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CHECKLIST FOR CONCEPT NOTE FOR HYDROGEN

GAS GENERATION & STORAGE SYSTEM

TCE CONSULTING ENGINEERS LIMITED

414, Veer Savarkar Marg
Prabhadevi
MUMBAI 400 025

FLOPPY NO : TCE.970-CH-FP-DOC-005
FILE NAME : CL107R1.DOC

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DATE 96-03-27 2001-03-29

FORM NO. 20R2

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107 CHECKLIST FOR CONCEPT NOTE FOR HYDROGEN
GAS GENERATION & STORAGE SYSTEM

For preparing a Concept Note for Hydrogen gas generation and storage
system, refer the concerned PCS procedure for ‘Preparation of Concept
Note’. The structure of Concept note shall be as per following points:

1.0 SCOPE

1.1 Mention purpose for which hydrogen gas is required – e.g. hydrogenation
of reaction mass, generator cooling in power plants, for fuel purpose etc.

1.2 List out the scope in details covering individual equipment.

1.3 Specify quality of hydrogen required i.e. purity required ( e.g. 99.7% )

1.4 Specify peak and average requirement, duration of peak, and whether
requirement is continuous / intermittent.

1.5 Specify supply pressure / temperature of hydrogen at plant battery limit

during normal and peak conditions.

2.0 SYSTEM DESCRIPTION

The process design for hydrogen gas generation is dependent on the

available raw materials and energy sources such as natural gas, naphtha,
gas oils, various coals, heat and electricity. In almost all operations the
reaction of steam with carbon or hydrocarbons produces synthesis gas (
CO + H2 ). Hydrogen of the desired purity is then recovered from the
synthesis gas after purification.

Process collaborator or client requirements, if any, regarding type of

generation process, type of compressors and storage etc. to be
specified. Cracked ammonia, steam hydrocarbon reforming, partial
oxidation process of heavy oils and electrolysis are possible sources for
H2 gas.

2.1 Steam Hydrocarbon Reforming

Steam hydrocarbon reforming process is followed for capacities more

than 100 Nm3 / hr and purity of hydrogen more than 99.5% with balance
0.5% being hydrocarbons like methane, propane etc. By this process
hydrogen can be produced up to a pressure of 40 kg/cm2 (g).

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2.1.1 Steam Methane Reforming

Sulfur free natural gas is reacted with steam over a nickel catalyst at
temperatures of 760-930 deg.C and 14-42 kg/cm2(g). Reforming
reactions are as follows :

CH4 + H20 = CO + 3H2 ------------------------------------- ( 1 )

Mixture of CO and H2 is known as Synthesis gas, which is further reacted

with steam to convert carbon monoxide to carbon di oxide in the Water
Gas Shift reaction.

CO + H20 = CO2 + H2------------------------------------------------( 2 )

Conventional Hydrogen manufacturing plant includes the following units :

• Desulfurisation unit
• Primary steam reformer
• Secondary steam reformer
• HT and LT shift conversion unit
• CO2 absorption and removal
• Methanation unit to remove residual CO and CO2
• PSA separation of hydrogen ( alternative to previous two steps
) produces H2 at 90-99.999% purity.

2.1.2 Steam Naphtha Reforming

Sulfur free preheated naphtha is reacted with steam over alkali promoted
nickel catalyst on an inert support.

CnHm + nH2O = nCO + (n+m/2) H2----------------------------( 3 )

As in previous case, Water gas shift reaction is further followed.

Set up of plant is similar to Steam naphtha reforming.

2.2 Partial Oxidation Of Heavy Oils

Pretrated heavy hydrocarbons, oxygen, and steam are reacted at

temperatures of 1260-1370 deg.C and pressures of 21-84 kg/cm2(g) in a
gasifier without any catalyst.
CnHm + (n/2)O2 = nCO + (m/2) H2-----------------------------( 4 )

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The processing sequence for synthesis gas production is as follows :

• Gasification of feed with oxygen and steam

• Recovery of heat through generation of high-pressure steam
• Removal of carbon and ash
• Removal of H2S and sulfur recovery
• Water gas shift reaction to allow the required H2_/ CO ratio
• Removal of CO2
• Methanation of carbon oxides

2.3 Coal Gasification

Pulverised coal, oxygen, and steam are passed thro’ high temperature
and pressure depending on the design of gasifier. Following reactions
result in the production of synthesis gas :

C + O2 = CO2-----------------------------------------------( 5 )
C + H2O = H2_+ CO---------------------------------------( 6 )

Water gas shift reaction is further followed .

Above processes in 2.1 to 2.3 are large scale processes. Process

description, basic flow diagrams and philosophy of operation is to be
furnished by the Process licensors. Processes discussed below in 2.4 to
2.6 are to be adopted for small to medium size operation.

2.4 Cracked Ammonia Process

A mixture of nitrogen and hydrogen in ratio 1:3 by volume may be

prepared from cracking or dissociation of ammonia. The process
consists of vaporizing the liquid ammonia from cylinders, heating it to 870
deg. C, passing it over an active catalyst, and cooling in heat exchangers
to heat incoming gases.
2NH3 = N2 + 3H2 -------------------------------------------- ( 7 )

2.5 Electrolysis Process

High purity hydrogen is produced by passing direct current thro’ nickel

electrodes in an alkali solution.

2H2O = 2H2_+ O2----------------------------------------------( 8 )

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In electrolysis process, unipolar (conventional Knowell) and bipolar cells

design are available.

2.5.1 Unipolar cells

a) Each unipolar cell generates approx. 0.82 Nm3 of H2 gas.

b) Unipolar cell produces H2 gas of purity 99.5% with balance 0.5%
being oxygen.
c) Unipolar and bipolar cells with deoxo unit ( palladium) can generate H2
gas of purity 99.99% ( in deoxo unit, residual oxygen in hydrogen is
converted to water). A suitable dryer can be provided if dry hydrogen
is required.
d) Unipolar cells generate gas @ 50 to 200 mmwc.
e) Unipolar cells use rayon grade caustic soda ( 16% conc.) as
electrolyte.
f) Electrolyte i.e. 16% NaOH solution required for Unipolar cell is
provided with pump for circulation and dosing to cells.

2.5.2 Bipolar cells

a) Each bipolar cell generates approx. 0.82 Nm3 of H2 gas.

b) Bipolar cell produces H2 gas of purity 99.8% with balance 0.2% being
oxygen.
c) Bipolar cells generate gas at approximately 5-30 bar(g) pressure.
d) Bipolar cells based hydrogen plant requires 15% of the space
required for unipolar cells based plant.
e) Bipolar cells plant costs approx. 60-70% higher than unipolar cells
plant.
f) Bipolar cells use caustic potash solution (30% conc.)

2.5.3 Both designs of cells require DM quality water (approx. 1 lit / Nm3 of gas
generation.

2.5.4 Bipolar cells consume approx.20% less power than that for unipolar.

2.5.5 H2 gas compression

a) In case higher hydrogen gas pressures are required in the process

plant, it is compressed. The selection of hydrogen compressor is
based on the following :

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• If ingress of oil can be tolerated in the hydrogenation process,

lubricated reciprocating compressor is provided followed by oil
separators / filters ( to remove oil).

• If ingress of oil cannot be tolerated, non-lubricated reciprocating

compressor is provided up to 50-60 bar(g), since this type is not
offered for higher pressures.

• In case of non-lubricated type requirement,diaphragm compressor is

recommended for low gas flow rates ( upto 100 Nm3 /hr ) and higher
pressures (up to 200 bar(g)).

• Standby compressor to be provided depending on the criticality of the

application. Manual switchover is recommended from one
compressor to another since the standby compressor will have to be
purged with nitrogen gas before connecting to the process.

• When hydrogen gas is required to be stored before feeding to the

process, it could be compressed to higher pressure( than required at
battery limit ) to reduce the storage vessel size. The gas is fed to the
process through pressure reducing station (PRS). Standby PRS is
also recommended depending on the criticality of the application.

2.5.6 Storage System

a) Storage of Hydrogen in Unipolar design

• In unipolar design, gas is stored above water in Low Pressure(

L.P.) gas holders which are bell type. Two numbers of L.P. gas
holders are normally provided; one receiving gas from generation
and other supplying gas to process plant. Each of the gas holders
is sized for minimum one hour generation capacity. These holders
are equipped with high, low, high-high and low-low level switches.
Switching over of LP gas holders is carried out using 3-way valves
provided on the gas lines upstream and downstream of the LP gas
holders.

b) Storage of Hydrogen in Bipolar design

• Bipolar cell requires pressure vessels for gas storage since the
gas is generated at 5-30 bar(g).

c) Buffer storage for compressed gas is sometimes provided

depending on the type of application e.g. if hydrogen is required for ISSUE
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various users or if requirement is not continuous or to take care of

peaks.

d) Generally only one compressed gas storage is recommended,

pressure being limited by the thickness of plate used for shell of
pressure vessel.

e) When hydrogen gas is directly fed to the process, compressed gas

buffer storage is not required; however to take care of variation of flow
to the users, bypass from compressor outlet to compressor inlet is
provided through pressure control valve which is designed for reducing
the compressor discharge pressure to suction conditions for full range
of compressor flow. Standby control valve in the by-pass line is also
recommended depending on the criticality of the application.

2.6 Hydrogen Recovery from Refinery Offgases

A great deal of H2 gas is available from refinery offgases. Combination of

PSA and cryogenics can produce high purity H2 gas. Offgases from
refinery units are economically H2 source. Table-1 shows typical hydrogen
contents of various offgases.

Table-1- Typical hydrogen contents of refinery offgases

Source Typical hydrogen concentration, vol %

Naphtha reformer 65-90
Hydroprocessing
High pressure 75-90
Low pressure 50-75
Fluid catalytic cracking 10-20
Toluene hydrodealkylation 50-60
Ethylene manufacture 70-90
Methanol manufacture 70-90

Table-2 lists the main characteristics of the technologies available for

processing available refinery offgases.

Table-2- Hydrogen recovery technologies

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Technology Membrane Adsorption cryogenics

Hydrogen product <95 99.9+ 95-99
purity, %
Typical hydrogen <90 75-90 90-98
recovery, %
Hydrogen product < feed pressure feed variable
pressure pressure
Feed pressure, bar 16-126 11-56 16-36
(a)

Combination of PSA with cryogenics is followed for producing hydrogen

gas.

3.0 LIST OF INPUT PARAMETERS & THEIR SOURCES

3.1 For steam reforming process, the feedstock viz. Natural gas,
naphtha or heavy oils , nickel catalyst supported by alumina, calcium
aluminate, or magnesia and steam are main inputs.

3.2 For Coal gasification process, Solid coal feed and steam are main
inputs.

3.3 For cracked ammonia process, ammonia and catalyst are main inputs.

3.4 Electrolysis Process

3.4.1 DC electric supply ( equivalent to no. of cells * 2.2 volts * 2000 amp.)
required for cells is obtained from dedicated transformer-rectifier( LT or
HT depending on KVA required).

3.4.2 Electrolyte i.e. 16% NaOH solution required for Unipolar cell is prepared
from NaOH flakes or caustic lye. The rubber-lined vessel is used for the
same.

3.4.3 Electrolysis cells (unipolar design) are required to be washed everyday

from outside and effluent generated is alkaline. Alkali resistant tile lining
may be used for the effluent drain. Effluent is taken to a pit located outside
of the plant and pumped to effluent treatment plant.

3.4.4 Since hydrogen forms explosive mixture with oxygen, ( LEL 4%, HEL
76%), H2 plant and equipment and piping is flushed with N2 gas to drive
out the oxygen before the H2 gas generation is started. N2 gas may be
obtained from N2 cylinders or from the centralised N2 generation plant.
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Dedicated N2 source i.e. N2 cylinders are recommended for purging of

the plant. N2 gas manifold and N2 pressure reducing station may be
included in the H2 plant vendor’s scope.

4.0 DESIGN / SELECTION CRITERIA

4.1 Catalytic Steam reforming operates at lower temperatures than that

required for noncatalytic partial oxidation of heavy oils. Feedstock such
as heavy oils , residual oils, and asphalt can not be used for steam
reforming because of their sulfur content and higher boiling point.

4.2 Ammonia cracking process is used where reducing atmosphere is

required, since Nitrogen gas is also present in cracked ammonia gases;
e.g. Heat treatment furnaces.

4.3 Electrolysis Process

4.3.1 Selection between unipolar and bipolar is made based on the space
requirement and capital versus operating (power) cost of generation and
compression.

4.3.2 Unipolar cell plants are preferred up to capacities of 100 Nm3 /hr above
which reforming process (provided hydrogen purity is acceptable) or
Bipolar cells may turn out to be economical. Bipolar cell plants are
available up to 300 Nm3 /hr.

4.3.3 Hydrogen plant (electrolysis type) has cell room, compressor room and
electrical room. Cell room and compressor room being prone to hydrogen
gas leakage is isolated / separated from electrical room by having fire
proof partition wall. Compressors may be located in cell room only. In
case of bipolar cell plant, since bipolar cells are skid mounted requiring
almost no maintenance, no separate room for compressor is required.

4.3.4 On-line oxygen (in hydrogen) analyser is recommended for monitoring

purity of hydrogen generated. In case of off-spec. gas, the same is
vented. All vents are let off at sufficiently high elevation above roof.
Portable analyser is also recommended for random off-line analysis.

4.3.5 Gas holders are located in the open area.

4.3.6 On line conductivity meter is provided to monitor the DM water quality.

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4.3.7 Electrical equipment and instruments in cell and compressor rooms

including motor are required to be explosion-proof conforming to Eexd
IICT4. MCC, control panel and all electricals and instrumentation located
in electrical room are considered for safe area.

4.3.8 Gas leak detectors with alarm and rectifier trip interlocks are provided
below the ceiling in the cell room and compressor room to monitor
hydrogen leakage.

4.4 Transformer rectifier is located outside the electrical room.

4.5 Hydrogen storage vessel if required is located outside as per the

guidelines of Chief Controller of Explosives ( CCE ) under SMPV rules.

4.6 Fencing is provided around the hydrogen plant with minimum 2 gates (
front and back side ) at a clear distance of 10 m from the outside edge of
the equipment / building.

4.7 Indegenous hydrogen cylinders are available as per follows :

• Cylinder size : 1.6 m length * 21 cm diameter

1.45 m length * 25 cm diameter
• Cylinder storage pressure when fully charged at 15 deg.C : 150
kg/cm2g
• Cylinder colour : Red

5.0 CONCLUSIONS / RECOMMENDATIONS

5.1 Following table shows a comparison of the major processes for the
hydrogen production :

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Table-3- Comparison of different processes for H 2 Gas Manufacture

Steam Partial Coal Electrolysis

reforming oxidation gasification
Of heavy oils
Approx. overall 70 55 60-65 21-25
thermal efficiency
State of the art Well known Well known Mature Proven,
technology technology technology reliable
available technology
Environmental Depletion of Possible Impacts of coal Pollution
effects natural gas & release of mining, air problems
other light harmful pollution likely with
hydrocarbons chemicals to be less than electricity
via electricity generation
from coal
Advantages Cheapest can use Cheapest and Small plant
method nonfossil fuel most secure size, can use
near-term nonfossil fuel
alternative to
methane
reforming
Disadvantages Depends on Materials Depends on High cost,
supply of natural problems in coal resources, low net
gas reactant plant size large energy
containment; efficiency
large complex
plant

5.2 Steam hydrocarbon reforming processes are cheapest. For small size
plants less than 300 cu.m/hr, where on-site applications such as fat
hardening, metallurgical processes etc., Electrolysis processes may be
used.

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