Feasibility study of production of

Hydrogen

Report submitted in partial fulfilment

Of the requirement for degree of
B.TECH
IN
CHEMICAL ENGINEERING
Under the supervision of
Dr. RAKESH ANGIRA
BY

MAYANK
SCHOOL OF CHEMICAL TECHNOLOGY
GURU GOBIND SINGH INDRAPRASTHA UNIVERSITY
DWARKA SEC-16C

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Acknowledgeme
nt
I wish to thank DR. RAKESH ANGIRA, my supervisor, for his constant support and guidance
throughout the course of the project report.
I also wish to thank for the guidelines, suggestions and encouragement that contributed
immensely to the ideas of making this report successfully complete.
I want to thank all the faculty members and my fellow batchmates for sharing their ideas and
knowledge with me.
I must thank university school of chemical technology for providing the opportunity to
investigate the production of hydrogen.

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INDEX
S.NO
1)
a)
b)
c)
d)
e)
f)
g)
h)
i)

2)

TOPIC

PAGE NO.

CHAPTER 1 1
INTRODUCTION 1
HISTORY
2
PHYSICAL PROERTIES 2
THERMODYNAMICAL PROPERTIES.....2
CHEMICAL PROPERTIES .....7
CHEMICAL REACTIONS ...8
USES 9
INDUSTRIAL USES ....10
MANUFACTURING PROCESSES .......12
1) PARTIAL OXIDATION OF HYDROCARBON .12
2) HYDROGEN FROM COAL ..12
3) HYDROGEN PRODUCTION FROM COAL .13
4) STEAM REFORMING PLANT .14

CHAPTER 2 ...19

a)
b)

MATERIAL BALANCE ...19

ENERGY BALANCE.26

Feasibility Study

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Production of
Hydrogen
CHAPTER -1
INTRODUCTION

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Hydrogen was first separated and identified in the second half of the 18th century. From many
years the industrials demands for hydrogen were limited to the relatively small quantities used in
operating oxy-hydrogen lamps used for projection purpose and for use in the oxyhydrogen
blowpipe for melting refractory materials. But in 1900s we started using it in production of
ammonia, methanol and on a alcohol's and for the refinery purpose other than this now it is used
in chemical refinery, metal treating, fats and oil hydrogenation. However, hydrogenmanufacturing process developed the last 75years where primarily for the use in hydrogen in
ammonia and methanol production rather than the above uses. The process design is dependent
on the final product as well as available raw materials and energy sources such as natural gas,
naphtha, gas oils etc. among all industrial process for hydrogen production. Hydrogen enjoys a
long tradition as an energy carrier as well as a chemical resource. Its high energy content 1 kg
corresponding to 3.5 l of petroleum quickly led to its recognition as an ideal fuel in
applications where weight rather than volume was the important factor: applications such as
providing the lift for Balloons or Zeppelins and more recently as a fuel for spacecraft. In the first
half of this century the entire gas supply consisted of town gas, a coal gas consisting of more
than 50% hydrogen. Only with the discovery of Oil and Natural Gas reserves was hydrogen
gradually forced out of the public supply system. While decreasing coal usage continues to force
hydrogen out of the energy sector, the long term chances for its return remain good as long as its
advantages of renewable production and carbon-free nature continue to be demanded. The basis
for a long term change is caused on the one hand by the concern about the depletion of fossil fuel
resources and on the other hand by the need of drastically reducing all (and in particular climate
affecting) emissions.The move to a large scale hydrogen based energy sector will also be seen as
an important option when the contribution by fluctuating generation electricity producers
(Wind,Solar) reaches such a level that the electricity supply and demand can only be matched
with the aid of a storage mechanism. Hydrogen presently has the most attractive properties as a
"Storage Medium" of electricity: Compared with the storage of electricity in batteries, the
material costs are many times lower. hydrogen can be used as a pollution free fuel for traffic
applications. The advantages of no pollution and reduced fuel weight are however coupled with
an increase in the volume and weight of the required fuel tank, which for small vehicles would
lead to a reduction in range and payload. If one is to follow the long term strategy of establishing

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hydrogen as an energy carrier, then the early "niche applications" in the transport area or fuel cell
applications present the first available markets. A low cost introduction and testing phase can
take place in the surroundings of conventional chemical hydrogen production. Within the next
five to ten years, this should lead to an economical market penetration that could be sustainably
extended in the medium-term with imported hydrogen and other hydrogen sources (e.g. biomass
gasification).

History
In 1800 first production of hydrogen and oxygen by electrolysis and after that in 1898
liquefaction of hydrogen using linde process was done. In 1902 first commercial electrolysis
installation was done. In 1954 led the ignition of the first hydrogen bomb on the bikini atoll
(USA). In 1955 hydrogen was started using as energy carrier medium Syngas can be produced
from natural gas in several ways. Used in commercial plants since 1956, the process has several
advantages. It is a direct process without the need for a catalyst, it has a very high process
efficiency and is highly reliable as well as cost effective.

PHYSICAL PROPERTIES OF HYDROGEN

Hydrogen is lightest an simplest of all elements. It is fairly but not exceptionally reactive
gas. It enters into chemical combination with most of the elements and hydrogen forms
more compounds than any other element.
Ortho & Para hydrogen insist in different quantum states this fact result in
difference in many properties for the two forms of hydrogen. In particular, those
properties that involve heat, such as enthalpy and entropy and thermal conductivity.
The conversion of ortho hydrogen to Para hydrogen is an endothermic process.
THERMODYNAMIC PROPERTIES
The difference in the masses of isotopes is relatively large, so that thermodynamics

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properties differ considerably. At low temperature P-H2, O-D2 can be present in a

virtually pure state.
Hydrogen gas is color less, non poisonous odorless and tasteless. Contrary to most other
gases, the inversion temperature of hydrogen lies below ambient temperature. Liquid
hydrogen is colorless, very mobile liquid with low viscosity and surface tension.
Solubility of hydrogen in liquids
Hydrogen is only slightly soluble in liquids. In contrast to the highly soluble
gases however the solubility generally increases with increasing temperature. The relative
solubility differences in between hydrogen compound is few percent and diminish with
increasing temperature.
Solubilitys of hydrogen in metals
Metals with not completely occupied inner electron levels have a particularly high
solubility potential for hydrogen. Hydrogen is dissolved in metals and not in the
molecular but in the atomic from where by non-stoichiometrical or stoichiometrical
compound may be formed.
The solubility of hydrogen in metals at small hydrogen concentrations is
proportional to the root of the hydrogen partial pressure. The hydrogen solubility
decreases with increasing temperature. Impurities in the metals and in the hydrogen can
lower the solubility or cancel it completely dissolved property, magnetic properties and
can cause super conductivity.

Table 1: Physical and thermodynamic properties of Hydrogen

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Chemical properties
The chemistry of hydrogen depends mainly on three processes,
1. Loss of the valency electron to yield the hydrogen ion H+
2. Gain of an electron to form the hydride ion H3. Formation of an electron pair bond.

Properties
1. Hydrogen is not exceptionally reactive, although hydrogen atoms with all other

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elements with the exception of noble gases.

2. The strength of the H X bond in covalent hydrides depends on the
electronegativity and size of the element X.
3. The strength decreases in a group with increasing atomic number and generally
increases across any period.
4. The most stable covalent bond are those formed between two hydrogen atoms,
or with hydrogen, oxygen carbon and nitrogen
CHEMICAL REACTION'S
Hydrogen producing reactions
1.On a laboratory scale, hydrogen can be made from the action of an aqueous
acid on a metal or from the reaction of an alkali metal in water.

2. Hydrogen gas can also be produced on laboratory scale by the electrolysis of

an acidic solution.

3. Hydrogen can also produced by steam reforming using hydrocarbons such as

natural gas, petroleum, and coal

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4. Reaction with hydrogen and other elements

Hydrogen forms components with almost every other element possible in
many cases.
a) Hydrogen combines directly with increasing relatively iodine, bromine,
chlorine, and fluorine. The reaction with fluorine occurs spontaneously and
explosively even in dark at low temp and generally used in rocket propellant
system.

Hydrogen reacts with oxygen

Hydrogen combines directly with oxygen, either thermally or with an aid of catalyst

Above 550C, the reaction occurs with flame propagation explosion or detection.
Hydrogen reaction with nitrogen:
At elevated temperature in presence of catalysts, hydrogen will react with nitrogen to
form ammonia.
Reaction with hydrocarbons:
Unsaturated hydrocarbons are converted to saturated or partially saturated hydrocarbons
by hydrogenation.
Hydrogen as a reducing agent:
Hydrogen reacts with a number of metals oxides at elevated temperature to produce
metal.

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Atomic Hydrogen
Atomic hydrogen is much more reactive than the molecular form. The dissociation
reaction is highly endothermic.
Atomic hydrogen can be produced by supplying sufficient energy. The hydrogen atom
has a short life and reacts even at room temperature with non-metallic element such as
halogen, oxygen etc. At room temperature it reduces many oxides to elements.
Hydrogen ion
The ionization potential of above reaction is 13.595eV, which is even higher then first
ionization potential of noble gas Xenon.
Hydrogen bond
Substance containing hydrogen coupled to most electronegative elements exhibit.
Properties that can be best explained by assuming that the hydrogen atom of an H X
bond still has a small but significant affinity for other electronegative atom. This
relatively weak secondary bond is called a hydrogen bond
X H ---1. Hydrogen bonds results in molecular association
E.g. NH3, H2O, HF
2. The presence of hydrogen bonds also causes formation of crystalline
hydrateThe existence of H bond can be shown by infrared
spectroscopy
Uses of Hydrogen:
CONVENTIONAL USES:
Hydrogen in the chemical industry
Hydrogen is all-important raw material for the chemical industry. It takes part in reaction
either by addition or by means of its reduction potential. Most of hydrogen is used for
these hydrogenation and reduction process. A part from ammonia synthesis, synthesis with
hydrogen-carbon monoxide gas mixture to produce methanol, hydrocarbons. The use of

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hydrogen in metallurgy is based in particular on its reducing properties. At present, pure

hydrogen is not used directly to reduce energy.

Different process in which Hydrogen is used are: 1. Ammonia synthesis

2. Hydrogen in refinery processes
3. Hydrogen in coal refinement
4. Hydro pyrolysis.
5. Hydro gasification of coal.
6. Methanol synthesis.
7. Fischer-Tropsch synthesis
8. Methane synthesis
9. Hydro formulation of olefins
10. Hydrogen in organic synthesis.
11. Hydrogen in inorganic synthesis
12. Hydrogen in metallurgy
13. Hydrogen in non-ferrous metallurgy.
Other uses:
1. Use of the high temperature of the only hydrogen flame.
2. Hydrogen plasma as heating agent.
3. Hydrogen in metal processing.
4. Semiconductor technology.
5. Water treatment.
6. Other uses.
7. Hydrogen energy.
Great quantities are required commercially for the fixation of nitrogen from the air in the
Haber ammonia process and for the hydrogenation of fats and oils. It is also used in large
quantities

in

methanol

production,

in

hydrodealkylation,

hydrocracking,

hydrodesulfurization. Other uses include rocket fuel, welding, producing hydrochloric

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and

acid, reducing metallic ores, and filling balloons.

The lifting power of 1 cubic foot of hydrogen gas is about 0.07 lb at 0C, 760 mm pressure.
The Hydrogen Fuel cell is a developing technology that will allow great amounts of
electrical power to be obtained using a source of hydrogen gas. Public acceptance, high
capital investment, and the high cost of hydrogen with respect to today's fuels are but a few
of the problems facing such an economy. Located in remote regions, power plants would
electrolyze seawater; the hydrogen produced would travel to distant cities by pipelines.
Pollution-free hydrogen could replace natural gas, gasoline, etc., and could serve as a
reducing agent in metallurgy, chemical processing, refining, etc. It could also be used to
convert trash into methane and ethane.

Industrial uses of Hydrogen

Hydrogen finds use in diverse applications covering many industries, including:
Food to hydrogenate liquid oils (such as soybean, fish, cottonseed and corn),
converting them to semisolid materials such as shortenings, margarine and peanut
butter.
Chemical processing primarily to manufacture ammonia and methanol, but also to
hydrogenate non-edible oils for soaps, insulation, plastics, ointments and other
specialty chemicals.
Metal production and fabrication to serve as a protective atmosphere in high
temperature
operations such as stainless steel manufacturing; commonly mixed with argon for welding
austenitic stainless. Also used to support plasma welding and cutting operations.
Pharmaceuticals ... to produce sorbitol used in cosmetics, adhesives, surfactants, and
vitamins A and C.
Aerospace ... to fuel spacecraft, but also to power life-support systems and computers,
yielding drinkable water as a by-product.
Electronics ... to create specially controlled atmospheres in the production of
semiconductor circuits.

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Petroleum Recovery and Refinery ... to enhance performance of petroleum products

by removing organic sulfur from crude oil, as well as to convert heavy crude to
lighter, easier to refine, and more marketable products. Hydrogen's use in
reformulated gas products helps refiners meet Clean Air Act requirements.
Power Generation ... to serve as a heat transfer medium for cooling high speed turbine
generators. Also used to react with oxygen in the cooling water system of boiling
water nuclear reactors to suppress intergranular stress corrosion cracking in the
cooling system.

Manufacturing process

partial oxidation of Hydrocarbons

There are two commercial processes for producing Hydrogen and hydrogen containing
synthesis gases by the non catalytic partial oxidation of hydrocarbons under pressure.
Theses are:
1. Texaco process (1954)
2. Shell gasification process (1956).
Both processes carry out the partial oxidation by burning hydrocarbon with oxygen or
oxygen-rich mixtures to produce gas that contains hydrogen and carbon monoxide small
quantities of carbon dioxide, water vapor and methane.
Chemistry of partial oxidation
The process is carried out by injecting preheated hydrocarbon, preheated and steam
through a specially designed burner into a closed combustion vessel. Where partial
oxidation occurs at 1290 14000 C, with less than stoichiometric oxygen for complete
combustion reaction is given by

The processes is divided into three steps

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1. Heating and cracking phase

2. Reaction phase
3. Soaking phase

Hydrogen from coal

The Texaco coal gasification system of those used for raw gas generation. Under higher
temperature conditions, methane formation is minimized and no tars and oils are produced.
High-pressure gasification results in significant power savings from elimination of raw-gas
compression. A low temperature gasification process such as the lurgi gasifier or BGC/
Lurgi slugging gasifier requires a more complex processing sequence.
All coal gasification processes can be used to manufacture hydrogen. The highest
yield in the primary gasification step however is achieved if pulverized coal is gasified
with oxygen at high temperatures.
Coal gasification on an industrial scale produces:
1. Synthetic gases, rich in CO and hydrogen
E.g. gas for fisher-Tropsch synthesis of gasoline
2. Synthetic gas for the production of acetic an Hydride
3. Ammonia Synthesis gas
4. Substitute natural gas
5. Pure Hydrogen from a side stream of a synthesis gas unit.

Hydrogen production by electrolysis

Electrolysis has been used for approximately 100 years for hydrogen production. The
first installation was by Norsk Hydro in 1927 in Norway. The election of large
electrolysis plant generally depends on the availability of cheap electricity from hydro
power station. A total of 5% of the world hydrogen production is by means of electrolysis.
The following reaction occurs at the electrodes

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Pure water is not suitable as an electrolyte because of its very low conductivity.
Therefore aq. Solution of potassium or sodium hydroxides etc are used.
Types of electrolysis Plants:
1. Normal pressure electrolysis units.
2. Pressure electrolysis.
3. Advanced conventional electrolysis.
4. Water vapor electrolysis.
Electrolysis plant:
A part from the electrolysis unit electrolysis plant consists of number of different
Installations. Such as electricity supply water treatment, electrolyte from product gases.
Gas purification and the instrument and the control system dedicated thermal electric
plants for the production of hydrogen may build in the future.

Steam reforming Plant

In this process, hydrocarbon feeds are converted to synthesis gases is usually operated at
650 10000C at 0.79 4.93 Mpa, using catalysts that we originally Pt group metals but
are now generally Ni- based different stages in steam reforming are.
1. Desulphurization.

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2. Steam reforming.
3. Co conversion.
4. Gas purification.
1. Desulpurization: Because hydrogen feed for steam reforming should be free
of sulfur, feed Desulpurization is required. This is done by using Co Mo
catalyst in the presence of H2
2. Steam reforming: In this desulphurized gas is introduced in the primary
reformer. This reformer is a direct-fired chamber containing multiple high
nickel alloy tubes. The gas leaving the primary reformer is about 76% H2 12%
co. 10% Co2 and 13% CH4.
3. Co-conversion: Water gas shifts or co-conversion of exit gases from the
secondary reformer is carried out in this section.

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Partial oxidation

Partial oxidation of heavy oils shell and Texaco processes

Partial oxidization of heavy oils (shell and Texaco processes) for production of synthesis
gas.Shell and Texaco processes permit controlled oxidation by burning hydrocarbons
with oxygen, which then provides heat and steam to support the thermal steam
hydrocarbon reactions.

Controlled amount of oxygen, steam and CO2 are added to attain desired ration CO/H2 in
the synthesis gas. The advantage of both processes lie in the tolerance to sulphur in the

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feed and the capability of utilizing any hydrocarbon as feed reaction converts CO to CO2
in two stages.
1. High temperature shift.
2. Low temperature shift.
Carbon Dioxide Removal
The gases from LTS discharge contain about 22% CO2 which is removed in this section.
The carbon dioxide is removed by scrubbing with water under pressure a 15 20% MEA.
The CO2 absorbed is stripped and recovered and the absorbing solution is recycled.
Methanation
Methanation of trace impurities of CO and CO2 removal is often preferred to
physical or chemical absorption. Removal of carbon dioxide to the SPPM level in the
methanator is essential to prevent poisoning of the catalyst used for ammonia synthesis.

The above reactions are exothermic

Process selection for design of Hydrogen plant

1. Process selection: shell gasification.
Application: Gasification of a wide range of hydrocarbon feed stocks by
controlled partial oxidation with oxygen and steam. The product, principally
hydrogen and carbon monoxide, may be used after further processing for:
hydrogen, methanol and ammonia-synthesis gas, oxo-synthesis gas, fuel gas and
reducing gas for direct reduction of ferrous and non ferrous ores.
2. Feed stocks: Range from natural gas to heavy asphalt.

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3. Commercial Installations: 140 commercial installation (1979). With a total

capacity of 3 billion SCFD of H2 +CO are in operation throughout the world.
The principal advantage of the partial oxidation process over Stem reforming is that they
can operate on any hydrocarbon feedstock that can be compressed or pumped, from
natural gas to oil, residual oils or asphalt .No desulfurization is required prior to the
partial oxidation step. Their principal disadvantage is the necessity for providing a supply
of 95-99% pure oxygen.
General consideration, which was done before selecting the process
1. Feed stock (raw material)
2. No desulphurization unit is required
3. Gasification of feed with oxygen and steam.
4. Recovery of heat through generation of high pressure steam.
5. Removal of carbon.
6. Removal of H2S and sulfur recovery.
7. Water gas shift reactions to allow the required H2/CO ration.
8. Removal of CO2.
9. Methanation (depends on % purity)
In the shell process the feed enters the homogenizer where carbon agglomerates from
soot recovery are broken and dispersed. The Discharge from the homonizer then follows
to reactor. In the reactor the feed after first mixing with preheated steam, is cracked to
carbon, methane and hydrocarbon radicals during react with oxygen to form carbon
dioxide, steam and exothermic heat which in turn is used for the hydrocarbon hydrogen
steam endothermic reactions. Finally the product gases reach equilibrium composition of
the water gas Shift reaction. The synthesis gases thus produce contains hydrogen sulfide
and carbonyl sulfide.

Manufacturing of Hydrogen by shell gasification process

Chemistry of partial oxidation
The process is carried out by injecting preheated hydrogen, preheated oxygen and
steam through a specially designed burner into a closed combustion vessel, where the

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partial oxidation occurs at 1290 14000C, with less than stochiometric oxygen for
complete combustion. The overall reaction is represented by

The overall process can be divided into three phases.

1. Heating cracking phase: The atomized
hydrogen is heated and vaporized by back radiation from the flame front and the
reactor walls some cracking to carbon, methane and hydrocarbons radicals occurs
during this brief phase.
2. Reaction phase: Hydrocarbons react with oxygen according to highly exothermic
combustion reaction partially all of the available oxygen is consumed in this
phase.

The main endothermic reaction is the

reforming of hydrogen by water viper

The complex reactors results in thermal equilibrium at 1300 1400C

3. Soaked phase: The final phase takes place in the rest of the reactor where the gas
is at higher temperature. A portion of the carbon disappears by reaction with CO2
and steam. Some carbon is present in the product gas

O9

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Equipment: partial oxidation equipment consists essentially of

1. Gasification reactor.
2. Waste heat exchanger.
3. Economizer heat exchanger.
4. Carbon removal system.
5. CO conversation unit.
6. CO2 absorber unit.

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CHAPTER - 2
Material balance

Amount of Hydrogen required to be produced =1x106 m3/day

=41666.67 m3/hr

Basis : 1 hr of operation
Amount of gas at NTP is given by
PV=nRT
n=PV/RT= (41666.67 x 1)/(0.08256 x 298)
No. of moles of Hydrogen = 1703.97 kmol/hr
material balance is divided into different stages which includes
1) Reactor

5)high temperature shift

2) Waste heat boiler

6)low temperature shift

3) Quenching

7)carbon dioxide scrubber

4)hydrogen sulfide removal

feed stock : Natural gas (Raveena offshore)

component

vol%

Methane

99.52

Ethane

0.06

Propane

0.01

Nitrogen

0.40

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In this case it is assumed that all other component are negligible as compared to Methane
so all other are neglected.i.e only Methane and Nitrogen are present in Feed.
Now synthesis gas composition for shell type process is given by -----------(ref1)
Gas composition

vol%

CO2

4.32

CO

46.55

H2

47.15

CH4

0.60

N2

0.56

H2S

0.81

Let 100 kmol of synthesis gas is formed in 1hr operation then we have
Gas composition

kmol

CO2

4.323

CO

46.55

H2

47.15

CH4

0.60

N2

0.56

H2S

0.81

At inlet of H2S removal tower

Assumption made
1) No CO2 removal takes place in Hydrogen sulfide removal tower
2) No loss of gas takes place in leakage after hydrogen sulfide removal
After H2S removal vol% will be :

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Gas composition

vol%

CO2

4.36

CO

46.93

H2

47.54

CH4

0.60

N2

0.57

Material balance for high temperature shift and low temperature

Shift

From literature amount of co remainig after conversion =7.9% (Ref1)

At inlet of HTS we have

Gas composition

vol%

kmol

CO2

4.36

4.32

CO

46.93

46.55

H2

47.54

47.54

CH4

0.60

0.60

N2

0.56

0.56

For H.T.S
Let X moles of CO is converted into H2 and CO2

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Then we have
%CO after H.T.S
7.9/100 =(46.55 X)/{ (46.55-X) +(4.32+X)+(47.15+X)+0.60+0.56}
X=35.85 Kmol
Therefore amount after H.T.S
Gas composition

vol%

kmol

CO2

29.76

40.2

CO

7.90

10.67

H2

61.48

83.03

0.44

0.60

CH4
N2

0.41

0.56

Total no of moles in mixture =135.06 kmol/hr

Low temperature shift balance

From literature range of conversion of CO is given 1.5% to 1.8%

Assuming CO is converted to 1.6% of gas mixture.

1.6/100 =(46.55 X)/{ (46.55-X) +(4.32+X)+(47.15+X)+0.60+0.56}
X=44.2 Kmol

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We have
Gas composition

vol%

kmol

CO2

33.86

48.52

CO

1.60

2.35

H2

63.73

91.74

CH4

0.42

0.60

N2

0.39

0.56

ABSORBER BALANCE

It is assumed that here that only CO2

removal takes place we have Hydrogen
remaining
constant.and

95%

pure

after

the

process.
At inlet of absorption coloumn we
have
Gas composition
kmol
CO2

33.86

48.52

CO

1.60

2.35

H2

63.73

91.74

0.42

0.60

CH4

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vol%

N2

0.39

0.56

Also since only carbondioxide is removed amount of hydrogen is constant.

Therefore we have
(63.73/100)x(Y) =1703.97 kmol/hr (amount of hydrogen to be produced is 1703.97)
kmol /hrof mixture=2650.3442
Now kmoles of other components in gas mixture are
At inlet of absorption coloumn we have

Gas composition

vol%

kmol

CO2

33.68

892.64

CO

1.60

42.40

H2

63.90

1693.57

CH4

0.42

N2

0.39

11.13
10.33

Now X moles of CO2 is removed, also amount of hydrogen is constant is constant

Therefore
95/100 = (1703.97)/{(1703.97) +(905.36-X) +(42.68) +(11.3) +(10.40)}
X =867.64kmol

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Gas composition

vol%

kmol

CO2

1.41

24.995

CO

2.38

42.40

H2

95.00

1693.57

CH4

0.63

11.13

N2

0.58

10.33

Mass balance for the shell partial oxidation process

Inlet of Absorption column we have

Gas composition

vol%

kmol

CO2

33.68

892.635

CO

1.60

42.40

H2

63.90

1693.57

CH4

0.42

11.13

N2

0.39

10.33

At inlet of LTS we have

composition

vol%

kmol

CO2

29.76

745.15

CO

7.90

202.89

H2

61.48

1543.7

CH4

0.44

11.30

N2

0.41

10.40

At inlet of H.T.S we have

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Gas composition

vol%

kmol

CO2

4.36

64.19

CO

46.93

862.74

H2

47.54

883.85

CH4

0.60

11.3

N2

0.57

10.40

Gas composition

vol%

kmol

CO2

4.32

64.19

CO

46.55

862.74

H2

47.15

883.85

CH4

0.60

11.13

N2

0.56

10.40

H2S

0.81

14.96

At inlet of H2S removal tower

MATERIAL BALANCE FOR REACTOR

CHEMICAL REACTION INVOLVED

Now doing carbon balance for the system we get

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Moles of carbon in synthesis gas = 64.19*12/44 + 862.72*12/28 + 11.3*12/16

=395.72 kmol/hr
Now we have feed contains methane and nitrogen
So that moles of carbon in feed = 395.72 kmol/hr
Also moles of Methane in feed = 395.72*16/12 = 527.62
Feed Natural gas is 99.6% pure
Moles of feed = 527.62/0.996 =529.74 kmol/hr
(M )feed = (16)99.6/100 + 28*(0.4/100)
M = 16.048
Kg of feed required is given by = 529.74x 16.048 = 8501.26752
Also amount of oxygen required is
From literature we have
Steam = 0.75 kg/kg of feed.
Oxygen = 1.16 kg/kg of feed
Therefore
Steam = 0.75*(8501.2752)
= 6375.95 kg/hr
Oxygen = 9861.47 kg/hr
Moles of Oxygen = 308.17 kmol/hr

ENERGY BALANCE

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Energy balance for Pre heater

In this feed is heated from initial available temperature of 50C to 250C
By steam heating.steam is available at 600 psig.
Data :
Inlet temperature of feed = 50C
Outlet temperature of feed = 210C
Steam is available at 600 psig
Flow rate of feed gas = 529.74 kmol/hr
Flow rate of Methane in the feed mixture = 527.62 kmol/hr
Flow rate of nitrogen in the feed mixture = 2.12 kmol/hr
(CP)CH4 =0.625 cal/gm C =10 cal/gmol 0C = 41.8 kJ/kmol K
(CP)H2 = 0.265 cal/g0C = 7.42 cal/gmol0C = 30.430 KJ/kmolK
(CP)mix = 0.996 x 41.8 + 0.004*30.43
(CP)mix =41.75 KJ/Kmol0C
Also heat transferred by steam will be used by Feed gas for heating.
Heat received by gas = n x Cp x T
= 529.62 x 41.75 x 160

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= 3537861.6 KJ/h
Heat supplied by steam
Let steam flow rate be M Kg/h
Also
M x = 3537861.6 KJ/h
M = 0.44 kg/sec

Heat balance for waste heat boiler is given by

In W.H.B gas from reactor are cooled from cold water which is converted to
steam with the heat transferred by gas cooling.
Data :
Inlet temperature of gas = 1300C
Oultlet temperature of gas = 250C
Boiler water is available at = 20C
Steam is produced at 600 psig
Gas Flow rate =1832.48 kmol/h
Gas composition

(vol%))

CP (kJ/kmolC)

CO2

4.32

70.00

CO

46.55

36.43

H2

47.15

31.768

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CH4

0.60

100.48

N2

0.56

36.343

H2S

0.81

neglected

CP of mixture = 35.773 kJ/kmolC

Heat transferred by gas = 1832.48 x 35.773 x 1050
Heat taken by cold water = M x CP x T +M x
We have
M x CP x T +M x = 1832.48 x 35.773 x 1050
M(4.187 x 80 + 2210) =1832.48 x35.773 x1050
Mass flow rate of cold water = 27045.99 kg/h = 7.51 kg/s
Energy balance for high temperature shift reaction

CH4 = 7.73

CH 4 = 7.73

CO = 967.817

CO = 193.56

CO2 = 508.88

CO 2 = 1283.1

H2 = 2911.392

H 2 = 3685.6

N2 = 1292.51

N 2 = 1292.5

Ar = 16.575

Ar = 16.575

H20 = 2373.05

H 20 = 1598.6

Applying energy balance, we get

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LHS = 967.817 (-26416) + 508.88 (-94502) + 2373.05 (-57797.9) +

613
+ (68198.77 + 8.4298 T + 992.4 10-5 T2 3786.62 10 T3) dT
298
= - 187345367.1
RHS = 193.5634(-26416) + 1283.125 (-94052) + 1598.67 (-57797.9)
+ (66009.14 + 20.47 10-2 T 4949 10 5 T2 1031.23 10 9
T3 ) dT
T=

Energy balance around LTS

PROJECT WORK

CH4 = 7.73

CH4 = 7.73

CO = 193.56

CO = 8.417

CO2 = 1283.125

CO2 = 1465

N2 = 1292.51

N2 = 1292.51

H2 = 3685.65

H2 = 3685.65

Ar = 16.575

Ar = 16.85

H2O = 1598.67

H2O = 1416.67

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LHS
= - 210584342.2 + 66009.14( 473-287) + 10.235 (4732 2982)
16.39 10 5(4733-2983)-257.810-9(4734 2984)
= -210584342.2 + 12911926.19
=-197672415.99
RHS
=8.417 (-26416) + 1465 (-94052) +1416.67(-57797.9)
+65572.27(7.298) +2330.7 10 2/2 (T2-2982)-294.210-5/3(T32983) 382.210-9/4(T4-2984)
T=

References
[1]http://www.sbioinformatics.com
[2]Energy.gov/eere/fuelcells/hydrogen
[3]En.m.wikipedia.org/wiki/hydrogen

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[4]www.iea.org/publication/hydrogen
[5]www.altenergy.org/renewables/hydrogen

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