters the bed through a
grate or a distributor, where it meets with the hot bed or ash. Tar production is very high in
updraft gasifier which makes it unsuitable for highly volatile fuels.
1. DOWNDRAFT GASIFIER
A downdraft gasifier is a co-current reactor where air enters the gasifier at a certain height below
the top. The product gas flows downward and leaves through a bed of hot ash (fig 6.2). Since it
passes through the high temperature zone of hot ash, the tar in the product gas finds favorable
condition of cracking. That is why downdraft gasifier, of all types, has the lowest temperature
production rate.
100
Fig: 6.1. Schematic of an updraft gasifier
Fig: 6.2. Schematic for downdraft gasifier
101
2. CROSS DRAFT GASIFIER

A cross draft is a co-current moving bed reactor, in which the fuel is fed from the top and the air
is injected through nozzle from side (fig 6.3). It is primarily used for the gasification of charcoal
with very low ash content. Unlike down draft and updraft types, it releases the product from its
side wall opposite to the entry point of air for gasification.
This type of gasifier is being used for the small scale biomass gasification. The cross draft design
is less suitable for high ash or high tar fuels but it can handle high moisture fuels if the top is
open so that the moisture can escape.
Fig: 6.3. Schematic of cross draft gasifier
ADVANTAGES OF FIXED BED GASIFIER
Simple and reliable design

Capacity for wet biomass gasification
Favorable economic on small scale
102
DISADVANTAGES OF FIXED BED GASIFIER
Long residence time

Non uniform temperature distribution in gasifier
High tar contents
6.3.2 FLUIDIZED BED GASIFIER

Fluidized bed gasifiers are noted for their excellent mixing and temperature uniformity. A
fluidized bed is made of granular solids, called bed materials that are kept in a semi -suspended
condition by passage of the gasifying medium through them at appropriate velocities. The
excellent gas solid mixing is one of the features of the fluidized bed gasifier.
TYPES
There are two principal fluidized beds:
Bubbling bed
Circulating bed
ADVANTAGES
Short residence time

High productivity
Uniform temperature distribution in gasifier
Reduced ash related problem
DISADVANTAGES
High particulate dust in syngas

Favorable economics on a medium to large scale
6.3.3 ENTRAINED FLOW GASIFIER

Entrained flow is the most successful and widely used gasifier for the large scale gasification of
the coal coke and biomass gasification. High ash coal is also less suitable because cold-gas
efficiency decreases with increasing ash content. The suitability of entrained flow gasification
for biomass is questionable for number of reasons. Owing to short residence time (a few
seconds) in entrained flow reactors, the fuel to be very fine, and grinding fibrous biomass into
such fine particles is difficult. But they have advantage of easily tar destroying, which is very
103
high in biomass and the gas produced as a result of gasification is usually tar free and has very
methane content.
CLASSIFICATION
Entrained flow gasifier design may be classified into two broad groups:
1. Top fed down flow
2. Side fed up flow
1. TOP FED GASIFIER
Top fed gasifiers use a vertically cylindrical reactor vessel, into which pulverized fuel and
gasifying agents are converted by oxygen and injected from the top. The fuel and gasifying
agents are injected into the reactor through a jet that generally sits at the reactors middle section
(fig 6.4). One of the advantages is the flow of reactants occur from a single burner, reducing the
number of the burners to be controlled.
Fig: 6.4. Schematic of top fed down draft entrained flow

gasifier
104
2. SIDE FED GASIFIER

In side fed gasifiers, powered fuel is injected thorough horizontal nozzles set opposite each other
in the reactors lower section. The product gas move upward and exit through the top (fig 6.5).
Because of the high oxygen availability in this mixing zone, rapid exothermic reactions take
place, raising the gas temperature to well above the ash-melting point. Thus, the ash, instead of
travelling up, is separated in this zone as slag from the fuel and drained.
Fig: 6.5. Schematic of side fed down draft entrained

flow gasifier
ADVANTAGES OF ENTRAINED FLOW GASIFIER
Low tar production

A range of acceptable feed
Ash produced as slag
High temperature and high pressure conditions
Very high conversion of carbon
Low methane content
DISADVANTAGES
The residence time in the entrained flow gasifier is very short. For the reaction to
complete, biomass particles must be finely ground
Molten ash from the biomass is highly aggressive because of its alkaline compounds and
can corrode the gasifiers refractory or metal lining.
105
6.4 GASIFICATION AGENTS

The most commonly used gasifiying agents are:
Steam
Air
Carbon dioxide
TABLE: 1
GASIFYING MEDIUM
GASIFYING AGENTS
AIR
STEAM
CARBON DIOXIDE
ADVANTAGES
DISADVANTAGES
1. Partial combustion for

heat supply of
gasification
2. Moderate char and tar
content
1. Low heating value

2. Large amount of N2 in
syngas
3. Difficult determination
of ER (0.2-0.4)
1. High heating value

synngas
2. H2 rich syngas
1. Indirect or external
heat supply for
gasification
2. High content in tar
reforming
3. Require catalytic tar
reforming.
1. High heating value of

syngas.
2. High H2 and CO and
low CO2 in syngas
1. Indirect or external
heat supply for
gasification
2. Require catalytic tar
reforming.
(Reference: the status of biomass gasification, pg: 8 by P.Abdul Salam and S. Kumar and
Manjula Siriwardhana)
106
6.5 AFFECTS OF OPERATING CONDITION

The equilibrium data indicates that:
CH4 formation decreases with increasing temperature and increase with increasing
pressures.
CO and H2 formation increases with increasing temperature and reducing pressures.
Maximum concentration of H2 and CO can be obtained at atmospheric pressure and
temperature range of 800 to 1000 OC.
CO2 concentration increases with increasing pressures and decreases sharply with
increasing temperatures.
Reducing oxygen to steam ratio of reactant gases increases H 2 and CH4 formation, while
increasing the oxygen to steam ratio will increase CO and CO2 formation.
Therefore, gasifier temperature and pressure can be controlled to maximize the concentration of
desired product, CH4 or H2 and CO. however, in order to determine the optimum operating
conditions other factors such as the gasification kinetics and catalyst effects and mechanism by
which reactions occur must be considered.
Fig: 6.6. Temperature effect on the reaction

rate
Fig: 6.7. Pressure effect on gas composition
6.6 QUALITY OF THE PRODUCT

The following factors affect the quality of the product gas:
Feed stock composition

Feed stock preparation and particle size
Reactor heating rate
Residence time
107
Plant configuration such as:

Feed system dry or slurry
Feed stock reactant flow geometry
Mineral removal system dry ash or slag
Heat generation and transfer method direct or indirect
6.7 ATTRACTIVE FEATURES

Attractive features of gasification technology include:
The ability to produce a consistent product that can be used for the generation of
electricity or as primary building blocks for manufacturers of chemicals and
transportation fuels.
The ability to process a wide range of feed stocks including coal, heavy oils, petroleum
coke, heavy refinery wastes, hydrocarbon contaminated soils, biomass and agriculture
wastes.
The ability to remove contaminants in the feed stock and to produce a clean syngas
product.
The ability to convert wastes or low value products to higher value products.
The ability to minimize the amount of the solid waste requiring landfill disposal and solid
by-product have the market value can be used as fuel or construction material and are
non-hazardous.
6.8 DESIGN STEPS
Bed volume
Dimensions of gasifier
Minimum fluidization velocity
Maximum fluidization velocity
Terminal velocity
Superficial velocity
Pressure drop
108
6.9 DESIGN OF GASIFIER

6.9.1
BED VOLUME
The entrained flow gasifier behaves like a co-current plug flow reactor (Reference: Biomass
gasification and pyrolysis practical design, pg: 186 by Parbir basu).
The rate controlling reaction for determining the bed volume is:
2C3.2H5O3+0.4H2O6.4CO+5.4H2
Where;
Reaction rate kg/sec = dC/dt
Mass flow rate of the char kg/sec = m = 997 kg/sec
Steam quality = [H2O] = 1
Time constant = k = 0.44 /sec
So the reaction rate comes out to be:
dC/dt = 439 kg/sec
RESIDENCE TIME
From the knowledge of the reaction rate, the residence time, , can be calculated as:
Where;
Residence time =
Mass of the carbon in the biomass = Co = 498 kg
Reaction rate dC/dt = 439 kg/sec
Conversion of biomass = X= 73%
109
The residence time comes out to be:

= 0.89 sec
BED VOLUME
From the knowledge of the residence time, , the bed volume can be calculated as:
Char feed rate = F[C] = 997 kg/sec

Density of biomass = s = 2483 kg/m3
Void fraction = = 0.7
Reacting char = xchar = 5-8 %
Residence time = = 8.29 sec
The volume of the bed comes out to be;
Vbed = 13.86 m3
MASS OF THE BED

The mass of the bed can be calculated as:
Mb = s * Vb
Volume of the bed = 13.86 m3
Density of the bed = s = 2483 kg/m3
Mb = 34414.38 kg
DIMENSIONS OF THE GASIFIER
Allowances for the entrained bed = 40 %
Volume of the reactor = 13.86 + 13.86 (0.4)
= 18 m3
110
L/D ratio is between 2-5 and it approaches plug flow reactor when L/D = 4. So taking L/D = 4
and using the volume of cylinder in order to take out the dimensions of the gasifier. (Reference:
Fluidization: proceedings of the second Engineering Foundation Conference By John Frank
Davidson, D. L. Keairns.)
From the equation given above the diameter and height comes out to be:
D= 1.78 m
H= 7 m
Cross sectional area of bed = r2 = 2.48 m2

6.9.2 HYDRODYNAMIC DESIGN
MINIMUM FLUIDIZATION VELOCITY
The velocity at which the fluidization will first start is called minimum fluidization velocity.
(The gas stream supports the weight of the bed).
(Reference: chemical rector design pg 667 by Kunii and Levenspeil).

Where;
Diameter of particle = dp = 150 m
Density of solid = s = 2483 kg/m3
Density of gas = g = 0.52 kg/m3
Viscosity of gas = = 1.419 e-6 kg/m-s
Minimum fluidization velocity comes out to be;
Umf = 0.231 m/s
111
Reynold number at minimum fluidization velocity:

( )
And Reynold number comes out to be:
Re (m) = 12.69
(Range: 0.4-500)
(Reference: Prabir Combustion & Gasification, 2007 (CRC Press))
BUBBLING VELOCITY
It is the velocity greater than min. fluidizing velocity (the excess gas passes through the bed as
bubbles). The bed starts bubbling immediately after reaching Umf
Ub = 0.25 m/s
MAXIMUM FLUIDIZATION VELOCITY
112
Where;
Maximum fluidization velocity = Umax =
Diameter of the particle = dp = 150m
Density of solid = g = 0.52 kg/m3
Cd = 24/Re = 1.891
Maximum fluidization velocity comes out to be:
Umax = 2.56 m/s
ARCHIMEDES NUMBER
(
Where;
Archimedes number = Ar =
Density of gas = g = 0.52 kg/m3
Diameter of particle = dp= 150 m
Viscosity of gas = g= 1.419
Archimedes number comes out to be;

Ar = 21204.6
(Range: 36 83000)
(Reference: Prabir Combustion & Gasification, 2007 (CRC Press))
113
TERMINAL VELOCITY
It is the velocity greater than free fall velocity of particles in the gas stream
Ut = 3.167 m/s
VELOCITY AT THE ENTRAINMENT
The velocity at which entrainment of the particles occur is called entrained velocity and it is just
higher than the terminal velocity as shown by the graph.
Fig: 6.8. Graph for the entrainment velocity

SUPERFICIAL VELOCITY
Superficial Velocity is the velocity of gas in empty column and is calculated by
114
Volumetric flow rate of the gas entering= 37 m3/hr

Cross sectional area of gasifier= 2.62 m2
Ug = 0.253 m/s
6.8.3 HYDRAULIC DESIGN

PRESSURE DROP
P = (
Where;
Porosity of the bed = = 0.64
So
P = 61.3 kPa
Gasifier pressure drop should not exceed 120 kPa (Reference: Prabir Combustion &
Gasification, 2007 (CRC Press))
SPECIFICATION SHEET
Equipment
Operating temperature
Operating pressure
Diameter of gasifier
Length of gasifier
Volume of reactor
Pressure drop
Gasification medium
Heating medium
Particle size
Average density of solid
Steam density
Entrained Flow Gasifier

870 OC
150 kPa
1.78m
7m
18m3
61.3 kPa
Steam
Olvine
150 m
2483 kg/m3
0.52 kg/m3
115
REFERENCE
Don Green and Robert Perry, Perrys Chemical Engineers Hand Book, Ed. 8, 2007
(McGraw Hill)
Engelbrecht A.D., North B. C. and Hadle T. D., Investigation into the gasification, 2007
(CSIR Materials Science and Manufacturing)
Reed T, Thomas B. Reed, and Agua Das, Handbook of Biomass Downdraft Gasifier
Engine System,, 1988 (Biomass Energy Foundation)
Samy Sadaka, Gasification, Producer Gas & Syngas, 2009 (University of Arkansas)
Prabir Basu, Biomass Gasification & Pyrolysis, Ed.1, 2010 (Academic Press
Prabir Basu, Combustion & Gasification in Fluidized Beds, 2006 (CRC Press)
Rajvanshi, A.K., Biomass Gasification, 1986 (CRC Press)
John R. and Nicholas P. C., Gasification Technologies, 2005 (Taylor & Francis)
Max Peter, Klaus Timmerhaus and Ronald West, Plant Design and Economics for
Chemical Engineers, Ed. 5, 2002 (McGraw Hill
116
ABSORBER DESIGN
7.1 Absorber:
Gas absorbers are used extensively in industry for separation and purification of gas streams as
product recovery devices, and as pollution control devices. Gas absorbers are most widely used
to remove water soluble inorganic contaminants from air streams. Absorption is a process where
one or more soluble components of a gas mixture are dissolved in a liquid (i.e., a solvent).
7.1.1 Solute:
The component of gas that needs to be dissolved in a solvent
In our case the solute is ammonia that is dissolved in a lean solution of ammonia and water.
7.1.2 Solvent:
The substance that dissolved solute in it is called solvent.
Liquids commonly used as solvents include water, mineral oils, nonvolatile hydrocarbon oils,
and aqueous solutions. The solvent chosen should have a high solubility for the gas, low vapor
pressure, low viscosity, and should be relatively inexpensive.
Absorption, in chemistry, is a physical or chemical phenomenon or a process in
which atoms, molecules, or ions enter some bulk phase - gas, liquid or solid material. This
is a different process from adsorption, since the molecules are taken up by the volume, not
by surface. In gas absorption, soluble vapors are more or less absorbed in the solvent from its
mixture with inert gas. The purpose of such gas scrubbing operations may be any of the
following;
For separation of component having the economic value.
As a stage in the preparation of some compound.
For removing of undesired component (pollution).
7.2 Types of Absorption:
Physical absorption,
Chemical Absorption
119
7.2.1 Physical Absorption:

In physical absorption mass transfer take place purely by diffusion and physical absorption is
governed by the physical equilibria. Physical absorption occurs when the absorbed compound
dissolves in the solvent. Physical absorption depends on properties of the gas stream and solvent,
such as density and viscosity, as well as specific characteristics of the pollutant in the gas and the
liquid stream. These properties are temperature dependent, and lower temperatures generally
favor absorption of gases by the solvent. Absorption is also enhanced by greater contacting
surface, higher liquid-gas ratios, and higher concentrations in the gas stream.
7.2.1 Chemical Absorption:

Chemical absorption occurs when the absorbed compound and the solvent react. When oxides of
nitrogen absorb in water the chemical reaction take place and nitric acid form this is common
example of chemical absorption.
7.3 Types of Absorber:

There are three major types of absorbers which are mainly used for absorption purposes:
Packed column
Plate column
7.4 Packed Tower:

Packed towers, which are the most commonly, used gas absorbers for pollution control. Packed
towers are columns filled with packing materials that provide a large surface area to facilitate
contact between the liquid and gas. Packed tower absorbers can achieve higher removal
efficiencies, handle higher liquid rates, and have relatively lower water consumption
requirements than other types of gas absorbers. However, packed towers may also have high
system pressure drops, high clogging and fouling potential and extensive maintenance costs due
to the presence of packing materials. Installation, operation, and wastewater disposal costs may
also be higher for packed bed absorbers than for other absorbers.
120
Packed column 1
7.4.1 Application of Packed Column:

Columns used in certain types of chromatography consisting of a tube filled with packing
material can also be called packed columns and their structure has similarities to packed beds.
Column structure: Random and stacked packed columns
The column can be filled with random dumped packing or with structured packing sections,
which are arranged or stacked. In the column, liquids tend to wet the surface of the packing and
the vapors pass across this wetted surface, where mass transfer takes place. Packing material can
be used instead of trays to improve separation in distillation columns. Packing offers the
advantage of a lower pressure drop across the column, which is beneficial while operating under
vacuum. Differently shaped packing materials have different surface areas and void space
between the packing. Both of these factors affect packing performance.
Liquid and vapor distribution
Another factor in performance, in addition to the packing shape and surface area, is the liquid
and vapor distribution that enters the packed bed. The number of theoretical stages required to
make a given separation is calculated using a specific vapor to liquid ratio. If the liquid and
121
vapor are not evenly distributed across the superficial tower area as it enters the packed bed, the
liquid to vapor ratio will not be correct and the required separation will not be achieved. The
packing will appear to not be working properly. The height equivalent to a theoretical
plate (HETP) will be greater than expected. The problem is not the packing itself but the maldistribution of the fluids entering the packed bed. These columns can contain liquid distributors
and redistributors which help to distribute the liquid evenly over a section of packing, increasing
the efficiency of the mass transfer. The design of the liquid distributors used to introduce the
feed and reflux to a packed bed is critical to making the packing perform at maximum efficiency.
Packed column vapor-equilibrium curve
Packed columns have a continuous vapor-equilibrium curve, unlike conventional tray distillation
in which every tray represents a separate point of vapor-liquid equilibrium. However, when
modeling packed columns it is useful to compute a number of theoretical plates to denote the
separation efficiency of the packed column with respect to more traditional trays. In design, the
number of necessary theoretical equilibrium stages is first determined and then the packing
height equivalent to a theoretical equilibrium stage, known as the height equivalent to a
theoretical plate (HETP), is also determined. The total packing height required is the number
theoretical stages multiplied by the HETP.
7.4.2 Packed Bed Reactors

Packed bed reactors can be used in chemical reaction. These reactors are tubular and are filled
with solid catalyst particles, most often used to catalyze gas reactions.[2] The chemical reaction
takes place on the surface of the catalyst. The advantage of using a packed bed reactor is the
higher conversion per weight of catalyst than other catalytic reactors. The reaction rate is based
on the amount of the solid catalyst rather than the volume of the reactor
7.5 Plate Tower:

Plate, or tray, towers are vertical cylinders in which the liquid and gas are contacted in stepwise
fashion on trays (plates). Liquid enters at the top of the column and flows across each plate and
through a downspout (down comer) to the plates below. Gas moves upwards through openings in
the plates, bubbles into the liquid, and passes to the plate above. Plate towers are easier to clean
122
and tend to handle large temperature fluctuations better than packed towers do. However, at high
gas flow rates, plate towers exhibit larger pressure drops and have larger liquid holdups.
7.6 Packing Versus Trays

A tray column that is facing throughput problems may be de-bottlenecked by replacing a section
of trays with packings. This is because:
packings provide extra inter-facial area for liquid-vapour contact
efficiency of separation is increased for the same column height
packed columns are shorter than trayed columns
Packed columns are called continuous-contact columns while trayed columns are called stagedcontact columns because of the manner in which vapour and liquid are contacted.
123
7.7 Relative Merits of Plate and Packed Towers:

Plate column
Packed column
Can handle wide range of liquid rates Flooding can occur due to fluctuation in
without flooding
liquid rates
For large diameter column
For small diameter column
Cannot be used for highly corrosive Packed towers prove to be cheaper and
liquids
easier to construct if highly corrosive fluids

must be handled
Pressure drop more
Pressure drop is low
Total weight of dry plate tower is less Total weight of packed tower is high than
than packed tower
plate tower
Expensive
Less expensive
The choice between use of a plate tower or a packed tower for a given mass-transfer operation
should, theoretically, be based on a detailed cost analysis for the two types of contactors. In
many cases, however, the decision can be made on the basis of a qualitative analysis of the
relative advantages and disadvantages.
The following general advantages and disadvantages of plate and packed towers should be
considered when a choice must be made between the two types of contactors:
7.8 Absorber System Configuration:

Gas and liquid flow through an absorber may be
Countercurrent
Crosscurrent
Co current.
7.8.1 Countercurrent:
124
The most commonly installed designs are countercurrent, in which the waste gas stream enters at
the bottom of the absorber column and exits at the top. Conversely, the solvent stream enters at
the top and exits at the bottom. Countercurrent designs provide the highest theoretical removal
efficiency because gas with the lowest pollutant concentration contacts liquid with the lowest
pollutant concentration. This serves to maximize the average driving force for absorption
throughout the column.
7.8.2 Crosscurrent:
In a crosscurrent tower, the waste gas flows horizontally across the column while the solvent
flows vertically down the column. As a rule, crosscurrent designs have lower pressure drops and
require lower liquid-to-gas ratios than both co current and countercurrent designs. They are
applicable when gases are highly soluble, since they offer less contact time for absorption.
7.8.3 Co current:
In co current towers, both the waste gas and solvent enter the column at the top of the tower and
exit at the bottom. Co current designs have lower pressure drops, are not subject to flooding
limitation. Co current designs are only efficient where large absorption driving forces are
available. Removal efficiency is limited since the gas-liquid system approaches equilibrium at
the bottom of the tower.
7.9 Packed Tower Internals:

7.9.1 Tower Shell:
The tower shell may be made of steel or plastic, or some combination which may require the
addition of liners or inner layers of rubber, plastic or brick. The mechanical problems of
attaching depending on the corrosiveness of the gas and liquid streams, and the process operating
conditions.
7.9.2 Mist Eliminator:

At high gas velocities, the gas exiting the top of the column may carry off droplets of liquid as a
mist. To prevent this, a mist eliminator in the form of corrugated sheets or a layer of mesh can be
installed at the top
of the column to collect the liquid
droplets,
coalesce and fall back into the column.
which
125
7.10 Packing:
Packing materials provide a large wetted surface for the gas stream maximizing the area
available for mass transfer. Packing materials are available in a variety of forms, each having
specific characteristics with respect to surface area, pressure drop, weight, corrosion resistance,
and cost.
7.10.1 Requirements of Packing:
Provide a large surface area-for better contact.
Have an open structure-for low resistance to gas flow.
Promote uniform liquid distribution on the packing material.
Promote uniform vapor gas flow across the column cross section.
7.11 Packing Selection:

Packing materials are categorized as random or structured.
Dumped tower packing
Stacked tower packing
7.11.1 Dumped Tower Packing:

Random packing as the name implied, are dumped into a column during installation and allowed
to fall in random. Small packings poured randomly into a vessel is certainly the more popular
and commonly employed form of packed-tower design. However, in certain instances
where exceptionally low pressure drop and very high flow rates are involved, stacked or oriented
packing have also been used. Random packings are usually dumped into an absorption column
and allowed to settle.
126
7.11.2 Stacked Tower Packing:

Structured packings are considerably more expensive per unit volume than random packings.
They come with different sizes and are neatly stacked in the column. Structure packing usually
offer less pressure drop and have higher efficiency and capacity than random packing. Structured
packing may be random packing connected in an orderly arrangement,
7.12 Types of Packing:

7.12.1 Pall rings:
Pall ring that is improved on the basis of rashing rings. The design of pall rings provide higher
capacity and lower pressure drop than other packing the open cylindrical walls and inward bends
protrusions of pall rings allow greater capacity and lower pressure drop.
Lower pressure drop (less than half) than Raschig rings, also lower HTU (in some systems also
lower than Berl saddles), higher flooding limit. Good liquid distribution, high capacity.
Considerable side thrust on column wall. Available in metal, plastic and ceramic.
These are of two types:
7.12.2 Metal Pall Rings:

127
The rings are made up of metal.
7.12.3
Plastic Pall
Rings:
The rings are made up of
plastic material.
7.13 Distributor:
Distribution of the liquid onto the packed bed or structured packing is realsed by appropriate
liquid distributors. It is important to distribute the liquid flow equally across the column area in
order to secure an intensive mass transfer between the phases.
In addition to the task of regular liquid distribution the part has to meet following requirements:
pressure drop in the gas phase should be low
part should be resistant against dirt or solids in the liquid
high turn down ratio
low entrainment of droplets
prevention of irregular gas distribution
prevention of wall effect on liquid flow

128
Distributors are used for the good distribution of liquid over the packing so that the liquid come
in contact properly with incoming gas.
7.14 Types of The Distributors:

The following types of liquid distributors are available:
orifice distributor
trough distributor
rough-type distributor
ladder-type distributor
spray nozzle-type distributor
7.14.1 Trough Distributor:

Trough distributor provides good distribution under widely varying flow rates of gas and liquid.
the liquid may flow through simple V notched weirs, or it may flow through tubes that extend
from troughs to near the upper level of the packings.some deposition of solids can be
accommodated. Because of its large free area at is suitable for high gas rates.
129
Orifice trough liquid distributor
7.14.2 Orifice Distributor:

Orifice distributor type which gives very fine distribution though it must be correctly sized for a
particular duty and should not be used where is disk of plugging. The orifice riser distributor is
designed to lay the liquid carefully onto the bed, with a minimum of contact with gas during the
process.
7.14.3 Perforated Pipe Distributor:

The perforated ring type of distributor for use with absorption columns where high gas rates and
relatively small liquid rates are ecounter.this is specially suitable where pressure loss must be
minimized, for the larger size of tower where installation through manholes is necessary, it may
be made up in flanged sections. The orifices are of 4 to 6 mm in diameter, and can be subject to
plugging if foreign material is present. The pipe must be carefully leveled for larger diameter
column.
130
7.14.4 Redistributors:
The liquid coming down through the packing and on the wall of the tower should be redistributed
after a bed depth of approximately 4 tower diameter for rashing rings and 5-10 tower diameters
for saddle packings.Collector/Redistributors, is very similar to the distributor in that it will
contain a deck and chimneys. The collector is used under a packed bed section to collect the
liquid to aid in mixing and redistribution. The difference is that the redistributors will contain
caps or hats to prevent the water falling from the packing from bypassing the collector.
7.15 Support Plates:

These are the simplest and least expensive type of packing supports. They also utilize the least
vertical space. They are designed for low to medium gas loading when used for dumped packing
and
typically
have
50
to
90%
open
areas
depending
on
the
material
used.
The support grids are available in various materials such as plastic, FRP and metals. They can
131
also be used as bed limiters. Sometimes support beams are required for structural reasons
depending on the material and size of the support grate.
7.15.1 Gas Injection Support Plate:

It is a device used to hold the packing. It generally sits on a support ledge and can be supported
additionally by structural beams. There are two design criteria for the gas injection support plate.
It must hold the packing and liquid hold-up but also requires an open are greater than the cross
sectional area of the tower. The larger open area is accomplished by using slotted or perforated
plate that is corrugated or positioned in such a way to allow increased gas flow. Open area ranges
from 85% to greater than 100%.
7.15.2 Grid Type Support Plates (APS-GS):

Grid type packing supports are used for structured packing to provide a horizontal contact
surface and to prevent distortion of the packing. This design can also be considered for
random packing. A wide range of openings is available to prevent the packing from falling
through. The supports typically rest on support ledges. For larger towers with man ways,
sectional designs are standard.
132
7.16 Design of Absorber:

7.16.1 General Design Steps:
The designer is required to consider and determine
Select suitable column type
Select appropriate solvent
Select type and size of packing
Material and energy balance
Calculate column diameter
Pressure drop calculation
Determine the number of transfer units
Determine height of transfer unit
Find the height of column
Select column internals
7.17 Input Data:

Packing type
3 Ceramic Raschig Ring
Packing size
76mm
Packing factor, (Fp)
65m-1
Surface area of packing (a p)
69m2/m3
Bulk density
561 kg/m3
Voidage
75%
7.17.1 Gas Properties:

Gas flow rate
81368.6 kg/hr
Gas viscosity
1.752 * 10 -2 cP
Gas pressure at entry
3061 kPa
Gas temperature at entry
49 C
Gas mol weight (Mg)
18.70
133
Gas density (g)
21.84 kg/m3
7.17.2 Component to be Scrubbed:

Component Name
Hydrogen Sulfide
Component flow rate
73.029
Molecular weight of comp (Mg)
34
7.17.3 Liquid Properties:

Liquid flow rate, L
118456.3 kg/hr
Liquid Density, (l)
978.1 kg/m3
Liquid Viscosity, (l)
0.6752 cp
Molecular wt of liquid (Ml)
18.54
7.18 Column Diameter Calculations:

Assume pressure drop
= 42 mmH2O/m of packing
7.18.1 Column Diameter:
K4= 1.3
Annexure C
(Ref. Coulson and Richardson Vol 6, fig 11.4)
K4=2.23 at flooding
Gw* = [K4 v( l v) /13.1 Fp (l /l)0.1]1/2
=
11.47 kg/m2 s
Column Area Required = 22.602/ 11.47

= 1.969 m2
D =
= 1.58 m
7.19 Area Calculation:

134
Ac = /4(D)2
Ac =
1.77 m2
7.20 Liquid Mass Velocity:

L = 16.71 Kg/s m2
7.21 Percentage Flooding:

K4 at flooding from graph = 2.23
2
K 4 13.1Vw * Fp (l / l )0.1 /( v / l v )
K4 = 1.3
Percentage flooding = (K4/ K4) 0.5*100
= 76%
7.22 Height of The Column:

Height of packing:
Z = HOGNOG
HOG = height of overall gas phase transfer unit
NOG = number of overall gas phase transfer unit
As we know
HOG = HG + m ( G/L)HL
m = slope of equilibrium line
L/G= slope of operating line
To calculate HOG there are two methods:
Cornells method
Ondas method
We use Cornells method:
According to it
7.22.1 Individual Height of Gas Phase Transfer Unit Calculations:

HG = 0.01h (Sc)v0.5(Dc/0.305)1.11(Z/3.05)0.23/ (L*f1*f 2*f3)
HG = height of gas phase transfer unit
h = at 58% flooding = 80
(Annexure C)
Lw = 16.71 kg/m sec
135
f1 = liquid viscosity correction factor

f1 = (L/ w)
f1= 1.217
f 2 =liquid density correction factor
f 2 = (w / L)
1.25
f 2 = 1.0152
f3 = surface tension correction factor
f3 = (w/ L)
f3= 0.987
Dv = 1.86 * 10-3 m2/s

(Sc)v= gas phase Schmidt number= ( v/ vDv)
(Sc)v = 0.429
HG =0.699m
7.22.2 Individual Height of Liquid Phase Transfer Unit Calculations:

HL= 0.305h (Sc)L0.5K3 (Z/3.05)0.15
HL = height of liquid phase transfer unit
K3 = at 58% flooding = 0.87
Annexure C
h = 6.2 * 10-2
Annexure C
(Sc)L= liquid phase Schmidt number= ( l/ lDl)
136
(Sc)L = 976.47
HL = 0.6
7.22.3 Overall Height of Gas Phase Transfer Unit:

HOG = 1.03
Now
Y1/ Y2 = 0.0008/0.0000167
Y1/ Y2 = 47.90
NOG = 6.2
(Annexure)
Then
Z = HOGNOG
Z = 6.4m approximately same as calculated from the estimated value
7.23 Liquid Hold up Calculation:

Hlw =0.0004(L/dp) 0.6
Hlw = water holdup (ft3 liquid/ ft3 vol of tower)
dp = equivalent spherical packing diameter (inches)
L= liquid rate (lb/ft2hr)
So
Hlw =0.0004(16.71/2.9)0.6
Hlw = 1.14m3/m3 of tower (ref. applied process design for chemical & petrochemical
plant By Ernest E. Ludwig)
137
SPECIFICATION SHEET
Item
Packed Absorption Column
No. required
01
Function
To absorb hydrogen sulphide in

chelated iron solution.
Operation
Continous
Design Temperature
316 K
Design Pressure
3061 kPa
Size and type of packing
3 Ceramic Raschig Ring
Diameter
1.5 m
Packing arrangement
dumped
138
139
HEAT EXCHANGER DESIGN
8.1 INTRODUCTION
A Heat Exchanger is a heat transfer device that is used for transfer of internal thermal energy
between two or more fluids available at different temperatures. In most of the exchangers the
fluids are separated by a heat transfer surface and ideally dont mix with each other.
8.1.1 BASIC PRINCIPLE OF HEAT EXCHANGERS

The basic principle of a heat exchanger is the exchange of thermal energy on the basis of thermal
gradients between two bodies (fluids). The mechanism of heat transfer in heat exchangers is the
combination of the basic heat transfer mechanisms. The basic heat transfer mechanisms are:
Conduction
Convection
CONDUCTION
Conduction is the transfer of thermal energy from a region of higher temperature to a region of
lower temperature through direct molecular communication within a medium or between
mediums in direct physical contact without a flow of the material medium. The transfer of
energy could be primarily by elastic impact as in fluids or by free electron diffusion as
predominant in metals.
Conduction is greater in solids, where atoms are in constant contact. In liquids (except
liquid metals) and gases, the molecules are usually further apart, giving a lower chance of
molecules colliding and passing on thermal energy.
140
CONVECTION
Convection is a combination of conduction and the transfer of thermal energy by fluid circulation
or movement of the hot particles in bulk to cooler areas in a material medium. Unlike the case of
pure conduction, now currents in fluids are additionally involved in convection. This movement
occurs into a fluid or within a fluid, and cannot happen in solids. In solids, molecules keep their
relative position to such an extent that bulk movement or flow is prohibited, and therefore
convection does not occur. Forced convection, by contrast, occurs when pumps, fans or other
means are used to propel the fluid and create an artificially induced convection current. Forced
heat convection is sometimes referred to as heat advection, or sometimes simply advection.
Fig: 8.1. Mechanism of Heat Transfer
141
8.2 TYPES OF FLOW ARRANGEMENTS IN HEAT EXCHANGERS

The flow type in a heat exchanger, which is the most common in practice, may be of one of the
following types:
Parallel-flow
Counter-flow
Cross-flow
8.2.1 PARALLEL FLOW HEAT EXCHANGER

In parallel-flow heat exchangers, the two fluids enter the exchanger at the same end, and travel in
parallel to one another to the other side.
8.2.2 COUNTER FLOW HEAT EXCHANGER

In counter flow heat exchangers, which are often more efficient, the fluids enter the exchanger
from opposite ends. See countercurrent exchange. Counter current exchange is a mechanism
used to transfer some component of a fluid from one flowing current of fluid to another across a
permeable barrier between them.
8.2.3 CROSS FLOW HEAT EXCHANGER

In a cross-flow heat exchanger, the fluids travel roughly perpendicular to one another through the
exchanger. The required surface area, across for this heat exchanger is usually calculated by
using tables. It is between the required surface area for counter-flow and parallel-flow i.e.
A counter < A cross < A parallel
142
8.3 SELECTION CRITERIA FOR HEAT EXCHANGERS

The selection process includes a number of factors, depending upon heat transfer application.
These are as:
Space
Operating temperature
Efficiency
Flow rates
Availability
Flow arrangements
Ease of construction.
Intended application
Operating pressure
Fouling tendencies
Material Compatibility
Types and phases of fluids
Material of construction
Fabrication technique
Operational maintenance
Overall economy
Thermal requirement and repair

possibilities
Maintenance, inspection,
cleaning, extension,
8.4 SHELL AND TUBE HEAT EXCHANGER

In process industries, shell and tube exchangers are used in great numbers, far more than any
other type of exchanger. More than 90-95% of heat exchangers used in industry are of the shell
and tube type. The shell and tube heat exchangers are the work horses of industrial process
heat transfer.
They are the first choice because of well-established procedures for design and manufacture
from a wide variety of materials, many years of satisfactory service, and availability of codes and
standards for design and fabrication. They are produced in the widest variety of sizes and styles.
There is virtually no limit on the operating temperature and pressure.
143
Fig: 8.2. Shell & Tube Heat Exchanger
We employed shell and tube heat exchanger due to following reasons:
It occupies less space.
Its maintenance is easy.
Its compactness is more.
They can tolerate dirty fluids.
It is used for high heat transfer duties.
These are mostly employed in industry.
Means of directing fluid through the tubes.
Means of controlling fluid flow through the shell.
Used where large heat transfer surfaces are required
Consideration for ease of maintenance and servicing.
Consideration for differential thermal expansion of tubes and shell.
It can be fabricated with any type of material depend up fluid properties.
They can be operated at higher temperature difference b/w coolant and gas.
Shell and Tube heat exchangers are used on applications where the demands on high
temperatures and pressures are significant.
144
8.5 MAJOR COMPONENTS DESIGNED IN PRELIMINARY DESIGN

TUBES
Tubing that is generally used in TEMA sizes is made from low carbon steel, copper, Admiralty,
Copper-Nickel, stainless steel, Cast alloy, Inconel, titanium and a few others. Tubes are either
generally drawn and seamless or welded.
TUBE LAYOUT PATTERNS
There are four tube layout patterns, as shown,
Triangular (30),
Rotated Triangular (60),
Square (90),
Rotated Square (45).
Fig: 8.3. Tube Pitch
145
8.6 DESIGN OF HEAT EXCHANGER

8.6.1 HEAT LOAD
HEAT INPUT = HEAT OUTPUT
COLD STREAM
Q = mc Cp t
Where;
Mass flow rate of cold stream = mc =68400kg/hr
Cp = 4.79 kJ/kg.C
Temperature difference = t = (t2 t1) = (250-110)
= 140 OC
So Q comes out to be;
Q= 4.35 10^7 kJ/hr
HOT STREAM
Q = mh Cp T
Where;
Mass flow rate of hot stream = mh = 160905 kg/hr
Cp = 3.062 kJ/kg.C
Inlet temperature = T1 = 430OC
Outlet temperature = T2 =?
SO,
T2 = 306 OC
8.6.2 LMTD
Assuming counter current flow
Temperatures
Temperatures
Hot stream
430
306
water
110
250
146
T
320
56
LMTD comes out to be:

LMTD = 151.46 OC
R=
So,
R=0.89
S= 0.78
From graph correction factor found to be

FT = 0.85
Corrected LMTD:
LMTD = 128.7 OC
8.6.3 ROUTING
Rule of thumb: In the case of liquid and gas system the most expensive fluid is placed in the
tubes of exchanger and other one in the shell side.
Shell side = water
Tube side = gases
8.6.4 DETERMINATION OF AREA

Assume
Uo = 570 W/m2.K
(Reference: Coulson &Richardson Chemical Engineering, volume 6)

Q= A LMTD Uo
Where;
Area = A =
LMTD = 128.7 OC
Uo = 570 W/m2.K
Area = 190 m2
147
8.6.5 CHOICE OF TUBES

1 inch OD tubes with 1.25 inch tubular pitch, 16 BWG
(Reference: Perrys Chemical Engineering hand book)
do = 1 inch = 24.5 mm = 0.0245 m
di = 0.87 inch = 22.1 mm = 0.0221m
PT = 31.75 mm = 0.03175m
Let us assume the length of the tube be 6m
(Reference: Coulson &Richardson Chemical Engineering, volume 6)
8.6.6 NUMBER OF TUBES
NT= 411 tubes
8.6.7 CORRECTION OF HEAT TRANSFER AREA

From FT graph we have selected 3 shell passes and 6 tube passes.
From tube sheet count:
Ds = 0.7366 m
(Reference: D.Q.Kern, Process Heat Transfer, pg: 841)
From this
No of tubes = Nt= 338
Corrected area = Ac = 161.7 m2
Corrected Uoc = 669 W/m2.K
148
8.6.8 CALCULATION OF INSIDE HEAT TRANSFER COEFFICIENT

FLOW AREA OF THE TUBE:
Area of the tube = at =
Where;
Inside diameter = di = 0.0221m
Number of tubes = Nt = 338
Number of passes = Np = 6
at= 0.022 m2
MASS VELOCITY
G = mass flow rate of gases / flow area
Where;
Mass flow rate of hot stream = mh= 160905 kg/hr
Flow area =at = 0.022 m2
G = 2031.62 kg/m2.sec
8.6.9 VELOCITY INSIDE THE TUBES

Vt = m/ (*at)
Where:
Density of gas = 10.15 kg/m3
(Report: Biomass to Hydrogen Production Detailed Design and Economics Utilizing the
Battelle Columbus Laboratory Indirectly Heated Gasifier, National Renewable Energy
Laboratory).
Vt = 2.1 m/s
This is within acceptable range of 1-3 m/s
(Reference: John E.Edwards, Design and rating of shell & tube heat exchanger pg:11)
149
REYNOLD NUMBER
Where;
= 0.024 cp = 2.4 e -5 kg/m-s
Re = 1777125
PRANDTL NUMBER
Npr = Cp /k
Where:
k= 0.076 W/mK
Npr =9.66 e-4
For hi:
JH = 350
And
hi=1.82 e 5 KW/m2K
8.6.10 CALCULATION OF OUTSIDE HEAT TRANSFER COEFFICIENT

Length of the tube = Ln = 6m
Baffle spacing = Ls = 0.266 Ds
= 0.266 0.736
= 0.195 m
Number of baffles = Nb+1 = 6/Ls
Nb = 30
150
SHELL SIDE FLOW AREA
Where;
Shell side flow area = Sm =
Baffle spacing = Ls = 0.195 m
Tube pitch = Pt = 0.03175m
Do = 0.0254m
Ds = 0.736 m
Sm=0.029m2
VELOCITY
Where;
Mass flow rate of cold stream = mc =68400 kg/hr
Density of water = w = 887 kg/m3 (at 165 OC)
Vs = 0.73 m/sec
The above value of the velocity is also in the range of 0.3 -1 m/s so it is also acceptable.
EQUIVALENT DIAMETER
De =
( )
151
Where;
Pitch = Pt = 0.03175 m
De = 0.018m
REYNOLD NUMBER
For Gw;
Gw = mass flow rate /flow area
Where;
Flow area = 0.029 m2
Gw = 655.17 kg/m2.sec
And
= 2.049 e -5 kg/m.s
Re = 575551.9
jH = 200
OUTSIDE HEAT TRANSFER CO-EFFICIENT
Pr = Cp /k
Where;
Cp = 4.79 kJ/kg.C
= 2.049 e -5 kg/m.s
k= 0.6766 W/K.m
152
Pr = 0.143
So;
ho= 2.06 e 5 kW/m2K
[1/Uo] = [1/ho] + [Do/Di][1/ho] + [Do ln{Do/Di}/2Kw)] + [1/hod] +[Do/Di][1/hid]
Take
1/hid = 0.0005 m2 OC / W
1/hod= 0.0003m2 OC / W
Kw = 55 W/Km (for stainless steel material)
(Reference: Coulson & Rechardson , Chemical Engineering, Pg:634)
Uo = 664 W/m2K
8.6.10 PRESSURE DROP CALCULATIONS

FOR TUBE SIDE
f= 0.079 (Re) ^ (-0.25)
Re = 1777125
f= 2.16 e-3
As
Where;
Tube side velocity= Vt = 2.1 m/s
Density of fluid = f = 10.15 kg/m3
Inside diameter of the tube = di = 0.0221m
L = 6m
f= 2.16 e-3
153
P = 52.49 KPa
As the value of the pressure drop should be less than 70 KPa, the design is acceptable from the
tube side pressure drop consideration.
FOR THE SHELL SIDE

CROSS FLOW SECTIONS
Pressure drop in the cross flow sections is calculated by:
Ka = 1.5
Kf = 0.245 + (0.339 10^4/Re) (0.984 10^7/Re^2) + (0.113 10^11/Re^3)
(0.59910^3/Re^4)
(Reference: Max.S.Peters, Plant Design & Econimics For Chemical Engineering, pg: 711,
5th edition)
Where;
Re = 575551.9
Kf =0.251
Vs = 0.73 m/s
Nc= no of cross rows:
Nc= [Ds (1-2{Lc/Ds })/PTp]
Ds = 0.736m
Lc = Bc Ds /100
Where;
Bc = percentage baffle cut
Lc=baffle cut distance
154
For 25 % baffle cut

Lc = 0.184 m
For triangular pitch
PTP = 0.866PT
PT = 0.03175m
PTP = 0.0274 m
NC = 11.59
Pc = 12.11 Kpa
END ZONES
Pressure drop in end zone:
Pe= Pc (1+ {Ncw/Nc})
Ncw = Number of the effective cross flow rows in end zone
Ncw = 4.64
Pe = 16.96 kPa
WINDOW ZONES
Pw = [ mT^2(2+0.6Ncw)/{SmSw)]
Where:
Sm = 0.029 m2
Nt= 338
155
Sw =Swg Swt
Swg = 100 inch2
= 0.0645 m2
(Reference: Perry, Chemical Engineering Handbook, pg :10-26)
Swt = (Nt/8) (1-Fc) Do2
Where;
Fc = 0.65
(Reference: Perry, Chemical Engineering Handbook, pg 10-28)
Swt = 0.119m2
Sw = 0.0553 m2
Pw = 16 kPa
TOTAL PRESSURE ON SHELL SIDE

Ps(total) = 2 Pe +(Nb-1)Pc + Nb Pw
Where;
Nb=30
Ps = 65 kPa
As this value is on the shell side is less than 70 kPa, the design is acceptable from the pressure
drop less than 70 KPa, the design is acceptable from pressure drop view.
156
8.7 MECHANICAL DESIGN

SHELL THICKNESS
MATERIAL
Carbon steel
Permissible tensile strength = f= 950 kg/cm2
SHELL THICKNESS
ts = [{PDi}/(2fJ P)]
Where;
P=design pressure = 2.69 atm
Di = diameter = 736.6 mm
J = joint efficiency = 0.85
ts = 1.18 mm
it is found that minimum shell thickness when severe conditions are not expected is 8mm which
includes the corrosion allowances
(Reference: M.V Joshi, Process Equipment Design)
NOZZLES
Take inlet and outlet nozzles as 100mm diameter
Vent nozzle = 25 mm diameter
Drain = 25 mm diameter
Relief valve = 50 mm diameter
Nozzle thickness = [{PDi}/(2fJ P)]
= 0.16 mm
157
TRANSVERSE BAFFLES
No of baffles= 30
Baffle cut = 25%
Baffle thickness = 6mm (standard)
TUBE SIDE
Material: stainless steel
Thickness of tube = {PDo}/ {2 f J +P}
Where;
P = design Pressure = 2.721 N/mm2
Joint efficiency =1
Permissible stress =f= 100.6 N/mm2
(Reference: M.V Joshi, Process Equipment Design)
Thickness = 1.65 mm
TUBE SHEET
Thickness of tube sheet = FG [(0.25 P)/f]
Where
F= 1.25
G= mean diameter = 23.75mm
P= 2.7 N/mm2
Permissible stress =f= 100.6 N/mm2
Tube thickness = 243mm
158
SUPPORT FOR SHELL AND TUBE HEAT EXCHANGER

Length of the exchanger = L =6000mm
Inner diameter of the shell = Di =736 mm
Outer diameter of the shell = Do = 737.18mm
No of tubes = 338
Density of the steel = 7850 Kg/m3
(Reference: D.Q.Kern, Process Heat Transfer, pg 835)
Density of gases in tube = 10.35 kg/m3
VOLUME OF SHELL BODY
V = 0.022m3
Weight of the solid body =Ws= Vs = 172.7 kg
VOLUME OF THE TUBE

Outside diameter = do =0.0254m
Vt = 0.012m3
Total weights of the tubes =Wt = Vt s
Wt = 94.2 kg
159
VOLUME OF HEAD
Volume of the head = Vh = 0.087 Di^3
= 0.034m3
Weight of head=Wh = Vh s
Wh = 272 kg
Weight of the liquid=Wl= (/4) (di^2) L N l
Where;
Length of the tube = L= 6m
Wl =12.24 kg
Total weight = Ws +Wt +Wh +Wl
Where;
Wl =12.24 kg
Wt = 94.2 kg
Wh = 272 kg
Ws= 172.7 kg
Wt= 550 kg
160
SPECIFICATION SHEET
Heat exchanger type

Flow rate of the gases
Flow rate of the water
Outer diameter of the shell
Number of tubes
Tube OD
Pitch (triangular)
Tube length
Shell side pressure drop
Tube side pressure drop
No of Baffles
Shell material
Tube material
TEMA 3-6 Heat Exchanger

160905 kg/hr
168000 kg/hr
0.736m
338
0.0254m
0.03175m , 16 BWG
6m
65 kPa
52.49 kPa
30
Carbon steel
Stainless steel
REFERENCES
John E. Edward, Heat Exchanger Design & Rating Shell & Tube Heat Exchanger,
August 29, 2008
Donald Q.Kern, Process Heat transfer, International student Ed., pp: 830, Fig. 18.
(1950)
Coulson Richardsons R.K. Sinnott, Chemical Engineering Design, 3rd Ed, pp: 569,
Vol.6. (1991).
Max S.Peters Klaus D. Timmerhaus Ronald E.West Plant Design and Economics for
Chemical Engineers, 5th Ed. pp: 661, table 14-3. (1993).
161
DESIGN OF PRESSURE SWING ADSORBER

9.1 ADSORPTION
Adsorption is the accumulation of atoms or molecules on the surface of a material. This process
creates a film of the adsorbate (the molecules or atoms being accumulated) on the adsorbent's
surface. It is different from absorption.
Adsorption is present in many natural physical, biological, and chemical systems, and is widely
used in industrial applications such as activated charcoal, synthetic resins, and water purification.
Adsorption, ion exchange, and chromatography are sorption processes in which certain
adsorbates are selectively transferred from the fluid phase to the surface of insoluble, rigid
particles suspended in a vessel or packed in a column.
Similar to surface tension, adsorption is a consequence of surface energy. In a bulk material, all
the bonding requirements (be they ionic, covalent, or metallic) of the constituent atoms of the
material are filled by other atoms in the material. However, atoms on the surface of the adsorbent
are not wholly surrounded by other adsorbent atoms and therefore can attract adsorbates. The
exact nature of the bonding depends on the details of the species involved, but the adsorption
process is generally classified as physisorption (characteristic of weak van der Waals forces) or
chemisorption (characteristic of covalent bonding).
Fig: 9.1 Adsorption on the surface of activated charcoal [1]
Physisorption, also called physical adsorption, is a process in which the electronic structure of
the atom or molecule is barely perturbed upon adsorption.The weak bonding of physisorption is
164
due to the induced dipole moment of a nonpolar adsorbate interacting with its own image charge
in the polarizable solid.
Chemisorption is a classification of adsorption characterized by a strong interaction between an
adsorbate and a substrate surface, as opposed to physisorption which is characterized by a weak
Van der Waals force. A distinction between the two can be difficult and it is conventionally
accepted that it is around 0.5 eV of binding energy per atom or molecule. The types of strong
interactions include chemical bonds of the ionic or covalent variety, depending on the species
involved.
It is characterized by:
High temperatures.
Type of interaction: strong; covalent bond between adsorbate and surface.
High enthalpy: -50 kJ/mol >H> -800 kJ/mol
Adsorption takes place only in a monolayer.
High activation energy
Increase in electron density in the adsorbent-adsorbate interface.
Reversible only at high temperature.
Due to specificity, the nature of chemisorption can greatly differ from system to system, depending
on the chemical identity and the surface structure.
9.1.1 Importance of Adsorber in the Process

PSA systems for the purification of hydrogen where a wide range of impurities are adsorbed and
removed while high purity hydrogen is produced.
Typically the feed stream is delivered for processing at 100 - 400 psig with high purity hydrogen
produced at near feed pressure while the impurities are rejected at low pressure.
9.2 ADSORPTION ISOTHERMS

The adsorption isotherm is the relationship between the concentration in the fluid phase and the
concentration in the solid phase at a given temperature.
9.2.1 Types of Isotherms

Five types of isotherms are known which are shown in the graph below:
165
Fig: 9.2 Types of isotherm
1) Linear Isotherm: The linear isotherm goes through the origin and the amount adsorbed is
proportional to the concentration in the fluid.
2) Favorable Isotherm: Isotherms that are convex upward are called favourable because a
relatively high solid loading can be obtained at low concentration in the fluid.
3) Irreversible Isotherm: The limiting case of a very favourable isotherm is irreversible
adsorption where the amount adsorbed is independent of concentration down to very low values.
Dehydration of ethylene by molecular sieves falls in this class of isotherms.
4) Unfavorable Isotherm: An isotherm that is concave upward is called unfavorable, because
relatively low solid loadings are obtained and because it leads to large mass transfer zones.
Different theories have been given to explain these isotherms such as Gibbs, Langmiur, etc.
9.3TYPES OF ADSORPTION CYCLES:

1) Temperature-swing adsorption: In the temperature-swing cycle, a feed stream containing a
small quantity of an adsorbate at some partial pressure and some temperature is send through the
bed. After equilibrium is reached between the adsorbate and adsorbent, regeneration requires
raising the temperature of bed higher than that used in adsorption.
2) Inert-Purge Cycle: In this cycle, the adsorbate during regeneration is removed by sending a
nonadsorbing gas containing no adsorbate through the bed. This procedure lowers the partial
pressure of the adsorbate and initiates the desorption process. If sufficient pure purge gas is
directed through the bed, the adsorbate will be completely removed and adsorption can be
resumed.
3) Displacement Purge Cycle: This cycle differs from the inert purge cycle, since the cycle uses
a gas or liquid in the regeneration step that adsorbs about as strongly as the adsorbate.
166
4) Pressure swing adsorption: In this cycle, a fraction of the less adsorbed gas product is used
as a low pressure purge gas. Often the purge flow is in the opposite direction from that for the
feed flow. The total cycle involves four steps
Adsorption
Depressurization
Regeneration
Repressurization
9.4SELECTION OF APPROPRIATE ADSORPTION CYCLE

Keller et al have developed a simple matrix that can rapidly serve as a guide for making this
choice with essentially no calculations. The table is shown below:
Table: 9.1 Selection of appropriate adsorption cycle
9.4.1 Comparison of TSA and PSA

The classical method for the regeneration of an impurity-loaded adsorbent is to heat the
adsorbent to high temperature by hot gas. At high temperatures the adsorbents capacity is
reduced, and impurities are desorbed. After the adsorbent is regenerated, it must be cooled down
to be ready for a new adsorption step. Although the cleaning effect of temperature-swing
regeneration is effective, it has the disadvantage that the number of
cycles obtainable in any given time is limited by the relatively slow heating and cooling process
steps. For this reason, the temperature-swing process is limited to the removal of small quantities
of strongly adsorbed impurities. The removal of the adsorbed impurities in a pressure-swing
adsorption system depends on reducing adsorptive capacity by lowering the pressure at
167
essentially constant temperature. Because pressure-swing adsorption allows a much more rapid
cycling, it can remove large quantities of impurities and also maintain the ability to remove
impurities to low levels. A comparison between temperature-swing and pressure-swing
regeneration is graphically represented in Figure
6: the adsorption isotherms show the adsorbed impurity loading as a function of pressure and
temperature. In a temperature-swing adsorption (TSA) cycle, the regeneration is carried out at
constant pressure reducing the loading by increasing the temperature. The loading can also be
reduced at constant temperature by lowering the pressure, which is the case in a pressure-swing
adsorption (PSA) cycle.
9.4.2
TSA and PSA Regeneration Cycles
Fig: 9.3 PSA and TSA regeneration cycle

168
9.5 SELECTION OF HYDROGEN PURIFICATION TECHNOLOGY

To conclude, the choice of the optimum purification method for a particular specific industrial
applications must be considered very rationally. It should be perfectly based on the criterion of
technical and economics. Given below is the table that shows, the degree of purity of hydrogen that is
obtained from the different methods of separation. It could also be seen from the table that the
amount of recovery of hydrogen also varies considerably. Now these can play a major role on
process economics, especially in large scale applications.
9.5.1
Comparison between different separation techniques
Technique
Purity
Cryogenic
Separation
Principle
Typical feed
Gas
Hydrogen
Output(in%)
Extent of use
Notes
Recovery
90-98
95
Large
Prepurification
step essential
to remove
H2S and
water
Partial
condensation
of gas
mixtures at
low
temperatures
Petrochemic
al and
refinery offgases
Polymer
Membrane
Diffusion
Differential
rate of
diffusion of
gases
through a
permeable
membrane
Refinery offgases and

ammonia
purge gas
92-98
>85
Small-large
He, CO, and

water may
also
permeate the
membrane
Metal
Hybrid
Reversible
reaction of
ammonia
purge gas
99
75-95
Smallmedium
Hydrogen
absorption
contaminate
d by oxygen,
169
Separation
hydrogen with metals to form

hydride
nitrogen
Solid
Polymer
Electrolyte
Cell
Electrolytic
passage of
hydrogen
ions across a
solid
polymer
membrane
Purification
of hydrogen
produced by
thermochemi
cal cycles
99.8
95
Small
Sulphurcontaining
compounds
contaminates
the electrocatalysts
Pressure
Swing
Adsorption
Selective
adsorption of
impurities
from gas
stream
Hydrogen
rich gas
(any)
'99.999
70-85
Large
The recovery
is relatively
low as
hydrogen is
lost in the
purging step
Palladium
membrane
Diffusion
Selective
diffusion of
hydrogen
through a
palladium
alloy
membrane
Hydrogen
rich gas
(any)
More than or
equal to
99.9999
Up to 99
Smallmedium
Sulphurcontaining
compounds
and
unsaturated
hydrocarbon
impair the
permeability
9.6 PSA Unit

Pressure Swing Adsorption (PSA) is a technology used to separate some gas species from a
mixture of gases under pressure according to the species' molecular characteristics and affinity
for an adsorbent material. It operates at near-ambient temperatures and so differs from cryogenic
distillation techniques of gas separation. Special adsorptive materials (e.g., zeolites) are used as a
molecular sieve, preferentially adsorbing the target gas species at high pressure. The process then
swings to low pressure to desorb the adsorbent material .
170
Fig: 9.4 PSA unit
9.6.1 Process Description

The PSA process is based on the principle that adsorbents are capable of adsorbing more
impurities at a higher gas-phase partial pressure than at a lower partial pressure. The impurities
are adsorbed in a fixed-bed adsorber at high pressure and then rejected as the system pressure
swings to a lower level. Hydrogen is essentially not adsorbed. The ability to completely adsorb
impurities allows the production of a hydrogen product with very high (> 99.9 vol-%) purity.
The basic flow scheme of the PSA process is shown in Figure 1. The process operates at ambient
temperature on a cyclic basis. The PSA process is a semibatch-type process that uses multiple
adsorbers to provide constant feed, product, and offgas (for fuel) flows. The high-purity
hydrogen product leaves the system close to the feed gas pressure. The offgas (impurities and the
hydrogen losses) is available at low pressure as fuel.
171
9.6.2 PSA Process Steps

Although the PSA process is a batch process, it uses multiple adsorbers operating in a staggered
sequence. Therefore, the process appears to be a continuous process at the battery limits.
A complete pressure-swing cycle consists of the following five basic steps:
Adsorption
Cocurrent depressurisation
Countercurrent depressurisation
Purge at low pressure
Repressurisation
These basic steps apply to all PSA units regardless of the number of adsorber vessels
Fig: 9.5 Basic Steps of PSA unit

Adsorption (Step 1-2)
The feed gas is introduced at the high adsorption pressure, impurities are adsorbed, and high-purity
hydrogen is withdrawn as product. Flow is normally in the upward direction.
When an adsorber has reached its adsorption capacity, it is taken off-line, and the feed is
automatically switched to a fresh adsorber. This practice maintains constant feed and product flows.
Cocurrent depressurisation (Step 2-3)

To recover the hydrogen trapped in the adsorbent void spaces in the adsorber, the adsorber is
depressurized from the product side in the same direction as the feed flow (cocurrent), and highpurity hydrogen is withdrawn. This cocurrent depressurisation takes place in typically one to six
172
discrete steps. The hydrogen is used internally in the system to repressurise (equalise) and purge
other adsorbers.
Countercurrent depressuisation (Step 3-4)

The saturated adsorber is then generated in a series of steps. After the hydrogen recovery steps
are complete, the impurity fronts have migrated to the top of the adsorbent bed, and the bed has
no remaining capacity. The bed is then partly regenerated by depressurising towards the feed
end, and the desorbed impurities are rejected to the PSA offgas.
Purge at low pressure (Step 4 -5)
The adsorbent is then purged with high-purity hydrogen (taken from another adsorber on
cocurrent depressurisation) at constant offgas pressure to further regenerate the bed.
Repressurisation (Step 5-1)
The adsorber is then repressurised with hydrogen prior to being returned to the feed step. The
hydrogen for repressurisation is provided from the cocurrent depressurisation (step 2 above) and
with a slipstream from the hydrogen product. When the adsorber has reached the adsorption
pressure, the cycle has been completed, and the adsorber is ready for the next adsorption step.
Pressure Equalisations
The hydrogen removed during the cocurrent depressurisation steps is used to repressurise other
adsorbers by pressure equalisations and this reduces the hydrogen losses to fuel.
As a general rule, increasing the number of pressure equalisations increases the hydrogen
recovery. However, a minimum hydrogen purge is required to reject the impurities. Thus, for
every application, an upper limit of equalisations required to achieve maximum hydrogen
recovery exists. Once this maximum is reached, adding more pressure equalisations does not
improve the hydrogen recovery.
9.6.3 Selection of proper Adsorbents in a PSA process:
Mass Transfer Rates: Preferred adsorbents that are used in PSA separation processes
should be able to exhibit quick mass transfer rates. This is specially important when cycle
times are shorter and gas flow rates are relatively higher.
Equilibrium: The adsorbent beds must have high equilibrium selectivity.
Capacity: In selecting the appropriate adsorbent for a PSA process high working
adsorption capacity is a must.
173
Purge Gas requirement: Requirement of purge gas must be very low.
Shows mechanical properties such as:
Higher crush strength
Lower attrition
Lower dust
Higher stability against aging
9.6.4 Absorbents & Its Types

Adsorbents are used usually in the form of spherical pellets, rods, moldings, or monoliths with
hydrodynamic diameters between 0.5 and 10 mm. They must have high abrasion resistance, high
thermal stability and small pore diameters, which results in higher exposed surface area and
hence high surface capacity for adsorption. The adsorbents must also have a distinct pore
structure which enables fast transport of the gaseous vapors.
Most industrial adsorbents fall into one of three classes:
Oxygen-containing compounds Are typically hydrophilic and polar, including materials

such as silica gel and zeolites.
Carbon-based compounds Are typically hydrophobic and non-polar, including materials

such as activated carbon and graphite.
Polymer-based compounds - Are polar or non-polar functional groups in a porous

polymer matrix
174
The following table highlights the use of different adsorbents in gas separation processes:
Process
Gas Mixture
Adsorbent
Gas Bulk Separation
Acetone/Vent streams
Activated Carbon
Acethylene/Vent streams
Activated Carbon Zeolite
Normal Paraffins/IsoZeolite, CMS * Activated
paraffins, Aromatics
Carbon
N2/O2 CO, CH4, CO2,
N2, Ar, NH3, H2
Gas Purification
Organics/Vent streams
Odors/Air H2O/Olefincontaining cracked glass
Natural gas, Air, Synthesis
Gas, etc. CO2/C2H4,
Natural Gas, Hydrogen,
LPG NOx/N2 SO2/Vent
streams Hg/Chlor-alkali
cell gas effluent
Activated Carbon
Activated Carbon Silica,
Alumina Zeolite Zeolite
Zeolite Zeolite Zeolite
* CMS: carbon molecular sieve

Table: 9.1 Uses of different adsorbents in gas separation processes
9.6.5 Applications of PSA Hydrogen Purification Systems

The PSA Hydrogen purification systems has wide application in the following
industries:
Refinery
Petrochemicals
Vegetable Oils
Paper & Textiles
Steel Industry
Fuel Cells
175
9.7 DESIGN OF PSA

Design procedure
1. Selection a suitable adsorbent.
2. Selection of suitable size and shape.
3. Selection of adsorber pressure.
4. Assume bed length and superficial velocity.
5. Determine physical properties.
6. Determine Reynold no and Schmidt no.
7. Calculation of mass transfer coefficients.
8. Calculation of coefficient of linear adsorption isotherm.
9. Calculate bed length Parameter.
10. Use the Hougen-Marshall chart to determine .
11. Calculate t and pressure drop.
176
Temperature of
incoming feed
Pressure of incoming
feed
Flow Rate of Feed
Inlet Flow Rate Of
Adsorbate
Product From Adsorber
Molar Flow Rate of
Product
Outlet Flow Rate Of
Adsorbate
316 K
2481 kPa
mf
Co
109876 kg/hr
101683Kg/hr
mp
8193kg/hr
101682 kg/hr
Assume superficial velocity and bed length

Bed length =Z= 1.21m
Superficial velocity = s =0.45m/s
Adsorbent Properties [3]
Adsorbent Name = BPL activated Carbon
Porosity =0.4
External surface area =42.73 m2
Bulk Density =480.98 Kg/m3
Saturation Content = 11.4%
Diameter of Particle = Dp =0.0033
Physical Properties
Component
Methane
Carbon dioxide
Water
Ammonia
Carbon dioxide
Nitrogen
Overall schimidt no = /Di =1.13
Schimidt No= /Di

0.99
1.14
0.66
0.57
0.84
0.75
Diffusivity
16.0e-6
14e-6
24e-6
28.0E-6
19.0E-6
22.0E-6
Reynold no = v*d/ =212220.4

177
Mass Transfer Coefficient

By using of equation Dwivedi and Upadhyay
Jd =
kg = 0.003414m/s
kg*a=0.145m3 gas/m3 solid . s
Linear Adsorption Isotherm
kd= Saturation Content /content of adsorbate in feed=0.002575
Length Parameter
Z=
= 0.389
C/Co=0.999
From Hougen Marshall chart
=6
178
t= 65s
Utilization of bed=53%
No of coloumn =4
Pressure Drop
The most common Ergun equation is used to calculate pressure drop
P/L= 4.56 kPa

P = 4.56*1.21
= 5.51 kPa
Calculation of Volume
V= /4D2*L
V= 1.17 m3
References
1. "Adsorption." Adsorption. N.p., n.d. Web. 21 June 2012.
<http://www.daviddarling.info/encyclopedia/A/adsorption.html>.
2. Webserver. N.p., n.d. Web. 20 June 2012.
http://webserver.dmt.upm.es/~isidoro/dat1/Mass%20diffusivity%20data.htm
3. Walas, Stanley M. Chemical Process Equipment: Selection and Design. 1st ed. Boston:
Butterworths, 1988. Print
4. McCabe, Warren L., Julian C. Smith, and Peter Harriott. Unit Operations of Chemical
Engineering. 5th ed. Boston: McGraw-Hill, 2005. Web.
5. Inglezakis, Vassilis J., and Stavros G. Poulopoulos. Adsorption, Ion Exchange and
Catalysis: Design of Operations and Environmental Applications. Amsterdam: Elsevier,
2006. Print.
6. Lee, Max N. Y., and Imre Zwiebel. Adsorption Technology. N.p.: n.p., 1971. Print.
7. Kent S. Knaebel. "A How To Guide for Adsorber Design." Adsorption. N.p., n.d. Web.
1 Mar. 2012. <http://adsorption.com/publications/AdsorberDes2.pdf>.
179
180
HAZOP STUDY
10.1
Introduction
Traditionally, safety in the design of chemical plant relied upon the application of codes
of practice design codes and checklists based on the wide experience and knowledge of
professional experts and specialists in the industry. However, such approaches can only cope
with problems that have arisen before with the increasingly complexity of modern plant, these
traditional approaches are likely to miss other issues which need to be considered at the design
stage of a project.
Hazard and Operability studies (HAZOPs) were developed by ICI during the 1960s as a
technique to overcome this problem and to systematically identify potential hazards and
operability problem in new designs for chemical and petrochemical plant in both batch and
continuous processes HAZOPs can also be used for the modification and review of existing
processes.
10.2 What are HAZOPs?
HAZOPs are structured critical examination of plant and processes undertaken by an
experienced team of company staff in order to identify all possible deviations from an intended
design, along with the consequent undesirable effects concerning safety, operability and the
environment.
The possible deviations are generative by rigorous questioning, prompted by a series of
stand, guide words, applied to the intended design.
Table 10.1 Standard Guide words and their generic meanings
Guide Words
Meaning
No(not, none)
None of the design intent is achieved
More(more of, higher)
Quantitative increase in parameter
Less(less of, lower)
Quantitative decrease in parameter
As well as(more than)
An additional activity occurs
Part of
Only some of the design intention is achieved
Reverse
Logical opposite of the design intention occurs
181
Where else
Applicable
destination
for
flow,
transfer, sources and
Before/After
The step(or some part of it)is effected out of

sequence
Early/Late
The timing is different from the intention
Faster/Slower
The step is done/not done with the right timing
The deviation from the intended design are generated by coupling the guide words with a
variable parameter or characteristic of the plant of process such as reactant reaction sequence,
temperature, pressure, flow, phase etc in other words.
GUIDE WORD+PARAMETER=DEVIATION
For example, when considering a reaction vessel in which an exothermic reaction is to be

undertaken and one of the reactants is to be added stepwise, the guideword more would be
coupled with the parameter reactant and the deviation generated would be thermal runaway.
Systematic examinations are made of each part of a plant or process using these
guidewords having examine one part of the design recorded any potential hazard and operability
problems associated with it, the study progresses to focus on the next part of the desi gn and
recorded any potential hazards and operability problems associated within, the study progressed
to focus on the next part of the design or the next step in the operating procedure material or for
referral outside for further consideration can then be made to overcome the problems which has
been identified.
The approach described above will generate hypothetical deviations from the design
intention, the success or failure of study depends on four aspects:
The accuracy of the design drawings and other data used as the basis for the study
The technical skills and expertise of the team
The ability of the team to use the approach as an aid to their imagination in visualizing
possible deviations causes and consequences and
The ability of the team to maintain senses of proportion, particularly
When assessing the seriousness of the hazards which are identified care thought must,
therefore, be given to preparative work, team composition, keeping of records and so on.
182
10.3
Preparation for Carrying Out HAZOP:
The amount of preparation required for HAZOP depends upon the size and complexity of
the plant. Typically, the data required consists of various drawings in the form of line diagrams
flow sheets plant layouts isometrics and fabrication drawing operating instructions, instrument
sequence control charts, logic diagrams and compute programs. Occasionally there are plant
manuals and equipment manufacturers manuals the data must be accurate and sufficiently
comprehensive, in particular for the existing plant, the line diagrams must be checked to ensure
that they are up-to-date and those modifications have not been made since the plant constructed.
10.4
Composition of the Team to carry out a HAZOP:
HAZOPs are normally carried out by a multi disciplinary team including chemical
engineers and chemists with members being chosen for their knowledge and experience in
design, operation, maintenance or health and safety. A typical team would have between 4 to 7
members each with a detailed knowledge of the way in which plant is intended to work,
knowledge and expertise to bear systematically so that problems are less likely to be messed.
HAZOP is technique of bringing fresh minds to work on problem.
HAZOP studies generate recommendations for design changes: the team should have the
authority to agree changes there and then as progress is slow if every change has to be referred
elsewhere for a decision.
It is also essential that the team leader is an expert of the HAZOP techniques. The team
leaders role is to ensure the team follows the procedure he or she needs to be skilled in leading a
team of people who may not normally be responsible to him or her and the sort of person who
pays meticulous attention to detail. The team should have a secretary to prepare notes after each
meeting and to circulate them before the next meeting.
It is recommended that team leader should be an independent person .i.e. this should not
be somebody who is closely associated with the plan under study.
The team leader must have sufficient knowledge to guide the study properly but should
not be expected to make this technical contribution. It is beneficial if team members have had
some training in the HAZOP technique.
10.5
Record keeping:
It is usual to record each step of a HAZOP for all the physically meaningful deviations or
if a sunset is used to include those requiring an action plus those which considered significant
but required no action because the existing protection was deemed adequate. A particularly
useful type of record is the Hazard file.
183
This would normally include
A copy of the date (flow sheets, original and final process and instrument diagrams
running instructions bar sheets models etc) used by the team they have been examined
A copy of all working papers, questions , recommendations, redesigns etc, produced by

the team and others as a result of study, and
Confirmation that all the agreed actions have been carried out
The file should be retained on the plant to provide a source of information for future use
10.6
Result of HAZOP:
On completion of HAZOP study the likely outcomes are:
Some improvements in operation/maintenance, control programmers and instructions

which may have been implements together minor(low cost) hardware alterations these
will have been put in hand as parts of the study.
Some proposed changes may await the result of a more detailed quantitative assessment.
Major recommendations have yet to be implemented, most possibly awaiting capital

sanction.
The team members will already have both a better understanding of the plan/process and
a better appreciation of potential hazard and risks than if the study had not been carried
out.
10.7
Benefits of HAZOP:
The circumstances when HAZOP is likely to produce benefits
During the design of installation of any new plant or process, or major modification to an
existing one.
When there are novel hazard such as environmental hazard and quality or cost issues
associated with the operations.
Following a major incident involving fire, explosion, toxic release etc, and
To justify why a particular code of practice, guidance not or industry code is not to be
followed.
184
10.8
Caution:
Even the most rigorous HAZOP cannot be relied upon to foresee every hazard and some
accidents may well occur in the future.
When an accident occurs in a plant which has undergone a HAZOP study,
10.9
Had the set of conditions (deviations) which led to the incident considered by the
HAZOP study team If not, could the team reasonably have been expected to have
does so? And
If such deviations and their causes had been conceded, had the team made reasonable
judgments of the likely frequency of the events and had concluded that they were
unlikely to occur and thus posed acceptable risks?
In such circumstances it is clearly Important to document all the outcomes of study in

order to answer these questions
Conclusion:
HAZOPs are an essential tool for hazard identification and have been used successfully
to improve the safety and operability of both new and existing chemical plant. The technique a
not confined to the chemical and pharmaceutical Industries and has also been used successfully
in a number of other industries, including the off-shore oil and food industries.
10.10 Performance of HAZOP:
Now in order to perform HAZOP study following table is used industrially, first the item
number of process is mentioned then the deviation of that item is written on the column and
causes, consequences and safeguards are written
We have chosen to perform HAZOP on absorber in which H2S is removed with the help of
Chelated Iron Solution.
10.11 Types of HAZOP:
10.11.1 Process HAZOP:
The HAZOP technique was originally developed to assess plants and process systems
10.11.2
Human HAZOP:
A family of specialized HAZOPs. More focused on human errors than technical failures
185
10.11.3 Procedure HAZOP:

Review of procedures or operational sequences sometimes denoted SAFOP - Safe Operation
Study
10.11.4 Software HAZOP:
Identification of possible errors in the development of software
10.12 Important Terms:
The process is systematic and it is helpful to define the terms that are used:
10.12.1 Node:
A node is a specific location in the process in which (the deviations of) the design/process intent
are evaluated. Examples might be: separators, heat exchangers, scrubbers, pumps, compressors,
and interconnecting pipes with equipment.
10.12.2 Design Intent:
The design intent is a description of how the process is expected to behave at the node; this is
qualitatively described as an activity (e.g., feed, reaction, sedimentation) and/or quantitatively in
the process parameters, like temperature, flow rate, pressure, composition, etc.
10.12.3 Deviation:
A deviation is a way in which the process conditions may depart from their design/process intent.
These are discovered by systematically applying the guide words (e.g., "more pressure").
10.12.4 Parameter:
The relevant parameter for the condition(s) of the process (e.g. pressure, temperature,
composition).
186
10.12.5 Guideword:
A short word to create the imagination of a deviation of the design/process intent. The most
commonly used set of guide-words is: no, more, less, as well as, part of, other than, and reverse.
In addition, guidewords like too early, too late, instead of, are used; the latter mainly for batchlike processes. The guidewords are applied, in turn, to all the parameters, in order to identify
unexpected and yet credible deviations from the design/process intent.
187
10.13 HAZOP of an Absorber:

Table 10.1 HAZOP on Absorber
Deviation
Causes
Consequences
Safeguards
Actions
Use
blower
upstream
and
also use suitable
packing for the
absorber
Low Pressure
Unsuitable
Low
flooding
packing.
efficiency, flood
High
Liquid can occur
loading
Use
pressure
controller at the
upstream of the
absorber
High Pressure
Low
drop
Use
pressure Check blower
controller,
Working
Low temperature
Chocking
occur in
packing
of Use
controller
for
the
also measurement of
drop temperature of
inlet gases and
selexol
Use
control
valves
and
temperature
controllers
upstream
the
absorber
High
temperature
Quencher is not Low absorption, Use

controller
working
damage to the for
the
properly
packing
measurement of
temperature of
inlet gases and
selexol
Use
control
valves
and
temperature
controllers
upstream
the
absorber
pressure Good absorption,
can Efficiency
the absorption
reduces
pressure
increases
188
189
ENVIRONMENTAL IMPACT ASSESSMENT

11.1 Introduction:
ElA is both a decision making process and a document that provides a systemic, reproducible,
and interdisciplinary evaluation of the potential effects of a proposed action and its practical
alternatives on the physical, biological, cultural and socioeconomic attributes of a particular
geographical area.
When we perform an activity, we disturb the environment. For example, if we want to stand the
new plant unit before its installation we must inform the government and the general public
about the positive and negative impacts of this industry/plant on the environment. This is termed
as environment impact assessment.
EIA is done because many various federal and state laws may specify that, concentration of
chemical must be within certain limits, flow rate of the effluents from the plant should not effect
the environment.
EIA is prepared by industrialist in the form of comprehensive report. Finally, it helps to identify
actions needed to prevent future environmental damage from future anticipated impacts. The
approach identifies full range of environmental consequences associated with the product.
11.2 Why is EIA Important?

An effective EIA program brings multiple benefits to society; several principal benefits include
first, and most important, natural resources, environmental quality, and public health are
accorded appropriate degrees of protection through a substantive environmental policy and an
effective EIA process. Second, the EIA document brings together in a public document all
relevant information on the proposed action, the nature of the affected environment, and the
types of potential environmental impacts that might result from implementation of the proposed
alternatives to the action.
11.3 The Eight Guiding Principles

There are eight guiding principles that govern the entire process of EIA and they are as follows:
190
Participation: An appropriate and timely access to the process for all interested parties.
Transparency: All assessment decisions and their basis should be open and accessible.
Certainty: The process and timing of the assessment should be agreed in advanced and followed
by all participants.
Accountability: The decision-makers are responsible to all parties for their action and decisions
under the assessment process.
Credibility: Assessment is undertaken with professionalism and objectivity.
Cost-effectiveness: The assessment process and its outcomes will ensure environmental
protection at the least cost to the society.
Flexibility: The assessment process should be able to adapt to deal efficiently with any proposal
and decision making situation.
Practicality: The information and outputs provided by the assessment process are readily usable
in decision making and planning.
11.4 The Importance of an EIA Program

Establishment of a Substantive Environmental Policy. An effective program of EIA
expresses the intent at the national, regional, or local level to establish a sound and
sustainable environmental policy for governmental all private decision-making.
Protection of Natural Resources, Environmental Quality, and Public Health. An
effective EIA program serves to identify, in advance, action that could have significant
adverse effects on natural resources; on the quality of local, regional, or national
environment; and on human health and safety.
Full and Open Disclosure of All Environmental Consequences of a Proposed Action.
An effective program of EIA provides a standardized mechanism for documenting and
disclosing the full spectrum of effects of a proposed action. This disclosure encourages a
thorough examination of all actions that could affect the natural environment.
Objective Consideration of All Reasonable Alternatives.
191
The heart of the EIA process is the objective and systematic comparison of reasonable
alternatives to identify the least environmentally damaging alternative that would meet
the stated purpose and need of the proposed action
Establishment
of
Uniform
and Quantitative/Qualitative
Basis
for
the
Identification and Characterization of All Relevant Environmental Impacts:

The systematic steps included in an effective EIA program provide technical guidance
concerning the types of environmental effects that should be evaluated, the range of
technical methodologies that might be used in those evaluations, and the types of
techniques that can be used to predict potential effects resulting from a proposed action.
11.5 Environment Impact of Industrialization in Developing Countries

As industrialization is considered as back bone for the economic growth of every country but
increase industrialization causes destruction of natural resources which leads to many
environmental problems. The direct main impacts of environmental deterioration by industries
are given below:
Release of toxic or harmful gases into the working environment and throwing it into the
general environment.
Utilization of potentially hazardous substances and chemicals.
Great input and dissipation of energy involving fuel combustion.
Manufacturing techniques and processes necessitating excessive quantities of water or

other natural resources and leading to a marked ecological destruction.
11.6 Types of Impacts:

Following are the important types of impacts.
11.6.1 Biological and Physio-Chemical Impacts:

Impacts in this category relate to effect on biological resources such as vegetation, wildlife,
crops, and aquatic life. Impacts effecting soil and land forms or creation of a propensity for soil
erosion, floods and sedimentation, would be considered as physical impacts. Chemical impacts
relate to project activities that cause a chemical change in air/water/soil quality. Smoke emitted
from a factory.
192
For example, there may change the amount of sulphur dioxide, content of ambient air, while
untreated effluent discharged directly into a river by a factory may change the chemical
characteristics of river.
The biological component covers all elements, including different forms plant life, structure,
functions and their interaction with other components of an ecosystem. Another component of a
biological system is the animal life, which ranges from microscopic protozoan to large animals
such as elephants.
The biological systems interact with physical elements such as air, water, soil, rocks and solar
radiation, giving rise to a system known as an ecosystem. The material- cycling, assimilative,
and productive roles of an ecosystem are the process that maintains the balance of nature.
11.6.2 Social Impacts:

A study of socio-economic impacts would examine project action that alters the existing social
and economical impacts may prove either adverse or beneficial. For example an expanded
irrigation facility designed to enhance agricultural production would be beneficial. Social
impacts can be subdivided into the following.
Demographic impacts:
Includes such as displacement and relocation effects; and changes in population
characteristics.
Socio-economic impacts:
Including income and income multiplier effects, employment rates and partners,
prices of local goods and service and taxation effects.
11.6.3 Cultural Impacts:

A traditional pattern of life and work, family structures and authority, religious and tribal factors,
archaeological features, social networks an community cohesion.
Project impacts on cultural heritage should be considered .Areas of study should include historic
sites, religious shines or areas, or traditional practices that may be affected.
Cultural resources refer to archaeological, historical, religious, cultural and aesthetic values.
Cultural resources are part of the resources base, it is therefore important that the development
options, under consideration are screened for potential impacts on cultural properties. in the
process of conducting EIA, it is essential to check whether or not the area contains UNESCO
world heritage sites.
193
A project that involves a large scale modification or disturbance of land and is located in an
area where here are cultural resources require an intensive survey by qualified archaeologists on
the basis of findings of intensive survey the decision makers have to decide whether or not the
project should go ahead or whether to adopt project alternatives or devise mitigation measure to
be adopted, along with institutional training and monitoring requirements, etc. in all these
processes involvement of local communities is necessary.If in the project site, there are some
buried materials of archaeological/historical values. Discovered with in three meters under the
earth surface, they are called archaeological chance finds
11.6.4 Institutional Impacts:

Including demands on the government and social service, NGOs housing, schools, criminal
justices, health, welfare and recreation, and GENDER impacts the implications of development
projects on the roles of women in society, income-generating opportunities, access to resources,
employment opportunities and equity.
11.6.5 EIA of this project

EIA includes both positive and negative impacts on the environment.
Sulphur being produced in our process is either landfilled or sold for other industrial
applications. Landfilles sulphur may be proven bad regarding biological impacts of EIA
therefore in some cases it become necessary to transform into other product to minimize its
negative impacts on biological organism present in the environment.
Carbon dioxide is being produced in our process where flue gases are produced. Its amount is
reduced in our own process by using flue gases as a fuel in other reformer.
Or it can be separated and can be sold.
These all facts are assessed on the basis of planned and organized step of EIA. Screening of
project is done that how harmful or how beneficial impacts it may produced.
At what locality plant is or should installed, where the waste is being dumped.
It is also ensured that dumped waste should be untoxified.
194
INSTRUMENTATION AND CONTROL

12.1 INSTRUMENTS
Instruments are provided to monitor the key process variables during plant operation. They may
be incorporated in automatic control loops or used for the manual monitoring of the process
operation. They may also be part of an automatic computer data logging system. Instruments
monitoring critical process variables will be fitted with automatic alarms to alert the operators to
critical and hazardous situations.
It is desirable that the process variable to be monitored can be measured directly; often, however,
this is impractical and some dependent variable that is easier to measure is monitored in its place.
For example, in the control of absorber the continuous online monitoring is needed for the feed
control and composition of the outlet gas.
12.2 INSTRUMENTATION AND CONTROL OBJECTIVES

The primary objective of the designer when specifying instrumentation and control schemes:
1. SAFER PLANT OPERATION
To keep the process variables within known safe operating limits

To detect dangerous situations as they develop and to provide alarms and automatic shutdown systems.
To provide inter locks and alarms to prevent dangerous operating procedures.
2. PRODUCTION RATE
To achieve the design product output
3. PRODUCT QUALITY
To maintain the product composition within the specified quality standards
4. COST
To operate at the lowest production cost, commensurate with the other objectives.
195
12.3 COMPONENT OF THE CONTROL SYSTEM

PROCESS
Any operation or series of operations that produces a desired final result is a process. In
this discussion the process is biomass gasification.
MEASURING MEANS
Of all the parts of the control system the measuring element is perhaps the most important. If
measurements are not made properly the remainder of the system cannot operate satisfactorily.
The measured available is dozen to represent the desired condition in the process.
Variables to be measured:
Pressure measurements
Temperature measurements
Flow rate measurements
Level measurements
Variables to be recorded:
Indicated temperature
Composition
Pressure etc
CONTROLLER
The controller is the mechanism that responds to any error indicated by the error detecting
mechanism. The output of the controller is some predetermined function of the error.
In the controller there is also an error-detecting mechanism which compares the measured
variables with the desired value of the measured variable, the difference being the error.
196
FINAL CONTROL ELEMENT

The final control element receives the signal from the controller and by some predetermined
relationships changes the energy input to the process.
12.4 CLASSIFICATION OF CONTROLLERS

In general the process controllers can be classified as:
Pneumatic controllers
Electronic controllers
Hydraulic controllers
The pneumatic controller is varying rugged and almost free of maintenance. The
maintenance men have not had sufficient training and background in electronics, so
basically pneumatic equipment is simple.
The pneumatic controller appears to be safer in a potentially explosive atmosphere which
is often present in the petro-chemical industry.
12.5 MODES OF CONTROL

The various types of control are called "modes" and they determine the type of response
obtained. In other words these describe the action of the controller that is the relationship of
output signal to the input or error signal. It must be noted 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
In industry purely integral, proportional or derivative modes seldom occur alone in the control
system.
197
12.6 DIFFERENT TYPES OF CONTROLLERS

12.6.1 FLOW CONTROLLERS
These are used to control feed rate into a process unit. Orifice plates are by far the most type of
flow rate sensor. Normally, orifice plates are designed to give pressure drops in the range of 20
to 200inch of water. Venture tubes and turbine meters are also used.
12.6.2 TEMPERATURE CONTROLLERS

Thermocouples are the most commonly used temperature sensing devices. The tw o dissimilar
wires produce a produces voltage difference when they are subjected to temperature difference.
12.6.3 PRESSURE CONTROLLER

Bourdon tubes, bellows, and diaphragms are used to sense pressure and differential pressure. For
example, in a mechanical system the process pressure force is balanced by the movement of a
spring. The spring position can be related to process pressure.
12.6.4 LEVEL CONTROLLER

Liquid levels are detected in a variety of ways. The three most common are:
Following the position of a float, that is lighter them the fluid.
Measuring the apparent weight of a heavy cylinder as it buoyed up more or less by the
liquid (these are called displacement meters).
Measuring the difference in static pressure between two fixed elevations, one in the vapor
above the liquid and the other under the liquid surface. The differential pressure between
the two level taps is directly related to the liquid level in the vessel.
198
12.7 CONTROL SCHEMES OF ABSORBER
OBJECTIVES
In absorber control any of following may be the goals to achieve
Pressure inside the column
Level of the solvent in the column
Outlet product composition
MANIPULATED VARIABLES
Any one or any combination of following may be the manipulated variables
Flow rate of the out let product
Flow rate of the solvent
Feed flow rate
LOADS OR DISTURBANCES
Following are typical disturbances
Flow rate of feed
Composition of feed.
Temperature of feed.
Flow rate of the solvent
Temperature and pressure of the column
199
CONTROL SCHEME ACROSS THE ABSORBER
REFERENCE
George Stephanopoulos, Chemical Process Control, Department of Chemical

Engineering Massachusetts Institute of Technology.
200
COST ESTIMATION
Before the plant to be operated, specified money must be supplied to purchase and install
the equipment. The capital needed to supply the necessary plant facilities is called fixed capital
investment while that for the operation of the plant is called the working principal and sum of
two capitals is called total capital investment.
An acceptable plant design must present a process that is capable of operating under
conditions which will yield a profit. Since, Net profit total income-all expenses it is essential that
chemical engineer be aware of the many different types of cost involved in manufacturing
processes. Capital must be allocated for direct plant expenses; such as those for raw materials,
labor, and equipment. Besides direct expenses, many other indirect expenses are incurred, and
these must be included if a complete analysis of the total cost is to be obtained. Some examples
of these indirect expenses are administrative salaries, product distribution costs and cost for
interplant communication.
13.1 PURCHASE EQUIPMENT COST

Equipment no
Equipment Name
R-201
S-201
Gasifier
Gasifier cyclone
S-203
Char cyclone
R-202
Char combustor
K-201
Air blower
R-203
Tar reformer
M-301
Syn gas Quench

chamber
cooler
Recirculation Pump
H-303
P-303
Equipment delivered cost

($)
16,392,408
Include in gasifier cost R201
54,930
201
12,479,808
503,787
K-301A-E
S-301,S302A,B,C,S303
M-304
Compressor
Knock out drum
R-301
P-303
LOCAT Oxidizer
vessel
LOCAT Pump
H-304
H-306
R-302
R-401
K-401
LOCAT Preheater
ZnO bed Preheater
ZnO sulphur remover
Steam Reformer
Reformer blower
H-201
Reformer Syngas
cooler
Reformer Syngas
cooler 2
HTS
LTS Precooler
LTS Precooler 2
LTS
PSA Precooler
PRE-PSA Knock out
drum
PSA air precooler
PSA water cooler
Pre PSA knock out
drum
PSA
H-403
R-402
H-405
H-406
R-403
H-407
S-401
H-408
H-409
S-402
S-403
Total
LOCAT-Absorber
Include in LOCAT oxidizer

vessel cost R-301
2,463,758
202
Include in LOCAT oxidizer

vessel cost R-301
12,501
183,357
185,885
15,987,387
Include in reformer cost R401
170,578
55,987
1,092,238
181,456
57,245
758,307
56,263
303,580
783,766
83,040
137,689
12,521,394
63,321,744
13.2 DIRECT COST

Purchased equipment cost = E = $63,321744
Installation cost (9%E) = $5,698,957
Instrumentation and control cost (10%E) = $6,332,174
Piping cost (8% E) = $5,065,740
Electric cost (5%E) = $3166087
Building (including services) (5%E) = $3166087
Yard improvement (2%E) = $1266435
Land cost (2%E) = $1266435
Total Direct Cost = $88017224
13.3 INDIRECT COST

Engineering and Supervision Cost (8%E) = $5065740
Construction Expenses (10%E) = $6,332,174
Contractor fee (2%E) = $1266435
Contingency Cost (8%E) = $5065740
Total Indirect Cost = $17,730,088
13.4 TOTAL CAPITAL INVESTMENT

Fixed Capital Investment = Direct cost + Indirect cost
F.C.I
D.C
I.C
F.C.I
= $88017224+ $17730088
F.C.I
= $105747312
Working Capital (18%F.C.I) = $19034516
Total Capital Investment
= Working Capital Cost + Fixed Capital Investment
T.C.I
W.C
T.C.I
$84,437
T.C.I
$124781829
+
+
203
F.C.I
$469,095
13.5 PRODUCT COST

Assume that the Fixed Capital Investment depreciate by straight line method for 20 years.
Assuming 5 % Salvage value at the end of plant life
Depreciation = D = (V-VS)/N
V = F.C.I
V = $124781829
VS = 0.05*F.C.I
VS = $6239091
N = no. of years = 10
D = $11854274
Total Product Cost = Total Capital Investment + Depreciation
= $124781829 + $11854274
T.P.C
= $136636102
Fixed Charges (12%T.P.C) = $16396332
Direct Product Cost (55%T.P.C) = $75149856
Plant Overhead (10%T.P.C) = $13663610
Manufacturing Cost = Direct product cost + Fixed Charges + Plant Overhead Cost
Manufacturing Cost = $105209799
13.6 GENERAL EXPENSES

General Expenses = Administrative Cost + distribution and selling cost + research and
development cost
13.6.1 Administrative Cost

It is 2-6% of total product cost
Consider
Administrative cost = 5%of total product cost
Administrative cost = $6831805
13.6.2 Distribution and Selling Cost

It includes cost for sales offices, salesmen, shipping, and advertising.
It is 2-20% of total product cost
Consider that distribution and selling costs = 15% of total product cost
204
Distribution and selling costs = $20495415
13.6.3 Research and Development Cost

It is about 5 % of total product cost
Research and development cost = $6831805
13.6.4 Financing (Interest)

It is about 0-10% of total Capital Investment
Consider interest is 5% of total capital investment
Interest = $6239091
Thus:
General Expenses = $40398117
So
Total product cost = Manufacturing cost + General Expenses
Total product cost = $105209799 +40398117
Total product cost = $46637208
13.7 GROSS EARNING/ INCOME

Wholesale selling price of CS2 per Kg =2 $
Total income = Selling price * Quantity of product manufactured
Total income = 2 * 65010000
Total income = $ 130020000
Gross income = Total Income Total Product Cost
Gross income =130020000 4.47*105
Gross income = $ 83382792
Taxes = 40% of Gross income
Taxes = $ 33353117
Net profit = Gross income Taxes
Net profit = $ 83382792 33353117=50029675/year
205
REFERENCES
1. Sinnot, R.K., Coulson and Richardsons Chemical Engineering, 2 nd ed, vol 6,
Butterword Heinemann, 1993.
2. Plant Design and economics for chemical engineers 5 th edition
3. J. Jechura, P. Spath, A. Aden, T. Eggeman M. Ringer, B. Wallace,. "Biomass to
Hydrogen Production Detailed Design and Economics Utilizing the Battelle Columbus
Laboratory Indirectly-Heated Gasifier." NREL/TP-510-37408. N.p., May 2005. Web. 8
Oct. 2011
4.
206
ANNEXURE A
Fig: 1. Industrial sector energy consumption, PJ 2006/2007 HDIP

2008
Fig: 2. Industrial sector natural gas consumption, PJ 2006/2007

HDIP 2008
ANNEXURE B
ANNEXURE C
REFERENCES
Julian C. Smith. Warren L. McCabe Peter Harriott, Unit Operations of Chemical Engineering ,
5th edition
Coulson & Richardson, Chemical Engineering Design ,4 th edition ,Volume 6
Ernest E. Ludwig, Applied Process Design for Chemical and Petrochemical Plants, Vol.2, 3 rd
Edition.

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PRODUCTION OF HYDROGEN GAS BY

Syed Tahir Ali Rizvi

DEPARTMENT OF CHEMICAL ENGINEERING

Production Of Hydrogen Gas By Gasification Of Biomass

This project is being submitted to the Chemical Engineering Department,

DEPARTMENT OF CHEMICAL ENGINEERING

All praises to Almighty Allah,

Production Of Hydrogen Gas From Gasification Of Biomass

1.2 PRODUCTS OF BIOMASS

Liquid (ethanol, bio-diesel, methanol, vegetable oil, and pyrolysis oil)

From these come four major categories of product:

Chemical such as methanol, fertilizer and synthetic fiber

Production Of Hydrogen Gas From Gasification Of Biomass

Fig: 1.1. Uses of biomass

1.3 COMMON SOURCES OF BIOMASS

Production Of Hydrogen Gas From Gasification Of Biomass

1.4 MOTIVATION FOR BIOMASS CONVERSION

1.5 BIOMASS GASIFICATION

1.5.2 TECHNOLOGY ADVANTAGES

Production Of Hydrogen Gas From Gasification Of Biomass

1.6 AVAILABILITY OF BIOMASS IN PAKISTAN

1.7 USE OF BIOMASS IN PAKISTAN

Production Of Hydrogen Gas From Gasification Of Biomass

(Reference: PAK-IEM, Final Report Volume 1; December 2010)

1.8 BIOMASS FOR HYDROGEN PRODUCTION

The biomass that cannot be used to produce hydrogen by gasification is

Oil and oil seeds

Production Of Hydrogen Gas From Gasification Of Biomass

Urban wood wastes

Municipal solid waste landfill

Production Of Hydrogen Gas From Gasification Of Biomass

Report: International Resource Book, PAK-IEM, Final Report, Volume 1; December

Production Of Hydrogen Gas By Gasification Of Biomass

PROCESS AND CAPACITY SELECTION

2.1 HYDROGEN DEMAND IN THE WORLD

2.2 USES OF HYDROGEN

Production Of Hydrogen Gas By Gasification Of Biomass

Fig: 2.2. Uses of hydrogen

2.3 METHODS FOR THE HYDROGEN PRODUCTION

Natural gas Steam reforming

Production Of Hydrogen Gas By Gasification Of Biomass

2.3.2 GASIFICATION OF HIGHER HYDROCARBONS

2.3.3 COAL GASIFICATION

2.3.4 BIOMASS GASIFICATION

Production Of Hydrogen Gas By Gasification Of Biomass

2.4.1 NATURAL GAS CONSUMPTION

Fig: 2.2. Natural gas consumption by sector

Production Of Hydrogen Gas By Gasification Of Biomass

Fig: 2.3. Industrial natural gas consumption

2.4.2 NATURAL GAS RESERVES IN PAKISTAN

(Reference: PAK-IEM, final report volume 1; December 2010)

Production Of Hydrogen Gas By Gasification Of Biomass

(Reference: The Economics for biological Methods of Hydrogen Production, by Richard J.

Production Of Hydrogen Gas By Gasification Of Biomass

2.5 CAPACITY SELECTION

Production Of Hydrogen Gas By Gasification Of Biomass

Pak Arab Fertilizer

Production Of Hydrogen Gas By Gasification Of Biomass