PRODUCTION OF HYDROGEN BY STEAM

REFORMING PROCESS
A Project Report Submitted on
partial fulfillment for the award of the degree of
Bachelor of Technology
In
Chemical Engineering
By
B.ASHOK NAIK (11601012)

J.NAMRATHA MARGARATE (11601026)

M.SREE HARSHA (11601032)

P. CHANDRASEKHAR (11601062)

Under the esteemed guidance of

PROF.G. PRABHAKAR

DEPARTMENT OF CHEMICAL ENGINEERING

SVU COLLEGE OF ENGINEERING
SRI VENKATESWARA UNIVERSITY
TIRUPATI – (2019- 2020)

1
 DEPARTMENT OF CHEMICAL ENGINEERING
SVU COLLEGE OF ENGINEERING
TIRUPATHI - 517502

CERTIFICATE
This is to certify that this project entitled’’ PRODUCTION OF HYDROGEN BY
STEAM METHANE REFORMING PROCESS ‘’ is being submitted in partial

fulfillment of for the award of the degree of “BACHELOR OF

TECHNOLOGY” in the department of chemical engineering, Sri
Venkateswara University college of engineering, Sri Venkateswara
University, Tirupati and is a bonafide work carried out by

B. ASHOK NAIK (11601012)

J. NAMRATHA MARGARATE (11601026)
M. SREEHARSHA (11601032)
P.CHANDRA SEKHAR (11601062)

GUIDE :- HEAD OF THE DEPARTMENT:-

PROF. G.PRABHAKAR Dr. B. SARATH BABU
DEPT. OF CHEMICAL ENGINEERING DEPT. OF CHEMICAL ENGINEERING
S. V. U COLLEGE OF ENGINEERING S. V. U COLLEGE OF ENGINEERING
TIRUPATI, 517502 TIRUPATI, 517502

2
 ACKNOWLEDGEMENT
We express our deep sense of gratitude to our institution,
“Sri Venkateswara University College of Engineering”, Tirupati, which
has provided us an opportunity to fulfill our long cherished dream.
We take this opportunity to express my profound gratitude and
deep regards to our Prof .G. Prabhakar and for his exemplary
guidance, monitoring and constant encouragement throughout the
project. The blessing, help and guidance given by sir time to time shall
carry us a long way in the journey of life on which we are about to
embark.
It is pleasure to express our deep sense of gratitude and
indebtedness to the entire faculty, Department of Chemical Engineering,
Sri Venkateswara University College of Engineering, Tirupati, for their
support, who have directly or indirectly had a hand in the successful
completion of our project work.
It is pleasure to express our deep sense of gratitude and
indebtedness to the office staff, Department of Chemical Engineering,
Sri Venkateswara University for their support for the completion of our
work.
Most of all, we would like to thank the Almighty, my ever-loving
parents, family members and well-wishers for giving us the most
needed moral support for the successful completion of our project work.

B.ASHOK NAIK (11601012)

J. NAMRATHA MARGARATE(11601026)
M. SREE HARSHA (11601032)
P. CHANDRA SEKHAR (11601062)

3
 ABSTRACT

Energy supply and demand play a vital role in our modern life.
Among various energy supplies, fossil fuels such as coal, oil and gas
are the most common ones.
Although these energy sources are used extensively for
different purposes such as generating electricity in a large scale, their
application should be limited due to growing environmental
concerns.

Fossil fuels are the largest greenhouse gas emitters in the

world, contributing approximately 3/4 of all carbon, methane and
other greenhouse gas emissions. Burning coalalso produces sulfur
dioxide which contributes to acid rain .

Considering these disadvantages of using fossil fuels, there is an

increasing interest in modernizing energy supplies.

At the recent years , application of hydrogen as an alternative to

fossil fuel has been investigated widely. There is an increasing
interest in using hydrogen as a energy carrier in future.
Hydrogen is produced using steam methane
reforming process and it has been the leading technology for
generation of hydrogen in refining and petrochemical complexes.

In this process feed stock is introduced along with

suplhur other contaminants are removed and by using steam
methane reformer feed stock is converted to syngas at high
temperature and moderate pressure &again these syngas heat is
recovery takes place and water gas shift reaction is used to increase
the hydrogen yield. Finally raw hydrogen is purified using absorption
process using solvent called Monoethanolamine (MEA).

4
Table of contents page no

1. Introduction

1.1. History of Element…………………………………………………………….07

1.2. Physical properties…………………………………………………………….08

1.3. Chemical properties…………………………………………………………..10

1.4. Demand &supply……………………………………………………………….11

1.5. Storage………………………………………………………………………………15

1.6. Transport……………………………………………………………………………17

2.Process description

2.1.Available process

2.1.1. Naptha reforming……………………………………………………………19

2.1.2.Partial oxidation………………………………………………………………..20

2.1.3.Coal gasification………………………………………………………………..22

2.1.4.Water electrolysis……………………………………………………………….23

2.1.5.Steam reforming process…………………………………………………….25

5
2.2 .Process selection…………………………………………………………………………………25

2.3. Process description………………………………………………………………………………25

2.4.Process flow sheet………………………………………………………………………………..27

3. Process calculations

3.1 Material balance……………………………………………………………………….38

3.2. Energy balance…………………………………………………………………………48

3.3. Specific equipment design………………………………………………………..55

4. Plant design & economics………………………………………………………55

4.1.Plant location………………………………………………………………….59

4.2.Plant layout……………………………………………………………………63

5.Conclusion……………………………………………………………………………..69

Bibliography…………………………………………………………………………….70

6
 CHAPTER -1

History & Introduction:

One of the most serious gases we must use is Hydrogen - in our cars,
buses, Space shots from the cape etc. I have been studying
Hydrogen, Propane and many Bio-fuels and have found hydrogen to
be the best, the oldest and the cleanest. I feel this alternative product
is a win -win.
By James Jonas, Member of International Academy of Science
1776 Hydrogen was first identified as a distinct element by British scientist
Henry Cavendish after he evolved hydrogen gas by reacting zinc metal with
hydrochloric acid. In a demonstration to the Royal Society of London, Cavendish
applied a spark to hydrogen gas yielding water. This discovery led to his later
finding that water (H2O) is made of hydrogen and oxygen.

1788 Building on the discoveries of Cavendish, French chemist Antoine Lavoisier

gave hydrogen its name, which was derived from the Greek words—“hydro” and
“genes,” meaning “water” and “born of.”

1800 English scientists William Nicholson and Sir Anthony Carlisle discovered
that applying electric current to water produced hydrogen and oxygen gases.
This process was later termed “electrolysis.”

1874 Jules Verne, an English author, prophetically examined the potential use of
hydrogen as a fuel in his popular work of fiction entitled The Mysterious Island.

1958 The United States formed the National Aeronautics and Space
Administration (NASA). NASA’s space program currently uses the most liquid
hydrogen worldwide, primarily for rocket propulsion and as a fuel for fuel cells.

2003 President George W. Bush announced in his 2003 State of the Union
Address a $1.2 billion hydrogen fuel initiative to develop the technology for
commercially viable hydrogen-powered fuel cells, such that “the first car driven
by a child born today could be powered by fuel cells.”

Today-2050 Future Vision: In the future, water will replace fossil fuels as the
primary resource for hydrogen. Hydrogen will be distributed via national
networks of hydrogen transport pipelines and fueling stations. Hydrogen energy
and fuel cell power will be clean, abundant, reliable,affordable and an integral

7
part of all sectors of the economy in all regions of the U.S.

PHYSICAL PROPERTIES:
The Table lists the important properties of molecular hydrogen, H 2. The
extremely low melting and boiling points result from weak forces of
attraction between the molecules. The existence of these weak intermolecular
forces is also revealed by the fact that, when hydrogen gas expands from high
to low pressure at room temperature, its temperature rises, whereas the
temperature of most other gases falls.

According to thermodynamic principles, this implies that repulsive

forces exceed attractive forces between hydrogen molecules at room
temperature—otherwise, the expansion would cool the hydrogen. In fact, at
−68.6° C attractive forces predominate, and hydrogen, therefore, cools upon
being allowed to expand below that temperature. The cooling effect becomes
so pronounced at temperatures below that of liquid nitrogen (−196° C) that
the effect is utilized to achieve the liquefaction temperature of hydrogen gas
itself.

Atomic hydrogen

atomic number 1

atomic weight 1.0080

ionization potential 13.595 electron volts

electron affinity 0.7542 electron volts

nuclear spin 1/2

nuclear magnetic moment (nuclear

2.7927
magnetons)

nuclear quadrupole moment 0

electronegativity (Pauling) 2.1

8
 Atomic hydrogen

bond distance 0.7416 angstrom

dissociation energy (25 degrees C) 104.19 kilocalories per mole

ionization potential 15.427 electron volts

0.08671 gram per cubic

density of solid
centimetre

melting point −259.20 degrees Celsius

heat of fusion 28 calories per mole

density of liquid 0.07099 (−252.78 degrees)

boiling point −252.77 degrees Celsius

heat of vaporization 216 calories per mole

critical temperature −240.0 degrees Celsius

critical pressure 13.0 atmospheres

critical density 0.0310 gram per cubic centimetre

heat of combustion to water (g) −57.796 kilocalories per mole

Hydrogen is transparent to visible light, to infrared light, and to ultraviolet

light to wavelengths below 1800 Å. Because its molecular weight is lower
than that of any other gas, its molecules have a velocity higher than those of
any other gas at a given temperature and it diffuses faster than any other
gas. Consequently, kinetic energy is distributed faster through hydrogen than
through any other gas; it has, for example, the greatest heat conductivity.

A molecule of hydrogen is the simplest possible molecule. It consists of two

protons and two electrons held together by electrostatic forces. Like atomic
hydrogen, the assemblage can exist in a number of energy levels.

Chemical Properties :
9
 A hydrogen molecule consists of two hydrogen atoms. Hydrogen is a
colorless and odorless gas at room temperature and is the lightest gas,
being about 1/14 as dense as air. Liquefied hydrogen, which has very
low boiling point (−252.88 °CBut even in liquefied state, it is still very
light. Its density is about 0.07 g cm−3 .

Hydrogen itself is a rather stable molecule with high bond energy

(435.99 kJ mol−1 ), but it reacts with many different kinds of elements
to form compounds with them. As is well known, hydrogen easily reacts
(burns) with oxygen at a wide range of mixing ratios and forms water.
This makes it possible to use hydrogen as an energy medium.

The mixture of hydrogen and air can be ignited with very low
energy sparks and safety precautions are required. The reactivity of
hydrogen with other elements is used for various chemical industries,
but this article focuses on its application as an energy medium.

The reactions of hydrogen with some organic compounds can be

used to store and carry hydrogen. The most important chemical
properties of hydrogen as an energy medium are the ones related to
combustion

Hydrogen atom:

Atomic number: 1
Atomic weight: 1.00782519
Hydrogen molecule Formula: H2
Chemical structure: H–H
Molecular weight: 2.0159
Appearance: Colorless and odorless gas asst room temperature
Density (gas): 0.08988 g L−1 (0 °C, 1 atm)
Relative vapor density (air = 1): 0.07
Density (liquid): 70.8 g L−1 (at −253 °C )
Melting point: −259.35 °C
Boiling point: −252.88 °C (at 1 atm)
Solubility in water: 0.0214 cm3 g−1 (0 °C, 1 atm)
Energy content for 1 kg hydrogen (when reacting with oxygen to form water)
Higher heating value: 141 900 kJ; 33 900 kcal; 39.4 kWh
Lower heating value: 120 000 kJ; 28 680 kcal; 32.9 kWh
Auto-ignition temperature: 500–571 °C
Explosive limits: 4–76% (vol. % in air)

10
USES AND APPLICATION:
Hydrogen is versatile and can be utilized in various ways.
These multiple uses can be grouped into two large categories;

1. Hydrogen as a feedstock. A role whose importance is being

recognized for decades and will continue to grow and evolve.
2. Hydrogen as an energy vector enabling the energy transition. The
usage of hydrogen in this context has started already and is
gradually increasing. In the coming this field will grow
dramatically. The versatility of Hydrogen and its multiple
utilization is why hydrogen can contribute to decarbonize existing
economies. Hydrogen’s role in the decarbonization process can be
summarized as shown in the graph below:

11
Nowadays, hydrogen is used in several industrial processes. Among
other applications, it is important to point its use as raw material in the
chemical industry, and also as a reductor agent in the metallurgic
industry. Hydrogen is a fundamental building block for the
manufacture of ammonia, and hence fertilizers, and of methanol, used
in the manufacture of many polymers. Refineries, where hydrogen is
used for the processing of intermediate oil products, are another area
of use. Thus, about 55 % of the hydrogen produced around the world is
used for ammonia synthesis, 25 % in refineries and about 10 % for
methanol production. The other applications worldwide account for
only about 10 % of global hydrogen production.

Ammonia - Fertilizers
The most important hydrogen-nitrogen compound is ammonia (NH3),
also known as azane. Technically, ammonia is obtained on a large scale
by the Haber-Bosch process. This process combines hydrogen and

12
nitrogen together directly by synthesis. To this end, the starting
materials nitrogen and hydrogen must first be obtained. In the case of
nitrogen this is achieved by low-temperature separation of air, while
hydrogen originates today from natural gas steam reforming

Industrial Fields: Hydrogen is used in various in industrial

applications; these include metalworking (primarily in metal alloying),
flat glass production (hydrogen used as an inerting or protective gas),
the electronics industry (used as a protective and carrier gas, in
deposition processes, for cleaning, in etching, in reduction processes,
etc.), and applications in electricity generation, for example for
generator cooling or for corrosion prevention in power plant pipelines.
The direct reduction of iron ore – i.e. the separation of oxygen
from the iron ore using hydrogen and synthesis gas – could develop into
an important industrial process in steel manufacturing, because in the
traditional blast furnace method large amounts of carbon are released.
While direct reduction with natural gas is now well-established in steel
production (World Steel Association 2015), corresponding production
methods based on hydrogen so far exist only on a pilot scale.

Fuel Production

Hydrogen is used to process crude oil into refined fuels, such as gasoline
and diesel, and also for removing contaminants, such as sulphur, from
these fuels.
Approximately 75% of the hydrogen currently consumed worldwide by
oil refineries is supplied by large hydrogen plants that generate
hydrogen from natural gas or other hydrocarbon fuels.

Commencing uses - energy based uses

In the energy field, most hydrogen is used through Fuel Cells (FCs).

Hydrogen in transport

Hydrogen fuel is considered a good candidate to contribute to the

decarbonisation of the road transport sector if it is produced renewable

13
energy sources through the process of electrolysis. In this case, the main
advantages of fuel cell electric vehicles are the zero emission of CO 2
and pollutants and the higher efficiency of fuel cells compared with
internal combustion engines. Passenger cars and urban buses, among
other vehicles, as material handling equipment, etc., are good examples
of the new technology ready for mass commercialization in the coming
years.

Aviation

In civil aviation, hydrogen-powered fuel cells are regarded as potential

energy providers for aircraft as they have been in space travel for some
time now. Thus, fuel cell modules can supply electricity to the aircraft
electrical system as emergency generator sets or as an auxiliary power
unit. More advanced concepts include starting of the main engine and
the nose wheel drive for airfield movements by commercial aircraft.

Trains

Rail vehicles that use hydrogen as an energy store and energy source
can offer an additional alternative. Fuel cell-powered rail vehicles
combine the advantage of pollutant-free operation with the advantage
of low infrastructure costs, comparable with those for diesel operation.

14
In terms of road transport, buses in the public transport network are
the most thoroughly tested area of application for hydrogen and fuel
cells. Since the early 1990s, several hundred buses have been and are
being operated with hydrogen worldwide .

DEMAND AND SUPPLY:

The hydrogen economy is the use of hydrogen as a low
carbon fuel, particularly for heat; but also for hydrogen
vehicles, seasonal energy storage and long distance transport
of energy.
The hydrogen economy is developing as a small part of the low-carbon
economy. In order to phase out fossil fuels and limit global warming,
hydrogen is starting to be used as its combustion only releases clean
water, and no CO
2 to the atmosphere. As of 2019, however, hydrogen is mainly used as
an industrial feedstock, primarily for the production
of ammonia, methanol and petroleum refining.
Hydrogen gas does not occur naturally in convenient reservoirs. As of
2019 almost all the world's 70 million tons of hydrogen consumed
yearly in industrial processing is produced by steam methane
reforming (SMR). Small amounts of hydrogen are produced by the
dedicated production of hydrogen from water.
As of 2019 there is not enough cheap clean electricity (renewable
and nuclear) for this hydrogen to become a significant part of the low-
carbon economy, and carbon dioxide is a by-product of the SMR
process, but it can be captured and stored fueled primarily by natural
gas and transportation by petroleum. Burning of hydrocarbon
fuels emits carbon dioxide and other pollutants.
15
 The demand for energy is increasing, particularly in China, India,
and other developing countries. Hydrogen can be an environmentally
cleaner source of energy to end-users, without release of pollutants
such as particulates or carbon dioxide.

Current hydrogen market

Hydrogen production is a large and growing industry: with as of

2019 about 70 million tones of dedicated production per year, larger
than the primary energy supply of Germany.
The other half of current hydrogen production is used to convert
heavy petroleum sources into lighter fractions suitable for use as fuels.
Smaller quantities of "merchant" hydrogen are manufactured and
delivered to end users as well.
As of 2019 almost all hydrogen production is from fossil fuels, and emits
830 million tonnes of carbon dioxide per year. The distribution of
production reflects the effects of thermodynamic constraints on
economic choices: of the four methods for obtaining hydrogen, partial
combustion of natural gas in a NGCC (natural gas combined cycle)
power plant offers the most efficient chemical pathway and the greatest
off-take of usable heat energy. The large market and sharply rising
prices in fossil fuels have also stimulated great interest in alternate,
cheaper means of hydrogen production. As of 2002, most hydrogen is
produced on site and the cost is approximately $0.70/kg and, if not
produced on site, the cost of liquid hydrogen is about $2.20/kg to
$3.08/kg.

Storage:
Although molecular hydrogen has very high energy density on a mass
basis, partly because of its low molecular weight, as a gas at ambient
16
conditions it has very low energy density by volume. If it is to be used as
fuel stored on board the vehicle, pure hydrogen gas must be stored in
an energy-dense form to provide sufficient driving range.
Pressurized hydrogen gas:
Increasing gas pressure improves the energy density by volume making
for smaller container tanks. Tanks made of carbon and glass fibres
reinforcing plastic as fitted in Toyota Marai and Kenworth trucks are
required to meet safety standards. Few materials are suitable for tanks
as hydrogen being a small molecule tends to diffuse through many liner
materials and hydrogen embrittlement causes weakening in some types
of metal containers. The most common on board hydrogen storage in
today's 2020 vehicles is hydrogen at pressure 700bar = 70MPa.
Liquid hydrogen:
Alternatively, higher volumetric energy density liquid hydrogen
or slush hydrogen may be used. However, liquid hydrogen is cryogenic
and boils at 20.268 K (–252.882 °C or –423.188 °F). Cryogenic storage
cuts weight but requires large liquefaction energies. The liquefaction
process, involving pressurizing and cooling steps, is energy intensive.
The liquefied hydrogen has lower energy density by volume than
gasoline by approximately a factor 0f four, because of the low density
of liquid hydrogen — there is actually more hydrogen in a litre of
gasoline (116 grams) than there is in a litre of pure liquid hydrogen
(71 grams). Liquid hydrogen storage tanks must also be well insulated
to minimize boil off.

Storage as hydride:
Distinct from storing molecular hydrogen, hydrogen can be stored as a
chemical hydride or in some other hydrogen-containing compound.

Adsorption:
A third approach is to adsorb molecular hydrogen on the surface of a
solid storage material. Unlike in the hydrides mentioned above, the
hydrogen does not dissociate/recombine upon charging/discharging
the storage system, and hence does not suffer from the kinetic

17
limitations of many hydride storage systems. Hydrogen densities
similar to liquefied hydrogen can be achieved with appropriate
adsorbent materials. Some suggested adsorbents include activated
carbon, nanostructure carbons (including CNTs), MOFs, and hydrogen
clathrate hydrate.
Underground hydrogen storage:

Underground hydrogen storage is the practice of hydrogen storage

in caverns, salt domes and depleted oil and gas fields. Large quantities of
gaseous hydrogen have been stored in caverns by ICI for many years without
any difficulties. The storage of large quantities of liquid hydrogen
underground can function as grid energy storage.
Pipeline storage:
A natural gas network may be used for the storage of hydrogen. This
being economically seen, still cheaper than producing it .

18
 CHAPTER 2
The main commercial processes in the production of hydrogen are:
1) Naptha reforming
2)Partial oxidation
3)Coal gasification
4)Water electrolysis
5)Steam reforming process

Criteria for selecting best process:

1)The availability and relative cost of the different feed stocks
2)Capital costs.
3)Operating costs.
4)Environmental considerations.
5)End use of the hydrogen or syngas.

Naphtha reforming:-

The most widespread process for rearranging hydrocarbon molecules

is naphtha reforming. The initial process, thermal reforming, was
developed in the late 1920s. Thermal reforming employed temperatures of
510–565 °C (950–1,050 °F) at moderate pressures—about 40 bars (4
MPa), or 600 psi—to obtain gasolines (petrols) with octane numbers of 70
to 80 from heavy naphthas with octane numbers of less than 40. The
product yield, although of a higher octane level, included olefins, diolefins,
and aromatic compounds. It was therefore inherently unstable in storage
and tended to form heavy polymers and gums, which caused combustion
problems.

By 1950 a reforming process was introduced that employed

a catalyst to improve the yield of the most desirable gasoline components
while minimizing the formation of unwanted heavy products and coke.
In catalytic reforming, as in thermal reforming, a naphtha-type material
serves as the feedstock, but the reactions are carried out in the presence

19
of hydrogen, which inhibits the formation of unstable
unsaturated compounds that polymerize into higher-boiling materials.

In most catalytic reforming processes, platinum is the active catalyst; it is

distributed on the surface of an aluminum oxide carrier. Small amounts
of rhenium, chlorine, and fluorine act as catalyst promoters.

In spite of the high cost of platinum, the process is

economical because of the long life of the catalyst and the high quality and
yield of the products obtained. The principal reactions involve the
breaking down of long-chain hydrocarbons into smaller saturated chains
and the formation of isoparaffins, made up of branched-chain molecules.

Formation of ring compounds (technically, the cyclization of

paraffins into naphthenes) also takes place, and the naphthenes are then
dehydrogenated into aromatic compounds (ring-shaped unsaturated
compounds with fewer hydrogen atoms bonded to the carbon). The
hydrogen liberated in this process forms a valuable by-product of catalytic
reforming.

Partial oxidation:
Hydrogen production from natural gas or other hydrocarbons is
achieved by partial oxidation. A fuel-air or fuel-oxygen mixture is
partially combusted resulting in a hydrogen rich syngas. Hydrogen and
carbon monoxide are obtained via the water-gas shift reaction. Carbon

20
dioxide can be co-fed to lower the hydrogen to carbon monoxide ratio.
The partial oxidation reaction occurs when a substoichiometric fuel-air
mixture or fuel-oxygen is partially combusted in a reformer or partial
oxidation reactor.
A distinction is made between thermal partial
oxidation (TPOX) and catalytic partial oxidation (CPOX). The chemical
reaction takes the general form:

CnHm + n/2 O2 → n CO + m/2 H2

Idealized examples for heating oil and coal, assuming compositions

C12H24 and C24H12 respectively, are as follows:

C12H24 + 6 O2 → 12 CO + 12 H2
C24H12 + 12 O2 → 24 CO + 6 H2

21
3)COAL GASIFICATION PROCESS:
Chemically, coal is a complex and highly variable substance that can be
converted into a variety of products. The gasification of coal is one method
that can produce power, liquid fuels, chemicals, and hydrogen.
Specifically, hydrogen is produced by first reacting coal with
oxygen and steam under high pressures and temperatures to form
synthesis gas, a mixture consisting primarily of carbon monoxide and
hydrogen.
The process of coal gasification uses steam and a carefully
controlled concentration of gases to break molecular bonds in coal and
form a gaseous mix of hydrogen and carbon monoxide. [13] This source of
hydrogen is advantageous since its main product is coal-derived gas
which can be used for fuel .

The gas obtained from coal gasification can later be used to produce
electricity more efficiently and allow a better capture of greenhouse
gases than the traditional burning of coal.

Coal gasification reaction (unbalanced):

CH0.8 + O2 + H2O → CO + CO2 + H2 + other species

22
WATER ELECTROLYSIS:

Electrolysis consists of using electricity to split water into hydrogen and

oxygen. Electrolysis of water is 70–80% efficient (a 20–30% conversion
loss). while steam reforming of natural gas has a thermal efficiency
between 70–85%.
The (electrical) efficiency of electrolysis is expected
to reach 82–86%before 2030, while also maintaining durability as
progress in this area continues at a pace. Water electrolysis can
operate between 50–80 °C, while steam methane reforming requires
temperatures between 700–1100 °C.
The difference between the two methods is the
primary energy used; either electricity (for electrolysis) or natural gas
(for steam methane reforming).
Due to their use of water, a readily available
resource, electrolysis and similar water-splitting methods have
attracted the interest of the scientific community. With the objective of
reducing the cost of hydrogen production, renewable sources of energy
have been targeted to allow electrolysis.
There are three main types of cells, solid oxide
electrolyser cells (SOECs), polymer electrolyte membrane cells (PEM)
and alkaline electrolysis cells (AECs). SOECs operate at high
temperatures, typically around 800 °C. At these high temperatures a
significant amount of the energy required can be provided as thermal
energy (heat), and as such is termed High temperature electrolysis.
The heat energy can be provided from a number of different
sources, including waste industrial heat, nuclear power stations or
concentrated solar thermal plants. This has the potential to reduce the
overall cost of the hydrogen produced by reducing the amount of
electrical energy required for electrolysis.
PEM electrolysis cells typically operate below 100 °C and are
becoming increasingly available commercially. These cells have the
advantage of being comparatively simple and can be designed to accept
widely varying voltage inputs which makes them ideal for use with
renewable sources of energy such as solar PV.

23
Half reactions in the electrolysis of pure water at pH=7, and at 25°Care-
At cathode: 2H2O(l) + 2e– → H2(g) + 2OH– E° = -0.42 V
At anode: 2H2O → O2(g) + 4H+ + 4e– E° = +0.82 V
The net reaction of electrolysis of water is given as;
2H2O(l) → 2H2(g) + O2(g) E° = -1.24 V
The cell potential of electrolysis of pure water is negative and hence is
thermodynamically unfavourable. Because of the low concentration of
ions and the interfaces to be crossed electrons an extra voltage
(Overvoltage) at each electrode is needed to about 0.6V.
In practice, continuous electrolysis of pure water is possible only at an
external voltage of 2.4V. Since the electrolysis of pure water is
thermodynamically non-feasible, methods to make it kinetically feasible
are being investigated.

24
STEAM REFORMING PROCESS:
Steam reforming of natural gas at petroleum refining facilities is the
predominant means of producing hydrogen in the chemical process
industries (CPI). Areas where hydrogen is heavily consumed include
ammonia production, the cryogenics industry and methanol
production.
Because hydrogen needs within various sectors of the CPI are
at their highest levels in history, and are continuing to grow, an
understanding of this method of hydrogen production and purification
can be useful.

According to selection criteria steam

reforming process is considered as best and most used process
in the production of hydrogen.

STEAM REFORMING PROCESS:

1. Introduction

Energy supply and demand play a vital role in our modern life.
Among various energy supplies, fossil fuels such as coal, oil and gas are
the most common ones.

Although these energy sources are used extensively for

different purposes such as generating electricity in a large scale, their
application should be limited due to growing environmental concerns.

Fossil fuels are the largest greenhouse gas emitters in the

world, contributing approximately 3/4 of all carbon, methane and
other greenhouse gas emissions. Burning coalalso produces sulfur
dioxide which contributes to acid rain .

Considering these disadvantages of using fossil fuels, there is

an increasing interest in modernizing energy supplies.

At the recent years , application of hydrogen as an alternative

25
to fossil fuel has been investigated widely. There is an increasing
interest in using hydrogen as a energy carrier in future.
Hydrode alkylation , hydrodesulphurization, and
hydro cracking are the main consumers of H₂ in the petroleum plants.
H₂ is used as hydrogenating agent and in production of methanol. Pure
hydrogen or mixed hydrogen with nitrogen is employed as a tracer gas.

The Steam Reforming Hydrogen Plant For many years, steam methane
reforming (SMR) has been the leading technology for generation of
hydrogen in refining and petrochemical complexes.

The steam reforming plant consists of four basic sections:

1) The first is feedstock treatment where sulphur and other

contaminants are removed.

2) The second is the steam methane reformer, which converts

feedstock and steam to syngas (mainly hydrogen and carbon
monoxide) at high temperature and moderate pressure. In case of
multiple or heavy feeds and/or for large capacities, an adiabatic,
catalytic pre-reforming step is foreseen upstream the SMR.

3) The third section is the syngas heat recovery and incorporates CO

shift reactors to increase the hydrogen yield.

4) The final section is the raw hydrogen purification, in which

modern plants employ a pressure swing adsorption (PSA) unit to
achieve the final product purity.

The four basic steps are:

 Feeding the raw material Primary Reformer

 Desulphurization
 Reforming process
 Shift conversion process Secondary Reformer
 Absorption
26
 PROCESS FLOW SHEET

Steam Steam

Natural gas

Sweetened gas
SWEETENING PRIMARY SECONDARY
PROCESS REFORMER REFORMER

MEA

H2S, CO2
Liquid
DESORPTION
COLUMN
MEA

Final
product

MEA ABSORPTION
HTS LTS OF CO2

DESORPTION
COLUMN

CO2 MEA
27
1) Raw material:

The common feed stock used is Natural gas.

NATURAL GAS:
Natural gas (also called fossil gas; sometimes just gas), is
a naturally occurring hydrocarbon gas mixture consisting primarily
of methane, but commonly including varying amounts of other
higher alkanes, and sometimes a small percentage of carbon dioxide,
nitrogen, hydrogen sulfide, or helium.
It is formed when layers of decomposing plant and animal
matter are exposed to intense heat and pressure under the surface of
the Earth over millions of years.
The energy that the plants originally obtained from the sun is
stored in the form of chemical bonds in the gas.
Natural gas is a non-renewable hydrocarbon used as a
source of energy for heating, cooking, and electricity generation. It is
also used as a fuel for vehicles and as a chemical feedstock in the
manufacture of plastics and other commercially important organic
chemicals.
Natural gas is found in deep underground rock formations
or associated with other hydrocarbon reservoirs in coal beds and
as methane clathrates. Petroleum is another resource and fossil fuel
found close to and with natural gas. Most natural gas was created
over time by two mechanisms: biogenic and thermogenic.
Biogenic gas is created
by methanogenic organisms in marshes, bogs, landfills, and shallow
sediments. Deeper in the earth, at greater temperature and
pressure, thermogenic gas is created from buried organic material.

28
 CHEMICAL COMPOSITION OF NATURAL GAS:

This natural gas, because of the rotten smell provided by

its sulfur content, is commonly called 'sour gas'. Sour gas is
undesirable because the sulfur compounds it contains can be
extremely harmful, even lethal, to breathe. Sour gas can also be
extremely corrosive.
Therefore because of this reason sulphur content must
be removed from natural gas as it is extremely harmful. Removing
of sulphur content is called Desulphurization.

2)DESULPHURIZATION or SWEETENING
PROCESS:-
Natural gas, while ostensibly being hydrocarbon in nature, contains
large amounts of acid gases, such as hydrogen sulfide and carbon
dioxide.
Natural gas containing hydrogen sulfide or carbon dioxide is referred
to as sour, and natural gas free from hydrogen sulfide is referred to as
sweet.

Natural gas which contains acid gases is commonly referred to as

29
sour gas. Gas which contains no acid gases or has had them reduced to
an acceptable level by a treating process is called sweet gas.

The corrosiveness nature of hydrogen sulfide and carbon

dioxide in the presence of water (giving rise to an acidic aqueous
solution) and because of the toxicity of hydrogen sulfide and the lack of
heating value of carbon dioxide, natural gas being prepared for sales is
required to contain no more than 5 ppm hydrogen sulfide and to have a
heating value of no less than 920 to 980 Btu/scf.
However, because natural gas has a wide range of composition,
including the concentration of the two acid gases, processes for the
removal of acid gases vary and are subject to choice based on the
desired end product.
There are many variables in treating natural gas. The precise area of
application of a given process is difficult to define. Several factors must
be considered:
(1) types and concentrations of contaminants in the gas,
(2) the degree of contaminant removal desired,
(3) the selectivity of acid gas removal required,
(4) the temperature, pressure, volume, and composition
of the gas to be processed.
(5) the carbon dioxide-hydrogen sulfide
ratio in the gas, and
(6) the desirability of sulfur recovery due to process
economics or environmental

However, there are those processes that are not designed to

remove (or are incapable of removing) large amounts of acid gases.
These processes are also capable of removing the acid gas impurities to
very low levels when the acid gases are there in low to medium
concentrations in the gas.
Process selectivity indicates the preference with which the
process removes one acid gas component relative to another.
For example, some processes remove both hydrogen sulfide and
carbon dioxide; other processes are designed to remove hydrogen
sulfide only.
It is important to consider the process selectivity for say, hydrogen
30
sulphide removal compared to carbon dioxide removal that ensures
minimal concentrations of these components in the product, thus the
need for consideration of the carbon dioxide to hydrogen sulfide in the
gas stream.
The main focus is the treatment of natural gas to remove the
acid gases, carbon dioxide and hydrogen sulfide. However, because the
processes are integrated within the concept of gas treating or acid gas
removal or acid gas treating .
The acids formed can be very corrosive to equipment and piping.
Removal of both H2S and C02 from natural gas is one of the most
common treating problems for gas plants.
Hydrogen sulfide must be removed due to its corrosiveness and
toxicity. When burned, it forms sulfur dioxide (S02), which is another
toxic gas. Carbon dioxide must also be removed from natural gas due to
its corrosiveness and lack of heating value. Removing C02 raises the
heating value of natural gas and reduces the cost of pipeline
transmission.
As currently practiced, acid gas removal processes involve the
chemical reaction of the acid gases with a solid oxide (such as iron
oxide) or selective absorption of the contaminants into a liquid (such as
ethanolamine) that is passed countercurrent to the gas.

Then the absorbent is stripped of the gas components (regeneration)

and recycled to the absorber. The process design will vary and, in
practice, may employ multiple absorption columns and multiple
regeneration columns.
Liquid absorption processes are classified either as physical solvent
processes or as chemical solvent processes. Amine washing of natural
gas involves chemical reaction of the amine with any acid gases with
the liberation of an appreciable amount of heat and it is necessary to
compensate for the absorption of heat.
Amine derivatives such as ethanolamine (monoethanolamine),
diethanolamine. triethanolamine, methyldiethanolamine,
diisopropanolamine, and diglycolamine have been used in commercial
applications.
The process of removing acid gases from natural gas is called gas

31
sweetening. Although there are several processes used in the petroleum
industry for removing acid gases from natural gas, the most common
process utilizes substances known as alkanolamines or simply amines.
Therefore the solvent used for the treatment is Monoethanolamine

MONOETHANOLAMINE:

Monoethanolamine (MEA) is often used as the solvent of choice in

CO2 scrubbing processes. Such scrubbing systems are increasingly
being built (or designed to be built) during recent times due to the
increased attention on carbon dioxide capture and sequestration (CCS)
concept associated with CO2 free power generation initiatives.
Technical maturity of this solvent absorption system together with
its unique features like high loading capacity for CO 2 at low partial
pressures, fast reaction kinetics and high removal efficiencies (Goff,
2005) may ensure high use of this chemical for years to come.
A significant amount of MEA containing liquid wastes is generated
due to degradation of the solvent in gas scrubbing. Land filling and
incineration has been used for the disposal of such wastes in small
quantities but such disposal methods may neither be economical nor
environmentally sustainable for handling large quantities of such
liquid wastes.

Monoethanolamine (MEA) is a primary amine and the strongest

amine among others. MEA is a stable compound and, in the absence of
other chemicals, suffers no degradation or decomposition at
temperatures up to its normal boiling point.

MEA reacts with H2S and CO2 as follows:

2(RNH2)+H2S↔(RNH3)2S
(RNH3)2S+H2S↔2(RNH3)HS
2(RNH2)+CO2↔RNHCOONH3R

These reactions are reversible by changing the system temperature.

32
MEA can remove both H2S and
CO2 from gas streams to meet sales
gas specifications.
Therefore after this methane and
some compounds are sent to
reforming process.

STEAM REFORMING PROCESS: Steam

reforming or steam methane reformi
ng is a method for producing syngas (hydrogen and carbon monoxide)
by reaction of hydrocarbons with water.

CH4 + H2O CO + 3 H2
The reaction is strongly endothermic.
Production of H2 and CO from hydrocarbon gases (e.g. natural gas) is
performed by two well-known "primary" and "secondary" reformers.
Steam methane reforming (SMR) and autothermal reformer (ATR) are
two industrial examples.
The first one being the primary reformer operating at a temperature
around 900°C with pressure around 15–30 atm.

The latter is then followed by a secondary reformer, also

working with a nickel-based catalyst at a average temperature of
1000°C and using a combination of oxygen and steam in the feed.
The two following unit operations are generally used to adapt
the H2/CO ratio using successively a first water-gas shift reaction
operated at 400°C under an iron catalyst followed by a second water-
gas shift system operated at 200°C under a copper catalysmples of the
primary and secondary reformers, respectively.

33
Primary Reformer • Steam Reforming : •
It is the reaction of a hydrocarbon, such as methane with water and/or
carbon dioxide, to produce a mixture of carbon monoxide and hydrogen.

• Mixing Desulfurized stream with MP Steam , Preheating

CH4 + H2O CO + 3H2
CO + H2O H2 + CO2 •
90 % of CH4 is converted into synthesis gas (CO + H2) •
Excess steam is used to avoid side reactions such as:
CH4 2H2 + C
2CO CO2 +

SECONDARY REFORMER:

34
A portion of the product gas is burned in the Secondary Reformer with
added air or oxygen so that the gas mixture reaches a temperature that
is over 1,000°C
• Methane reacts with steam at this temperature until only an
insignificant amount remains (0.2 to 0.3 vol %

CH4 + H2O 3H2 + CO

2H2 + ( N2+O2 ) 2H2O + N2
-----------------------------------------
CH4 + O2 2CO + H2 + H2O

4)SHIFT CONVERSION REACTION:

Carbon Monoxide Shift

•removes most of the carbon monoxide (CO) & produces more
hydrogen. CO + H2O H2 + CO2
•The “shift” from carbon monoxide to carbon dioxide generally
occurs in two steps :
1)High temperature shift conversion
2)Low temperature shift conversion

1. High Temperature Shift Conversion

• The synthesis gas is passed through a bed of iron
oxide/chromium oxide catalyst at around 400°C and a
pressure of 25 to 28 bar.
• The CO content of the gas is reduced to about 3% (on a dry
gas basis)

35
2. Low Temperature shift conversion
Adding a LT‐shift (adiabatic reactor, inlet
temperature 205 °C) to a HT‐shift reactor when a Low Temperature Shif
t (LTS) converter is installed :

The gas from the HTS is cooled to increase

he conversion, and then it is passed through the LTS converter
( 99.8 % of CO is converted into CO2)

2. Low Temperature shift conversion

Adding a LT‐shift (adiabatic reactor, inlet
temperature 205 °C) to a HT‐shift reactor when a Low Temperature Shif
t (LTS) converter is installed :

The gas from the HTS is cooled to increase

he conversion, and then it is passed through the LTS converter
( 99.8 % of CO is converted into CO2)

5)Absorption:

Ethanolamine solutions are a kind of important absorbent for carbon

dioxide capture from flue gas. In this work, the absorption rate and
absorption capacity of carbon dioxide by ethanolamine and piperazine
solutions have been studied.
36
 Using a newly absorption equipment, the absorption
rate was measured in monoethanolamine, diethanolamine and
piperazine solutions with different concentration from 10 to 50 wt %,
respectively.

The experimental results showed that monoethanolamine

and diethanolamine both have a large absorption rate and capacity.
According to the experimental results and the zwitterion mechanism,
the kinetics of the reaction between carbon dioxide and ethanolamine
could be derived.

Previous studies showed that the aqueous ethanolamine

solutions such as monoethanolamine (MEA), diethanolamine (DEA) are
frequently used for removal of carbon dioxide from Absorption of
Carbon Dioxide in Ethanolamine Solution.

The advantage of using ethanolamine as absorbent is due to

its fast reaction kinetics with CO2, high selectivity, low hydrocarbon
solubility and low solvent cost.

37
 CHAPTER -3

3.1 Material Balance

1.Feed

1Kmol of Natural gas contains

Components Moles(Kmol) Mass(Kg)

CH4 0.85 13.6
C2H6 0.11 3.3
H2S 0.02 0.68
CO2 0.02 0.88

2.Sweetening Process:-

 MonoEthanolAmine [C2H4OHNH2] using in this process is of

concentration of 10%weight
 20% excess solution than requirement is taken

Reactions
RNH2 + H2S  RNH3HS
2RNH2 + CO2  RNHCOORNH3

From stoichiometry of above reactions and feed composition

0.06Kmol of MEA is required for 1Kmol of natural gas.

Since the solution taken is 20% excess and of 10% by weight

concentration so the taken MEA solution is of 43.92Kg weight(4.392 Kg
of MEA + 39.528 Kg of Water).
The efficiency of the column is taken as 99.9%.

38
Mole Balance

In(kmol) Out(Kmol)
Gas Gas
CH4 0.85 CH4 0.85
C2H6 0.11 C2H6 0.11
H2 S 0.02 H2S 0.00002
CO2 0.02 CO2 0.00002
Liquid Liquid
MEA 0.072 MEA 0.01206
H2 O 2.196 H2O 2.196
RNH3HS 0.01998
RNHCOORNH3 0.01998

Mass Balance

In(kg) Out(Kg)
Gas Gas
CH4 13.6 CH4 13.6
C2H6 3.3 C2H6 3.3
H2 S 0.68 H2S 0.00068
CO2 0.88 CO2 0.00088
Liquid Liquid
MEA 4.392 MEA 0.73566
H2 O 39.528 H2O 39.528
RNH3HS 1.8981
RNHCOORNH3 3.31668
Total 62.38 Total 62.38

39
3.Regenaration of Liquid from Sweetening Process
The liquid from the sweetening process should undergo Regeneration
process. Increasing the temperature the absorbed gases gets desorbed.
The efficiency of the column is taken as 99.9%.

Mole Balance

In(kmol) Out(Kmol)
LIQUID LIQUID
MEA 0.01206 MEA 0.07194006
H2O 2.196 H2O 2.196
RNH3HS 0.01998 RNH3HS 0.00001998
RNHCOORNH3 0.01998 RNHCOORNH3 0.00001998
GAS
H2S 0.01996002
CO2 0.01996002

Mass Balance

In(kg) Out(Kg)
LIQUID LIQUID
MEA 0.73566 MEA 4.38834366
H2O 39.528 H2O 39.528
RNH3HS 1.8981 RNH3HS 0.0018981
RNHCOORNH3 3.31668 RNHCOORNH3 0.00331668
GAS
H2S 0.67864068
CO2 0.87824088
Total 45.47844 Total 45.47844

40
4.Primary Reformer

The gas from sweetening process has 1.07002Kmol

[0.85+0.22+0.00002] of C .
Steam to carbon ratio is taken as 4.
So 4.28008Kmol of steam is taken.
Half is sent into primary reformer and remaining half is sent into
secondary reformer.

Reactions
CH4 + H2O  CO + 3H2(3)
C2H6 + 2H2O  2CO +5H2(4)
CO + H2O  CO2 + H2(5)

Assumption
 60% conversionof CH4 in Reaction (3)
 100% conversion of C2H6 in Reaction (4)
 10% conversion of CO in Reaction (5)

Mole Balance
In(kmol) Out(Kmol)
CH4 0.85 CH4 0.34
C2H6 0.11 H2S 0.00005
H2S 0.00002 CO2 0.07302
CO2 0.00002 H2O 1.17037
H2O 2.14004 H2 2.153
CO 0.657

41
Mass Balance
In(Kg) Out(Kg)
CH4 13.6 CH4 5.44
C2H6 3.3 H2S 0.00068
H2S 0.00068 CO2 3.21288
CO2 0.00088 H2O 24.06672
H2O 38.52072 H2 4.306
CO 18.396
Total 55.42228 Total 55.42228

5.Secondary Reformer
Reaction
CH4 + H2O  CO + 3H2(6)
CO + H2O  CO2 + H2(7)
Assumption
 99.9% conversion of CH4 in Reaction (6)
 10% conversion of CO in Reaction (7)

Mole Balance
In(Kmol) Out(Kmol)
CH4 0.34 CH4 0.00034
H2S 0.00002 H2S 0.00002
CO2 0.07302 CO2 0.172686
H2O 3.47708 H2O 3.037754
H2 2.153 H2 3.271646
CO 0.657 CO 0.896994

42
Mass Balance

In(Kg) Out(Kg)
CH4 5.44 CH4 0.00544
H2S 0.00068 H2S 0.00068
CO2 3.21288 CO2 7.598184
H2O 62.58744 H2O 54.679572
H2 4.306 H2 6.543292
CO 18.396 CO 25.115832
Total 93.943 Total 93.943

6.HTS Converter
Reaction
CO + H2O  CO2 + H2(8)
Assumption
 70% conversion of CO in Reaction (8)

Mole Balance

In(Kmol) Out(Kmol)
CH4 0.00034 CH4 0.00034
H2S 0.00002 H2 S 0.00002
CO2 0.172686 CO2 0.8005818
H2O 3.037754 H2O 2.4098582
H2 3.271646 H2 3.8995418
CO 0.896994 CO 0.2690982

43
Mass Balance
In(Kg) Out(Kg)
CH4 0.00544 CH4 0.00544
H2S 0.00068 H2S 0.00068
CO2 7.598184 CO2 35.2255992
H2O 54.679572 H2O 43.3774476
H2 6.543292 H2 7.7990836
CO 25.115832 CO 7.5347496
Total 93.943 Total 93.943

7.LTS Converter
Reaction
CO + H2O  CO2 + H2(9)
Assumption
 99.9% conversion of CO in Reaction (9)

Mole Balance

In(Kmol) Out(Kmol)
CH4 0.00034 CH4 0.00034
H2S 0.00002 H2S 0.00002
CO2 0.8005818 CO2 1.0694109018
H2O 2.4098582 H2O 2.1410290982
H2 3.8995418 H2 4.1683709018
CO 0.2690982 CO 0.0002690982

44
Mass Balance

In(Kg) Out(Kg)
CH4 0.00544 CH4 0.00544
H2S 0.00068 H2S 0.00068
CO2 35.2255992 CO2 47.0540796792
H2O 43.3774476 H2O 38.5385237676
H2 7.7990836 H2 8.3367418036
CO 7.5347496 CO 0.0075347496
Total 93.943 Total 93.943

8.Absorption of CO2

 MonoEthanolAmine [C2H4OHNH2] using in this process is of

concentration of 10%weight.

 20% excess solution than requirement is taken

Reactions
RNH2 + H2S  RNH3HS
2RNH2 + CO2  RNHCOORNH3
The efficiency of the column is taken as 99.9%.

45
Mole Balance

In(Kmol) Out(Kmol)
Gas Gas
CH4 0.00034 CH4 0.00034
H2S 0.00002 H2S 0.00002
CO2 1.069410902 CO2 0.001069410902
H2O 2.141029098 H2 4.168370902
H2 4.168370902 CO 0.0002690982
CO 0.0002690982
Liquid Liquid
MEA 2.56658616 MEA 0.4299031782
H2O 78.2808778 RNHCOORNH3 1.068341491
H2O 80.4219069

Mass Balance
In(Kg) Out(Kg)
Gas Gas
CH4 0.00544 CH4 0.00544
H2S 0.00068 H2S 0.00068
CO2 47.05407968 CO2 0.04705407968
H2O 38.53852377 H2 8.336741804
H2 8.336741804 CO 0.0075347496
CO 0.0075347496
Liquid Liquid
MEA 156.5617558 MEA 26.22409387
H2O 1409.0558 RNHCOORNH3 177.3446875
H2O 1447.594324
Total 1659.560556 Total 1659.560556

46
9.Regenaration of Liquid from Absorption column

The liquid from the sweetening process should undergo Regeneration

process. Increasing the temperature the absorbed gases gets desorbed.
The efficiency of the column is taken as 99.9%.

Mole Balance

In(kmol) Out(Kmol)
LIQUID LIQUID
MEA 0.4299031782 MEA 2.564449477
H2O 80.4219069 H2O 80.4219069
RNHCOORNH3 1.068341491 RNHCOORNH3 0.001068341491
GAS
CO2 1.067273149

Mass Balance

In(kg) Out(Kg)
LIQUID LIQUID
MEA 26.22409387 MEA 156.4314181
H2O 1447.594324 H2O 1447.594324
RNHCOORNH3 177.3446875 RNHCOORNH3 0.1773446875
GAS
CO2 46.96001857
Total 1651.163106 Total 1651.163106

47
 3.2 Energy balance

1)Sweetening process:-

Energy balance of Sweetening process

Gas enters the Reformer at 320K
Gas leaves the Reformer at 373K
Flow Cp (Kj/Kg-K) at M*Cp*(320-
Component rate(Kg/Day) 320K 298)
CH4 163133.2758 2.1123 155753061.2
C2H6 39583.80957 1.878 33600954.26
H2S 8156.66379 0.288 1061801.866
CO2 10555.68255 0.813 3878960.002
0
Total(Qin) 194294777.3

Flow Cp (Kj/Kg-K) at M*Cp*(373-

Component rate(Kg/Day) 373K 298)
CH4 163133.2758 2.442 304754166.5
C2H6 39583.80957 2.095 0
H2S 8.15666379 0.514 3207.281769
CO2 10.55568255 0.918 7412.939186

Total(Qout) 304764786.8

Delta
Q(Kj/Day) 110470009.5

48
 Energy balance of Sweetening process
liquid enters the Reformer at 353K
liquid leaves the Reformer at 453K
Flow Cp (Kj/Kg-K) at M*Cp*(353-
Component rate(Kg/Day) 353K 298)
MEA 52682.45201 0.893 21264534.2
H2O 474142.0681 1.5402 330083673.2

Total(Qin) 351348207.4

Flow Cp (Kj/Kg-K) at M*Cp*(453-

Component rate(Kg/Day) 453K 298)
MEA 8824.310712 3.6948 24942108.36
H2O 474142.0681 1.1423 0
RNH3HS 22767.88756 2.2104 38499496.08
RNHCOONH3 39783.88774 3.1413 95604441.81

Total(Qout) 159046046.2

Delta
Q(Kj/Day) -192302161.2

49
2)Primary reformer and Secondary reformer;-

Energy balance of primary reformer

Gas enters the Reformer at 750K
Gas leaves the Reformer at 1063K
Flow Cp (Kj/Kg-K) at
Component rate(Kg/Day) 750K M*Cp*(750-298)
CH4 163133.2758 3.79649 279938900.3
C2H6 39583.80957 3.43973 61543243.02
H2S 8.15666379 1.22297 4508.860512
CO2 10.55568255 1.14816 5478.064841
H2O 462059.65 2.10461 439549822.7
Total(Qin) 781041953

Flow Cp (Kj/Kg-K) at M*Cp*(1063-

Component rate(Kg/Day) 1063K 298)
CH4 65253.31032 4.68554 233896451.7
C2H6 0 4.209 0
H2S 8.15666379 1.37238 8563.442323
CO2 38538.797 1.24929 36831792.28
H2O 288682.5641 2.33329 515288807.1
H2 51650.87394 15.0135 593227202.9
CO 220661.7457 1.19938 202462822.7
Total(Qout) 1581715640

Delta
Q(Kj/Day) 800673687.1

50
 Energy balance of Secondary reformer
Gas enters the Reformer at 1063K
Gas leaves the Reformer at 1293K
Flow Cp (Kj/Kg-K) at M*Cp*(1063-
Component rate(Kg/Day) 1063K 298)
CH4 65253.31032 4.68554 233896451.7
H2S 8.15666379 1.37238 8563.442323
CO2 38538.797 1.24929 36831792.28
H2O 750742.2141 2.33329 1340049965
H2 51650.87394 15.0135 593227202.9
CO 220661.7457 1.19938 202462822.7
Total(Qin) 2406476798

Flow Cp (Kj/Kg-K) at M*Cp*(1293-

Component rate(Kg/Day) 1293K 298)
CH4 65.25331032 5.16861 335582.5677
H2S 8.15666379 1.45596 11816.39733
CO2 422534.3669 1.29744 545471924
H2O 520316.5532 2.48799 1288069669
H2 93550.73941 15.4931 1442144006
CO 90380.02828 1.23587 111139475.7
Total(Qout) 3387172474

Delta
Q(Kj/Day) 980695675.9

51
3)HTS Converter & LTS Converter ;-

Energy balance of HTS Converter

Gas enters the HTS Converter at 633K
Gas leaves the HTS Converter at 723K
Flow Cp (Kj/Kg-K) at M*Cp*(633-
Component rate(Kg/Day) 633K 298)
CH4 65.25331032 3.38496 73994.74818
H2S 8.15666379 1.16152 3173.832922
CO2 91140.92986 1.09304 33372928.46
H2O 655886.5956 2.02642 445249074.5
H2 78487.40136 14.656 385354303.7
CO 301266.7609 1.0931 110320423.3
Total(Qin) 974373898.6

Flow Cp (Kj/Kg-K) at M*Cp*(723-

Component rate(Kg/Day) 723K 298)
CH4 65.25331032 3.70507 102751.4351
H2S 8.15666379 1.2089 4190.751114
CO2 422534.3669 1.13652 204092972.4
H2O 520316.5532 2.08591 461266738.1
H2 93550.73941 14.6926 584164027.4
CO 90380.02828 1.11642 42883380.25
Total(Qout) 1292514060

Delta
Q(Kj/Day) 318140161.8

52
 Energy balance of LTS Converter
Gas enters the LTS Converter at 483K
Gas leaves the LTS Converter at 548K
Flow Cp (Kj/Kg-K) at M*Cp*(483-
Component rate(Kg/Day) 483K 298)
CH4 65.25331032 2.82158 34061.72554
H2S 8.15666379 1.08382 1635.46574
CO2 422534.3669 1.00045 78204033.86
H2O 520316.5532 1.9402 186760862.6
H2 93550.73941 14.5842 252407098.3
CO 90380.02828 1.06038 17729877.26
Total(Qin) 535137569.3

Flow Cp (Kj/Kg-K) at M*Cp*(548-

Component rate(Kg/Day) 548K 298)
CH4 65.25331032 3.06679 50029.54989
H2S 8.15666379 1.11695 2277.646405
CO2 564418.0999 1.04412 147330056.6
H2O 462273.2079 1.97524 228275132.8
H2 100000 14.6218 365545000
CO 90.38002828 1.07318 24248.50969
Total(Qout) 741226745.1

Delta
Q(Kj/Day) 206089175.8

53
4)Desorption column;-

Energy balance of Desorption column

Gas enters the Reformer at 353K
Gas leaves the Reformer at 453K
Flow Cp (Kj/Kg- M*Cp*(353-
Component rate(Kg/Day) K) at 353K 298)
MEA 8824.310712 0.897 435347.369
H2O 474142.0681 2.741 71479287.48
RNH3HS 22767.88756 1.1218 1404755.895
RNHCOORNH3 39783.88774 2.3414 5123249.711

Total (Qin) 78442640.45

Flow Cp (Kj/Kg- M*Cp*(453-

Component rate(Kg/Day) K) at 453K 298)
MEA 52638.59387 1.1423 45998735.32
H2O 474142.0681 3.6948 1340172987
RNH3HS 22.76788756 2.2104 38499.49608
RNHCOORNH3 39.78388774 3.1413 95604.44181

Total(Qout) 1386305826

54
 3.3 Specific Equipment Design :

Sweetening process equipment : sour natural gas compositions can

vary over a wide concentration of H2S and CO2 and a wide concentration
of hydrocarbon components. If the H2S content exceeds the sales gas
specification limit, the excess H2S must be separated from the sour gas.
The removal of H2S from sour gas is called “sweetening.”

Schematic diagram :

55
2) Primary reformer :

A primary reformer converts a hydrocarbon feed (e.g. natural gas)

to hydrogen and carbon monoxide by means of an endothermic
catalytic reaction with typically steam and CO2. It provides a mixture
of H2, CO, and H2O with various fractions of CO2 (depends on the
process) and non-reacted CH4

3)Secondary reformer

To minimize the content of methane which comes out from the primary
reformer.

56
4)HTS Converter:

Usually, a high temperature shift (HTS) catalyst is used as the first

stage and typically converts over 80% of the CO. ... More recently,
copper has been added to the formulation to increase the activity per
unit bed volume and to provide protection against catalyst over-
reduction at low
steam–gas ratios

5) LTS Converter :

A low temperature shift catalyst (LTS) then converts the majority of the
remaining CO [1]. As well as maximizing the hydrogen production, the
water gas shift reaction also maximizes the CO 2 production from an
ammonia plant. ... CO is converted into CO2 for easier removal in the
CO2 removal system.

57
6)Absorber column:

An absorber is a vessel in which liquid is absorbed during distillation.

An absorber extracts a substance from a gas by absorbing the
substance into a liquid. Absorbers are typically tall cylinders in which
the liquid flows down and gas bubbles upward.

7)Desorption column:

If the column conditions favour adsorption of a molecule, then the

molecule will adhere to the stationary phase and be separated from the
other sample chemicals. When the conditions favour desorption, the
opposite will happen — and the chemicals will be released into the
mobile phase

58
 CHAPTER 4

4.2 .Plant location ;-

1)Primary factors
2)Secondary factors

*Selection is a vital decision to be made

*Strong influence on the success of an individual
venture

Primary factors:

1)Raw materials :- The main raw material for the

production of hydrogen is Natural gas.

The largest reserves are found in the Western

Offshore (Mumbai High, Krishna-Godavari Basin) and Assam.

Almost 70 percent of India's natural gas reserves are found

in Bombay High basin and in Gujarat. rest found in Andhra
Pradesh and Tamilnadu, Maharashtra,
Mumbai.

Therefore ,the rawmaterial is mostly available

in Bombay ,& Assam .

2)Market :-

It has strong influence on the establishment of

industries.

As natural gas cannot be given directly to

the consumer .It has long process.

Therefore , the plant must be located

nearer to the seashores in order to reduce
the transportation costs. Bombay and
Assam would be ideal places to distribute
the products.
59
3)Energy availability:-

However, steam reforming of natural gas is an energy extensive

process and produces a large amount of air pollutants.

Therefore energy requirement is high to operate the plant. Energy

consumption is more while operating the process equipment.

We can also create own power generation facility as it has near by sea
shore.

4)Labour supply :-
*Therefore people are very much imp to
complete the work.

*Low wages and abundant labourer help in

localization.

*Skilled ,better paid, highly mobile labour is required.

Therefore its better to choose the local people of assam for labour.

5) Transportation facility:-

*If there is better transportation for bringing rawmaterials to the

industry it will be easy.

*Therefore its better to have direct transport of raw material natural

gas through pipelines to the industry which is located near by shores.

* If the process industry is near to the shore there is advantage of

exporting the materials through ships etc.

60
2)Secondary factors :-

1)Climate & soil :-

 As it is highly difficult to dig the gas from sea shores if the climate
is cool and humid.
 Therefore constructing protective shelters around the process
equipment is very important.
 Soil also places a prominent role while digging the gas.

2)Government concessions:-

 Govt subsidies and concessions have been provided for the

industries located near certifies areas.
 These areas have been declared as industrially backward
and the govt offers low wages, cheap power,tax concessions.
 So, the plant location must get certified by the government
by fulfilling all the required criteria.

3)Water supply :-

 Large quantities of water required for cooling,steam

generation and also as raw material.
 Before setting up a plant study should be conducted
regarding the availability of underground water or
surface water and their seasonal variation.
 Temprature, mineral content ,silt or sand
content,bacteriological content,cost of supply and
purification treatment must also be considered while
choosing a water supply.
 Detailed estimate of water requirements for the
present and the future must be
made.

61
4)Water disposal:-

 Legal restrictions must be considered

 Site selected should have adequate capacity and facilities for
correct waste disposal.
 Attention should be given to potential requirements for additional
waste treatment facilities.

5)Site characteristics:-

 Topography of the land and soil

should be considered since both
may influence the construction cost.
 Cost of land ,local building costs and
living conditions are also
important.
 Expansion of the plant in future
should also be considered.

6)Flood and fire protection:-

 A regional history of natural events like floods and

hurricanes must be conducted because plant must be
constructed near sea shores.

 As natural gas is flammable because of the content of

methane in it. Therefore the assistance from fire
department should be easily available.

 Fire hazards in the immediate surrounding area of the plant

site must not be overlooked.

62
7)Provisions near industries;-

 It must be located in a sanitary place

away from filthy surroundings

 It must not be adjacent to an open

sewage,drainage or public lavatories.

 The plant should not constitute undue danger to adjacent life

and property..

 Indian factories act must be considered.

4.3 .Plant layout :

Plant layout is a coordinated effort to achieve the final objective to

integrate machines, materials,and personnel for economic production.

Plant layout can be described as location of different

departments and arrangement of machinery in a departments.

Plant layout has the advantage from the point of workers

,labour costs ,other production costs ,supervision and capital
investment.

It is the most effective physical arrangement, either existing or

in plans of industrial facilities i.e arrangement of machines, processing
equipment and service departments to achieve greatest co-ordination
and efficiency of 4M’s (Men, Materials, Machines and Methods) in a
plant.

63
 According to James Lundy , “Layout identically involves the
allocation of space and the arrangement of equipment in such a
manner that overall operating costs are minimized”.

Types of layout :-

1)Process or functional layout.

2)Product or straight line layout

Process or functional layout:-

 In this type ,all machines of a particular class doing a particular

type if work are arranged together in a separate department.

Advantages :

 More effective supervision can be achieved.

 Division of labour or specialized work can be provided.
 Less disruption of production is possible.
 Good scope for expansion.

Product or straight line layout:-

All machines doing various operations aare arranged in a line.

Advantages:-

 Facilitates quick and smooth processing of work.

 Reduces cost of material handling using conveyor.
 Reduces manufacturing time and speeds up the
manufacturing cycle.
 Facilitates proper use of the floor.
 Reduces inventory in work of progress.
 Reduces inventory of finished goods.

64
Different units:

Processing Equipment
area layout unit

Processing
Structural
unit layout
layout

Piping Electrical
layout layout

Drawing of plant layout:

Scale drawing with elevation for

equipment and process

Analysis of layout :3D Model ,computer

graphics

Detailed drawing
65
Factors influencing layout:

 New site development or additions to developed site.

 Type and quantity of products to be produced.
 Types of process and product control.
 Space available and space required.
 Operational convenience and accessibility.
 Economic distribution of utilities and services.
 Type of buildings and building code requirements.
 Health and safety considerations.
 Waste disposal problems.
 Auxiliary equipment.
 Possible future expansion.

The objectives of a good layout are as follows:

(i) Should provide overall satisfaction to all concerned.

(ii) Material handling and internal transportation from one operation

to the next is minimized and efficiently controlled.

(iii) The production bottle necks and points of congestions are to be

eliminated so that input raw materials and semi-finished parts move
fast from one work station to another.

(iv) Should provide high work in process turnover.

(v) Should utilize the space most effectively; may be cubical utilization.

(vi) Should provide worker’s convenience, promote job satisfaction and

safety for them.

(vii) Should avoid unnecessary investment of capital.

(viii) Should help in effective utilization of labour.

(ix) Should lead to increased productivity and better quality of the

product with reduced capital cost.

66
(x) Should provide easy supervision.

(xi) Should provide space for future expansion of the plant.

(xii) Should provide proper lighting and ventilation of the areas of work
stations.

Principles of Plant Layout:

According to Muther there are six basic principles of “best layout”.

These are:
1. Principle of Overall Integration:
According to this principle the best layout is one which provides
integration of production facilities like men, machinery, raw materials,
supporting activities and any other such factors which result in the best
compromise.

2. Principle of Minimum Distance:

According to this principle, the movements of men and materials should
be minimized.

3. Principle of Flow:
According to Muther, the best layout is one which arranges the work
station for each operate process in same order or sequence that forms
treats or assembles the materials.

4. Principle of Cubic Space Utilization:

According to this, the best layout utilizes cubic space i.e. space available
both in vertical and horizontal directions is most economically and
effectively utilized.

5. Principle of Satisfaction and Safety:

According to this principle, best layout is one which provides
satisfaction and safety to all workers.

67
6. Principle of Flexibility:
In automotive and other allied industries where models of products
change after sometime, the principle of flexibility provides adoption
and rearrangements at a minimum cost and least inconvenience.

68
CONCLUSION :

The interest in steam reforming process as a efficient method for

hydrogen production has been greatly increasing ,due to its efficiency
during hydrogen production and low environmental problems
compared too other techniques .
It is the most common and cheapest way to produce hydrogen.The
mainobjective was to present a comprehensive study of environmental
,economic aspects of hydrogen production from steam reforming of raw
materials such as natural gas.
From literature review it was found that methane hydrogen
production, steam reforming of natural gas has lowered installed
capital due to the presence of high amounts of unconverted
hydrocarbons in the produced gas during other methods such as steam
reforming of bio-gas.
More over ,the steam reforming is a key technology for promoting
decarbonization of fossilfuels pathways. Pre combustion carbon
capture strategies based on the reforming of hydrocarbons appear to
be the most needy and affordable to reduce carbon dioxide emissions
while waiting for a future energy transition.

69
BIBLIOGRAPHY:

 Hydrogen properties from ncert text book of class tenth chemistry.

 Hamdi Abdi, Ramtin Rasouli Nezhad, Mohammad Salehimaleh Razi
University, Kermanshah, Iran University of Western Ontario, London,
ON, Canada University of Mohaghegh Ardabili, Ardabil, Iran on fuel
cells.
 PHYSICAL AND CHEMICAL PROPERTIES OF HYDROGEN Isao Abe
Office Tera, Chiba, Japan
 Kirk – othmer encyclopedia of chemical technology
 Natural gas steam reforming for hydrogen production over metal
monolith catalyst with efficient heat-transfer Hyun-Seog Roh a,*,
Deuk Ki Lee b, Kee Young Koo c, Un Ho Jung c, Wang Lai Yoon c,** a
Department of Environmental Engineering, Yonsei University, 234
Maeji, Heungeop, Wonju, Gangwon-do 220-710, South Korea.
 The enhancement of hydrogen recovery in PSA unit of domestic
petrochemical plant M.R. Rahimpour a,b,⇑, M. Ghaemi a, S.M. Jokar a,
O. Dehghani a, M. Jafari a, S. Amiri a, S. Raeissi a a Department of
Chemical Engineering, School of Chemical and Petroleum
Engineering.
 Hydrogen from steam methane reforming with co2 capture john
C.Molburg & Richard D. Doctor Paper for 20 th Annual international
Pittsburgh coal conference, September 15-19 , 2003.
 Alderton, P.D., "Natural Gas Treating Using Membranes," paper
presented at the 2nd GPA Technical Meeting, GCC Chapter, Bahrain
(Oct.27, 1993).
 Hand book of natural gas transmission and processing.

70
71