Operating Manual

Ferro Steel -EOP 300Nm3/h hydrogen project
Hydrogen Generator
CDH21-007
OPERATING MANUAL
项目名称
Ferro Steel -EOP 300Nm3/h hydrogen project
Project Name 操作手册目录
分项名称 List of Operating Manual
Hydrogen Generator
Subproject
项目号文件号
CDH21-007 CDH21-007-1000
Project No. DWG NO.
序号图纸名称图号复用或标准图号图幅张数备注
NO. TITLE DWG NO. REUSED/STD NO. SIZE QNTY REMARKS
操作手册目录
1 CDH21-007-1000 A4 1
List of Operating Manual
天然气转化操作手册
2 Steam Methane Reforming CDH21-007-GY-1001 A1 23
Operating Manual
变压吸附单元操作手册Pressure Swing
3 CDH21-007-GY-1002 A3 22
Adsorption Unit Operating Manual
安全技术规程
4 CDH21-007-GY-1003 A1 16
Safety and Technical Regulations
分析规程
5 CDH21-007-GY-1004 A2 26
Analysis Procedures
自动控制系统说明书
6 CDH21-007-5101 A2 13
Automatic Control System Manual
10
11
12
13
14
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Ferro Steel Power Engineering CO., LTD Operating Manual
Ferro Steel Power Engineering CO., LTD

EOP 300 Nm3/h hydrogen project
Steam Methane Reforming

Operating Manual
CDH21-007-GY-1001
Shanghai Evian Industrial Technology CO., Ltd
June 2022
Evian Industrial
Table of Contents
CDH21-007-GY-1001 ........................................................................................................................................... 1
I. Overview .................................................................................................................................................................... 1
1.1 Preface ................................................................................................................................................................ 1
1.2 Preparation scope ............................................................................................................................................. 1
1.3 Composition of feed gas and product gas ................................................................................................... 2
II. Description of the Basic Principle and Process Flow .................................................................................. 3
2.1. Basic principle ................................................................................................................................................. 3
2.2 Brief introduction to the process ................................................................................................................... 3
2.2.1 Steam reforming of hydrocarbons ................................................................................................... 3
2.2.2 Hydrogen extraction by PSA device................................................................................................. 4
2.3 Brief introduction of the key equipment ..................................................................................................... 4
III. Preparation before the Initial Start-up .......................................................................................................... 5
3.1 Equipment inspection and hydrostatic test ................................................................................................. 5
3.2 Single-unit commissioning of pumps and compressors .......................................................................... 5
3.3 Inspection and calibration of instruments ................................................................................................... 5
3.4 Pipe purging, gas tight test and nitrogen displacement............................................................................ 5
3.5 Catalyst loading and discharging .................................................................................................................. 6
3.5.1 Loading and discharging of catalyst from reformer ................................................................... 6
3.5.2 Loading and discharging of MT shift catalyst ............................................................................... 6
3.5.3 Loading and discharging of desulfurization catalyst .................................................................. 7
IV. Initial Start-up ....................................................................................................................................................... 8
4.1 Preparation before the initial start-up .......................................................................................................... 8
4.1.1 Inspection before the start-up........................................................................................................... 8
4.1.2 Start-up of running equipment ......................................................................................................... 9
4.2 Temperature rise and reduction of catalyst................................................................................................. 9
4.2.1 Temperature rise of desulfurizer .................................................................................................... 10
4.2.2 Temperature rise and reduction of reforming catalyst ........................................................... 10
4.2.3 Temperature rise and reduction of MT shift catalyst............................................................... 11
4.3 Chemical feeding........................................................................................................................................... 12
4.3.1 Feeding steps: ....................................................................................................................................... 12
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4.3.2 Normal operation and maintenance............................................................................................. 13
V. Shutdown and Restart-up............................................................................................................................... 14
5.1 Normal system shutdown ............................................................................................................................ 14
5.2 Steam oxidation of reforming catalyst...................................................................................................... 15
5.3 Emergency shutdown of the system.......................................................................................................... 15
5.4 Short-term shutdown and restart-up .......................................................................................................... 16
5.5 Restart-up after long-term shutdown ........................................................................................................ 17
VI. Safety Production and Labor Protection ................................................................................................... 18
6.1 Nature and hazards of the raw materials and intermediate products of the device ........................ 18
6.2 Main safety precautions ............................................................................................................................... 19
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I. Overview
1.1 Preface
This operating manual is designed for the start-up and operation of this H2 producer
from natural gas, including process description, technique-related operating principles and the
procedures for original commissioning preparation, start-up and shutdown of the device, etc.
This operating manual is prepared to introduce the basic principles and features of the
device to those who will be operating it, as well as some basic points to be noted during
start-up and operation, and to serve as a basis for the preparation of future operating
procedures for the plant. However, the operating manual can never be used as an operation
method. The start-up team and the operator can only develop a start-up plan by referring to
the operating procedures described in the operating manual and then following the design
drawings, information and operating instructions provided by the equipment manufacturer.
As it is impossible to anticipate all the problems encountered by operators during

chemical feeding and start-up and shutdown of the device, some cases cannot be presented
and the parameters listed in the operating manual shall not be considered as strict criteria
(unless specifically stated in the text). In a word, operating principles cannot be
all-encompassing and the most practical operating procedures can only be developed
gradually from the plant's operating practice. In this way, the operators are able to find the
most suitable and most economical conditions for the optimum utilization of the device
capacity.
It must be emphasised that operators must not, under any conditions, violate the safety
procedures and safety practices generally followed in chemical production.
The device relates to several stereotype equipment and requires strict adherence to the
operating instructions for safe operation.
1.2 Preparation scope
This operating principle includes natural gas (NG) compression, desulfurization,

reforming, pressure swing adsorption (PSA), etc., excluding utilities and other process units
outside the battery limit.
The operating manual is prepared under the condition that the installation of the device
has been completed in accordance with the construction drawing and the mechanical
completion and acceptance, and the materials and conditions required for external public
works have been all available.
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1.3 Composition of feed gas and product gas
1) Feed gas (subject to actual components)

Methane Ethane Propane N Butane I Butane N Pentane Nitrogen
NO. co2
ch4 c2h6 c3h8 n_c4h10 i_c4h10 n_c5h12 n2
1 83.6703 5.8801 2.6938 0.7277 0.6613 0.1654 0.9519 4.7283
2 84.2577 5.8998 2.7546 0.7364 0.6693 0.1586 0.8605 4.1541
3 84.5967 5.9257 2.7855 0.7397 0.6644 0.1555 0.7688 3.8726
4 84.0003 5.9531 2.8110 0.7481 0.6812 0.1579 0.8563 4.2989
5 83.8427 6.1881 3.0329 0.7934 0.7177 0.1661 0.7788 3.9658
6 84.8782 5.8955 2.7160 0.7257 0.6552 0.1515 0.7603 3.7440
7 83.8382 5.6024 2.5288 0.7036 0.6457 0.1620 1.0072 5.0036
2) Product gas
S/N Item Value Remarks
3
1 Output, Nm /h 300
2 Purity, vol. % 99.9%
3 Product output pressure, barG ≥7 Operating pressure of the system: ~10barG;
4 CO, ppmv ≤10ppm
CO2, ppmv ≤10ppm
CH4, ppmv ≤10ppm
H2O, ppmv ≤3ppm
N2, ppmv ≤50ppm
5 Operating flexibility 50 - 110%
6 Annual operation time, hours ≥8000 Continuous and stable operation
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II. Description of the Basic Principle and

Process Flow
2.1. Basic principle
The project includes: natural gas (NG) compression (V101, C101A/B, V102), desulfurization (R101),
steam reforming (F101, E101, Y101, X101A ~C, C102A/B), carbon monoxide conversion (R102), PSA
hydrogen extraction (T201A - D), etc. The inlet reform pressure is 0.8 MPa (G). The crude hydrogen is
transformed and the impurities are separated by PSA purification to obtain the product hydrogen, which
enters the hydrogen storage tank and is finally output at reduced pressure after the storage tank.
2.2 Brief introduction to the process
2.2.1 Steam reforming of hydrocarbons

The natural gas(NG) from the battery limit is pressurized to ~1.0 MPaG by the natural gas compressor
(C101A/B) and enters the natural gas preheater (E103) for heat exchange with the reforming gas. The
natural gas temperature rises to 300-360°C and enters the desulfurization tank (R101), where the proportion
of sulfur is reduced to less than 0.2 ppm, then mixed with process steam at a water-carbon ratio of 4.0, and
enters the reforming tubes in the reformer (F101), where the methane reacts with water vapor in the catalyst
layer H2, CO and CO2 are produced.
The heat required for the reform of methane is provided by the combustion of fuel natural gas and
PSA off gas in the top burner of the reformer.
The reforming gas leaves the reformer at a temperature of 370-430°C, enters the natural gas preheater
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(E103) to preheat the raw natural gas and cools down to 330-370°C, enters the MT furnace (R102) to
reform the CO in the reforming gas to H2. After the transform reaction, the temperature of the reforming
gas rises to 360-400°C, then enters the desalted water preheater (E103) and the water-cooled separator
(E104), which finally reduces the temperature of the reforming gas to ~40°C and enters the PSA unit after
gas-liquid separation by the gas–liquid separator (V201).
2.2.2 Hydrogen extraction by PSA device

The PSA unit of the device mainly uses 4-1-2/P process (4 adsorption columns, only 1 adsorption
column in the adsorption step, 2 pressure equalization and atmospheric desorption). Each adsorption
column has to go through the steps of adsorption (A), equalization 1 depressurization (E1D), equalization 2
depressurization (E2D), providing purge (PP), dump (D), purging (P), equalization 2 repessurization (E2R),
equalization 1 repessurization (E1R) and final repessurization (FR) in one cycle. The adsorption columns
are staggered each other in the execution program, forming a closed loop to ensure continuous input of raw
materials and continuous output of products. The adsorption process can be adjusted to the actual load and
the pressure of the product gas.
2.3 Brief introduction of the key equipment

There are three modular reformers in Indonesia project. Each reformer corresponds to a hydrogen
production scale of 100Nm3/h.
Structure: vertical cylindrical furnace, top burner (feed gas from the upper part) reformer; each
reformer has a total of 4 reforming tubes in the radiation section, arranged in a compact ring, with 1 nozzle
at the top of the reformer, arranged centrally. The high temperature flue gas from the radiation section is
discharged into the atmosphere after heat exchange in the flue gas exchanger.
Material: HP-Nb centrifugal casting for the furnace tubes in the radiation section of this design; the
furnace chamber is made of carbon steel and lined with ceramic fibre for heat-insulated purpose.
Temperature of the reforming tube outlet: 410-450°C Operating pressure: 1.0 MPaG.
Purpose: Steam reforming reaction of natural gas (NG).
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III. Preparation before the Initial Start-up
3.1 Equipment inspection and hydrostatic test
After the installation of the system, the installers shall be organized to carry out a
comprehensive inspection of the device of reform section in collaboration with the technicians
and operators of the relevant departments such as process, equipment, electrical and
instrumentation according to the design and construction requirements, in order to verify the
quality of the project and create conditions for safe and long-cycle operation in the future.
The inspection content mainly includes: process pipeline, valves, equipment, instrument
control points, analytical sampling points, and other ancillary facilities. Safety devices are
also checked for compliance with design requirements. The inspection is based on the design
drawings, specifications and relevant specifications.
In the inspection, any other objects left in the equipment container during the installation,
which are potential dangers of accidents, must be removed.
The purpose of the hydrostatic test on the equipment pipe is to check the quality of the
equipment and pipe installation and whether it can meet the maximum pressure that the
equipment pipe can withstand. Therefore, it is important to follow the pressure specified in
the relevant drawings and instructions of the equipment to do the hydrostatic test, and never
exceed the value. Hydrostatic test is generally carried out by installers. For process pipelines
that cannot undergo a hydrostatic test, a gas pressure test must be carried out as required.
3.2 Single-unit commissioning of pumps and compressors
There is air blower, feed pump and natural gas (NG) compressor in the battery limit of
the device, all of which have been tested and passed the solo test run.
3.3 Inspection and calibration of instruments
After the installation, before the system is put on chemical commissioning, the entire
instrumentation system shall be fully checked and tested by professionals and operational
workers to see if it meets the requirements of the process design.
3.4 Pipe purging, gas tight test and nitrogen displacement
After the installation of the device, the pipework shall be purged and cleaned in
accordance with Chapter 9 of the Code for Construction of Industrial Metallic Piping
Engineering (GB50235). Pipeline purging and gas tight tests are an important preparation
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before the chemical commissioning and are generally carried out after the completion of the
hydraulic/air pressure test of the equipment pipeline installation. Pipelines where the working
medium is a fluid shall be purged with water. Steam pipes shall be purged with steam.
Pipelines whose working medium is gas shall be purged with air. The purpose of purging and
flushing is to remove impurities such as iron filings, rust, welding slag, sand and grease from
the construction of the equipment pipe left inside during installation, so as to ensure safe
operation in the future. Purging shall be carried out in phases from front to back.
Gas tight test and nitrogen displacement (can be combined) are carried out after purging
of the process system and prior to chemical commissioning. The purpose of the gas tight test
is to remove some major potential dangers and quality issues to ensure that the chemical
feeding is successful at once and that the system will not cause accidents like shutdown due to
leaking at the flange connection after start-up.
The process system in the device is full of flammable and explosive media. In order to
avoid mixing with air to produce explosive mixture, the air in the system shall be replaced
with nitrogen after the gas tight test, so that the oxygen content in the system can be reduced
to less than 0.5% of the specified indicator.
3.5 Catalyst loading and discharging
3.5.1 Loading and discharging of catalyst from reformer
The loading condition of catalyst in the reformer tube has a great impact on the future
operation and the service life of the tube and catalyst. Due to the different bulk density, even
if the catalyst with the same weight is loaded, the gas flow through the device during
operation will be uneven. Those with more passing gas will not achieve the expected
conversion rate, while those with less passing gas will cause the tube temperature to rise due
to less heat absorption. What is more serious is the bridge formation caused by the catalyst,
and the heat transferred from the outside of the tube cannot be absorbed, resulting in hot spots
or tropics in the tube, which seriously affects the service life of the tube.
Because of the tiny difference in the weight and particle size of catalyst and the
reforming tube diameter, even though the catalyst with the same volume or weight is installed
in every reforming tube, the uniform distribution of gas flow will not be completely
guaranteed either.
In practice, the best scheme will be selected according to the site conditions, and
pressure drop measurement is required for each reforming tube.
3.5.2 Loading and discharging of MT shift catalyst
Carbon monoxide completes the transformation in the MT furnace. The MT shift catalyst
is an iron-chromium catalyst, and its specifications and shapes provided by manufacturers are
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different. All catalysts shall be prevented from contacting with water, because water will wash
away the binder in the catalyst, resulting in the reduction of mechanical strength. It is also
necessary to prevent the catalyst from repeated freezing and thawing.
After the catalyst is used and ready to be unloaded, it is in reducing state. When
contacting with oxygen in the air, it will oxidize and raise the temperature, or even self-ignite.
It is very important that the catalyst in the reducing state in the MT furnace must be
injected with nitrogen for positive pressure protection until all the catalysts are safely
discharged. Under uncontrolled conditions, the oxygen in the air will contact with the natural
catalyst to produce excessive temperature, which will exceed the design temperature limit of
the equipment, causing damage to the furnace shell and internals.
It is necessary to wear a dust mask and take dust prevention measures when removing
the catalyst.
3.5.3 Loading and discharging of desulfurization catalyst
The total sulfur content in natural gas must be removed desulfurization catalyst to less
than 0.2ppm before entering the reformer.
It is necessary to wear a dust mask and take dust prevention measures when removing
the catalyst.
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IV. Initial Start-up
4.1 Preparation before the initial start-up
4.1.1 Inspection before the start-up

1) Check natural gas, circulating cooling water, desalted water, electricity, steam, instrument
nitrogen, etc.;
2) Close all drain valves, blowdown valves, vent valves, feed valves, root valves and
sampling valves. Open the valves in the battery limit of circulating cooling water and the
inlet and outlet valves of all cooling equipment to exhaust at high points;
3) Inform the analysis room to prepare for production control analysis;
4) Check that the power equipment is in good condition, and that the power supply, air source
and signal of all instruments are normal;
5) Check that fire-fighting and safety facilities are in good condition;
6) Operators, analysts, management and maintenance personnel shall receive technical

training and pass the examination before taking up their posts;
7) Nitrogen displacement of the system: Displace the nitrogen by single units, sections and
single pipes from front to back, and discharge at the coagulation guide valve and vent
valve. After the displacement, analyze that O2<0.5% at each sampling point is qualified,
and close the above valves;
8) Preparation before the start-up of compressor and pump station:
a) Check the lubricating oil level.
b) For the first start-up after assembly or shutdown with some reason, the turning gear must
be turned for more than a few weeks to hear whether there is an impact or other sound, and
whether it is extremely heavy.
c) Remove other objects near the machine. Clean the inlet filter.
d) Check that the drainage pipeline is connected with the main pipeline, the outlet valve is
closed, and the discharge valve is open.
e) Connect the circulating water source and open the water inlet and outlet valves on the
cooling water circuit.
f) Check the motor and electric control equipment before start-up according to the
corresponding instructions.
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9) Preparation before the start-up of the draught fan:
a) Confirm whether the bearing needs to be greased according to the factory instructions of
the manufacturer. If necessary, add grease. In normal operation, the bearings should be
replaced quarterly and filled with grease.
b) For the first start-up after assembly or shutdown with some reason, the turning gear must
be turned for more than a few weeks to hear whether there is an impact or other sound,
and whether it is extremely heavy.
c) Remove other objects near the machine.
4.1.2 Start-up of running equipment
1) Start of air blower: The start-up inspection is completed. Open the manual damper at
the inlet, adjust the frequency of the air blower to the minimum, and start it without
load. After checking the vibration and sound of the equipment for normal operation,
gradually increase the frequency of the air blower.
2) Start-up of feed pump: After the start-up inspection and exhaust, choose one from A/B
to start, and the other one is used as a standby machine. Adjust the frequency of the
feed pump to the minimum, fully open the inlet valve, fully close the outlet valve,
open the discharge valve, and start the pump without load. Set the pump flow
according to the water-carbon ratio parameter.
3) Start-up of compressor: After the start-up inspection, choose one from A/B to start, and
the other one is used as a standby machine. Close the inlet and outlet valves of the
standby machine, open the inlet manual valve, minimize the allowable frequency of
the compressor, and start the compressor at low load. After checking the vibration and
sound of the equipment for normal operation, gradually increase the frequency to
control the outlet pressure of the compressor.
4.2 Temperature rise and reduction of catalyst
Reduce and activate Ni-containing catalysts before use. Ni in the reforming catalyst
generally exists in the form of NiO, which needs to be reduced to active metal Ni by H2 (or
natural gas) before being put into production. The reaction formula is as follows:
Ni0 (solid) + H2 (gas, or CH4) = Ni (solid) + H2O (vapor, or CO2 at the same
time)-610kcal/kmol
According to the specific conditions of the plant, nitrogen temperature rise and natural
gas reduction are recommended (if natural gas cannot be reduced well, a small amount of
hydrogen can be appropriately provided through hydrogen steel cylinder for better reduction).
The purpose of nitrogen temperature rise is to preheat the temperature of desulfurization tank,
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reformer catalyst bed and MT furnace from normal temperature to a certain extent, so that
condensate will not be produced and the catalyst will not be damaged when water vapor is
introduced in the next step.
4.2.1 Temperature rise of desulfurizer
After all the preparation is finished, all utilities are ready for start-up, and the solo test
run is qualified, the catalyst temperature can be increased.
Nitrogen is taken as the medium for temperature rise in the device.
The process is as follows:
N2→Natural gas compressor(C101A/B)→Natural gas preheater(E102)→ Desulfurization

tank(R101)→ Flue gas exchanger(E101)→Reformer(F101)→ Natural gas preheater(E102)→
High temperature CO shift reactor(R102)→ Feed water preheater(E103)→ Water-cooled
separator(E104)→ Shift gas separator(V201)→N105→ Natural gas buffer tank(V101);
Rate of temperature rise: Rise to 150°C at the rate of 30 - 50°C/h.
4.2.2 Temperature rise and reduction of reforming catalyst
The temperature rise is completed in two steps: Heat up with nitrogen first, and then with
steam, as follows:
1) Nitrogen:
A liquid level is established in the Desalting water tank (V103).
The inlet pressure of the reformer is controlled at 0.3MPa (G) (the site could change
according to the nitrogen pressure), and the burner is controlled according to the rate of
temperature rise.
The circulating process of temperature rise:
N2→Natural gas compressor(C101A/B)→Natural gas preheater(E102)→ Desulfurization

tank(R101)→ Flue gas exchanger(E101)→ Reformer(F101)→ Natural gas preheater(E102)→
High temperature CO shift reactor(R102)→ Feed water preheater(E103)→ Water-cooled
separator(E104)→ Shift gas separator(V201)→N105→Natural gas buffer tank(V101);
The rate of temperature rise: 25 - 30°C /hr.
Before the temperature rise via steam, the medium is changed from nitrogen to natural
gas that is followed by desulfurization. The natural gas route is as follows:
NG101→V101→C101A/B→V102→E102→VG105(vent to atom sphere)
2) Steam
When the temperature of CO shifter (R101) TI110 and TI111 is > 150 °C, it can be
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transferred to the temperature rise via steam.
There is no steam at the start-up in the system but is produced by the flow gas exchanger
(E101). The pressure is controlled at about 1MPaG, and the temperature is about 180 °C. This
steam is used to go to the reaction system of the reformer to bring out the heat and finally
condense at the water-cooled separator.
Steam-(MS101) →reformer(F101)→Natural gas preheater(E102)→High temperature

CO shift reactor(R102)→Feed water preheater(E103)→ Water-cooled
separator(E104)→condensate(PL101)-drainage
The rate of temperature rise: 25 - 30°C /hr.
3) Feed gas is introduced for catalyst reduction:
When the temperature of Ti107 steam at the outlet of the reforming tube rises to more
than 350-400 °C, and the total sulfur at the outlet of desulfurization tank (R101) is less than
0.2 ppm and the system pressure is ~ 1.0 MPa (g), the natural gas is gently introduced into the
reformer in several times to start the reduction of the catalyst. In the reduction stage, the
amount of natural gas introduced is very small, generally 0.5% of the steam volume fraction.
Adjust the load of the burner according to the outlet temperature of the reforming tube
(TI107).
After the outlet temperature (TI107) of the reforming tube is stable, the feed gas is
gradually increased to control the outlet temperature of the reformer. When the feed gas
volume is increased to 30% of the design value, the outlet temperature (TI107) of the
reforming tube is maintained at a constant temperature of 350 - 400 °C for 2 - 3 hours.
During reduction, the resistance of the catalyst layer shall not exceed the design value.
Analyze the gas composition at the outlet of the reformer every hour.
Maintain low-load production for a period of time, and gradually increase the load and
turn into normal production after the operation is stable.
4.2.3 Temperature rise and reduction of MT shift catalyst
1) Temperature rise of MT shift catalyst
After the temperature rise via nitrogen and steam, the MT shift catalyst starts heating
up together with the reformer.
2) MT shift catalyst reduction
The catalysts of MT furnace and reformer are reduced by using hot steam flow of
reformer as carrier and adding desulfurized raw natural gas. Hydrogen is produced in the feed
gas in the reforming system due to reaction. When the gas is introduced into the MT furnace,
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MT shift catalyst begins to reduce, and the temperature shall be kept at a stable working
condition.
Since reduction is an exothermic reaction that produces strong reaction heat in the first
reaction, it is necessary to severely control the CH4 content in the intake air, generally
beginning from 0.5%, 1%, 2%... slowly rise in turn, taking the analyzed data as a guide. The
temperature of the catalyst rises gradually during the reduction, with the maximum
temperature that shall be lower than that (430°C) of the normal operation, usually below
400°C. When the catalyst reaches the maximum allowable reduction temperature, it shall be
maintained for several hours. After the temperature turns stable and CO content in the vent
gas is qualified in analysis, the reduction can be considered as completed. Afterwards, the
quantity of feed gas and steam can be gradually increased and then the process can be
transferred to normal production. In pressurized operation, the pressure shall be lifted slowly
to avoid the too fast rising, causing a sharp rise in temperature.
4.3 Chemical feeding
After the catalyst is reduced and qualified, the chemical feeding continues as the case of
hydrogen users may be, and the load is controlled at 30%-40%.
4.3.1 Feeding steps:
1) The alarm value of water-carbon ratio shall be set to 4, and the frequency of feed
pump will be switched automatically. Adjust the flow of raw natural gas control valve
(FV102) manually according to the displayed water-carbon ratio, and it is better when
the ratio is 4.5.
2) During the feeding process, the outlet temperature (TI107) of the reforming tube shall
be adjusted by regulating the fuel gas volume of the top nozzle through HV101 in
time to guarantee that the rest methane in the outlet reforming gas component is less
than or equal to 7% (dry basis).
3) After the shift gas is led to the MT shift gas separator, it is vented manually. And the
component of the shift gas is analyzed. After qualified, it is introduced into the PSA
section.
4) Proceed to the next process when the hydrogen is qualified after PSA.
5) After PSA stabilized, the vent valve is gradually closed, and the off gas is introduced
to the burner for combustion.
6)
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4.3.2 Normal operation and maintenance
1) Loading
a. In the sequence of fuel gas → process steam → feed gas.
b. Adjust the combustion thermal load in time according to the temperature at the
outlet of the reforming tube;
d. Adjust the process indicators to the normal range.
2) Load shedding
a. In the sequence of fuel gas → feed gas → process steam;
b. Adjust the reformer nozzle;
d. Adjust the process indicators to the normal range.
3) Adjustment of temperature of the catalyst bed
Control principle: Guarantee the gas shift indicator and prolong the service life of
the catalyst.
4) Normal maintenance
a. Check the operation, sound, cooling water volume, pressure and temperature of
the pump; the pressure, temperature, flow and liquid level of medium; the oil quality, oil
level and oil temperature of the bearing; the motor is in good running state;
b. Check the operation of each control valve;
c. Check the combustion of the reformer nozzle, whether there is tempering, flame
lifting and deviant combustion; flame length shall be symmetrical;
d. Check whether the operating color of the reforming tube and the expansion of the
upper and lower gas collectors are normal; whether there is air leakage in each flange;
whether the pressure difference PT104/PT107 indicator of the inlet and outlet of the
reformer tube is under control;
e. Check the liquid level of each separator to ensure smooth discharge and regular
drainage.
f. Check whether other equipment runs normally; the pressure and temperature are
under control; no leakage on each flange face.
g. Periodically check and reverse the standby pump, so that the standby machine is
always in a good standby state at any time.
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V. Shutdown and Restart-up
5.1 Normal system shutdown
To check and repair the whole system or partial equipment (such as annual overhaul)
under the normal condition of the device, the scheduled and step-by-step shutdown operation
shall be carried out according to the normal shutdown procedures. This kind of shutdown
operation is completely different from emergency shutdown in accident state. No tension
factor occurs. In order to protect the equipment and ensure safety, it must be carried out in an
orderly manner. If check and repair are needed, the relevant parts shall be cooled and relieved.
For the catalyst, it needs to be passivated and displaced to be qualified according to relevant
safety regulations. The rest of the parts can be kept warm and pressed under system isolation,
so that once the maintenance is finished, normal operation can be quickly resumed.
When the load of the subsequent section is shed, the load of the reforming section shall
be reduced accordingly. The rate of load shedding is 10%/hr, in the sequence of fuel gas, feed
gas and steam. Attention shall be paid to controlling the temperature of catalyst bed. The
outlet temperature of the furnace tube is lower to below 200°C at a cooling rate of 60°C per
hour. Attention shall be paid to controlling the water-carbon ratio, and maintaining the ratio
greater than 4.0 above half load and 5.0 below half load.
When the inlet temperature of the reforming tube is lower than 150°C and the outlet
temperature is lower than 200°C, cut off the valve of raw natural gas after desulfurization, and
the feed gas pipeline is protected by nitrogen. The fuel gas valve shall be adjusted to maintain
a certain temperature in the furnace to keep the cooling rate and a certain steam output of the
flue gas exchanger (E101), which can be used as passivator;
When the temperature of TE109 is lower than 150°C, it shall be forbidden to introduce
the reforming gas into the catalytic bed of the MT furnace, but converted into nitrogen for
temperature rise and reduction in advance.
When the outlet temperature of the reforming tube drops to 200°C, close the fuel gas
valve and all the nozzles, and use nitrogen to pressurize and displace the reformer and the
whole system. Turn off feed pump;
Open the furnace for natural ventilation, and the air blower shall be turned off after half
an hour.
After the desulfurization tank and the MT furnace are qualified for nitrogen filling and
displacement, the inlet and outlet pipelines and the blind plates of the blow-down pipe are
inserted after pressurizing 0.2MPaG with nitrogen.
De-energize all operating equipment.

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5.2 Steam oxidation of reforming catalyst
If shutdown and is not ready for full check, follow the above normal shutdown
procedure. If the reformer is to be opened for check, steam oxidation cooling operation shall
be carried out. After stopping the feeding of the raw natural gas, the nozzle is not extinguished,
and the outlet temperature of the reforming tube is maintained at 350°C, which is the suitable
temperature for the oxidation of the nickel catalyst. The nickel catalyst passes through the
reformer at about 50 kg steam per hour and is vented after the separator, where the steam
oxidizes the reduced nickel to nickel oxide and produces hydrogen, which is the
non-condensable gas in the effluent. Continue to reform the catalyst via steam oxidation until
the outlet gas contains no non-condensable gas. If so, it proves that the catalyst has been
substantially passivated, and this process takes about 8 hours.
When the outlet gas does not include hydrogen, cool the reformer at the rate of 55 - 80°C
per hour, and decrease the fuel natural gas gradually and keep the pressure of combusting
natural gas at 0.05 MPa until the outlet temperature of the reforming tube is lower than 250°C;
extinguish the natural gas, and then switch to nitrogen to let it cool down naturally. For
operating procedures, please refer to the catalyst manufacturer's instructions.
5.3 Emergency shutdown of the system
In the process of the normal production, internal fault, deterioration of external

conditions or interlocking action may occur in the device. The quick unscheduled shutdown to
ensure the safety of the device and operators is referred to emergency shutdown. When
emergency shutdown occurs, work can be performed according to the following principles.
1) The cause and condition of shutdown shall be found out by the on-duty person in
charge.
2) The shutdown interlock actions, the startup and shutdown state of automatic valves
and the shutdown action of rotating equipment shall be checked for precision.
3) The shutdown conditions and contact processing requirements shall be reported to the
control center.
In short, the impact of the accident shall be limited in local range as far as possible for
fear of expansion, in order to prevent greater losses.
During the running of devices, the causes for interruption of the various medium used in
the production are numerous. In addition to the emergency shutdown of the reforming system
caused by the impact of the rear system, emergency shutdown is also required when the
following situations occur, and corresponding measures shall be taken:
1) Sudden breakoff of feed gas.

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2) The desalting water tank (V103) has a low water level and cannot be
replenished.
3) Breakoff of fuel gas.
4) Breakoff of cooling water.
5) Sudden outage of power.
6) Insufficient pressure of instrument gas.
7) Rupture of the steam pipeline.
8) Rupture of the reforming tubes.
9) Other major equipment accidents.
When the above situations occur, the following measures shall be taken in principle:
1) Cut off the feed gas as soon as possible, reduce the fuel gas flow, and adjust
HV101 to about 5% to keep a slight fire combusting in the furnace. Turn off the
reformer when the system temperature gradually drops.
2) Tail gas and off gas shall be vented;
3) Steam shall be continued to supply, with the attention of steam pressure and
temperature. When the outlet temperature of the reforming tubes drops to about
300°C, the system maintains temperature and pressure.
4) During this shutdown process, the desulfurization tank and blind plate at the
inlet and outlet of MT furnace may not be temporarily installed.
5) If the draught fan is not faulted, it shall be kept running during shutdown to
maintain the negative pressure in the furnace.
5.4 Short-term shutdown and restart-up
When one part of the system fails, a temporary short-term shutdown is required. The
method is:
1) HV101 shall be turned off gradually in the central control room, so as to keep the
outlet gas of the reformer not overheated. The outlet temperature of reformer shall be reduced
at a rate of 60°C per hour, and the fuel gas shall be cut off gradually, then the root valve of the
nozzle shall be closed on site.
2) The process gas shall be gradually reduced to 1/3 of the design load and be cut off at
one time.
3) When the outlet temperature of the reforming tubes drops to about 250°C, the system
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keeps heat and pressure.
4) The feed pump can be stopped for closed insulation.
5.5 Restart-up after long-term shutdown
The original start-up procedure can be followed.
The difference is that the three agents are all reduced catalysts, and it is absolutely
forbidden to contact with air. Therefore, according to the situation at that time, the
temperature can be heated to 150°C in the following ways, and then changed to steam
heating.
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VI. Safety Production and Labor Protection
6.1 Nature and hazards of the raw materials and intermediate products of
the device
Natural gas (NG) is taken as raw material in the device, and flammable, explosive and
harmful media may occur in the whole production process. Attention must be paid to start-up,
shutdown and production to ensure safety production.
Such flammable and explosive medium as CH4, H2 and CO, and poisonous CO may
occur in the production process of the device, which are described as follows:
1) CH4
It accounts for 94.08% in the feed gas. It is colorless and tasteless at normal temperature
and pressure, lighter than air and non-toxic to people. When its content in air is higher than
80%, people will feel hard to breath and even suffocate. Because it is easy to combust, it is
classified as flammable and explosive gas according to the risk of fire. Its minimum ignition
point is 632°C, and the explosion range in the air is 5.3 - 15% (V) in air.
2) Hydrogen (H2):
Hydrogen has no direct toxicity to the human body and is lighter than air. The human
will suffocate and die of the high levels of hydrogen in the air. Because it is easy to combust,
hydrogen is also a sort of combustible and explosive gas according to the risk of fire. Its
lowest ignition point is 572°C, the explosive range in the air is: 4 - 74.2% (V), and that in
oxygen is 4.0-94% (V).
3) Carbon monoxide (CO)
It is a colorless, odorless (light garlic smell is generally imperceptible) and flammable

gas, with a specific gravity of 0.9 to air, and its spontaneous ignition point is as follows:
In air: 610°C; in oxygen: 590°C
When CO is mixed with air or oxygen, an explosive mixture is formed with the
following explosion limits:
In air In oxygen
Lower limit 12.5% 15.5%
Upper limit 74.2% 94%
The flame propagation speed of the mixture of CO and air is 0.15 - 0.4 m/s. CO is a
highly toxic gas that causes human poisoning if inhaled. CO will expel the oxygen when it
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enters into the bleed of the human body, causing oxygen deficiency and even suffocation. In
addition, CO also has a toxic effect on cells, which can poison the central nervous system.
CO accounts for 0.1 to 0.12% of the air and can cause death if inhaled for more than one
hour. CO poisoning is generally acute, with typical symptoms like slow pulse, headache,
dizziness, vomiting, swollen red skin, dyspnea, loss of consciousness, coma, and even death.
The general symptoms of chronic poisoning include: headache, vomiting, nausea, anemia,
palpitation, insomnia, memory loss, etc. The limit allowable concentration of CO in air is 0.03
mg/L.
4) Carbon Dioxide (CO2)
It is a colorless and tasteless gas and heavier than air. When there is a high content of
CO2 in the air, it can irritate the mucous membrane and skin. But if the concentration is below
2%, the human body would not have obvious poisoning symptoms. Its function is the same as
anesthetic with oxygen, and as asphyxiating gas if it is oxygen-free.
6.2 Main safety precautions
1) The operators shall go through safety education and pass the safety examination
before taking up their posts.
2) Operate strictly according to the process indicators of the plant; do not alter them
without approval, or run beyond the standard.
3) The device is seated in Class A fire prohibition area. It is strictly forbidden to do hot
work and smoke in the battery limit (in case of any hot work, analysis and a hot work
certificate are required, together with safety measures).
4) Cut off the gas source immediately and treat it as emergency shutdown if any
combustion and explosive accident occurs. What's more, cut off the contact between the
accident site and the surrounding as soon as possible to prevent the accident from expanding.
5) No repair is allowed when the rotating equipment is in running state. If maintenance

is required, it shall be done after reversing. In addition, cut the power off and hang a "No
Energization" sign.
6) Wear a gas mask, a protective mask, a protective suit and fire-fighting appliances.
7) Calibrate and test the safety facilities, instruments, anti-virus and fire-fighting
appliances of various equipment regularly to ensure good use.
8) Control the speed of heating, boosting, cooling, and pumping down during start-up
and shutdown as required and protect the equipment and catalysts.
9) Wear protective masks when loading and unloading heavy metal contained catalysts.
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10) The emergency lighting must be in good condition. If the device fails, the emergency
lighting shall turn on automatically.
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Pressure Swing Adsorption Unit

Operating Manual
CDH21-007-GY-1002
Shanghai Evian Industrial Technology CO., Ltd

June 2022
Evian Industrial 1
Table of Contents
CDH21-007-GY-1001 ............................................................................................................................ 1
1. PROCESS .......................................................................................................................................... 2
1.1 WORKING PRINCIPLE AND BASIC STEPS OF PSA ........................................................................... 2

1.1.1 WORKING PRINCIPLE ................................................................................................................... 2
1.1.2 BASIC STEPS .................................................................................................................................. 2
1.2 WORKING PROCESS ......................................................................................................................... 2
2. AUTOMATIC REGULATION SYSTEM AND PROCESS PARAMETER DETECTION ..... 5
2.1 SEQUENCE CONTROL SYSTEM (KC-201) ....................................................................................... 5

2.1.1 BUTTON DESCRIPTIONS ................................................................................................................ 5
2.1.2 OPERATING INSTRUCTIONS OF THE MENU FOR THE HOST MACHINE ........................................ 5
2.1.3 PANEL DISPLAY ............................................................................................................................. 5
2.1.4 INSTALLATION METHOD ............................................................................................................... 6
2.2 FUNCTION DESCRIPTION OF AUTOMATIC PRESSURE REGULATING SYSTEM ............................... 6
2.3 FUNCTIONAL DESCRIPTION OF FR CONTROL VALVE .................................................................... 6
2.4 FUNCTIONAL DESCRIPTION OF PURGE CONTROL VALVE .............................................................. 6
2.5 PLC CENTRALIZED DISPLAY AND CONTROL INSTRUMENT ........................................................... 7
2.6 DETECTION POINTS FOR ON-SITE PROCESS PARAMETERS ............................................................ 7
3. START-UP ........................................................................................................................................ 8
3.1 PREPARATION BEFORE FIRST START-UP ........................................................................................ 8

3.1.1 INSPECT THE FUNCTION OF PLC ................................................................................................. 8
3.1.2 FULL-PROCESS DISPLACEMENT OF DEVICE WITH NITROGEN .................................................... 9
3.2 FEEDING START-UP .......................................................................................................................... 9
3.2.1 VALVE SETTINGS ........................................................................................................................... 9
3.2.2 PROGRAM CONTROLLER SETTINGS ........................................................................................... 10
3.2.3 NORMAL OPERATION REGULATION ........................................................................................... 10
4. SHUTDOWN AND RESTART AFTER SHUTDOWN .............................................................. 12
4.1 NORMAL SHUTDOWN ..................................................................................................................... 12

4.2 EMERGENCY SHUTDOWN .............................................................................................................. 12
Evian Shanghai Engineering Technology Co., Ltd 2

4.3 TEMPORARY SHUTDOWN ............................................................................................................... 12

4.4 LONG-TERM SHUTDOWN ............................................................................................................... 12
4.5 RESTART AFTER SHUTDOWN ......................................................................................................... 13
4.5.1 RESTART AFTER NORMAL SHUTDOWN ...................................................................................... 13
4.5.2 RESTART AFTER EMERGENCY SHUTDOWN ............................................................................... 13
4.5.3 RESTART AFTER TEMPORARY SHUTDOWN ............................................................................... 13
4.5.4 RESTART AFTER LONG-TERM SHUTDOWN ................................................................................ 13
5. FAULTS AND HANDLING .......................................................................................................... 14
5.1 ABNORMAL SUPPLY UNDER OUT-OF-BOUNDS CONDITIONS ........................................................ 14

5.1.1 FEED GAS WITH WATER .............................................................................................................. 14
5.1.2 POWER OUTAGE .......................................................................................................................... 14
5.1.3 THE PRESSURE OF INSTRUMENT AIR DROPS ............................................................................. 14
5.1.4 OPERATING DISORDERS ............................................................................................................. 14
5.1.5 RAW MATERIAL HANDLING CAPACITY AND CYCLE TIME ........................................................ 14
5.2 DEVICE FAILURE ............................................................................................................................ 15
5.2.1 PLC FAILURE .............................................................................................................................. 15
5.2.2 VALVE FAULT .............................................................................................................................. 15
5.3 ADJUSTMENT OF PRODUCT PURITY FROM UNQUALIFIED TO QUALIFIED .................................. 15
6. SAFETY TECHNOLOGY ............................................................................................................. 16
6.1 PROPERTIES OF HYDROGEN .......................................................................................................... 16

6.2 SAFETY FACILITIES FOR DEVICE .................................................................................................. 16
6.3 KEY POINTS OF OPERATION SAFETY OF HYDROGEN SYSTEM ..................................................... 16
6.4 FIRE-FIGHTING .............................................................................................................................. 17
6.5 GENERAL PRECAUTIONS IN SAFETY PRODUCTION ...................................................................... 18

Preface
The device uses pressure swing adsorption (PSA) to purify hydrogen from the reforming
natural gas. Hydrogen with different purity can be produced by changing the operating
conditions, with the highest purity up to 99.999%.
Because the raw material, reforming gas and product H2 are all flammable and explosive,
the operating pressure shall be about 0.7MPaG. While the product purity, consumption
indicator and production stability depend on the operating level to a great extent. Much
attention shall be made to the operating process. Before the operation of PSA system,
personnel involved in production management, operation and maintenance must know well
about this manual and pass the examination before taking up their posts.
The pressure referred to in this manual is gauge pressure, the concentration is molar
percentage, and the flow rate refers to the flow rate under normal state.

1. Process
The PSA hydrogen purification device is composed of 4 adsorption columns (T201A - D,
hereinafter referred to as Columns A, B, C, D) and a series of PLC valves.
1.1 Working principle and basic steps of PSA
1.1.1 Working principle
The principle of purifying hydrogen from gas by PSA gas separation process is to use the
selectivity of absorbent to different adsorbates and the different adsorption capacity of
absorbent to adsorbates with the change of pressure, to adsorb impurities component in raw
materials under high pressure and desorb these impurities under low pressure, so that
adsorbents can be regenerated.
The whole operation process is carried out at ambient temperature.
1.1.2 Basic steps
The basic steps of PSA are divided into two steps: adsorption and regeneration.
Regeneration is completed in the following three steps.:
l The pressure of adsorption column drops to low level
The first step is to depressurize along the direction of adsorption (hereinafter referred to
as providing purge), and the next step is to depressurize against the direction of adsorption
(hereinafter referred to as dump). In the process of providing purge, part of the absorbent is
still in the adsorption state. During the dump, some of the adsorbed impurities are desorbed
from the absorbent and removed from the adsorption column.
l Remove the impurities remaining in the absorbent by purge.
l The adsorption column rises to adsorption pressure to prepare for the separation of feed
gas again.
The device is designed with 4-1-2/P process. It is a PSA process with single column
adsorption and 2 times pressure purge desorption. In the 4-1-2/P process, each adsorption
column has to go through the steps of adsorption (A), equalization I depressurization (E1D),
providing purge (PP), second equalization II depressurization (E2D), dump (D), purge I (P1),
purge II (P2), equalization II repessurization (E2R), equalization I repessurization (E1R) and
final repessurization (FR) in one cycle.
The 4 adsorption columns are staggered each other in the execution program, forming a
closed loop to ensure continuous input of raw materials and continuous output of products.
1.2 Working process

As mentioned earlier, each adsorption column needs to go through 10 steps in one cycle.
The 4 adsorption columns are staggered each other in the execution program, forming a
closed loop to ensure continuous input of raw materials and continuous output of products.
The working relationship of each column is as follows:
① Adsorption (A)
Open PCV201a; the reforming gas from natural gas reforming section enters Column A
from bottom to top through valve PCV201a, adsorbs impurities component under operating
pressure, and unabsorbed product component flow out through valve PCV202a, most of
which are output from the system as products, and the rest shall undergo final repessurization
in Column B through valve PCV202b. After adsorption, close the valve PCV201A to stop
feed gas, while the valve PCV202A has no product gas output.
② Equalization I depressurization (E1D)
Open PCV205a; after the adsorption of Column A stops, it will be connected with
Column C just finished the equalization II repessurization step, that is, the first stage pressure
balance is carried out with Column C through valves PCV205a and PCV205c, and the
pressure of Column A is reduced. After pressure equalization, the pressures of Columns A
and C are basically equal. Close PCV205c.
③ Equalization II depressurization (E2D)
Open PCV204a; The residual gas in the column still passes through valves PCV204a and
PCV204d along the outlet direction to balance the second stage pressure with Column D. The
pressure of Column A decreases until the pressure of both columns are basically equal.
Shutoff PCV204c.
④ Providing purge (PP)
Continue to open valve PCV205a; the residual gas in the column still enters the
adsorption column D through valves PCV205a, PV202 and PCV204d along the outlet
direction, and purges the adsorption column D. The pressure of Column A decreased by - 0.1
MPa. Shutoff valve PCV205a, PV202.
⑤ Dump (D)
Open valve PCV203a; after the step of depressurization and pressure in Column A is
balanced, discharge the residual gas in the column from the inlet end of the column, and then
residual gas will enter the off-gas buffer (V203) after being voltage-stabilized by HV201.
⑥ Purge I (P1)
Continue to open valve PCV204a; after the dump step is completed in Column A, the
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impurities remaining in the column are purged along cocurrent depressurization in Column C,
so that the impurities in the tower are further desorbed and the absorbent is regenerated.
⑦ Purge II (P2)
Continue to open valves PCV204a, PCV203a and PCV206, and close HV201; The
impurities in Column A are further desorbed and vented directly through the blow-down pipe,
so that the absorbent can be further regenerated. And Column A is completely resolved to
normal pressure.
Close the valve PCV203a, PCV206.
⑧ Equalization II repessurization (E2R)
Open valves PCV204a, PCV204b;
Column A is connected with the outlet of Column B. Through valves PCV204a and
PCV204b, the second stage pressure balance is carried out with Column B, and the pressure
of Column A is increased.
⑨ Equalization I repessurization (E1R)
Open valve PCV205a; After the equalization II repessurization of Column A is finished,
the first stage pressure balance is carried out by connecting the Column C which is in the first
equalizing step with the outlet end of the Column C through valves PCV205a and PCV205c.
The pressure of Column A is further increased till the pressures of both columns are basically
equal.
⑩ Final repessurization (FR)
Continue to open the valve PCV202a, PCV202d; the final repessurization of Column A
is carried out by product gas, which enters Column A through PCV203A, and finally makes
the pressure of Column A almost close to the adsorption pressure. After passing through this
step, the regeneration process is completely finished, and then the next cycle is carried out.
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2. Automatic Regulation System and Process Parameter Detection

This section has a high degree of automation. All remote indication, important control
systems are PLC-controlled. The main control systems are as follows:
Sequence control system (KC-201);
Automatic pressure regulating system PIC203 of PSA system;
In order to enable operators to monitor and intervene the whole production process in
time, the monitoring and control of all process parameters of the device can be realized by on-
site HMI or PC operation station located in the control room.
2.1 Sequence Control System (KC-201)

The PSA realizes the adsorption and regeneration of each column according to a certain
sequential relationship. The PSA process in this section is controlled by using several PLC
valves and PLC control valves according to procedures. The host machine of HMI and PC
operation stations is equipped with PSA flow diagram, which shows the switch of valves,
working state of adsorption column and working time of each step. Refer to Chapter 1 (1.2
PSA working process) for the steps and mutual working relationship of each column.
2.1.1 Button description
1) Start-up (Shutdown): to start or stop the program.
2) Reset: to restore the program to its original state.
3) Step: in the program-controlled state, press this button, the PSA control program will
immediately enter the next step.
4) Pause (continue): When the program runs automatically, press this button, the running
program pauses and the valve keeps the current state; press this button again, the program
proceeds.
5) Self-inspection: In the self-inspection mode, PLC will not transmit the switch signal to
the PLC valves. This function button is only used when checking the timing in the
commissioning stage.
2.1.2 Operating instructions of the menu for the host machine
This kind of button is used for time setting, permission input operation and manual
operation.
2.1.3 Panel display
1. Valve status display: display the valve switch status on the main flow screen. The red
color of the valve body indicates that the valve is closed. Green indicates that the valve is
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open;
2) Working steps display: On the main flow screen, the running status of the columns
will be displayed on the column.
3) Time display: Displays the elapsed time of each time slice. At the beginning of each
process, the time starts to be timed until the end of this step; after switching to the next step,
the time starts to be timed again from the set time.
2.1.4 Installation method
PLC real-time monitoring.
2.2 Function description of automatic pressure regulating system

Set up a single-loop automatic regulating system (PICAS-108). According to the setting
value, the system can relieve the pressure of overpressure MT shift gas in time to ensure the
safety of the system.
2.3 Function description of FR control valve
The device is equipped with a hand-operated control valve to control the dump flow, and
its main functions are described in the following table.
SN. Instrument Name of manual Description
tag No. adjustment
1 HV-201 Dump gas flow The dump gas and purge gas pass through the dump flow
control valve control valve HV201, and then enter the off-gas buffer
tank after stabilizing the pressure. By adjusting the initial
opening, final opening and opening factor of the control
valve HV201. The off gas can enter the off-gas buffer tank
stably. Keep the pressure of the off-gas buffer tank stable
and balanced, and then make sure the pressure of off gas
entering the reformer nozzle stable.
2.4 Function description of purge control valve
The device is equipped with a hand-operated control valve to control the purge flow,
and its main functions are described in the following table:
S/N Instrument Name of manual Function description
tag No. adjustment
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1 PV-202 Purge air flow The providing purge gas is regenerated by stabilizing the
control valve purging tower through the providing purge flow control
valve PV202. Adjust the starting opening, final opening and
opening factor of control valve PV202 to regulate the
product gas purity.
2.5 PLC centralized display and control instrument

A system for flow meter display, controller and pressure regulation system of the device,
and its instruments are PLC-controlled centrally. See Table 2-2 for the list of instruments.
Table 2-2 List of Main Centralized Display and Control Instruments
Pressure
Tag No. Description Medium MPaG
PICAS108 Overpressure venting of adsorption feed MT shift gas ~0.85
PI201a~d Operating pressure indication of adsorption column H2≥99.99% 0-0.8
PIC201 Adsorption pressure control, indication and alarm H2≥99.99% 0.7~0.8
PI202 Pressure indication of providing purge gas tank H2≥99.99% ~0.1-0.2
PT204 Overpressure venting of off gas Tail gas ~0.04
PIC205 De-combustion pressure indication control of off gas Tail gas ~0.02
2.6 Detection points for on-site process parameters

Detection points for on-site process parameters are listed in Table 2-3. Spring pressure
gauge is used for pressure indication, and manual valve is installed at analysis point, which
can be sampled and analyzed when necessary.
Table 2-3 List of Main On-Site Detection Points
Pressure
Tag No. Description Medium
MPaG
PG201a~d Operating pressure indication of adsorption column H2≥99.99% 0-0.8
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3. Start-up
Device start-up is divided into initial start-up and normal start-up. Preparation is
required before the initial start-up, but only some valves and control points are set as required
before the normal start-up.
3.1 Preparations before initial start-up
It is necessary to check and commission the automatic control system to ensure that the
device can be put into operation at any time, after the PSA is installed, the purging and gas
tightness test of the device is completed, and the adsorption column is filled. However, the
entire equipment and piping of the device must be displaced with dry, oil-free nitrogen before
the feed gas is introduced, so that the oxygen content is reduced to less than 0.5% (by
volume). If the oxygen in the device is not displaced in advance, it is easy to form an
explosive mixture at the initial start-up and cause explosive combustion, because the raw
material, product and off gas of this device all contain a lot of hydrogen, especially the
product gas. After the above work is completed, all valves shall be closed.
3.1.1 Check the function of PLC
The main control signal controlled by the PLC program operates each PLC valve on site
through the electrical conversion of the solenoid valve. After the system is installed and the
wiring is checked as required, dynamic examinations are conducted according to the
following steps
1. Turn on the power supply; Set the process mode.
2. Set the time of E1, E2 and purge at will, and the program will be executed from the
initial state. Check the function buttons of step, pause, self-inspection, shutdown, alarm, mute
and time.
3. Make PSA in a stop state, and commission each PLC valve according to the
numerical serial number. In order to prevent the power supply from overloading, only ten
valves can be turned on at the same time.
4. Commission the empty load function of the programmed control system (PLC
solenoid valve). All solenoid valves are supplied with instrument air, so that signals can be
transmitted to the site. Press the pause key to check that the components of the program
system work normally under the working conditions of this step. After pressing the step key,
the program executes the next step. Check the whole system working condition again, and
execute in cycles, until the whole system under each step of the program is checked.
Check the PLC time setting.
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Check the stop function: press the stop key to make sure all the PLC valves are closed.
5. Check PLC alarm interlocking system
Input alarm signal, which shall sound an audible alarm; then press the mute button to
check that the button works.
3.1.2 Displacement of the whole process of the device with nitrogen
The displacement can be carried out in the same steps of normal operation, i.e. with
nitrogen as raw material through the device until the oxygen content of the product outlet and
the off-gas outlet is less than 0.5%. In the process of displacement, all analog operations are
manually controlled.
It can be operated in stages in case of insufficient nitrogen. Displace the nitrogen of the
adsorption column before of the buffer tank and piping. Displacement may be conducted
column by column in adsorption column. When the oxygen content in the outlet gas of one
adsorption column is less than 0.5%, the replacement of another adsorption column can be
carried out, and the displacement of other tanks and pipelines can be carried out after the
adsorption column is completed. At the junction of the battery limit, the valve to the user's
system shall be closed and the flange connecting to the user's system shall be removed before
the above displacement process begins. The same nitrogen displacement is conducted at the
junction, so that the oxygen content of the pipe down to 0.5% or less. The flange is installed
after the displacement is completed.
After the displacement of the whole device, close all process valves.
3.2 Feeding start-up
After the process and instrument of the whole device are checked and the nitrogen
displacement is confirmed to be qualified, the device is ready to be put into operation at any
time.
3.2.1 Valve setting
1. Valve opening setting
Fully open all pressure gauge valves. Note that open them gradually to prevent damage;
2. Setting of control valve and interlocking valve (see Table 3-1)
Table 3-1 Setting of Control Valve and Interlocking Valve
Instrument signal Operating valve code Control method Setpoint
50% of the whole
HV201 HV201 Manual
opening
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50% of the whole

PV202 PV202 Manual
opening
3. Check the instrument air input pressure and open all valves using instrument air
source.
3.2.2 Setting of the program controller
Put the PSA program in the stop state, set the providing purge time as 1/3-1/4 of the
operating parameters of normal operation, and the rest of the time settings as normal operation.
Start the PSA program, and the PSA starts to run.
1. Gradually open the intake valve (shut-off valve on PG201) to control the feed gas
flow at a rate that raises the adsorption column pressure by 0.2Mpa per adsorption cycle.
2. When the adsorption pressure of the adsorption column rises to the adsorption
pressure, the feed gas flow rate can be gradually increased to the full load, while the final
repessurization at the end is adjusted to 0.01-0.05 MPa lower than the adsorption pressure.
3. After the product quality meets the requirements, notify the subsequent section to
prepare to accept the product gas.
3.2.3 Normal operation regulation
1. Main operating parameters of PSA system
Pressure and time distribution table of each step of the PSA system (the pressure is
calculated according to gauge pressure)
4-1-2/p
S/N Step Pressure (MPa) Time (S)
1 Adsorption(A) 0.8 120
2 Equalization I 0.8→0.5 30
depressurization (E1D)
3 Equalization II 0.5→0.4 20
depressurization (E2D)
4 Providing purge (PP) 0.4→0.20 70
5 Dump (D) 0.20→0.02 30
6 Purge I (P1) 0.02→0.01 60
7 Purge II (P2) 0.01→0.005 10
8 Equalization II 0.05→0.2 20
repessurization (E2R)
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9 Equalization I 0.2→0.5 30
repessurization (E1R)
10 Final repessurization 0.5→0.8 120
(FR)
2. Run inspection items and adjustments

In order to obtain good running performance, the following items shall be checked and
adjusted during running:
Adsorption pressure
Adsorption pressure is the main parameter that determines the capacity of the device.
Within the design range of this device, the device capacity increases by increasing the
adsorption pressure. Keep the adsorption pressure as high as possible within the allowable
range of the device by means of the automatic pressure regulating system (PIC203).
Pressure equalization time
Due to the resistance, adsorption and desorption rate and other factors, it takes a long
time to reach a complete pressure equilibrium when the two adsorption columns are equalized.
Therefore, the pressure equalization is completed if the pressure difference between the two
adsorption columns for pressure equalization is less than 0.05Mpa.
FR flow
Before another adsorption, the product gas is used for the final repessurization of the
adsorption column. At the end of the step of final repessurization, the pressurized adsorption
column just reaches the specified adsorption pressure. This not only keeps the adsorption
pressure stable, but also reduces the fluctuation of raw material treatment capacity and
product output.
Product purity
An adsorption column has a fixed capacity to load impurities and to purify a certain
amount of feed gas in an adsorption-regeneration cycle. Too long cycle time or too large feed
gas will dilute the product purity; Too short cycle time will condense the product purity, but
the bed is not fully utilized, resulting in increased loss of product components.
By means of adjusting the cycle time, the device can produce products with different
purity, which is controlled at 99.9%-99.999%. The higher purity, the lower recovery rate of
component. Therefore, it is not necessary to pursue the purity, but to choose the appropriate
hydrogen purity to obtain higher benefits as required.
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4. Shutdown and restart after shutdown

4.1 Normal shutdown
Normal shutdown is a scheduled shutdown. Notify the relevant procedures before and
after the device, and then follow the steps below:
1. Close the inlet valve of the PSA section;
2. Close the product outlet valve in the battery limit of the device
3. The time setpoint of PSA program providing purge is gradually reduced as the
adsorption pressure decreases, so that each absorber pressure gradually drops to about 0.2
MPa (each tower can maintain positive pressure).
4. The PSA program stops running;
4.2 Emergency shutdown
Emergency shutdown is required in the event of a sudden power blackout, water
stoppage or device failure as follows:
1. Cut off the power supply and close all PLC valves (in case of sudden power blackout,
all PLC valves will automatically close);
2. Close the PSA intake valve and outlet valves quickly;
3. Depending on the situation, refer to the steps for normal shutdown.
4.3 Temporary shutdown
Shutdown less than 1 hour for any reason is temporary shutdown, and its operating
procedures are as follows:
1. Close the intake valve of the PSA section;
2. Press the pause button to keep the PSA working steps in the current state;
3. Close the outlet main valve.
4.4 Long-term shutdown
1. The same as normal shutdown in 4.1-1, 2;
2. The setpoint of the providing purge time of the program controller will gradually
decrease with the decrease of the adsorption pressure, which makes the pressure of each
adsorption column drop to zero;
3. Open the nitrogen inlet valve for displacement in the device;
4. We set the programmed adsorption columns to a manual method and turned them on
to PCV201a~d separately, then fill all the adsorption columns with nitrogen and maintain the
pressure at 0.2 MPa;
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5. The same as normal shutdown in 4.1-4, 5.

4.5 Restart after shutdown
4.5.1 Restart after normal shutdown
Follow the method in Chapter 3.
4.5.2 Restart after emergency shutdown
After emergency shutdown and temporary shutdown, the working steps and pressures
before shutdown are maintained in the adsorption column. The start-up under such working
condition shall be carried out as follows:
1. Turn on the PLC power supply, and the PSA program is in the pre-start state. Check
that the pressure state of each absorber is accordance with the program steps in the PSA
program. The PSA program has a memory function after shutdown. If there is no operation,
PSA program should be in the program step when shutdown.
If the pressure state of each adsorption column cannot be determined to belong to a
certain program step, then the pressure of the absorption column shall be depressurized by
manually switching the corresponding PLC valve at the stop state of PSA program, so that the
pressure state between each absorption column is in a certain step, and the steps executed by
PSA program shall be synchronized with it.
2. Open the intake valve gradually, feed gas enters the device, and the device is put into
operation.
4.5.3 Restart after temporary shutdown
According to Articles 1 and 2 of 4.5.2.
4.5.4 Restart after long-term shutdown
Restart after long-term shutdown shall be carried out according to Sections I and II of
3.1 - 3.2. Whether the whole device needs nitrogen displacement before start-up shall depend
on specific situations.
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5. Faults and Handling

Faults occur when the abnormal supply of out-of-bounds conditions or the operation of
the system itself is out of adjustment or a part fails during operation, causing a decrease in
product purity. However, before the cause of the fault is determined, the device does not need
to be stopped and can continue to be observed. At this time, the unqualified hydrogen can be
discharged to the flare system through the automatic venting system. After the fault is
identified, the decision to stop or continue to operate will be made. If there is a major problem
with the system, it shall be emergency shutdown.
General faults are as follows:
5.1 Abnormal supply of out-of-bounds conditions
5.1.1 Feed gas with water
If water enters the adsorption column due to the uncontrolled liquid level or operation
error in the conversion section, resulting in the failure of the absorbent, the feed gas shall be
reformed to the blow-down pipe immediately, and then the intake valve shall be closed
quickly to remove the water from the device, check the degree of water and make
corresponding treatment.
5.1.2 Power outage
In the event of power outage, the PLC valves are automatically closed, and the device is
out of operation. This situation can be treated as an emergency shutdown.
5.1.3 Instrument air pressure drop
For the device, the instrument air pressure is not lower than 0.4Mpa. If the pressure is
too low, the PLC valve will not open or close normally, resulting in confusion of operation of
each adsorption column and degradation of product quality. At this time, it shall be shut down.
5.1.4 Operation disorders
The key to normal operation of the PSA process is good operating condition of each
adsorption column; the operation disorder can immediately or gradually deteriorate the
regeneration of the tower. As the PSA process is a cyclic process, as long as one of the
adsorption columns regenerates and deteriorates, it will quickly spread and contaminate the
others, eventually leading to deterioration in product quality.
5.1.5 Feed handling capacity and cycle time
The adsorption capacity of absorbent to impurities in the adsorption column is
quantitative. Once the handling capacity is increased, the cycle shall be shortened accordingly,
so that the amount of impurities brought in by the feed gas does not exceed the capacity of the
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adsorbent. If the cycle is not adjusted in time, impurities will quickly contaminate the product.
5.2 Device faults
5.2.1 PLC faults
Its faults may be manifested by no signal output, program staying in a certain state in
switching or program disorder. See the relevant chapters of PLC technical manual for its
faults and handling methods.
5.2.2 Valve faults
There are 21 PLC valves and some series of control valves in PSA of the hydrogen
production device. If one of them faults, the normal operation of the whole system will be
affected. Operators shall timely and accurately identify the faulty valve in order to take
measures of handling.
5.3 Adjustment of product purity from unqualified to qualified
Decreased product purity indicates that the impurities component in the adsorption
column has reached the outlet of the absorption column during the adsorption step due to
improper operation adjustment or failure of the automatic control system. Once the cause has
been found out, it shall be restored to its normal state as soon as possible after handling. One
of the effective ways to adjust is low load (small handling gas volume), running for a period
of time. The second is to shorten the cycle time. If the two methods are combined, the purity
of the product will recover more quickly. In case of the second method, it is necessary to
ensure the time required for the final repessurization. At this point, the FR control valve
HV201 shall be turned up appropriately.
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6. Safety Technology
As a major issue related to people's lives and national property, safety production is the
fundamental policy of the state and also a mass work. Therefore, operators shall master the
basic knowledge of safety production and consciously abide by the relevant rules and
regulations to ensure safe and civilized production.
The product of the device is hydrogen, classified as Class A by GB50016-2014 Code for
Design of Building Fire Protection; the area of PSA equipment and PLC valve is classified as
zone 2, according to the provisions of the division of explosion danger sites.
6.1 Properties of hydrogen
Hydrogen is a flammable and explosive gas that is colorless, odorless and non-toxic at
atmospheric pressure and room temperature. It has a low boiling point (-252°C) and is also
non-corrosive. However, at high temperatures (>220°C), it will corrode certain metals, such
as carbon steel, and it acts with the carbon in the metal to produce "hydrogen embrittlement".
Hydrogen is the lightest of all elements, with a molecular weight of 2, a specific gravity of
0.07 to air (air specific gravity 1), and a minimum density of 0.09kg /m3. It is also highly
permeable, with an explosive range of 4.0-75% in the air. It cannot be used as a breathing gas
and can suffocate in high concentrations. Its spontaneous combustion point is 300°C.
6.2 Safety facilities of the device
The PSA system is equipped with an automatic pressure relief system. When the system
pressure is too high, the reforming section automatically opens the vent valve to vent the
reforming gas through the flame arrester. The automatic instrumentation system has been
designed to automatically place the device in a safe state in the event of a sudden power
failure. The selection of process pipelines, valves and pipe fittings in the design has taken into
account the special requirements of hydrogen-containing medium transportation and conforms
to the relevant provisions. Non-standard equipment shall also be accepted in strict accordance
with "Regulation of Safety Supervision for Pressure Container".
6.3 Key points of operation safety of hydrogen system
First, the oxygen content of the hydrogen entering the system shall not exceed 0.5%.
Two, when hydrogen system is running, it is forbidden to knock, repair and tighten with
pressure, overpressure and negative pressure.
Three, when pipes, valves and water sealing devices are frozen, they can only be thawed
by hot water or steam, and open flame is strictly prohibited.
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Four, for leakage inspection of equipment, pipes and valves, soapy water or portable
flammable gas explosion-proof detectors can be used, and open flame is prohibited.
Five, hydrogen is not allowed to be discharged indoors. The hydrogen of flushing
displacement and venting depressurization must be discharged through the blow-down pipe.
Six, when hydrogen leakage or accumulation occurs in large quantities, the gas source
shall be cut off for ventilation. At this time, do not carry out all operations that may generate
sparks.
Seven, the hydrogen system must undergo pressure resistance test, cleaning and gas
tight test to meet the relevant inspection requirements before it can be put into use after new
installation or overhaul.
Eight, nitrogen (or other inert gas) displacement or water-injecting exhaust can generally
be used for the purge displacement of the hydrogen system.
Nitrogen displacement shall meet the following requirements:
1. The oxygen content in nitrogen shall not exceed 1%;
2. Full displacement is required to prevent residual gas remaining at the end of the dead
corner;
3. The content of oxygen or hydrogen in the system must be qualified in three
consecutive analyses at the end of the displacement.
Nine, the maintenance of hydrogen hot work must ensure that the maximum content of
hydrogen in the system and hot work area does not exceed 0.4%.
Ten, prevent open flames and other sources of ignition, and prohibit the use of electric
furnaces, electric drills, fireplaces, blowtorches and all other tools and hot objects that
produce open flames and high temperatures; do not carry kindling materials into the fire
prohibition area; select and use copper or copper alloy tools; wear cotton work clothes and
anti-static shoes.
Eleven, see "Safety and Technical Regulations" for the rest.
6.4 Fire-fighting
One, fire demand shall be provided in accordance with the relevant provisions of
GB50016-2014, and fire-fighting equipment such as dry powder, foam and carbon dioxide
shall be equipped or nitrogen and steam fire extinguishing system shall be set as required.
Two, the following measures shall be taken for hydrogen ignition:
1. Cut off the power supply;
2. Prevent fire expansion by cooling and isolation;
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3. Keep the hydrogen system under positive pressure in case of tempering.

Three, hydrogen flames are difficult to detect, so ambulance crews shall prevent
exposed skin combusts.
6.5 General precautions in safety production
One, operators must follow the operating manual. All newcomers must undergo safety
education and learn operation methods before internship operation. Those who have not
passed the examination of safety technology and operation method are not allowed to operate
independently.
Two, operators must wear the required clothing at work, and are not allowed to carry
flammable and explosive substances into the site; observe labor discipline strictly; carry out
shift handover strictly, carry out itinerant inspection strictly; control process indicator strictly;
implement operating procedures strictly; implement relevant safety regulations strictly.
Three, keep the battery limit of the device clean at all times; do not stack up
inflammables and explosives; do not pile up items, especially in the vital communication line
to ensure the smooth flow of the road.
Four, fire-fighting equipment shall be installed in the battery limit of the device
according to the regulations. Operators shall know the place and use of fire-fighting
equipment. It is strictly forbidden to tamper with fire-fighting equipment. The fire-fighting
equipment should also be checked regularly.
Five, it is absolutely forbidden to weld or tighten screw, etc. when the equipment has
not finished unloading the pressure, and it is forbidden to use iron to knock the equipment.
Six, the pressure gauge used must be qualified and sealed. If the pressure gauge pointer
does not return to zero or the error is greater than the series, it is not allowed to be used. The
pressure gauge must be checked and sealed once a year. Zero must be adjusted before using
pressure indicator instrument with pressure transmitter.
Seven, smoking and hot work are strictly prohibited in the battery limit of the device.
Before the maintenance of the containers and pipelines with explosion and combustion gas, it
shall be reported to the safety technology department of the plant and the workshop for
approval. If nitrogen displacement and purge is used first, and the on-site analysis is qualified,
the fire can be ignited after taking safety measures and obtaining the fire certificate.
Illegal hot work is prevented. Hot work is strictly prohibited if no hot work permit is
obtained, the production system is not isolated, and the cleaning and displacement is
unqualified. Hot work is strictly prohibited if the inflammables and explosives around are not
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removed, the hot work analysis is not carried out on time, there are no fire-fighting measures
and there is no supervision.
Eight, ensure the gas tightness of equipment, pipes and valves. After maintenance, it
shall also be able to start up after passing the leaking test. In the process of usage, pay
attention to the elimination of gas leaks at any time.
Nine, periodically check that grounding and lightning protection facilities of the
equipment are in good condition.
Ten, the instrumentation system shall be repaired by the instrumentation personnel in
case of malfunction. Instrument personnel shall closely cooperate with process operators, and
pay attention to the pressure in the adsorption column of the fatigue pressure container when
it is restarted after shutdown maintenance, in order to prevent the high-pressure dump.
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Safety and Technical Regulations

CDH21-007-GY-1003
Evian Shanghai Engineering Technology Co., Ltd

June 2022
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Table of Contents
Preface ..........................................................................................................................1
1. Brief Introduction of the Device and Safety Facilities .............................................2
1.1 Process introduction ........................................................................................2
1.2 Device composition ........................................................................................2
1.3 Device safety facilities ....................................................................................2
2. Security Techniques ..................................................................................................3
2.1 Material properties and poison protection ......................................................3
2.2 Workshop poison protection ...........................................................................6
2.2.1 Material hazards and protection ...........................................................6
2.2.2 Workshop poison protection ................................................................6
2.3 Fire and explosion prevention ........................................................................9
2.3.1 No fireworks and open flames .............................................................9
2.3.2 Elimination of "releasing, emitting, dripping and leaking" .................9
2.3.3 Prevention of sparks from friction and impacts .................................10
2.3.4 Prevention of fire or explosion of electrical equipment ....................10
2.3.5 Prevention of electrostatic sparks and lightning strikes ....................10
2.3.6 Fire-fighting measures .......................................................................10
2.4 Noise prevention ...........................................................................................11
2.5 Other precautions ..........................................................................................11
3. Workshop Sanitation ..............................................................................................12
4. Life Hygiene ...........................................................................................................13
5. Treatment of "Industrial Wastewater, Waste Gases and Residues" .......................14
5.1 Waste gases ...................................................................................................14
5.1.1 Waste gas - PSA off gas ....................................................................14
5.1.2 Industrial wastewater and residues ....................................................14
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Preface
As a major issue related to people's lives and national property, safety production is
the fundamental policy of the state and also a mass work. Therefore, operators shall and
must master the basic knowledge of safety production and consciously conform with the
relevant rules and regulations to ensure safe and civilized production.
The product of the hydrogen production device is hydrogen, and most of the raw
materials used in the process, including raw natural gas, process reforming gas and
auxiliary materials, are flammable, explosive and poisonous chemicals. The product of the
device is classified as Class A by GB50016 Code for Design of Building Fire Protection;
In accordance with GB50058 Code for the Design of Electrical Devices in Explosion and
Fire Hazardous Environments, the device shall be divided into 2 zones, i.e. "an
environment where explosive gas mixtures are not produced during normal operation, or
where explosive gas mixtures exist for a short period even if they do occur". In order to
strengthen the labor protection awareness of workers, ensure safety production and
eliminate safety accidents, this safety procedure is formulated according to the
characteristics of the device process. Based on the main points of this regulation and
reality, and in accordance with the safety and health regulations issued by national
ministries and committees, the plant can formulate and implement workshop safety and
technical implementation rules upon approval of promulgation. Leaders at all levels and
functional departments in the plant shall address workers and management cadres on
safety education and seriously implement the safety operation certificate system, so as to
ensure that each worker is aware of safety production and everyone attaches importance to
safety; and each department and post is responsible for the division of labor, and shall
work together to improve the safety of the workshop.
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1. Brief Introduction of the Device and Safety Facilities
1.1 Process introduction

The device takes natural gas as the raw material for hydrocarbon steam reforming,
produce hydrogen-rich reforming gas through desulfurization, catalytic reforming and
medium temperature shift, then sent it to the PSA device for refining, and finally get the
hydrogen gas with purity ≥ 99.999% for customers.
The operating pressure of the system is 0.2-1.2 MPaG, a low-pressure operating
device with the conversation reaction temperature in the range of 700-780°C. The
radiation section of the reformer combusts the off gas and raw natural gas for heating.
1.2 Device composition
The device includes two main bodies of natural gas reforming section and PSA
section, along with a distribution room and control room of the device.
Other utility facilities such as cooling water, instrument air, and total power
distribution are considered by the plant.
natural gas reforming and PSA devices are placed in the open air to maintain good
ventilation. The whole device belongs to Class A of the fire and explosion prevention
category. The control room and power distribution room belong to the non-explosion-
proof area.
1.3 Device safety facilities
Each system is equipped with overpressure venting interlocking valves or safety
valves to prevent overpressure of the device. All or a large amount of off gas is recovered
for combustion, and a small amount of the gas in fault condition is vented at a high
altitude via a flame arrester through the main vent pipe. On-site electrical appliances and
instruments are explosion-proof or isolated. In addition to the safety alarm function, the
automatic control instrument is designed to automatically protect the system in the event
of a sudden power outage or other emergencies. The process pipeline, valves and fittings
in the device design are selected in accordance with the relevant regulations and taking
into account the special requirements of hydrogen-containing mediums Acceptance of
pressure equipment shall be strictly in accordance with the Pressure Vessel Safety
Technical Supervision Regulations, and reinforced management shall be done for fatigue
vessels such as adsorption columns.
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2. Security Techniques
2.1 Material properties and poison protection

The main materials in this device are natural gas, water, hydrogen, carbon dioxide
and a small amount of carbon monoxide, etc. The well-known physical and chemical
properties of water will not be elaborated. The properties and protective measures of other
major materials are listed in Table 2-1 (see below).
Nitrogen is used in the process of device displacement, etc. Nitrogen is a colorless,
odorless, inert gas that does not spontaneously combust or fuel combustion. When the
nitrogen level in the air increases and causes the oxygen rate to fall below 18%, it makes
difficult breathing and threatens life.
Table 2-1 Main Material Properties and Protective Measures in the Workshop
Name Natural gas Hydrogen Carbon Carbon
dioxide monoxide
Molecular formula CH4, etc. H2 CO2 CO
Property Colorless, Colorless Colorless Colorless,
flammable and and odorless and odorless odorless and
explosive combustible non- tasteless gas;
mixed gas; gas flammable partially
insoluble in gas called soluble in
water; a smell dry ice in water
of slightly the solid
rotten eggs or state
gasoline
Physicoche molecular weight ----- 2.02 44.01 28.01
mical Melting point (°C) ----- -259.2 -56.6 -199.1°C
constants Boiling point (°C) ----- -252 -78.5 -192°C
Flash point (°C) ----- <-50 ----- <-50°C
Spontaneous 550 400 ----- 610
ignition point (°C) 0.79 0.07 1.52 0.97
Relative density 5-15 4.0-75 ----- 12.5-74.2
Explosion limit %
Prohibited substances Oxygen; Oxygen; Active metal Strong
flammable flammable oxidants;
source source fireworks
Fire-proof Nature Flammable Flammable Non- Flammable,
properties and explosive and flammable explosive,
gas mixtures explosive poisonous
with methane
as the main
component;
poisonous
natural gas
containing
hydrogen
sulfide;
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Fire Use dry Stop the Use dry

extinguishing powder and leakage first, powder
and carbon dioxide and then extinguishing
explosion fire extinguish agents and cool
prevention extinguishing the fire with the container in
agents. dry powder, the fire with
carbon water to avoid
dioxide or explosion.
halogen
extinguishing
agents.
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Name Natural gas Hydrogen Carbon dioxide Carbon monoxide

Protective No fireworks; Keep the site Keep the site No fireworks, and
measures keep the site well ventilated, ventilated; wear wear a gas filter mask
well ventilated, prevent open air-supplied in case of low carbon
prevent open flames and respirators in monoxide
flames and other other sources case of high concentration; wear
sources of of ignition, and concentration; self-contained air
ignition, and prohibit the use wear protective supply respirators in
prohibit the use of electric clothing to case of high
of electric furnaces, avoid freezing concentration.
furnaces, electric electric drills, of the skin;
drills, fireplaces, fireplaces, select
blowtorches and blowtorches appropriate
all other tools and all other respirators.
and hot objects tools and hot
that produce objects that
open flames and produce open
high flames and
temperatures; high
wear cotton temperatures;
work clothes and wear cotton
anti-static shoes. work clothes
and anti-static
shoes.
Storage Place it in a Heat-insulated Avoid Keep it away from

cool, ventilated storage; no contacting with prohibited substances;
and heat- fireworks; active metals to place it in a cool,
insulated place; avoid oxygen. prevent damage heat-insulated, fire-
keep it away Ensure that the to containers proof and light-proof
from oxidants; containers is place; place the metal
no fireworks; equipped with container containing
open and close self-closing more than 23L of this
the container valves, vacuum product firmly on the
with a non-spark pressure plugs ground; ensure that
tool and fire the barrel containers is
avoidance equipped with self-
devices; use closing valves,
non-spark tools vacuum pressure
to open and plugs and fire
close the avoidance devices;
container, and use non-spark tools to
equipped it open and close the
with explosion- container; no
proof electrical fireworks
equipment for
storage
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Transportation Attach it with Attach it with Attach it with Attach it with the
the label of the label of the label of label of "Poisonous
"Flammable and "Flammable "Non- and Flammable
Explosive and Explosive flammable Gases"; air and rail
Gases"; air and Gases"; air and Gases"; transportation are
rail rail capacitated air strictly prohibited
transportation transportation and rail
are strictly are strictly transportation
prohibited prohibited
2.2 Workshop poison protection

2.2.1 Material hazards and protection
Table 2-2 (see the attachment) lists the hazards to human health of the main materials
in the device, and protective measures and methods for leakage treatment. In case of
poisoning or leakage, stay calm and take appropriate emergency measures to ensure
orderly rescue.
2.2.2 Workshop poison protection
1) The natural gas reforming and PSA of the workshop system are for low and
medium pressure operation, so it must be ensured that the equipment, piping, instruments,
valves, etc. are intact and airtight, and regular or irregular inspection of the tightness must
be carried out to eliminate releasing, emitting, dripping and leaking, ensuring that the
content of poisonous substances in the air of the workshop is lower than the maximum
allowable concentration stipulated by the state.
2) Natural gas reforming and PSA devices are open-air for good ventilation.
3) The workshop shall be equipped with appropriate protective equipment at clearly
marked places, such as gas masks, oxygen respirators, protective glasses, rubber gloves,
boots, etc.
4) Operators shall wear necessary protective equipment when operating or
maintaining the device to prevent poisonous substances from coming into direct contact
with the skin or splashing into the eyes.
(5) When maintaining equipment, piping and valves, the cooperation with process
operators shall be ensured to implement relevant maintenance regulations and carry out
on-site supervision to avoid accidents.
Table 2-2 The Main Material Hazards and Protection of the Device
Name Natural gas Hydrogen Carbon dioxide Carbon
monoxide
Ways of invasion Inhalation Inhalation, skin Inhalation
contact
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Hazards Health The main Deep Exposure to dry It will bind to

and hazards composition is exposure ice or low- hemoglobin
symptoms methane. It is will cause temperature gas and interferes
non-poisonous, hypoxia and will cause with the
but when the asphyxia; frostbite; oxygen-
methane content exposure to exposure to the air carrying
in the air reaches liquid with a carbon capacity of the
10% or above, hydrogen dioxide blood if
people will have will cause concentration of inhaled,
difficulty frostbite 10% will cause resulting in
breathing due to coma or death due tissue hypoxia,
lack of oxygen, to lack of oxygen; headache,
causing dizziness, short breaths and dizziness,
weakness, headache if the nausea,
unconsciousness, concentration is hypomania and
coma or even 5%; physiological coma until
death. Natural gas changes if it is death; it will
is also poisonous 1.5%; high levels result in pale
if it contains a of carbon dioxide faces, reddish
certain amount of concentration in skin and
hydrogen sulfide. the blood will mucous
Hydrogen sulfide affect the membrane if
is a colorless gas respiratory rate poisoned; in
with a strong more serious
smell of rotten cases, it will
eggs. When the damage brain
concentration of cells and cause
hydrogen sulfide secondary
in the air reaches disease,
0.31 mg/L, the damaging the
human eyes, myocardium in
mouth and nose mild cases or
will be strongly the
irritated to cause extracorporeal
tears, fear of light, vertebral
headache and system in
vomiting; people severe ones,
will die if the including the
concentration of basal ganglia
hydrogen sulfide
in the air reaches
1.54 mg/L.
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Protective Eye contact Move the patient Soak the Seek medical Move the
measures and skin to fresh air affected treatment if dry patient to fresh
assimilation immediately and area with ice gets into eyes; air immediately
perform artificial warm seek medical and perform
respiration water, treatment if dry artificial
move the ice contacts with respiration
patient to skin; move the
fresh air, patient to fresh air
and perform and perform
artificial artificial
respiration respiration
if breathing
stops;
perform
CPR if the
heartbeat
stops;
Leakage treatment Wear protective Wear Keep the site Wear protective
equipment if protective ventilated if gas equipment to
entering the leak equipment leaks; wear enter the site;
site; eliminate all to enter the protective eliminate all
fire hazards; keep site when equipment to fire hazards;
the site ventilated; leaking; enter the site for keep the site
perform leaking eliminate leaking stoppage; ventilated;
stoppage; move it all fire move it to an open perform leaking
to an open and hazards and and safe place for stoppage; move
safe place for keep the repair or venting it to an open
repair or venting site if the leakage of and safe place
if the leakage of ventilated steel cylinders for repair or
the barrel cannot be venting if the
container cannot stopped; keep the leakage of the
be stopped site ventilated and barrel container
wear protective cannot be
equipment to stopped
enter the site for
leakage treatment
if carbon dioxide
liquid or solid
leaks
6) Report to relevant departments immediately after poisoning accidents, and

organize rescue work under the command of leaders or security technologists; find out the
cause of poisoning quickly, and then deal with it in accordance with the first-aid measures
in Table 2. Those who are seriously poisoned shall be sent to the hospital for rescue
quickly.
7) Water shall be provided at appropriate places in the workshop for washing in case
of chemical burns.
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8) Ensure that the environmental testing department shall monitor the workshop's
environment regularly or irregularly, and notify the person in charge of the workshop to
perform inspection and maintenance in time to eliminate potential leakage hazards.
9) Ensure that the medical department shall conduct regular physical examination of
the workshop's staff and ensure timely treatment of patients.
2.3 Fire and explosion prevention
The device system is of low and medium pressure operation, and the raw natural gas
and product hydrogen are flammable and explosive in need of special attention to fire and
explosion prevention.
2.3.1 No fireworks and open flames
1) Place the device in the fire prohibition area. Post warning signs such as "NO
SMOKING AND TINDER, ETC." in prominent places.
2) Do not use open flames (such as candles) for lighting in the plant.
3) Perform lightning protection grounding for plants and static electricity protection
grounding for equipment pipes.
4) Strictly implement the hot work system and obtain the hot work approval by the
relevant management department as required if the hot work is needed in the plant, and
start the operation under the supervision of the security technology department and the
fire-fighting inspection
5) Complete relevant formalities if the equipment and pipes need maintenance.
Replace the material with nitrogen after venting it, and isolate it from other connected
equipment as far as possible. Do not start the hot work before hot work permits and
qualified sampling are completed. Stop immediately if any abnormality occurs during
maintenance.
2.3.2 Elimination of "releasing, emitting, dripping and leaking"
Eliminate "releasing, emitting, dripping and leaking" to prevent flammable and
explosive substances from combining with the air to form explosive mixtures.
1) Keep the device well ventilated to eliminate the accumulation of explosive
mixtures, and avoid any sparks-generating operation.
2) Conduct gas tightness testing towards the system in segments, or towards the
equipment individually, and ensure it is qualified before start-up.
3) Frequently check the leaking parts such as all infusion pumps, pipes, valves and
flange joints in the workshop, and maintain or repair any of them if there is leakage or
damage immediately.
4) Use soapy water or chemical test paper with no open flame to check the leakage of
the equipment, valves and pipes in operation.
5) Ensure that flammable liquids are not stored in open, large and unprotected glass
bottles. Ensure that all discharge lines must extend out of the workshop.
6) Ensure that the health monitoring department of the plant shall regularly measure
the concentration of flammable gases in the air within the scope of the workshop. And
take timely measures to eliminate the potential danger if any abnormality is found.
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2.3.3 Prevention of sparks from friction and impacts

1) Lubricate the machine bearings and other rotating parts well; use the bearing
bushes made of materials that do not easily produce sparks for machine friction parts.
2) Avoid wearing shoes with nails to enter the device and do not direct beat the
equipment or pipeline with iron at any time.
3) No throwing or dragging of the metal storage barrels stored flammable materials
on the ground to prevent them from colliding with the ground and causing sparks.
2.3.4 Prevention of fire or explosion of electrical equipment
1) Select explosion-proof electrical power equipment and install explosion-proof
electrical buttons or switches in the plant as required. Use explosion-proof lamps for
lighting installation.
2) Ensure that wires shall also have good corrosion resistance in addition to good
insulation, and check regular inspection for damage.
3) Use the electrical equipment as required.
4) Cut off the power supply of the device and the electrical equipment of the
pumping house immediately after the work is finished.
2.3.5 Prevention of electrostatic sparks and lightning strikes
1) Production equipment, storage tanks, pipes, valves and other places prone to static
electricity shall be reliably grounded. Equipment in each layer of the plant uses ring
grounding grids, and metal conducting wires are used to connect the grounding wires of
each equipment.
2) The motor and equipment or machine are directly driven by coupling. When
adopting the belt transmission, use anti-static belts to prevent the accumulation of
electrostatic charge caused by friction.
3) The flow rate of liquid in the pipe shall not exceed 2-3m/s, and when the operating
pressure is greater than 3.0Mpa, the hydrogen flow rate in the carbon steel pipe shall not
be more than 10m/s; when the operating pressure is less than or equal to 3.0Mpa, the flow
rate must not exceed 15m/s to avoid electrostatic sparks.
4) Install lightning protection devices on the top of production plants, chimneys of
induced draft fans, reformers and other positions.
2.3.6 Fire-fighting measures
The fire category of the natural gas reforming for hydrogen production device is the
First-B type (i.e. the serious hazard level). According to the policy of "take prevention a
top priority and combine prevention with elimination", a series of fire prevention measures
shall be taken and the fire-fighting facilities shall be improved.
1) Improve the fire-fighting water supply system to ensure a sufficient amount of
water for fire-fighting.
2) Install fire-fighting equipment in appropriate places: select carbon dioxide fire
extinguishers, dry powder fire extinguishers, carbon tetrachloride fire extinguishers, foam
extinguishers, etc. in the main plant; set carbon tetrachloride fire extinguishers and carbon
dioxide fire extinguishers in the power distribution rooms, control rooms and analysis
rooms, and avoid using foam extinguishers and atomized water.
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3) Set fire hydrants connecting atomized water nozzles in appropriate places around
all the workshops by the whole plant.
4) Clear the main traffic lines to ensure that the fire engine can enter the scene in time
to put out the fire if the fire alarm breaks out.
2.4 Noise prevention
The noise of the devices mainly comes from power equipment and venting sounds,
which has been fully considered in selecting the device's power equipment. Hence, the
total decibel of the workshops' noises is less than 85db in normal operation, meeting the
general requirements of the production workshop as required by the Permissible Noise
Standards for Production Plants and Auxiliary Buildings. The off gas is fully or mostly
recovered for combustion, and the main vent pipes only discharge a small or no amount of
waste gases, thus reducing the venting sounds greatly.
2.5 Other precautions
1) Ensue that the workshop staff shall not start working before passing the safety
technology education examination, and each operator must be familiar with the chemical
hazard properties of relevant production processes, raw materials, products, relevant first-
aid knowledge and the performance and using methods of fire-fighting equipment in the
workshop.
2) Ensure that the operation data shall be recorded timely, truthfully and accurately,
and the sensitivity of the instruments and safety facilities shall be checked for timely
repair and replacement if damaged for they are necessary to ensure normal operation and
avoid accidents.
3) Prepare in advance the emergency measures against the outage of water or power
and other abnormal situations.
4) Set up an accident reporting system for immediate organized rescue after accidents,
timely and accurate reporting, cause determination and specific preventative measures.
5) Control the speed of heating, boosting, cooling, and pumping down during start-up
and shutdown as required and protect the equipment and catalysts.
6) Wear protective masks when loading and unloading heavy metal contained
catalysts.
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3. Workshop Sanitation
Most of the raw materials and intermediates used in the device are poisonous
mediums. The sealing of process pipelines and equipment has been reinforced in the
device design, and the detection and control of main production devices are carried out
mainly in the control rooms. Hence, operators have relatively few opportunities to contact
poisonous mediums. Nonetheless, such protective measures have been taken as controlling
the concentration of hazardous substances in the workshop below the national health
standards and installing alarm devices at the main detection points.
The maximum allowable concentration of hazardous substances in the air of the
workshop is listed in Table 3-1. If it is exceeded, the workshop security technologist shall
take measures immediately to keep the concentration well within the allowable range.
Table 3-1 Maximum Allowable Concentration of Hazardous Substances in the
Air of the Workshop
Substance name Natural gas Carbon monoxide
Concentration (mg/m3) 50 30
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4. Life Hygiene
According to the hygiene characteristics classification of workshops as set forth in
Hygienic Standards for Industrial Enterprises, the device belongs to class 4, and hence,
there is no separate trunk room, but it is allowable to store the clothes in appropriate
places in control rooms. All other auxiliary sanitary facilities such as bathrooms, toilets,
medical and sanitary facilities shall be taken into consideration by the plant. Some
commonly used medical supplies, such as special antidotes, flushing fluids, safety eye
washers and other emergency drugs or instruments shall be prepared in the workshop in
case of urgent needs.
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5. Treatment of "Industrial Wastewater, Waste Gases and

Residues"
There are few "three wastes" produced during the workshop process, which will not
affected the environment after treatment.
5.1 Waste gases
5.1.1 Waste gas - PSA off gas
After the pressure swing adsorption (PSA) device of the device separates and purifies
the hydrogen in the reforming natural gas, the off gas enters into the radiation section of
the reformer to serve as the combust gas of heat sources, and it is not emptied to the
outside during normal operation. The waste gas contains hydrogen (31%), carbon dioxide
(53%), carbon monoxide (7.8%) and methane (6.7%). The designed height of the main
vent pipes is not less than 12 meters to avoid environmental pollution. The waste gas
contains high levels of carbon dioxide, which can be further recycled to reach the food-
grade standard by the pressure swing adsorption technology. The recycling of the off gas
can also be taken into consideration.
5.1.2 Industrial wastewater and residues
During the process of the device, the medium temperature shift gas separator shall
discharge the cooled water intermittently during normal operation, almost without other
pollutants discharged.
No residues are discharged in the production of the device. In case of the permanent
deactivation of the natural gas conversation catalyst, desulfurizer, MT shift catalyst or
absorbent of adsorption columns, they shall be taken out for replacement. The conversion
catalyst can be sent to the manufacturer for recycling and there shall be no harmful
ingredients in the absorbent.
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Analysis Procedures
CDH21-007-GY-1004
Evian Shanghai Engineering Technology Co., Ltd
June 2022

Table of Contents
1. Brief Introduction of Natural Gas Decomposition for Hydrogen Production
Technology ................................................................................................................... 1
2. Main Analysis Items of Natural Gas to Hydrogen Production ................................ 3
3. Compositions and Principles of Gas Chromatograph .............................................. 4
4. Operating Procedures of Gas Chromatograph ......................................................... 6
4.1 Host and installation ....................................................................................... 6
4.1.1 Host ....................................................................................................... 6
4.1.2 Installation of gas chromatograph ......................................................... 6
4.2 Thermal conductivity detector calibration .................................................... 10
4.3 Flame ionization detector and methane reformer ......................................... 12
5. Chromatographic Workstation ............................................................................... 15
5.1 Compositions and functions of chromatographic workstation ..................... 15
5.2 Operating procedures .................................................................................... 15
5.3 Retention of standard sample files of chromatographic workstation ............ 16
6. Analysis of Natural Gas Reforming ....................................................................... 17
6.1 Overview ....................................................................................................... 17
6.2 Analysis of nitrogen and hydrogen gas mixtures in catalyst reduction - gas
chromatography .................................................................................................. 17
6.3 Control and analysis in natural gas reforming - gas chromatography .......... 18
6.4 Natural gas to hydrogen production: analysis of the product gases CO, CO2
and CH4 - gas chromatography .......................................................................... 20
6.5 Gas detection tube determination for H2S analysis ...................................... 21
6.6 Precautions and safety tips ............................................................................ 21
7. Utility Conditions Before Start-up ......................................................................... 22
7.1 Workbench .................................................................................................... 22
7.2 Three gases and gas cylinder reduction valves for gas chromatograph ........ 22
7.3 Standard gases (as required by the contract) ................................................. 22
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7.4 Taking tools for gases to be analyzed ........................................................... 23
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1. Brief Introduction of Natural Gas Decomposition for
Hydrogen Production Technology
The natural gas decomposition for hydrogen production technology means using
the natural gas as the raw material to produce crude hydrogen by the steam reforming
to gas production process, and obtain the product hydrogen after the crude hydrogen
is transformed and impurities are separated via PSA.
Basic steps:
Desulfurization of the raw natural gas: at a certain temperature and pressure, the
raw material is absorbed by the zinc oxide desulfurizer, and the H2S in the feed gas is
decreased to below 0.1ppm to meet the sulfur requirements of steam reforming
catalyst.
The steam reforming of hydrocarbons: during the process, the feed gas for
hydrogen production is obtained with the water vapor as an oxidant to converse the
hydrocarbon substances under the act of the nickel catalyst. The process is
endothermic, and hence, external heating is required. The heat required for reforming
is provided by the radiation section of the reformers.
Carbon monoxide conversion: when the temperature of the reforming gas is 330
- 360°C, the CO enters into the reformer and its transform reaction is exothermic due
to the MT shift catalyst. Low temperature is beneficial to maintain the reforming
balance to improve the reform rate of CO, and increase the hydrogen production per
unit of raw materials.
Purification by pressure swing adsorption (PSA): after the cracked gas of the
natural gas enters the hydrogen extraction tower from the bottom, the impurities
except hydrogen are adsorbed at a time by the sequential selection and adsorption of
absorbents filled in the tower, and the product hydrogen with a purity ≥ 99.9% is
produced.
There are two main purification processes of reforming steam to hydrogen

production, that is, chemical purification and PSA purification. Chemical purification
is widely adopted in the early produced hydrogen production devices in China. As the
improvement of the PSA technology in recent years (multiple rounds of pressure
equalization on the bed, the improvement of absorbent performance, etc.), the
hydrogen recovery rate is up to 95%. Moreover, the localization of PSA technology
greatly reduces the investment and operation cost of PSA devices, making it standing
out in the newly built hydrogen production devices.

This set of equipment uses natural gas as raw materials to produce hydrogen, and
the PSA purification gas is selected for its cost is lower than that of chemical
purification. Meanwhile, PSA technology is featured with short hydrogen production
processes, high degree of automation and high purity of the product hydrogen.
In the hydrogen production purification, analysis is very important, for it controls

the production process to ensure that all processes meet certain design requirements,
and guide operators to operate the hydrogen production purification device correctly
and flexibly.
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2. Main Analysis Items of Natural Gas to Hydrogen Production
The device takes natural gas and water as raw materials, produces hydrogen and
carbon dioxide by steam reforming via catalysts, and separates CO, CO2, CH4 as
impurities and obtains purified H2 through PSA. The analysis manual specifies the gas
chromatography for the analysis and control of products in the process of natural gas
reforming, and the analysis of the purity of the product hydrogen.
Analysis frequency: normal analysis: once every 2 hours for the reforming gas;
once an hour for the product gas; once every 8 hours for hydrogen sulfide.
Table 2-1 Term List of Main Analysis
Analyzed items
S/N Sample names and control Analysis methods Remarks
indicators
Reforming CO≤10 Gas
TCD: TDX-01
1 gas CH4≤7 chromatography
column
v/v,% CO2≤10 TCD:
Medium
CO≤3 Gas
temperature TCD: TDX-01
2 CH4≤7 chromatography
shift gas column
CO2≤18 TCD
v/v,%
Gas
CO≤10-5 chromatography
Product gas
3 CH4≤2.x10-5 FID + methanation
v/v,%
CO2≤2.5×10-5 reformer + TDX-01
column
H2S gas detection
H2S content Feed gas after tube - type 1
4 determination desulfurization Measuring range:
ppm ≤ 0.5ppm 1-120ppm
(Consumables)
Analysis means of the hydrogen production purification process: special

chromatographic analyzers, on-site sampling, and laboratory analysis.
Analysis purposes of the hydrogen production purification process: for

economical and practical purposes. Chuangda puts forward a set of economical and
practical analysis methods based on the company's years of experience in hydrogen
production purification technology. In the production analysis of hydrogen production
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purification, the purity of the product hydrogen can be ensured by a strict analysis of
the intermediate products and control of the process. Analyze the constant and trace of
CO, CH4 and CO2 only, and the purity of hydrogen can also completely meet the
requirements of process design. And ignoring other impurities can be accepted.
3. Compositions and Principles of Gas Chromatograph
Gas channel adjustment & display system; Gas/liquid sample injection system;
Component separation system; Component detection system; Temperature control
system; Signal detection & amplification system; Data collection & calculation
system.
Gas channel for flow adjustment & display system
Gas-liqui Compone Compone Signal Data

d sample nt nt amplificat calculation
injection separation detection ion &
system system system system processing
system
Temperature control system
Gas chromatography refers to the process during which the carrier gas (mobile
gas phase) flows into the vaporizer with stable pressure and precise flow rate to bring
the vaporized sample or the gas sample in the quantitative volume sample injection
tube into the chromatographic column. Due to the difference in the distribution
solubility or adsorption coefficient between the mobile phase (mobile gas phase) and
the stationary phase of each component in the sample in the chromatographic column,
the sample is distributed repeatedly in the gas phase and the fixed phase under the
purge of the carrier gas. After a certain column length, each component in the sample
will be separated and leave the chromatographic column in sequence to enter the
detector. The concentrations of each separated component of the sample will be
converted by the detector into corresponding electrical signals (convert physical
quantities into electrical quantities) easy to measure, and after being amplified by the
micro-current amplifier and converted from physical quantities into electrical
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quantities by each controller unit, they will be painted as chromatographic peaks by

the recorder. And the purpose of qualitative and quantitative analysis can be achieved
by using the length of their retention time and the area or height of peaks.
FID
detector
Sample
injector
Data collection and

Column Converter
calculation
separation
Sample Column TCT detector

injector separation
Column
Sample
separation
injector
Drain
Qualitative gas chromatography components: Qualitative gas chromatograph

components are based on the different retention time of each component flowing out
of the chromatographic column under the same analytical condition.
Quantitative gas chromatography components: Quantitative gas chromatograph

components are based on the different peak areas of each component flowing out of
the chromatographic column under the same analytical condition.
The position X in chromatogram is displayed with time: the retention time of

different components. Qualitative gas chromatograph components are based on the
retention time.
The position Y is displayed with the peak area of voltage (MV) value: the
concentrations of different components. Quantitative gas chromatograph components
are based on by the peak area. (peak height × half peak width)
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Flow Chart of the Special Gas Chromatograph for Hydrogen Production:
A special gas chromatograph for hydrogen production by natural gas process,

which has two channels of six-way valve sample injection systems and two channels
of vaporizer injection systems.
Six-way sample
injection valve
Joint
Equalizer Stable-flow
valve valve
vaporizer
Reformer
Air-resistor
4. Operating Procedures of Gas Chromatograph
4.1 Host and installation
4.1.1 Host
The chromatograph of the device has been specially reformed, with a host
installed with carrier gas channels with three packed columns, a thermal conductivity
detector with dual gas channels, a flame ionization detector and a methanation
reformer.
4.1.2 Installation of chromatograph
1) Requirements for the chromatograph analysis room
a. Keep the analysis room away from strong magnetic fields or flammable and
corrosive gases.
b. Keep the indoor ambient temperature around 5-35°C, the humidity less than or
equal to 85% (relative humidity), and keep the indoor air circulating. Install air
conditioners in plants with conditions
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c. Prepare a working platform that can support the whole set of instruments, has
moderate width and height, and is easy to operate. Chose cement platforms for
common plants, (with height of 0.6-0.8 meter). Stay the platform away from the wall
with a width of 0.5-1.0 meter for easy wiring and maintenance.
d. Use power wiring with a capacity of around 10KVA for the instrument, and ensure
that the power supply used by the instrument is different from that of high-power
electrical equipment or electrical equipment with frequent and large changes. Ground
the power supply well, nail an iron bar (wire) about 0.5-1.0 meter long into wet
grounds (or perfuse with salt solution), and then connect the power grounding point to
the iron bar. Ensure that the grounding resistance is less than 1ohm. (Note: Ground
both the power supply and outer shell for better effects)
2) Gas source preparation and purification
a. Gas source preparation
Prepare high-pressure steel cylinders for gas in advance (generally available in

large and medium-sized cities), and the color of each cylinder representing one kind
of gas and cannot be interchanged. Use nitrogen, hydrogen and air in general, and
better prepare 2 steel cylinders for each gas for backup. Use hydrogen generators and
air compressors in some plants are also acceptable, but the air compressors must be
oil-free. Change the gas cylinder when the pressure of steel cylinder drops to 1-2MPa.
Use the above gas with a purity of 99.999% for common manufacturers.
b. Gas source purification
Purify the gas before entering the instrument strictly to remove moisture, ashes
and organic gas components that may be contained in various gases. If using the steel
cylinder gas, some chromatographs are equipped with purifiers, which are filled with
5A molecular sieve, activated carbon and silica gel can basically meet the
requirements. If using common hydrogen generators, enhance the purification of
moisture, increase the usage of drying pipes (above 450cm3 volume and filling with
5A molecular sieve are acceptable), and set a reservoir barrel with large volume
behind the generator to reduce or overcome the influence on the instrument baseline
when the gas source pressure fluctuates. If using the compressor as air sources,
enhance the filtration of air at the compressor gas inlet, increase the volume of the
purification pipe and fill half 5A molecular sieve and half activated carbon into the
drying pipe. Domestic oil-free gas compressors are acceptable.
3) Complete inspection and placement of the chromatograph
Count the accessories according to the attachment in the data bag one by one
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after unpacking the instrument, and keep the spare parts of the vulnerable parts
properly. Place them on the working platform according to the instruction manual,
and connect all parts of the instrument against the wiring diagrams, plugs and sockets,
and finally connect it to the chromatographic workstation. Avoid connecting the joints
incorrectly.
4) Connect the external gas channel
a. Install the reduction valve
Use 2 oxygen reduction valves and 1 hydrogen reduction valve. Install the 2
oxygen reduction valves and 1 hydrogen reduction valve on the nitrogen, air and
hydrogen steel cylinders respectively (note that the threads of hydrogen reduction
valve are reversed and the O-shaped plastic gasket is attached at the interface for
sealing), close the reduction valve adjustment handle (i.e. loosen) and open the high
pressure valve of the steel cylinder after tightening the screw cap, and the
high-pressure gauge of the reduction valve shall have an indication now. After closing
the high-pressure valve, the indicated pressure shall not drop, otherwise there is a
leaking which shall be eliminated in time (seal it with gasket or Teflon tape). Note
that the high-pressure valve will also have leaking sometimes. Rotate the adjusting
handle to exhaust the residual gas then.
b. Connect the external gas channel
Introduce the gas in the steel cylinder into the chromatograph and use the
pressure resistant plastic pipe (φ3 × 0.5mm). Use the stainless steel liner (φ2×20mm)
and some plastic materials for sealing in the joints. Arrange the length of the plastic
pipe from the steel cylinder to the instrument based on the needs, and ensure that it
shall not be too long. Connect the gas source and the instrument (the gas inlet) with
plastic pipes.
c. Leaking detection of external gas channel
Turn off the valve knob of the carrier gas, hydrogen and air on the gas channel
of the host panel, turn on the high pressure valve of each steel cylinder, and adjust the
output pressure of the low-pressure gauge on the reduction valve to set the carrier gas
and air pressure to be 0.35-0.6MPa (about 3.5-6.0kg/cm3) and the hydrogen pressure
to be 0.2-0.35MPa. Then turn off the high-pressure valve, and ensure that the
indicated value of the low-pressure gauge on the reduction valve shall not fall; if it
falls, it means that there has leaking in the connecting gas channel which shall be
found out and excluded.
5) Gas tightness detection for the gas channel of chromatograph
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Gas tightness detection is a very important work. If there has leaking in the air
channel, it will lead to the unstable operation of the instrument or decrease its
sensitivity and has the risk of explosion. Therefore, it is necessary to carry out the
detection before operation (gas tightness inspection is generally to check the carrier
gas channel, and if the hydrogen and air channel have not been dismantled, they may
not be checked).
The method is to open the box cover of chromatographic column, remove the
column from the detector, block the column port, then open the carrier gas channel to
lower the output pressure to 0.35-0.6 MPa. Open the carrier gas knob on the host
panel when the pressure gauge shall give prompts. Finally, turn off the carrier gas
knob and ensure that the indicated value of the pre-column shall not fall within half an
hour; if it falls, it means that there has leaking in the connecting gas channel which
shall be found out and excluded. Remove the relevant side plates if the leaking occurs
in the gas channel of the host, detect the leaking one by one with soapy water
(preferably sodium dodecyl sulfonate solution), and dry the soapy water (hydrogen
and air can also be checked in this way) finally.
4.1.3 Instrument commissioning
Connect the gas channel and instruments as above, and carry out the following
detection and commissioning work after the installation.
1) Connect the carrier gas channel first before starting the detectors of each
component of the chromatograph circuit, and adjust the gas knob (i.e.: carrier gas
steady valve) on the host panel to set the carrier gas flow to be 20-30ml/min.
a. Start the host
Turn on the main power of the host panel to start the motor in the
chromatographic column box, and check whether there is any abnormal sound; if
there is, cut off the power immediately, and further check and eliminate the
abnormality. Some chromatographs perform self-diagnosis when started and display
the operation of the instrument: normal or abnormal, and abnormal display including
which part has problems, wiring errors and so on.
b. Detect the temperature control of each instrument
Detect the temperature of columns, (including temperature programming),

sample injectors and detectors according to the instruction to check whether they can
be kept constant at high, medium and low temperatures, and especially ensure that the
control accuracy of the column temperature reaches 0.1 degree.
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4.2 Thermal conductivity detector calibration
1) The detection principle of thermal conductivity detector (TCD):
The thermal conductivity detector is based on different gaseous substances that

have different thermal conductivity, and when the measured component is mixed with
the carrier gas, the thermal conductivity of the mixture is not the same as that of pure
carrier gases. When the composition and concentration of the gas passing through the
thermal conductivity cell change, the temperature of the thermal element installed on
the cell will also change, and the change will cause the thermal element to have a
corresponding change in the resistance value. The change of the value is reflected into
certain electrical signals by the wheatstone bridge, and the content of the sample
component can be obtained from the magnitude of the obtained signals. The key
thermal conductivity element of the thermal conductivity cell is made of tungsten wire.
The diameter of the tungsten wire is generally only 15μ-30μ, and the material is
Input
Balanced bridge circuit the output
voltage is zero
Output
Imbalanced bridge circuit the output
voltage is above zero
Cold resistance value of the

bridge circuit
relatively easy to be oxidized. After oxidation or pollution, the resistance value

changes or breaks, which leads to the destruction of the symmetry of the measuring
bridge of the thermal conductivity detector and the failure of the instrument to work
normally. Therefore, when using the thermal conductivity detector, if the output
baseline of it is a smooth straight line, and the zero point is adjustable, it means that
the detector works normally, or conversely, the detector is faulty.
2) Precautions for the use of TCD:
a. Note the following points regardless of the model of chromatographs:
First feed the carrier gas, then power on the electricity; turn off the power first, and
then the carrier gas when shutting down the chromatograph. Otherwise, the thermal
conductivity detector will be combusted. After the instrument is shut down, since the
outside air tends to return to the thermal conductivity cell and the separation system, it
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is necessary to feed the carrier gas for more than 10 minutes before turning on the
power. The longer the shutdown time is, the longer the time to feed the carrier gas
when restarting, or otherwise the residual airborne oxygen in the system will oxidize
or combust the tungsten wire part.
b. When installing the instrument and replacing the chromatographic column, it must
be carried out on the premise of turning off the power supply and gas source of the
chromatograph, and its air tightness must be strictly checked afterwards.
Special tips: This chromatographic analyzer uses hydrogen as the carrier gas, so
it is necessary to prevent explosion caused by hydrogen leaking!
c. When the chromatographic column is aged at a high temperature, the power supply
and temperature control of the thermal conductivity cell must be turned off, and the
joint between the column outlet and the inlet of the cell shall be disconnected, so that
the carrier gas (N2) aged at a high temperature flows into the oven to avoid
contamination of the thermal conductivity cell elements due to column aging.
d. In the process of catalyzing and reforming the gas samples of hydrogen production
control and analysis, the six-way sample injection valve shall only be rotated in the
"Analysis" or "Sampling" state. If it is turned to the neutral state, the carrier gas will
be disconnected to cause the combusting out of the thermal conductivity detector!
e. Setting of temperatures, bridge currents and carrier gas types:
Set the temperature of the thermal conductivity detector higher than that of the
column temperature to avoid contamination of the detector caused by condensation of
the sample into the thermal conductivity cell. Reduce the thermal bridge current if the
setting temperature of the detector is higher to avoid combusting the thermal sensor.
Set the current of the thermal conductivity detector based on the concentration of the
sample, the type of carrier gas, and the temperature. This will ensure the analytical
sensitivity of the thermal conductivity detector and avoid combusting the thermal
conductivity detector.
Bridge current of the thermal conductivity detector: The larger the bridge current of
thermal conductivity detector, the higher the sensitivity and the greater the noise.
Ensure that appropriate working conditions shall be selected when using the thermal
conductivity detector.
Allow the setting of the carrier gas, temperature and bridge current of the thermal
conductivity detector (TCD)
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Carrier gas 50°C 80°C 100°C 150°C 200°C
Hydrogen 250mA 200mA 150mA 100mA 80mA
Nitrogen 80mA 80mA 70mA 60mA 50mA
f. Select the flow of carrier gas for the thermal conductivity detector (TCD):
The TCD of the gas chromatography of the hydrogen production device is equipped
with straight-through thermal conductivity cells. Select the flow from 40 to 50ml/min
when the carrier gas is hydrogen Select the flow from 20 to 30ml/min when the
carrier gas is nitrogen.
3) Start-up procedures for using the thermal conductivity detector (TCD):
a. Turn on the carrier gas for 20 minutes before turning on the main power of the
instrument.
b. Set the temperature of the detection room, the column box and the vaporizer to the
setpoint after the instrument is powered on.
c. Rotate the bridge power potentiometer slowly to adjust the bridge power supply to
the required current setpoint accurately according to the needs of analyzing the
operating conditions.
d. Check the sample under the condition that the instrument is powered on and
balanced and the baseline has not drifted.
4.3 Flame ionization detector and methane reformer
1) Detection principle of the flame ionization detector (FID):
The carrier gases used in flame ionization detector, H2 + N2, pass through FID and
combust at a sufficient oxygen (air) content to form a flame. As the organic matter is
carried into the flame by the carrier gas, a corresponding amount of ion flow is
generated. And due to a potential difference caused by an electric field applied above
the flame, the ions are amplified and sent to the chromatography data processor or
chromatographic workstation to be processed and calculated for qualitative and
quantitative analysis.
2) FID properties:
As a kind of high-sensitivity detector, FID is used for the micro analysis of organic
matters, and in addition to high sensitivity (with a hydrocarbon detection limit of
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10-12g/s), it also features fast responses, wide quantitative linear ranges, relatively
simple structures, stable operation and other advantages. However, FID will have no
response when analyzing the permanent gases such as O2, CO, and CO2. Therefore,
in order to analyze the trace amount of CO and CO2 in the product gas, it shall first
convert the CO and CO2 into CH4 with high sensitivity by the methanation reformer
for CO and CO2 analysis.
3) Methanation converter:
The device is equipped with methanation converters. After the quantitative sample
injection by the six-way valve, the product gas passes through the TDX-01
chromatographic column with the CO, CH4 and CO2 completely separated and
entering the converter in sequence. CO and CO2 are heated in the nickel catalytic tube
and react with H2 to produce CH4 which has high sensitivity to FID.
The reforming reaction equation is as below:
350 ℃— 380 ℃
CO +3H 2 CH 4 +H 2 O
Ni
350 ℃— 380 ℃
CO 2 +4H 2 CH 4 +2H 2 O
Ni
4) Selection of operating conditions of the flame ionization detector: (different models

of chromatograph shall be operated according to the instructions)
a. Chose hydrogen as the carrier gas, air as the oxidant gas and nitrogen as the
complementary gas if using FID to analyze the device. Select the flow of three
gases as follows:
Air: 150-200ml/min Nitrogen: 15-30ml/min
Select the flow of hydrogen larger than that of the hydrogen used in general FID,
because hydrogen is not only a carrier gas, but can also react with carbon monoxide
and carbon dioxide in the reformer. Range: 20-50ml/min.
b. Selecting principle of the FID temperature:
Select the column temperature depending on the condition of sample component

separation, and set the temperature of FID larger than the column temperature (120°C
is appropriate). Set the temperature of FID chromatograph of any models larger than
the vaporization temperature of water, because the hydrogen and oxygen used by FID
can form water after combustion. Set the reform temperature of the reformer to
360°C.
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Precautions: In chromatography analysis, the selection of the flow of the three gases
for FID shall be based on the FID structure. The flow of air, hydrogen and
complementary gases vary for different models of instruments. When different
models of chromatographs are used in the analysis of product gas, the
chromatographic column, column temperature and the temperature of the detector,
vaporizer and reforming gas can be the same, and the gas flow shall refer to the
instrument manual.
c. FID commissioning procedures:
Select hydrogen as the carrier gas, connect TDX-01 column and select nitrogen as the
complementary gas and air as the oxidant gas as required by the analysis.
Set temperatures:
Detection room: 140°C;
Column temperature: About 100°C;
Reformer temperature: 360°C.
Calibrate the instrument:
Turn on the carrier gas and hydrogen, adjust the flow to about 50ml/min, and adjust
the flow of air and nitrogen valves according to 4.1 or the selected analysis conditions
after the temperature reaches the setpoint. Unscrew the nut with a small hole on the
top of the detector during ignition, and aim the ignition gun in the spare part at the ion
chamber to ignite. Ensure that there is a slight "Pu" sound during ignition, at which
point the "current baseline" value of the chromatographic workstation changes
significantly, and water vapor can be seen by placing a glass sheet or chromium
plated tube on the top of ions. Adjust the hydrogen to the setting flow slowly after
ignition. Adjust the "Base Compensation" potentiometer to remain the baseline value
of the workstation at 150μV-800μV.
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5. Chromatographic Workstation
5.1 Compositions and functions of chromatographic workstation
As a special program for qualitative and quantitative analysis of chromatograph,

chromatographic workstation shall be equipped with a general-purpose computer that
meets the performance requirements of special programs and a hardware interface
card for the programs. The computer is connected with the chromatograph by the
hardware interface to ensure that the analog signal of the chromatograph can be
converted into a digital one. After turning on the computer and entering the special
program, click and set all kinds of analysis and calculation parameters with the mouse.
The chromatographic workstation performs the signal collection, peak shape
processing and peak area (or peak height) measurement of the station according to the
set analysis parameters. Then, the quantitative calculation is done by the calculation
parameters.
5.2 Operating procedures
1) Ensure that the analysts are familiar with the workstation instruction manual and
have general computer skills.
2) Select the corresponding channel of the workstation, and enter the experimental
information such as "Experimental Unit", "Experimenter Name" and so on.
3) Set sampling control parameters: "Sampling Stop Time", "File Saving Method",
"Saving Path", etc.
4) Pre-run of chromatographic analysis:
Prepare standard samples with known component content, open the corresponding
collection channel, and check the chromatographic baseline. Adjust the polarity of the
detector after the baseline is stable, and adjust the baseline level of the chromatograph
to be about 100μV to 500μV. Then inject the standard samples to select the optimal
operating conditions for chromatographic analysis.
5) Calculate the quantitative calibration factor with the known concentration of

standard samples:
a. Select the chromatographic analysis conditions, and inject the standard sample
to collect the standard sample chromatogram and set the calculation parameters
according to the same operation method as set forth in section 2.4, chromatographic
analysis pre-run.
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b. Set the "Analysis Method" according to the analysis requirements, and set the
integral parameters according to the chromatogram situation: "Peak Width", "Slope",
"Drift", "Lock Time", and edit the "Chromatogram Display" parameters and "Report
Editing" parameters.
c. Edit the component table (ID table) for the calibration factor
Select the standard sample chromatogram to set "Component Name", "Time Width
(Time Window)", "Retention Time", "Component Concentration", etc., to obtain the
standard sample calibration factor of the corresponding method.
d. Calculate the sample component concentration with known calibration factors:
Ensure that the chromatographic operating conditions for measuring sample

component concentration are the same as those for calculating calibration factors.
Turn on the remote-control switch of the workstation or press "Collect Data" while
injecting samples to ensure that the chromatographic workstation can automatically
complete sample collection and calculate sample concentration.
5.3 Retention of standard sample files of chromatographic
workstation
The biggest advantage of the chromatographic workstation is that it can save the
chromatogram, analysis and calculation data and analysis results, and can take them
out at any time to compare with or recalculate the current analyzed chromatogram and
results. The properly processed peak shapes of different samples can also be classified
with the calculation results and standard sample chromatograms, and the
corresponding file names can be saved for future use.
5.4 The routine analysis involved in the analysis of natural gas to hydrogen
production
a. Analytical column of the analysis of CO, CH4 and CO2 in the reforming gas
(external standard method): TDX-01
b. Analytical column of the microanalysis of CO, CH4 and CO2 in the product gas
(external standard method): TDX-01
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6. Analysis of Natural Gas Reforming
6.1 Overview
The device uses natural gas and water as raw materials, and carries out steam
reforming under the action of catalyst, thereby producing hydrogen and carbon
dioxide.
This chapter covers the analysis of CO, CH4, CO2 in the catalyst reduction gas,
the control of the reforming gas, and the analysis of the product hydrogen CO, CH4,
and CO2.
6.2 Analysis of nitrogen and hydrogen gas mixtures in catalyst
reduction - gas chromatography
According to the process requirements, the reducing gas used in the catalyst
reduction is a mixture of natural gas, steam and hydrogen. And the hydrogen content
is gradually increased from 0.5% to 10%; at the outlet of the reformer tube, the
content is CH4 < 10%, H2S < 0.5PPM; at the outlet of the MT furnace, the content is
CO < 3%, H2S < 1PPM and remains stable, and then the reduction is over.
1) Instruments and chromatographic support
Instrument: TCD for gas chromatograph
Support TDX-01 Ф3×1M
Hydrogen reduction valve: 1
Nitrogen reduction valve: 2
Carrier gas: nitrogen, purity ≥99.999%.
2) Chromatographic column processing
13X: must be filled evenly and activated at 150°C for 6-8 hours.
3) Operating conditions of chromatography
Instrument: TCD for gas chromatograph
Chromatographic column: Column 1: Ф3×1000mm 80-100 mesh
Column temperature: 40°C
Measured temperature: 60°C
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Vaporization: 60°C
Flow rate: 20-30ml/min, carrier gas: H2, purity≥ 99.99%
Bridge current: 50 - 70mA
4) Standard gas:
Composed of purchased standard gases
Reforming gas: CO: 12%, CH4: 5%, CO2: 15%, bottom gas: H2,
5) Test for standard samples and general samples
Inject the standard samples in a fixed volume as set forth in 2.2.4 via the
six-way valve as required by the workstation instruction manual into the second
gas channel of the chromatographic column. Select operating conditions to
obtain satisfactory chromatograms. Take one or more chromatograms with better
reproduction (including analysis parameters and calculation parameters), and
obtain the appearance of the chromatogram to obtain the quantitative calibration
factor for the catalytic reduction CH4 residuals. Name the file Standard Samples
of CH4 Residuals and save it for future use. Refer to the Standard Samples of
CH4 Residuals when analyzing the catalyst reducing gas, and inject the sample
gas at the inlet and outlet of the converter under the same operating conditions as
the standard sample. Obtain the sample gas chromatogram and finish the
calculation of CH4 residual contents.
In the process of catalyst reduction, as the water-carbon ratio decreases,

standard samples with different CH4 residual contents can be added for
calibration and determination.
6.3 Control and analysis in natural gas reforming - gas
chromatography
The composition of the reforming natural gas: CO2, CO and CH4, and the above
components are measured with the TCD with dual gas channels and dual
chromatographic columns.
1) Instrument and support
Instrument: gas chromatograph, TCD
Chromatographic support: TDX-01 60-80 meshes
2) Chromatographic column processing
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Respectively fill chromatographic columns with TDX-01.
3) Operating conditions of chromatography
Instrument: gas chromatograph, TCD
Chromatographic column:
Column 2: Ф3×1000mm, filled with TDX-01
Column temperature: 40-80°C
Vaporizer: 140°C-150°C
Detector: 100°C-150°C
Carrier gas hydrogen flow rate: about 40mL/min (refer to the TCD carrier gas
flow rate on instrument manual).
Bridge current: Around 100mA
4) Standard gas:
Composed of purchased standard gases
Reforming gas: CO: 12%; CH4: 5%; CO2: 15%; bottom gas: H2
5) Determination of calibration factors:
By virtue of the standard gas above, inject the samples in a fixed volume via the
six-way valve into the second gas channel of the chromatographic column.
Select operating conditions to obtain satisfactory chromatograms. Take one or
more chromatograms with better reappearance (including analysis parameters
and calculation parameters), and refer to the workstation instruction manual to
obtain the quantitative calibration factor by the external standard method. Name
the file Standard Samples of Reforming Gas and save it for future use. (TDX-01
column analyzes the CO2, CO and CH4 in the reforming gas)
6) Sample determination
Take the reforming gas after water cooling, open the Standard Samples of
Reforming Gas in the chromatographic workstation; feed the reforming gas
under the exact same operating conditions as the standard sample analysis to
obtain the reforming gas chromatogram and calculate its content of CO, CH4
and CO2.
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6.4 Natural gas to hydrogen production: analysis of product gas CO,
CO2, CH4 - gas chromatography
1) Instruments and chromatographic columns
Instruments: gas chromatograph, methanation reformer, flame ionization detector,

1 hydrogen reduction valve and 3 oxygen reduction valves.
Chromatographic column: TDX-01, 1m column
Carrier gas: H2 ≥ 99.999% (the purity of the carrier gas must be one order of
magnitude greater than that of the analyzed component, or it does not contain the
measured component)
N2 ≥ 99.999%
1 bottle of compressed air
Column temperature: 100°C
Reformer temperature: 350°C
FID temperature: 140°C
Please refer to the instrument manual for operating conditions of the

chromatograph.
2) Standard gases: (allocate standard gases of different component contents

according to the control of a certain impurity in the product gas)
CO: 8ppm
CO2: 15ppm
CH4: 5ppm
Bottom gas: Hydrogen
3) Determination of calibration factors:
Inject the standard sample via the sample injection valve by volume sample
injection Find out the conditions for sound peak separation, and fix the
conditions, analysis parameters and calculation parameters, etc. for sound peak
separation after multiple sample injections. Then take the standard sample
chromatogram with repeated results, and use the external standard method to
calculate the CO, CO2 and CH4 calibration factors, and name the file Standard
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Samples of Product Gas to save it for future use.
4) Sample determination
Use a special gas bag to remove the air in it, then take the product gas, inject
and analyze it under the same conditions as the standard sample according to the
file Standard Samples of Product Gas to obtain the CO, CO2 and CH4
chromatograms of impurities in the product and calculate their concentration.
Adopt TC-TIC for the product hydrogen purity detection: the calculation
method of hydrogen purity as set forth in section 4.1 in the GB/T7445-1995:
H2 content%=100%-(CO%+CH4%+CO2%)
The laboratory analysis of the chromatograph only needs to control the content
of CO, CO2 and CH4, and the purity of the product hydrogen can achieve
0.9999.
6.5 Gas detection tube determination for H2S analysis
Sampler model: CK-50D Cylindrical positive pressure sampler
H2S sampling tube range: 0.0001-0.012%
Please refer to the instruction manual for the determination method.
6.6 Precautions and safety tips
1) The product gas analysis is easily interfered by hydrocarbons in the air, so the
product gas sampling bag shall be dedicated. Or the product gas can be
introduced into a sample injection system of laboratory chromatograph gas.
2) During the analysis of natural gas reforming for hydrogen production, a large
amount of carbon monoxide and carbon dioxide in the reforming gas shall not
enter the methanation converter, or otherwise the nickel catalyst can be reduced
or invalidated, therefore affecting the reforming efficiency of carbon monoxide
and carbon dioxide.
3) The hydrogen purity of the FID carrier gas is one order of magnitude greater
than that of the analyzed gas, or the carrier gas does not contain the tested
components. Hydrogen produced and tested by itself cannot be used as the
carrier gas.
4) The instrument (chromatograph) must be shut down when replacing the

carrier gas, and then started up after the carrier gas has been replaced.
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5) If there is any disagreement with the analysis results, calibrate the instrument
with standard gases.
7. Utility Conditions Before Start-up
7.1 Workbench
Prepare the chromatograph workbench according to the requirements of gas

chromatograph working conditions, and lay 3-5mm thick rubber or plastic pads
on it. Equip it with a 220V high-quality multi-hole power supply board with a
reliable ground wire.
7.2 Three gases and gas cylinder reduction valves for gas
chromatograph
1) Hydrogen cylinder with gas: H2 purity ≥ 99.9999%, 1-2 cylinders;
2) Nitrogen cylinder with gas: N2 purity 99.999%, 1-2 cylinders;
3) Air cylinder with gas: 40L, 1-2 cylinders;
4) 3-5 oxygen reduction valves (full scale of the output meter of the pressure
reducing gauge: 1.6MPa), 2 hydrogen reduction valves (full scale of the output
meter of the pressure reducing gauge: 1.6MPa); 1 Nitrogen reduction valve (full
scale of the output meter of the pressure reducing gauge: 1.6MPa).
7.3 Standard gases (as required by the contract)
1) Standard product gas ± 1.5 ppm
Bottom gas: H2, including CO: 8ppm, CH4: 5ppm, CO2: about 15ppm (8L
aluminum alloy cylinders).
2) Standard reforming gas ± 1%
Bottom gas: H2, including CO: 12%, CH4: 5%, CO2: 15±1%. (8L aluminum
alloy cylinders).
3) Standard gas cylinders equipped with 2 reduction sampling valves.
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7.4 Taking tools for gases to be analyzed
5-10 sampling gas bags and water stop clips; 3-5 meters of latex tubes.
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Discp
Date
Sign
Project Name Ferro Steel -EOP 300Nm3/h hydrogen project Phase D.D.
Subproject Hydrogen Generator Discipline INS.
Project No. CDH21-007 Document No. CDH21-007-5101 Sheet 1 / 13
Automatic Control System Manual

Project
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Automatic Control Doc No. CDH21-007-5101

System Manual
Version
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Content
1 Overview ...................................................................................................................................... 3
2 Automatic Control of the Device ................................................................................................. 3
3 Instrument Selection .................................................................................................................... 3
4 HMI Operating Instructions ......................................................................................................... 5
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1 Overview
The standard codes of the project design include, but are not limited to, the following codes.
1.1 Code for the Design of Electrical Installations in Explosive Atmospheres (GB 50058-2014);
1.2 Code of Construction and Quality Acceptance of Automation Instrumentation Engineering
(GB50093-2013);
1.3 Instrument Hook-ups (HG/T 21581-2012);
1.4 Design Code for Instrument Selection HG/T 20507-2014;
1.5 Standard for Design of Combustible Gas Toxic Gas Detection and Alarm for Petrochemical Industry
GB 50493-2019;
1.6 Design Code for Instrument Power Supply HG/T 20509-2014;
1.7 Design Code for Instrument Air Engineering HG/T 20510-2014;
1.8 Design Code for Signal Alarm and Interlock System Engineering HG/T 20511-2014;
1.9 Design Code for Instrument Piping and Wiring HG/T 20512-2014;
1.10 Design Code of Instrument Grounding HG/T 20513-2014;
2 Automatic Control of the Device
The hydrogen generator is under the monitoring of field control station, composed of PLC and HMI.
All parameters such as alarm interlock values and process adjustment setpoint can be modified and set on
the HMI. A remote operation station is provided in the user's main control room, the station is exactly the
same as the field HMI in terms of function, and both the local HMI and remote PC operation station can
independently monitor the whole hydrogen generator.
3 Instrument Selection
3.1 Temperature measuring instrument:
Bimetal thermometer for in-situ temperature measurement.
Smart integrated temperature transmitter with explosion-proof level Exd ⅡC T4 Gb is selected for
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remote temperature measurement.
3.2 Pressure measuring instrument:
Stainless steel spring pressure gauges are used for in-situ pressure measurement and shock-resistant
stainless steel pressure gauges for power equipment outlet.
Smart pressure transmitter with HART protocol or differential pressure transmitters (for
micro-pressure measurement) with the explosion-proof level of Ex d ⅡC T4 Gb is used to measure remote
pressure signal.
3.3 Liquid level measuring instrument:
The magnetic flap liquid level meter with a magneto strictive liquid level meter transmitter issued for
level measurement, and the transmitter explosion-proof level is Ex d ⅡC T4 Gb.
3.4 Flow measuring instrument:
The integrated balanced orifice plate flowmeter with an explosion-proof transmitter of Ex d ⅡC T4 Gb
is used for flow measurement.
3.5 Control valve:
The control valve is a single-seat pneumatic control valve with a smart positioner, and the
explosion-proof level of Ex d IIC T4 Gb.
3.6 Switching valve:
The switching valve body is an angle seat valve with a two-position three-way solenoid valve and a
mechanical valve position switch, the executive body is pneumatic, the explosion-proof level of the
solenoid valve is Exm IIC T4 Gb, and the explosion-proof level of the valve position switch is Exd IIC T4
Gb.
3.7 PLC valve:
The switching valve body is an angle seat valve with a two-position three-way solenoid valve and a
mechanical valve position switch, the executive body is pneumatic, the explosion-proof level of the
solenoid valve is Exm IIC T4 Gb, and the explosion-proof level of the valve position switch is Exd IIC T4
Gb.
3.8 Online analyzer:
The flue gas residual oxygen analyzer uses a high-temperature zirconia probe analyzer. The product
gas online analyzer uses thermal conductivity type.

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4 HMI Operating Instructions
4.1 Main screen
The operation modes of the whole system are presented in this screen. By touching different buttons, it
can be switched to the corresponding screen, and the switching of each screen can also be realized by the
drop-down text box at the top of the screen.
4.2 NG Compression
This screen shows the flow chart of the natural gas compression process, and the functional symbol
blocks are explained as follows:
4.2.1 Process parameter display function blocks:
This function block displays the process parameters of the corresponding Tag No. If the
process parameters are set with alarm function, the alarm setpoint pop-up window can be popped up by
clicking the function block.
4.2.2 Function block for displaying accumulative flow process parameters:
This function block is used to display accumulative flow process parameters. The
"RST" button is used to reset the accumulative flow and can be activated with engineer's permission.
4.2.3 Control valve function blocks:
This function block display unit displays the real-time opening (set opening) of the control
valve corresponding to the Tag No. The color of the valve is green (open) if the real-time opening is greater
than 5.5%, otherwise the color is red (closed). If the valve is a control loop actuator, the regulator and alarm
setpoint pop-up window can be enabled by clicking on the control valve.

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4.2.4 PID regulator pop-up window:
The PID regulator setpoint (SP), manual output value (M) and alarm value can be programmed in this
function block, and the regulator can be switched manually and automatically via the "M" button and "A"
button. When this mode is active, the corresponding button backlight color will flash alternately. Click the
"Exit" button or "X" to exit the adjuster pop-up window.
4.2.5 Manual switching valve display and operational function block with valve position feedback:
This block can display online switching valve control signal status and valve position
feedback status, the valve symbol "cylinder" and "stem" shows the switching valve control signal status,
and the green represents "open", while the red represents "closed". And the "valve body" shows the
switching valve position feedback status, and the green represents "open", while the red represents "closed".
If the control signal status isn't conform to the valve position feedback status, a solid circle will flashes
alternately in red and yellow in the upper right corner of the function block. When switching the on/off
status, click on the switching valve render the secondary confirmation window, and the switching will be
realized by clicking the corresponding button.
4.2.6 Compressor control buttons:

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Clicking on the "Start A" button triggers a secondary confirmation window, select the corresponding
button to start the compressor C-101A, note that: The button is "inoperative" when the C-101A is in
operation. If the C-101A does not operate after clicking the "Start A" button, the process interlock may
prohibit start-up or the "Reset" button is not reset. Please solve the problems one by one before starting the
operation.
Clicking on the "Stop A" button triggers a secondary confirmation window, select the corresponding
button to stop the compressor C-101A, note that: The button is "inoperative" when the C-101A is off.
The "Start A" button and the "Stop A" button have the same function and operation as above.
Clicking on the "Set point page" button brings up the compressor interlock setpoint window, where
you can set the interlock and alarm values, and double-click on the corresponding interlock fling-cut switch
to put in or remove the interlock for the corresponding process parameters. Once any interlock is removed,
the "Set point page" button flashes alternately in red and yellow to warn that the compressor is operating
without protection.
Click the "Reset" button to bring up the secondary confirmation window and select the appropriate
button to reset the compressor to allow it to start normally, note that: After interlock shutdown or normal
shutdown, the compressor needs to be reset before the next startup.
4.2.7 Compressor status display:
This function block can display the compressor status online, "red" means the
compressor is "off", "green" means the compressor is "on"; when the compressor motor fails (thermal relay
trips), a solid circle will flash alternatively in red and yellow in the upper right corner of the function block.
4.3 Reformation
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This screen shows the flow chart of the natural gas reforming process, and the functional symbol
blocks are explained as follows:
4.3.1 Draught fan status display and operation function block:
This function block can display the draught fan status online, "red" means the draught fan
is "off", "green" means the draught fan is "on"; when the draught fan motor fails (thermal relay trips), a
solid circle will flashes alternatively in red and yellow in the upper left corner of the function block. Click
the draught fan to pop up the control panel for starting, stopping and resetting, which can be operated
through the corresponding buttons in the pop-up window.
4.3.2 : Burner ignition control panel
This pop-up can appear by clicking the "Ignite control panel" button, and the burner ignition function
can be realized here.
By clicking the "Auto" button or "Manual" button, the ignition mode can be switched to "automatic
mode" or "manual mode". And in the "HV102_SP" input field, you can preset the openness of the air
supply control valve during ignition in the automatic mode. Note: In the auto-ignition mode, start with
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X-101B, after successful ignition, turn to the other two burners.
In the automatic mode, click the "AutoStart" to activate the automatic ignition program. In addition,
the button cannot be operated in the manual mode or when the ignition conditions are not met; in the
automatic ignition process, click the "End" to terminate the automatic ignition program; click the "Reset"
to reset the ignition program for re-ignition in the event of an ignition failure.
In manual mode, click the "Ignite" button to start the ignition transformer, the program will
automatically stop igniting the transformer 8 seconds after the transformer starts. Click the "control valve"
to open the fuel intake valve. In addition, the "Ignite" button and "control valve" cannot be operated in
automatic mode.
4.3.3 Stop the burner
The burner can be stopped at any time by clicking the "Stop burner" button and selecting the
corresponding button in the secondary confirmation pop-up window.
4.4 Shift Reaction & Water System
This screen displays the flow chart of Shift Reaction and water system, and the functional symbol
blocks are described as follows:
4.4.1 Two-position control panel pop-up window:
The pop-up window can appear by clicking on the "LV101" switching valve, in which the control
value and alarm value can be set and the manual automatic switching of the control loop can be realized.
"HH": it means the setpoint of high-high alarm; "LL": it means the setpoint of low-low alarm; "H": it
means the setpoint of high valve action; "L": it means the setpoint of low valve action;
By clicking the "A" button or "M" button, the control loop can be switched to "automatic mode" or
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"manual mode". In manual mode, the valve can be manually switched by double-clicking the "switch
button". The switch button cannot be operated in automatic mode.
4.4.2 PID controller with the function of starting or stoppings the pump;
The pop-up appears by clicking the "P101A" pump or "P101B" pump, in which the pump of the
corresponding Tag No. can be started and stopped, and the PID regulator setpoint (SP), manual output value
(M) and alarm value can be set. And the regulator can be manually and automatically switched by the
button "M" and "A". When this mode is activated, the background color of the corresponding button will
flash alternately. Click the button "Exit" or "X" to exit the adjuster pop-up window.
4.5 PSA
This screen shows the flow chart of the PSA process, and the functional symbol blocks are explained
as follows:
4.5.1 Status display of adsorption column:
The displayed text box in the middle of the adsorption column shows the current state of
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the adsorption column, and the displayed text will update the status text in real time according to the
different stages of the adsorption column.
4.5.2 PSA control button:
Control the start and stop of the PSA by clicking the "Start (Stop)" button and selecting the
corresponding button in the secondary confirmation window.
Control the pause of PSA by clicking the button "Pause (Continue)" and selecting the corresponding
button in the secondary confirmation window. Pause means that the states of each adsorption column of
PSA are always in the state before the pause and will not be changed. When the PSA is in the pause state,
the background color of the button flashes alternately in yellow and green to alert the operator.
Control the output state of the PSA program by clicking the button "Check (Normal)" and selecting the
corresponding button in the secondary confirmation window. Check Mode means that the PSA program
cuts off the switch control signal of the PLC valve and does not output it to the actual valve only within the
program. This function is used for engineers to check PSA sequence, and when PSA is in "Check (Normal)",
the background color of the button flashes alternately in yellow and green to alert the operator. The
functions of this button can be activated with engineer's permission.
The PSA sequence can be turned to the next step by clicking the button "Step". To activate functions of
this button, the engineer's permission is required.
The PSA sequence can be turned to the first step in the adsorption of column A by clicking the button
"Reset". To activate functions of this button, the engineer's permission is required.
4.5.3 PSA time setting and running display:
"T" and "S" can be updated automatically when the PSA is running. "T" represents the column
currently in the adsorption state, 1-4 correspond to A-D respectively, "S" represents the current PSA
running sequence, 1-7 correspond to T1-T7 respectively.
"Set time" is the setting of PSA running time, among which T1, T3 and T6 are fixed times and cannot
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be changed, while T2, T4, T5 and T7 are adjustable times and can be modified according to the operating
conditions.
"Run time" is the running time of each step of PSA.
4.5.4 PSA control valve setting panel:
HV201 and PV202 are control valves for PSA program to automatically control openness and opening
time. The panel can be popped up by clicking on the corresponding "regulating valve".
"Factor" is the opening factor, which can be modified according to the operating conditions;
"Initial_OP" is the initial openness, which can be modified according to the operating conditions;
"Final_OP" is the final openness, which can be modified according to the operating conditions;
"Actual_OP" is the real-time openness, which is manually modified when the PSA is stopped, and
cannot be modified manually during the PSA operation.
4.5.5 PLC valve display and operation function block with valve position feedback:
This function block can display the state of the PLC valve control signal and valve position
feedback state online. The PLC valve cannot be operated manually when the PSA is running. Only when
the PSA is stopped, the secondary confirmation window of the PLC valve switch can pop up by clicking the
corresponding PLC valve. And the PLC valve can be switched on and off by clicking the corresponding
button.
4.6 Real-time Trend
This screen group displays the real-time trend curve of process parameters.
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4.7 History Trend
This screen group displays the historical trend curve of process parameters.
4.8 Real-time Alarm
This screen displays real-time alarm information.
4.9 History Alarm
This screen displays historical alarm information.

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Ferro Steel -EOP 300Nm3/h hydrogen project

Ferro Steel Power Engineering CO., LTD

Steam Methane Reforming

Shanghai Evian Industrial Technology CO., Ltd

1.1 Preface ................................................................................................................................................................ 1

1.2 Preparation scope ............................................................................................................................................. 1

1.3 Composition of feed gas and product gas ................................................................................................... 2

II. Description of the Basic Principle and Process Flow .................................................................................. 3

2.1. Basic principle ................................................................................................................................................. 3

2.2 Brief introduction to the process ................................................................................................................... 3

2.2.1 Steam reforming of hydrocarbons ................................................................................................... 3

2.2.2 Hydrogen extraction by PSA device................................................................................................. 4

2.3 Brief introduction of the key equipment ..................................................................................................... 4

III. Preparation before the Initial Start-up .......................................................................................................... 5

3.1 Equipment inspection and hydrostatic test ................................................................................................. 5

3.2 Single-unit commissioning of pumps and compressors .......................................................................... 5

3.3 Inspection and calibration of instruments ................................................................................................... 5

3.4 Pipe purging, gas tight test and nitrogen displacement............................................................................ 5

3.5 Catalyst loading and discharging .................................................................................................................. 6

3.5.1 Loading and discharging of catalyst from reformer ................................................................... 6

3.5.2 Loading and discharging of MT shift catalyst ............................................................................... 6

3.5.3 Loading and discharging of desulfurization catalyst .................................................................. 7

IV. Initial Start-up ....................................................................................................................................................... 8

4.1 Preparation before the initial start-up .......................................................................................................... 8

4.1.1 Inspection before the start-up........................................................................................................... 8

4.1.2 Start-up of running equipment ......................................................................................................... 9

4.2 Temperature rise and reduction of catalyst................................................................................................. 9

4.2.1 Temperature rise of desulfurizer .................................................................................................... 10

4.2.2 Temperature rise and reduction of reforming catalyst ........................................................... 10

4.2.3 Temperature rise and reduction of MT shift catalyst............................................................... 11

4.3 Chemical feeding........................................................................................................................................... 12

4.3.1 Feeding steps: ....................................................................................................................................... 12

V. Shutdown and Restart-up............................................................................................................................... 14

5.1 Normal system shutdown ............................................................................................................................ 14

5.2 Steam oxidation of reforming catalyst...................................................................................................... 15

5.3 Emergency shutdown of the system.......................................................................................................... 15

5.4 Short-term shutdown and restart-up .......................................................................................................... 16

5.5 Restart-up after long-term shutdown ........................................................................................................ 17

VI. Safety Production and Labor Protection ................................................................................................... 18

6.2 Main safety precautions ............................................................................................................................... 19

As it is impossible to anticipate all the problems encountered by operators during

1.2 Preparation scope

This operating principle includes natural gas (NG) compression, desulfurization,

1.3 Composition of feed gas and product gas

1) Feed gas (subject to actual components)

II. Description of the Basic Principle and

2.1. Basic principle

2.2 Brief introduction to the process

2.2.1 Steam reforming of hydrocarbons

2.2.2 Hydrogen extraction by PSA device

2.3 Brief introduction of the key equipment

III. Preparation before the Initial Start-up

3.1 Equipment inspection and hydrostatic test

3.2 Single-unit commissioning of pumps and compressors

3.3 Inspection and calibration of instruments

3.4 Pipe purging, gas tight test and nitrogen displacement

3.5 Catalyst loading and discharging

3.5.1 Loading and discharging of catalyst from reformer

3.5.2 Loading and discharging of MT shift catalyst

3.5.3 Loading and discharging of desulfurization catalyst

IV. Initial Start-up

4.1 Preparation before the initial start-up

4.1.1 Inspection before the start-up

3) Inform the analysis room to prepare for production control analysis;