Section 5 Index: Proj. 2098 Pag. 5-1

Technip Italy S.p.A.
Proj. 2098
Pag. 5-1
SECTION 5
INDEX
5. START UP PROCEDURES
5.1. General Information
5.2. Start-up Sequence Survey
5.3. Detailed Start-up Description of Syngas Production
5.3.1. Preparing Plant Start-up
5.3.2. Filling the Steam Drum and Preparing for Steam Production
5.3.3. Heating up the Reforming Section
5.3.4. Heating Up the Desulphurization Section with Natural Gas
5.3.5. Introduction of Steam to Primary Reformer
5.3.6. Introduction of Natural Gas Feed
5.3.7. Cracking of Liquid Ammonia
5.3.8. Steam Generation
5.3.9. Preparing the CO2 Removal Section for Operation
5.3.10. Taking the CO2 Removal Section into Operation
5.3.11. Pressurizing the Hydrogen Recycle System
5.3.12. Increasing Load to 40%
5.3.13. Ignition of the Secondary Reformer
5.3.14. Taking LT CO Converter into Operation
5.3.15. Taking Methanator into Operation
5.3.16. Taking the Process Condensate Stripper into Operation
5.3.17 start of Hydrogen recovery unit
5.4. Start of Ammonia Refrigeration System
5.5. Start of Ammonia Synthesis Loop
5.5.1. General Remarks
5.5.2. Starting the Synthesis Gas Compressor, 10-K-4031
5.5.3. Heating Up the Ammonia Synthesis Loop
5.6. Start of Ammonia Recovery Unit
5.7. Special Procedures During Initial Start-up
5.7.1. Reduction of High Temperature CO Converter Catalyst
5.7.2. Reduction of Low Temperature CO Converter Catalyst
5.7.3. Reduction of Ammonia Synthesis Catalyst
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5.8. Start-Up After Shutdown

5.8.1. Introduction
5.8.2. Desulphurization Section
5.8.3. Reforming Section
5.8.4. CO Conversion Section
5.8.5. CO2 Removal Section
5.8.6. Methanation Section
5.8.7. Ammonia Synthesis Section
Appendix 1
Appendix 2
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5. START UP PROCEDURES
5.1. General Information
The purpose of this section is to describe the steps to be taken during start-up.
This chapter consists of three main sections:
- an outline of the start-up sequence
- a detailed description of a normal start-up
- special procedures required during initial start-up
Proper functioning of the safety interlock trip system should be confirmed before
initiating start-up activities.
During start-up, regularly check the surface temperatures of brick-lined

equipment and pipes, and the thermal expansion of critical equipment and pipes.
All recommendations given by equipment suppliers (particularly of valves,

refractory, burners, boilers and rotating equipment) should be incorporated into
the start-up procedures.
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5.2. Start-up Sequence Survey
This section describes the sequence of the main steps involved in a normal start-
up of the ammonia plant. It is assumed that the plant has been shut down in
accordance with the procedures given in Section 7 and that the catalyst are
in reduced state.
Special procedures relevant for the initial start-up only or for start-up with new,
unreduced catalyst are described in para. 5.7
The start-up of the plant is to some extent depending on the availability of

hydrogen.
Hydrogen is required for the hydrogenation of the natural gas feed to remove the
organic sulphur compounds before the gas is introduced to the reformer. In many
cases hydrogen can be supplied from the ammonia synthesis loop being under
pressure. However, if the synthesis loop is depressurized it is necessary to
generate the required hydrogen by cracking ammonia in the primary reformer.
The hydrogen formed is then recycled back to the natural gas line upstream the
hydrogenator. Reference is made to paragraph 5.3.7 describing the procedure for
cracking of ammonia.
The following sequence is based on hydrogen gas being available from the
synthesis loop.
1 Check that the plant is ready for start-up and utilities ready to supply
required utilities (cf. para. 5.3.1).
2. Bypass, isolate and pressurise the LT CO converter with nitrogen to 5 bar g

(cf. para. 5.3.14).
3. Isolate and pressurise the methanation section with nitrogen to 5 bar g (cf.
para. 5.3.15).
4. Isolate and pressurise the reforming section with nitrogen to 6-7 bar g (cf.
para. 5.3.3.1).
5. Bring the boiler feed water system online and prepare for steam production
(cf. para. 5.3.2).
6. Start the flue gas blower, ignite the primary reformer burners and heat up
the reforming section in stagnant atmosphere until the flue gas temperature
at the outlet of the furnace chambers reaches 300-400C (cf. para.5.3.3.4)
7. While heating the primary reformer in stagnant atmosphere, begin heating

up the desulphurization section in once-through flow of natural gas through
a wide open vent 10-PV-2027 B (cf. para. 5.3.4). The pressure should
preferably be kept below the pressure in the reforming section.
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8. Introduce 25-30 t/h process steam to the primary reformer and continue
heating up. (cf. para.s 5.3.5). Keep minimum pressure in reforming section.
9. When the flue gas temperature upstream of the steam superheat coil 10-E-
2003-1 exceeds the dew point of the steam by about 50C, start venting the
generated steam through 10-PV-2029 to establish protection of the coil.
Gradually increase the pressure in the steam generation system (cf. para.
5.3.8).
10. When steam has been admitted to the reformer, pressurize the CO 2
absorber with reformed gas (initial pressurization of CO 2 removal section
has been done with N2 or natural gas just to put MDEA in circulation at
reduced rate) and stabilize circulation of MDEA solution. Start heating up
the section by venting the steam through the vent 10-HV-3022 upstream of
the motorized valve 10-HV-3029 at the inlet to the CO 2 absorber (cf. para.
5.3.9).
11. When steam has been admitted to the reformer, start the NG compressor
10-K-4011 and pressurize the desulphurization section. Continue heating
up the hydrogenator and the sulphur absorbers towards normal operating
temperature by venting at 10-PV-2027 B. Downstream 10-E-2004-2
introduce hydrogen through 10-FV-2035 before the temperature reaches
300 °C (cf. para. 5.3.4).
12. Establish a small flow of steam through 10-FV-2017 to the process air
preheat coil 10-E-2002-1 to protect the coil and to enable reset of the
natural gas feed valves ( IS-1 ).
13. Introduce natural gas to the primary reformer, when the temperature exit
the reformer is 550-650 °C, and when confirmed that the total sulphur
content in the exit gas from 10-R-2002 B is less than 0.05 vol. ppm (cf.
para. 5.3.5).
14. Stabilize the conditions of the reforming section and continue heating
towards temperatures of normal operation. Gradually increase the pressure
to 15-20 barg.
15. Gradually increase the load in the reforming section and stabilize at about
40% of normal natural gas feed flow and a S/C ratio of 5 (cf. para. 5.3.12)
NOTE: during the start-up the methane slippage is not critical for the
reforming section.
16. Start the process air compressor 10-K-4021, following supplier's

instructions (cf. para. 5.3.13).
17. Ignite the secondary reformer 10-R-2003 (cf. para. 5.3.13).

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18. Bring the CO2 removal section online by venting the CO2 through 10-PV-
3015 and venting the process gas through 10-PV-3036 downstream from
the CO2 absorber 10-T-3002 (cf. para. 5.3.10).
19. Heating up of the LT CO converter 10-R-2005 in circulating nitrogen, by

means of start-up blower 10-K-2003, may be started in advance. Introduce
process gas when the catalyst temperatures are minimum 20°C above the
dew point of the process gas (cf. para. 5.3.14)
20. Heat up and take the methanator 10-R-3001 into operation (cf. para.
5.3.15). Vent the process gas downstream of the final gas separator 10-V-
3011 through 10-PV-3037.
21. The process condensate stripper 10-T-7001 should be taken into operation
when the syngas production section has been stabilized and HP steam for
heating up is available (cf. para. 5.3.16).
22. Stabilize the units upstream of the methanation section at 70% load and at
normal operating conditions. Steam drum pressure should be at normal
operating pressure of 118 bar g.
23. Start the ammonia compressor 10-K-4041 and bring the chillers on-line.
Establish normal level in the ammonia accumulator and all chillers (cf. para.
5.4).
24. Start the synthesis gas compressor 10-K-4031 following the manufacturer's
instructions. Heat up the ammonia synthesis catalyst and take the loop into
operation (cf. para. 5.5)
25. When the synthesis loop starts to produce ammonia and the ammonia
separator level increases, route ammonia to the let-down vessel. Start the
ammonia booster compressor 10-K-4051. Route ammonia to the flash
vessel, start the ammonia product pumps 10-P-5001 A/B and export the
product to storage or to urea plant (cf. para. 5.4)
Start up the ammonia recovery unit. Establish normal levels in columns and
start circulation. Route purge gas, let-down gas and inert vent gas to
absorbers and start distillation column (cf. para. 5.6)
26. Once the ammonia recovery unit is operating at stable conditions, sending
off-gases to flare, the hydrogen recovery unit 10-PK-5001 should be taken
into operation, following the supplier's instructions.
Route purified hydrogen from the hydrogen recovery unit back to the
synthesis gas compressor and increase the process air flow to the
secondary reformer to maintain a H2/N2 ratio of approximately 3 in the
make-up gas to the synthesis loop.
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27. When the hydrogen recovery unit has been taken into operation and the
ammonia recovery unit is operating at stable conditions, off-gas should be
introduced as fuel at the primary reformer burners, as described in section
5.3.3.5).
28. Increase plant load to 100% and stabilize all units at normal operating
conditions.
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5.3. Detailed Start-up Description of Syngas Production
5.3.1. Preparing Plant Start-up
Check the availability of feedstock and utilities.
Confirm the completion of the preparatory work as described in Section 4 Plant

Preparation for Initial Start-up.
Confirm the operability of the:
 Emergency power system

 Fire water system and fire alarms
 Telephone and intercommunication systems
 Water Demineralization Unit
 Auxiliary Steam Generator 10-B-8001
 Electric Turbo-generator 10-G-9001
5.3.2. Filling the Steam Drum and Preparing for Steam Production
Check to make sure that the block valves around the control valves in the line
from the BFW pumps 10-P-8001 A/B to the steam drum 10-V-2001 are all open.
The BFW pre-heater in the loop 10-E-5002 is bypassed by closing 10-HV-2071B
and open 10-HV-2071A.
Open the blow-down valve outlet the steam drum and the 2" vent valves on top of
the steam drum. Close the isolation valve on the steam outlet.
Start the motor-driven BFW pump or, if enough HP steam is available, the
turbine-driven pump and fill the steam drum 10-V-2001 and the boilers 10-E-
2008, 10-E-2010 and 10-E-5001 with boiler feed water to minimum level through
10-LV-2055. Keep 10-LV-2055 open corresponding to the blow-down flow.
A small blow-down flow must be maintained to have a continuous flow through
the BFW pre-heaters to protect them from boiling when process gas is
introduced. As long as the pressure in the steam system is low, 10-LV-2055 must
be used for filling, because the differential pressure across 10-FV-2056 is too
high for proper control.
Add HP steam to the shell side of 10-E-2008 and 10-E-2010 to preheat the
boilers to reduce condensate formation when process steam is added to the
primary reformer. HP steam addition will also start the boiler water circulation in
the waste heat boiler 10-E-2008, required when steam production in the boilers
begins. The level in the steam drum must be watched carefully and kept at
minimum level. If it starts to increase, the blow-down valve must be opened
further.
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5.3.3. Heating up the Reforming Section
5.3.3.1 Preparatory Steps
It is assumed that the reforming section including the HT CO converter 10-R-

2004 has been tested for tightness and purged as described in the preparatory
procedures in Section 4.
Check to make sure that the reforming feed inlet section is completely isolated
from the desulphurization section by double block and bleed, i.e. that 10-FV-
2026, 10-FV-2028, 10-XV-2027-A and the vent valve XV-2027-B has block
valves around the control valve open.
In order to prevent any accidental leakage of hydrogen containing gas to the
primary reformer, close control valve 10-FV-2034 and all downstream block valve
in the line for addition of recycle gas 2" –H2-1208009. Open the 3/4" purge valve
for bleed.
Valves on line for liquid ammonia 2"-NHL-1103020 to steam line must be closed
and the 3/4" purge valve open.
The steam control valves 10-FV-2030 and 10-FV-2033 with associated block
valves, block valve for steam from process condensate stripper, block valve
upstream of the addition point to natural gas and main 14" block valve are closed.
The 6" valves on the steam vent are opened to bleed any steam leakage.
Bypass valves 10-TV-2079 in waste heat boiler 10-E-2008 and 10-TV-2080 in

steam superheater 10-E-2009 should be approximately 50% open to reduce
condensation, since the process gas will be relatively cold until the secondary
reformer 10-R-2003 has been heated up and the primary reformer firing
increased.
Prior to heating up, the reformer system must be purged with nitrogen added
upstream of the feed gas/steam preheater 10-E-2001 through 4"-N2-1203303
and vented downstream of the LT CO converter 10-R-2005 through 10-PV-2076.
We recommend analyzing for hydrocarbons in the nitrogen (less than 0.2 vol%)
before the heating of catalyst is started.
After thorough purging the vent valve 10-PV-2076 is closed and the reforming
section is pressurized to about 6-7 bar g (maximum available nitrogen pressure).
The pressure should be kept above the pressure in the desulphurization section.
NOTE! When the CO2 absorber is kept pressurized with natural gas or process
gas there is a potential risk of hydrocarbons leaking back to the hot reformer
catalyst with resulting carbon formation. The absorber should therefore be not be
pressurized before the process steam has been introduced. Alternatively the vent
10-PV-2076 may be cracked open and a small flow of nitrogen purge established
from the reformer inlet.
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5.3.3.2 Start Flue Gas Blower and Ignite Primary Reformer Burners
It is assumed that the fuel gas system has been tested for tightness and purged
as described in the preparatory procedures in Section 4.
Check that all burner fuel isolation valves are closed and that all block valves on
the individual burners are closed.
The flue gas blower 10-K-2001 is taken into operation the following way:
Open all peepholes and the two false air dampers 10-HV-2028A/B at the top of
the radiant section.
Switch the flue gas damper controller 10-PIC-2031 to manual and close the
damper completely.
Start the flue gas blower with the steam turbine 10-STK-2001 as driver. Increase
the turbine speed to minimum governor speed 10-SIC-2002. Continuously check
the draught in the reforming section. The draught must never exceed -30 mm
WG, as the furnace walls may otherwise be damaged. In case the flue gas
damper has a major air leakage, thus causing a high draught, it may be
necessary to open the secondary air registers on the non-operating burners
and/or the peepholes.
Gradually open the flue gas damper and adjust the draught in the top of the
radiant chambers to -5 mm WG by increasing 10-PIC-2031 output. At an early
stage, it should be possible to switch the pressure controller 10-PIC-2031 into
automatic mode. This will ensure a good and stable performance of the burners.
During the subsequent operation, where more and more burners are ignited, it
will be necessary to increase the speed of the blower using 10-HIC-2013 to allow
proper control of the pressure in the reformer.
The furnace must be purged for at least 15 minutes before the burners may be
ignited. It is extremely important to ensure purge of the reformer furnace, as the
block valves on the burners cannot be assumed to prevent a small leakage of
fuel gas into the furnace chambers.
When natural gas is available, the fuel gas system is put into operation in the
following way:
Check that all fuel isolation valves at the individual burners and the 2" ring vents
at the top of the reforming section are completely closed.
Switch the controllers 10-FIC-2046, 10-FIC-2047 and 10-PIC-2047 to manual

mode with an output of 0%.
Reset the natural gas fuel header isolation valves 10-XV-2036-1/2 and 10-XV-
2037 locally.
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Open the control valve 10-FV-2047 slightly by increasing 10-PIC-2047 output.

When the fuel headers have been pressurized, purge them by opening the 2" ring
vents at the top of the reforming section. Keep the ring vents slightly open, adjust
10-PIC-2047 output to obtain the minimum burner operating pressure (to be
defined during workshop test) and switch the controller to automatic mode. Later,
when a number of burners have been ignited and the fuel gas flow is sufficient to
enable proper control at 10-PIC-2047, the 2" ring vents should be closed.
The burners are lit one by one, starting at row one (bottom row) with uneven
numbered burners. Set the primary combustion air damper at 50% opening, open
the fuel block valve, and ignite the burner. The primary combustion air damper is
adjusted to give the correct flame conditions.
A correct flame is blue with yellow tip. If the flame is yellow, the combustion is
incomplete and the primary air damper must be adjusted. A large amount of
excess air will give a blue and very clear flame without a yellow tip.
All instructions given by the supplier of the burners must be followed. The flame
must always burn along the reformer wall. The flame must never touch the
reformer tubes as this will damage the tubes. Burners, which cannot be adjusted
to give the normal flat flame must be removed and checked in the workshop. The
reformer must never operate on reducing flue gas as this will damage the
reformer tubes.
During start-up operations, i.e. during heating with stagnant atmosphere, when
cracking ammonia and to some extent when operating on natural gas feed at low
capacity, the burners should operate with a larger than normal amount of excess
combustion air. This is necessary to achieve a higher flue gas flow and a
correspondingly better heat transfer, especially in 10-E-2001. Also, less
adjustment (manual) of the air flow will be required when the load and fuel gas
flow is increased.
It is important to fire symmetrically in both chambers and on both sides of

the furnace. In order to have a uniform heat release in the furnace chambers it is
essential to have as many burners as possible in operation at minimum capacity
rather than a few at full capacity.
The firing in the reformer is now increased by igniting more and more burners.
Initially, 8 burners in row one (bottom row, uneven numbered), i.e. 4 in each
reformer chamber, are ignited. The heating rate should not exceed 30C/h,
measured in flue gas leaving the re-former furnace 10-TI-2069 and 10-TI-2070.
Additional burners are ignited 4 at a time, one on each wall in each reformer
chamber, until every uneven numbered burner in the bottom row has been
ignited. Then the even numbered burners in row number two are ignited, 4 at a
time, until every second burner in the second row has been ignited. The rows
three to six should be ignited following the same procedure.
The endothermic reforming reaction begins when natural gas or ammonia is

added to the steam and additional burners must be ignited to maintain and
increase temperatures as required. The same is true when increasing the load.
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When all burners have been lit and when the fuel gas flow rate is sufficiently high
(30% of instrument range), adjust the set point of duty controller 10-FIC-2047 to
match the actual duty calculated in 10-FY-1-2047-A and switch to automatic
mode. Further increase in firing should now be done by increasing the set point of
10-FIC-2047, which automatically takes over the control. Keep 10-PIC-2047 on
automatic at minimum burner operating pressure.
5.3.3.3 Protection of Coils in the Waste Heat Section
Because of the high temperature of the flue gas leaving the radiant section of the
primary reformer, it is necessary to monitor and protect the coils in the waste heat
section during all phases of the start-up process.
The table shows the design temperatures of the coils in the waste heat section:
Item no. Hot end / cold end (C)

10-E-2001 715 / 555
10-E-2002 1 640
10-E-2003 1 570
10-E-2003 2 538 / 470
10-E-2004 1 435
10-E-2002 2 445
10-E-2004 2 425
10-E-2005 371
The design temperatures of the inlet and outlet manifolds of the coils in the waste
heat section are as follows:
Item no. Inlet / Outlet (C)

10-E-2001 380 / 560
10-E-2002 1 427 / 580
10-E-2003 1 500 / 540
10-E-2003 2 425 / 500
10-E-2004 1 427 / 430
10-E-2002 2 200 / 427
10-E-2004 2 100 / 427
10-E-2005 170 / 330
Note:Heating any coil above the design temperature must be avoided.
Overheating of the coils (especially during start-up) can be avoided by routing a

protective flow through the individual coils and adjusting the firing in the primary
reformer:
10-E-2001
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Pag. 5-13
When heating in stagnant atmosphere, protection of 10-E-2001 is not required.

During all other phases of the start-up sequences, the coil will have a flow of
steam, natural gas/steam or ammonia/steam, which gives sufficient protection.
However, if too many burners in the upper row of the reformer sections are put
into service at low reformer load, the maximum allowable outlet temperature of
560C for process feed to reformer could be exceeded. It is therefore necessary
to monitor this temperature in 10-TI-2038 closely.
10-E-2002-1
Except during stagnant heating this coil must be protected by a flow of process
air or steam. Before natural gas or ammonia is admitted to the primary reformer,
a small flow of steam must be added using controller 10-FIC-2017. This is to
ensure that no gases are leaking back into the process air header.
Continuously adjust the steam flow to keep the outlet temperature, as indicated
by 10-TI-2047, near the normal operating temperature of 550C. When the
secondary reformer 10-R-2003 is ignited, steam is gradually replaced by process
air and finally cut off completely, as the process air flow during normal operation
will cool the coil sufficiently.
10-E-2003-1/2
Throughout the start-up the coils will be protected by steam from the steam drum
10-V-2001 also passing through the steam superheater 10-E-2009 and vented at
10-PV-2029.
The pressure in the boilers governs the amount of steam generation. Initially the
pressure will be low (5-15 bar g). The rate of pressure increase must be
controlled to maintain sufficient flow through the superheat coils.
Do not send steam to the steam superheater coils 10-E-2003-1/2 until the flue
gas temperature, as indicated upstream by 10-TI-2050 is 50C above the dew
point of the steam in the steam drum, in order to prevent condensation of steam
in the coil.
10-E-2004-1
The coil is protected by natural gas admitted while heating up the
desulphurization section. Natural gas flows through 10-E-2004-2 before it
reaches 10-E-2004-1 from where it flows to the desulphurization section and is
finally vented at 10-PV-2027. Natural gas must at the latest be admitted when the
flue gas temperature (10-TI-2051) approaches 435C. The outlet temperature
(10-TIC-2039) to the desulphurization section should not exceed the normal
operating temperature of 400C.
10-E-2002-2
The coil is protected by process air during normal operation. During start-up no
particular measures are required for protection.
When the process air flow is below normal, i.e. during start-up and when the
hydrogen recovery unit 10-PK-5001 is not in operation, part of the process air
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Pag. 5-14
flow must be by-pass 10-E-2002-2, by means of 10-HIC/HV-2011, to maintain the

normal outlet temperature of 550C at 10-E-2002-1.
10-E-2004 -2
The coil is operated in series with 10-E-2004-1 and will therefore be protected by
natural gas admitted while heating up the desulphurization section. Natural gas
must be admitted before the flue gas temperature (10-TI-2024) reaches 390C.
The outlet temperature (10-TI-2017) to the mixing point upstream of 10-E-2004-1
must be below 427C.
10-E-2005
This coil is protected by adjusting the boiler feed water flow to the steam drum at
10-FIC-2076 which, in turn, is adjusted by controlling the amount of 10-V2001
blowdown or of vented steam
5.3.3.4 Control of Heat Distribution in the Primary Reformer
The heat distribution between the radiant and waste heat sections in the primary
reformer should be controlled during the heating-up process to avoid exceeding
the design temperatures of the coils in the waste heat section.
The heat distribution can be controlled by changing one or more of the following
operating parameters:
 the firing profile in the radiant section
 the false air flow into the waste heat section by means of 10-HIC-2028/2029.
 the excess combustion air to the radiant section
While maintaining a constant heat input, the heat distribution between the radiant
and waste heat sections and the temperature profile in the reformer tubes can be
changed by altering the firing profile. By moving the firing downwards in the
radiant zone, the heat distribution is shifted from the convection section to the
radiant section.
By admitting false air into the waste heat section, the heat distribution within the
waste heat section will be affected, moving the heat input towards the cold end of
the section.
By increasing the combustion air to the burners, heat is moved from the bottom to
the top of the reformer tubes and the heat input is shifted towards the waste heat
section.
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5.3.3.5 Taking Off-gas Fuel into Operation at Primary Reformer Burners
The purge gas recovery unit (PGRU) should be operating under stable conditions
before off-gas is introduced to the reformer burners.
Introduction of off-gas from PGRU PK-5002
1. The reformer duty controller 10-FIC-2047 should be in operation (automatic

mode), controlling the flow of natural gas fuel.
2. Check that the controllers 10-FIC-2052 and 10-PIC-2049 are switched to

manual with zero output.
3. Enter the correct heating value for the off-gas fuels; 10-FN-2048 for treated
purge gas and 10-FN-2051 for untreated purge gas.
4. Select the type of off-gas on 10-HS-2052; treated if the hydrogen recovery

unit is in operation or otherwise untreated purge gas.
5. Check that all the off-gas isolation valves at the individual burners are
completely closed.
6. The off-gas fuel header isolation valves 10-XV-2038-A/B and 10-XV-2039

are reset locally.
7. Open fully the off-gas isolation valve to all burners in operation.
8. Slowly introduce the off-gas fuel by increasing the output of 10-FIC-2052 on

manual. Check signal from flow transmitters 10-FI-2048/2051 against
opening of valve. Confirm that the natural gas fuel flow is reduced
correspondingly, maintaining the fired reformer duty constant.
9. When the flow is sufficient (about 30% of range) switch 10-FIC-2052 to

automatic.
10. Continue to increase the set point of 10-FIC-2052 until the pressure
controller 10-PIC-5043 takes over control, maintaining the pressure in the
off-gas absorber (10-T-5052).
11. Adjust the set point of 10-FIC-2048 to slightly above the actual flow (duty)
to ensure that the off-gas flow to the reformer is limited in case of upset in
the purge gas recovery unit.
During the whole exercise the performance of the burners must be observed
carefully in the field.
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Pag. 5-16
Introduction of flash gas fuel:

Flash gas from the HP flash drum 10-V-3002 in the CO 2 removal unit should be
vented to flare until the off-gas from the PGRU has been introduced. The flow of
flash gas is relatively small and the gas is hot and wet, introducing a risk of
condensate formation in the fuel header.
Enter the correct heating value for the flash gas on 10-FN-2050
Line up 10-FV-2050. Make sure to drain all low points for condensate before
introducing the flash gas.
Slowly increase the flow of flash gas by 10-FIC-2050 on manual until the
pressure controller 10-PIC-3014 takes over control, maintaining the pressure in
the HP flash drum 10-V-3002.
Adjust the set point of 10-FIC-2050 to slightly above the actual flow to ensure that
the flow to the reformer is limited in case of upset in the HP flash drum.
Introduction of process gas fuel:

A small flow of process gas may be taken from downstream the final separator
10-V-3011 and sent as fuel to the reformer. In this way it is possible to adjust the
CO2 production and the ammonia production to achieve the right stoichiometric
ratio for the urea process.
Enter the correct heating value for the process gas on 10-FN-2049
Line up 10-FV-2053. Make sure to drain all low points for condensate before
introducing the process gas.
The process gas should be introduced slowly with 10-FIC-2053 on manual. Keep
the controller on manual as long as the flow is small.
Provisions are made to use the process gas as substitute for the off-gas from the
purge gas recovery in case the purge gas flow is abrupted (synthesis loop is
tripped, IS-7). To what extent this substitution is required or not must be
determined based on actual operating experience. The controller 10-FN-2053
can set the amount of process gas substitution based on duty.
5.3.4. Heating Up the Desulphurization Section with Natural Gas
Start heating up the hydrogenator 10-R-2001 and the sulphur absorbers 10-R-
2002 A/B while heating the primary reformer in stagnant atmosphere.
It is assumed that the desulphurization section has been tested for tightness and
purged as described in the preparatory procedures in Section 4. The O 2
concentration must be below 0.5% by volume.
Proj. 2098
Pag. 5-17
Check that the desulphurization section is isolated from the reforming section by
double block and bleed, and that 10-FV-2026, 10-FV-2028, 10-XV-2027A the
block valves around the control valves are all closed and the bleed valve 10-XV-
2027B and associated isolation valves are all open.
Initially the bypass valve 10-TV-2039 over the feed gas preheater 10-E-2004-2
should be fully open.
Start heating up the desulphurization section with a minimum flow through the
wide open vent valve 10-PV-2027B. The pressure should preferably be kept
below the nitrogen pressure in the reforming section. For this reason the natural
gas compressor 10-K-4011 should initially be bypassed. Later when steam has
been admitted to the reforming section, the natural gas compressor should be
started, and the pressure gradually increased to keep it adequately above the
pressure in the reforming section to facilitate a good control of the natural gas
feed (when introduced).
The desulphurizer catalyst beds are heated up at a maximum heating rate of

50C per hour by natural gas flowing through the two feed gas preheaters 10-E-
2004 1/2. The heating up rate is controlled by the adjusting the flow of natural gas
and by adjusting the bypass valve 10-TV-2039.
If no hydrogen gas is available, the hydrogenator catalyst temperature must be

maintained below 300C to avoid cracking of higher hydrocarbons resulting in
carbon lay-down.
The absorption capacity of the ZnO catalyst is optimal at temperatures close to

400C, but the catalyst will absorb H2S even at ambient temperatures and COS
and CS2 at the normal operating temperatures.
Therefore, in case the natural gas only contains H 2S, the sulphur absorbers will
already at this stage pick up the sulphur to an extent that natural gas can be
introduced to the primary reformer without establishing a flow of recycle hydrogen
to the hydrogenator. Ammonia cracking is therefore not required.
In case the raw natural gas contains less reactive sulphur compounds like
mercaptanes, thioethers, disulphides or thiophenes, it is necessary to establish a
flow of recycle hydrogen to the hydrogenator before admitting natural gas to the
primary reformer. The source of hydrogen will then be cracked ammonia (cf.
para. 7) or synthesis gas from the loop.
After verifying by analysis that the total sulphur content in the exit gas from 10-R-
2002 B is less than 0.05 vol. ppm, natural gas can be introduced to the steam to
the reformer as described in sections 5.
If the natural gas has a very low sulphur content (below 0.2 wt ppm), sulphur will
be stripped off the hydrogenator catalyst. Desulphurized catalyst has a higher
tendency for methanation (risk of temperature run-away), which may occur if the
natural gas contains significant amounts of CO2 in the presence of hydrogen.
Proj. 2098
Pag. 5-18
Recycle hydrogen must not be sent to 10-R-2001 in this case. In the absence of
hydrogen in 10-R-2001 the catalyst temperature must be maintained below
300C due to the risk of cracking of higher hydrocarbons resulting in carbon lay-
down on the catalyst.
5.3.5. Introduction of Steam to Primary Reformer
When the flue gas temperature at the outlet of the furnace chambers reaches
300-400C as mentioned above, heat up the process steam line upstream from
10-E-2001.
Check that the 14” isolation valve on 14" HS 103.06 F24-H is completely closed
at the natural gas/steam mix point. Open low point drains upstream 10-FV-2033
to remove condensate. Open the 6" valves to the high vent on 14"-SP-1203022 ,
open the isolation valves around 10-FV-2033 and establish a flow of about 5 t/h
through the high vent.
When the steam from the high vent appears dry, close the vent and open the
isolation valve for steam on 14"-SP-1203022 . To prevent condensate from
reaching the reformer, all possible bleeder valves situated at low points in the
steam lines should be kept wide open.
The pressure in the reforming section is kept as low as possible during steaming
by keeping the vent valve 10-PV-2076 (downstream 10-R-2005) wide open. The
pressure should preferably be below 5 bar g.
Establish a flow of approximately 30 t/h steam by opening 10-FV-2033. The full

flow of steam should be added gradually over approximately 10 minutes in order
to minimise condensation in the reformer inlet system. The steam is vented at 10-
PV-2076 downstream of the LT CO converter (10-R-2005).
Initially, some condensation will occur in the secondary reformer 10-R-2003,

waste heat boiler 10-E-2008, steam superheater 10-E-2009 and the HT CO
converter 10-R-2004 due to heating up of the catalyst and the equipment. The
condensate should be drained at low point drains upstream and downstream of
10-R-2004.
Stop addition of nitrogen upstream of the process feed preheater 10-E-2001

through 4"-N2-1203303 .
Increase firing (cf. para.5.4) to obtain primary reformer outlet temperatures in the
hot collector of 550-650C (10-TI-2061/2062/2063/2064/2065/2066). The
reformer inlet temperature (10-TI-2038) should be 400-450C.
During introduction of steam to the reformer and subsequent heating up, steam
formed in the steam drum must be vented and the pressure gradually increased
as described in para. 5.
Protection of coils in the waste heat section must at all times be ensured as
described in par. 5.2.
Proj. 2098
Pag. 5-19
5.3.6. Introduction of Natural Gas Feed
Once heating up of the desulphurization section has been completed and it has
been verified by analysis that the total sulphur content in the exit gas from 10-R-
2002 B is less than 0.05 vol. ppm, natural gas should be introduced as described
below.
Steam is introduced and the primary reformer is heated up as described in

paragraph 5.3.5.
Check that the natural gas feed control valves 10-FV-2026 and 10-FV-2028 are
in manual mode and closed position. Open all block valves around the control
valves. Reset the natural gas feed block and bleed valves 10-XV-2027 A/B
locally.
Establish a natural gas flow of approximately 2000 Nm 3/h by gradually opening
10-FV-2028. Increase the reformer firing (primarily in the top of the furnace) to
maintain the inlet temperature at 400-450 °C and the outlet temperature at 550-
650 °C.
Gradually increase the natural gas feed flow to 4000 Nm 3/h to obtain a S/C-ratio
of 8-10. Simultaneously, the firing of the primary reformer is increased in order to
obtain a reformer inlet temperature (10-TI-2038) of 450-500C and reformer
outlet temperatures (10-TI-2061 to 10-TI-2066) of 700-750C. The flue gas
temperatures (10-TI-2069 and 10-TI-2070) exit the radiant chambers should not
increase by more than 30-50C per hour
If the primary reformer catalyst has not already been reduced, steam reforming
reactions in the prereduced reformer catalyst in the top will form hydrogen and
reduce.
The rate of temperature increase during heating of the HT CO converter is not

critical for the catalyst. However, the temperature controllers 10-TIC-2079 and
10-TIC-2080, the bypasses of the waste heat boiler 10-E-2008 and the steam
superheater 10-E-2009 should be adjusted to give a reasonable temperature rise
of about 50C per hour.
Continue to heat up until the inlet temperature (10-TI-2086) reaches the normal
operating temperature of the HT CO converter.
Reduction of the high temperature shift catalyst is performed as described in

para. 5.7.1.
5.3.7. Cracking of Liquid Ammonia
In case the raw natural gas contains sulphur compounds like mercaptans,
thiophenes, thioethers, or disulphides, ammonia must be cracked in the primary
reformer to produce the hydrogen required for desulphurization.
Proj. 2098
Pag. 5-20
Steam is introduced and the primary reformer is heated up as described in para.

5.3.5.
Turn the blind on line 2"-NHL-1203020, open the ball valve and check that liquid
ammonia is available on local pressure gauge 10-PI-2532. Please note that the
liquid ammonia line may have to be vented to remove gaseous ammonia.
Close all drain valves before the ammonia is introduced.
Establish a small flow of liquid ammonia controlled by 10-FIC-2025. Aim at a

molar ratio between steam and ammonia of approximately 12. With 28 t/h of
steam this corresponds to 2215 kg/h (3.26 m 3/h with density 680 kg/m 3). Initially
gaseous ammonia may be present. Await flow of liquid ammonia before setting
10-FIC-2025 into automatic mode.
As soon as ammonia is added, reformer firing must be increased in the upper

rows, due to the endothermic ammonia cracking reaction and to compensate for
evaporation of liquid ammonia. Stabilize reformer inlet temperatures at
approximately 450C and outlet temperatures at approximately 700C.
At these temperatures ammonia cracking will take place and form hydrogen. The
lower part of an unreduced reformer catalyst will become reduced, but total
reduction of all the catalyst will not take place till after introduction of natural gas
and hydrogen recycle gas. Hydrogen recycle to the reformer should be
established to ensure that the top layer of prereduced catalyst remains reduced
after prolonged exposure to steam.
Increase the system pressure at the minimum required to recycle the generated
hydrogen from the inlet the CO2 absorber back to the suction of the natural gas
compressor 10-K-4011 (keep minimum possible pressure at the compressor
suction).
The natural gas will now be desulphurised. When it is confirmed that the natural
gas total sulphur content is less than 0.05 vol. ppm, the natural gas is introduced
to the primary reformer as described in para 5.3.6 above. The flow of liquid
ammonia can then be gradually reduced and finally stopped.
The point of hydrogen recycle should be moved downstream the CO 2 absorber

as soon as possible (CO2 removal taken in operation). Hydrogen recycle from
inlet/outlet of the CO2 absorber must be continued until the normal supply of
hydrogen from the synthesis compressor is established.
When cracking ammonia, the high temperature shift catalyst should not be
reduced using the hydrogen formed by the cracking of ammonia, since it will
prolong the ammonia cracking period unnecessarily. For this reason the
temperature in the HT CO converter should preferable be kept at 200 - 250C, to
avoid hydrogen consumption by reduction of the catalyst.
Proj. 2098
Pag. 5-21
5.3.8. Steam Generation
When steam production begins, the generated steam is initially vented through
the 2" local vent on the steam drum to remove air. Close the vent and allow the
steam pressure to increase to 5 bar g; then depressurize by opening the vent.
Repeat this procedure three times. Continue to vent the steam at the 2" local vent
until the flue gas temperature (10-TI-2050) upstream of the WHS steam
superheater 10-E-2003-1 is 50C above the dew point of the steam, to avoid
condensation of steam in the coil.
Check 10-PV-2065 is closed. Open bypass on steam drum isolation valve to

equalise pressure. Open drains to remove condensate and open steam drum
isolation valve. Before the vent is transferred to 10-PV-2029, check that 10-PV-
2029 and upstream block valve are fully open. Open all drip legs on 10-E-2009
and 10-E-2003 1/2 and keep them open until the steam appears dry. Crack open
10-PV-2065 and close the 2" vent on the steam drum.
Gradually increase the pressure on the steam header by throttling 10-PV-2029,

while observing the flue gas temperature (must be above dew point). Open 10-
PV-2065 as required to maintain the pressure in steam drum. When 10-PV-2065
is fully open, switch the pressure controller 10-PIC-2029 to automatic mode.
Gradually increase the set point sufficient to allow control of the temperature inlet
the HT CO converter, while maintaining sufficient flow through the superheat
coils.
Furthermore, boiler supplier recommendations must be taken into consideration.

As a rule of thumb, the set pressure should be minimum 100 barg multiplied by
the load factor to avoid excessive heat flux in the boiler. Above can be
considered as a rough guideline. Full steam pressure of 118 barg may be applied
at 80% load.
During initial start-up, and if the boiler has been exposed to air, the steam drum
pressure should be kept if possible at approximately 65 barg for 48 hours in order
to obtain formation of a dense layer of magnetite in the steam drum. After this the
pressure may be increased further.
The continuous blow-down must be fully open during the initial start-up, until the
boiler water appears clean. Intermittent blow-down from 10-E-2008 and 10-E-
2010 should initially be opened frequently, as a guideline for approximately 4
seconds every second hour.
Oxygen scavenger and ammonia water should continuously be added to the

boiler feed water to keep the pH and the O 2 content in conformity with supplier
recommendations. Phosphate must be added immediately upstream of the steam
drum.
Proj. 2098
Pag. 5-22
PIC-2065 should be operated on manual until PV-2065 is fully open and the
pressure control is shifted to PIC-2029. During normal operation, keep PIC-2065
on automatic with a set point approximately 2 bar g lower than the prevailing
pressure in the steam drum.
5.3.9. Preparing the CO2 Removal Section for Operation
It is assumed that the CO2 removal section is already filled with the proper
amount of MDEA solution and that a successful foam test has been performed as
described in Section 4.
Make sure that the CO2 absorber 10-T-3002 is isolated:
In the feed line to T-3002 close 10HV-3029, 10-HV-3022 and the 2 inch bypass
valve connecting the recycle hydrogen. In the overhead line close 10-PV-3036,
10-XV-3036 and the upstream isolation valve and its 2" bypass valve.
In T-3002 bottom the controller 10-LIC-3026 and 10-LIC-3026-A and 10-LIC-

3026-B should be in manual mode with both valves 10-LV-3026-A/B closed.
At 10-T-3001 the controllers 10-LIC-3003 and 10-FIC-3002 should be in manual

mode with control valves closed.
At 10-V-3002 the 10-LIC-3011 must be in manual mode with control valve in the
closed position.
Pressurize the CO2 absorber to 10-15 bar g by introducing natural gas through
2"-NG-1201010. The HP flash drum 10-V-3002 is pressurized to approximately
5.9 bar g by introducing nitrogen through 2"-N2-1302301.
Stabilize levels and reset IS-4 and IS-5.
Switch the lean and semilean MDEA flow controllers to manual mode and open
the valves slightly. Start pumps 10-P-3001 A, 10-P-3002 A and 10-P-3003 A, and
check to make sure that each minimum flow valve and lean solution sealing is
working properly.
Switch controllers 10-LIC-3003 to automatic and 10-FIC-3002 to remote mode.
Switch 10-LIC-3026 and 10-LIC-3011 to automatic mode and check that the
controls are working properly within their operating range. The segregation valve
10-HV-3024 of rich amine to the hydraulic turbine shall remain close. The 10-
LV-3026-A controlling the flow to the hydraulic 10-HT-3001 turbine should
remain close..
Switch lean solution to 10-T-3002 flow controller 10-FIC-3022 and semilean

solution to 10-T-3002 controller 10-FIC-3021 to automatic mode with as low a set
point as possible, i.e. 30% of flow instrument range.
Heat up the CO2 removal section with process gas or quenched HP steam:
Proj. 2098
Pag. 5-23
When heating up with process gas, open the vent 10-HV-3022 upstream of the
CO2 absorber, routing part of the process gas through the stripper reboiler.
When preheating with HP steam, a flow of approximately 10 t/h is recommended,

controlled at 10-HV-2552. The quench temperature (10-TIC-2101) should not
exceed 175C since the MDEA solution may otherwise degrade. The pressure of
the natural gas or feed gas, controlled by adjusting 10-HV-3022 upstream of the
CO2 absorber, should be as low as possible.
Raise the set points of 10-FIC-3021 and 10-FIC-3022 gradually to 50-80% of the
design flow rate and wait for the levels in 10-T-3001, 10-T-3002 and 10-V-3002 to
stabilize.
The temperature outlet the CO2 stripping column should be approximately 100C,
controlled by adjusting either the steam quench temperature or the process gas
flow to the stripper reboiler.
Establish normal flow of demineralized water to the DMW preheater (10-E-3004

and 10-E-3005).
When the level in the process gas separator 10-V-3004 has reached its normal
value, start the condensate pump 10-P-7004 A and check the function of the
level controller 10-LIC-3001. The 10-HV-7011Aand B, upstream of the process
condensate feed/effluent exchanger (10-E-7001 A/B), must be opened in order
for process condensate from 10-P-7004 A/B to be sent to demineralization
package 30-PK-3001.
Stabilize the temperatures in the CO2 removal section with normal flow of cooling
water through LP flash gas cooler 10-E-3006. Cooling water should not be routed
to the lean solution cooler 10-E-3003) until required for maintaining the usual
lean solution temperature at the outlet of the cooler as controlled by 10-TIC 3029
at 50°C.
5.3.10. Taking the CO2 Removal Section into Operation
Close valves and turn in close position blinds on the natural gas line to CO 2
absorber 2"-NG-1201010 and nitrogen line 2"-N2-1304305 and disconnect N 2
supply flexible hose.
Check that normal cooling water flow through lean solution cooler (10-E-3003)
has been established.
Switch pressure controller 10-PIC-3036 (gas to flare) into manual mode and
close it.
Pressurize the CO2 absorber (10-T-3002) by opening the 2" pressure

equalization valve at the motorized valve 10-HV-3029. Confirm equalization of
Proj. 2098
Pag. 5-24
pressures by using the local pressure gauges 10-PI-3526 and 10-PI-3527 and
open motorized valve 10-HV-3029.
Establish a gas flow through the CO2 absorber by gradually increasing the output
from 10-PIC-3036 and thereby opening the valve. At the same time, check that
the vent 10-PV-2076 closes. The gas flow is increased from 0 to 30% of normal
over a period of minimum 20 minutes. The flow may be increased to 50% within 1
hour, to 80% within the next hour, to 90% within the following hour and 100% in
another hour. Carefully monitor the pressure drops across the bottom and top
sections of the absorber while increasing gas load. When a smooth operation of
the plant is observed, the feed gas flow may be changed more rapidly, i.e. from
0-100% within 1 to 2 hours.
When all the process gas flows through the absorber and is vented through 10-
PV-3036, switch 10-PIC-3036 into automatic mode. Increase the set point of 10-
PIC-2076 to about 2 bar above the actual pressure.
Establish a normal flow of washing water to the top of the absorber.
Stabilize the temperatures in the CO2 removal section.
Initially, CO2 from the LP flash drum should be vented at 10-PV-3015,

downstream of the K.O. drum 10-V-3003. Switch the pressure controller into
automatic mode with a set point of 0.5 bar g.
When levels in the K.O. drum 10-V-3003 increase, the OH condensate pump 10-
P-3004 A must be started and the level controller 10-LIC-3019 put into automatic
mode. Check that it functions properly. Establish a normal flow of washing water
to the LP flash drum via 10-FI-3511.
Finally, when operation is stable, start the hydraulic turbine 10-HT-3001 for 10-P-
3001-A by resetting IS-5 and slowly increasing 10-HS-3024 output to open 10-
HV-3024. This will close level control valve 10-LV-3026-B to some extent. Switch
10-HS-3024 into remote mode to control it in cascade with the absorber level
controller 10-LIC-3026.
If the pressure drop across any column shows an increasing tendency, add
antifoam solution to the column.
Check that the pressure drop across the MDEA solution filter 10-FL-3001 is not
too high. Throttle the manual globe valve at the outlet of the filters as required.
5.3.11. Pressurizing the Hydrogen Recycle System
It is assumed that the hydrogen recycle system has been tested for leaks and
purged as described in the preparatory procedures in Section 4.
Proj. 2098
Pag. 5-25
In many cases hydrogen can be supplied from the ammonia synthesis loop being
under pressure. In this case 10-PIC-5012, in the outlet of 10-E-5005, should be
lined up to maintain the pressure in the recycle header.
However, if the synthesis loop is depressurised it is necessary to generate the

required hydrogen by cracking ammonia in the primary reformer. The hydrogen
formed is routed via the recycle hydrogen header back to the natural gas
upstream the hydrogenator.
The point of hydrogen recycle should be moved downstream the CO 2 absorber

as soon as possible (CO2 removal taken in operation), since the CO 2 (and the
CO) in the recycle gas affects the equilibrium of the zinc oxide absorption
reaction. Later when the methanator section is taken into operation the recycle
gas should be taken from downstream of the final gas separator 10-V-3011.
Hydrogen recycle to the natural compressor suction must be continued until the
normal supply of hydrogen from the synthesis compressor is established.
Hydrogen recycle is lined up as follows:
Turn the blind and open the isolation valves on 2"-GP-1305009; 2"-H2-1208008
to desulphurization feed heater.
Adjust the suction pressure of the natural gas compressor 10-K-4011 to 0.5-1 bar
less than the pressure on the recycle header. Since the pressure in the reforming
section should be as low as possible during ammonia cracking, the suction
pressure of 10-K-4011 should be minimised by maximising the compressor head
and by keeping a low pressure in the desulphurization section.
Line up 10-FV-2035 and admit the recycle gas at the 10-R-2001 feed
Adjust the flow on 10-FIC-2035 to obtain a ratio of 0.03-0.06 Nm 3 recycle
gas/Nm3 natural gas, assuming a hydrogen concentration of 75% in the recycle
gas and a natural gas composition as per process flow sheets. Increase the
recycle flow when load and natural gas feed flow have increased.
Once a flow of recycle hydrogen has been established the inlet temperature of
the hydrogenator (10-R-2001) should be raised from 300C to the normal
operating value of 400C, since there is no longer risk of cracking higher
hydrocarbons and getting carbon lay-down on the catalyst.
5.3.12. Increasing Load to 40%
Plant load must be increased in steps of about 5%. Flows should be increased in
the following order:
 Increase process steam flow

 Increase natural gas flow
 Increase primary reformer firing
 Increase process air flow (when secondary reformer has been taken in line).
Proj. 2098
Pag. 5-26
Load decrease is performed in the reverse sequence.
While increasing load, operating pressures are also increased towards the
normal operating values; in the desulphurization section at controller 10-PIC-
2003 and in the reforming section at 10-PIC-3036.
The load on the primary reformer is now increased to approximately 40%, aiming
at the following conditions, corresponding to a steam/carbon ratio of about 5.
Steam flow to primary reformer: 60 t/h

Natural gas flow to primary reformer: 13,500 Nm3/h
Recycle gas flow to 10-R-2001: 700 Nm3/h
Temperature inlet primary reformer: 450-500C
Temperature outlet primary reformer: 750C
Pressure downstream of CO2 absorber: 20 bar g
Simultaneously with increasing the natural gas flow to the process, check that
pressure controller 10-PIC-2027 gradually closes, reducing the vent flow.
As soon as conditions allow, control of steam and natural gas flow to the process
is shifted from the smaller bypass control valves to the main control valves 10-
FIC-2030 and 10-FIC-2026.
Set the steam bypass controller 10-FIC-2033 to a flow of 28 t/h in order to ensure
a flow of protection steam in case of trip of the primary reformer (IS-1).
Check that the flow of protection steam to the air preheater coil 10-E-2002-1 is
sufficient. The steam flow at 10-FIC-2017 must be adjusted to keep the outlet
temperature 10-TI-2047 near the normal operating temperature of 550C.
The pressure in the steam drum 10-V-2001 should be approximately 65 bar g

controlled by 10-PIC-2029 until the secondary reformer 10-R-2003 has been
ignited. The superheated steam temperature outlet WHS steam superheater 10-
E-2003-1 should be close to the normal operating temperature of 515C.
Preferably, this should be obtained by adjusting the set point of temperature
controller 10-TIC-2045 to a temperature where no quench flow is required, but at
the same time it must be checked that temperature controller 10-TIC-2044 is well
within controlling range.
5.3.13. Ignition of the Secondary Reformer
Addition of air to the secondary reformer 10-R-2003 may take place only when
the temperature outlet the secondary reformer exceeds 700C, the plant load is
at least 40%, and the system pressure is 20 barg, as indicated by 10-PIC-3036,
or more.
Check that the process air control valves 10-FV-2011 and 10-FV-2016 are in
manual mode and closed position. Open all block valves around the control
valves. Reset IS-2 to open the trip valve 10-XV-2011.
Proj. 2098
Pag. 5-27
Open bypass valve 10-HV-2011 over process air preheater 10-E-2002-2.
Start the air compressor (10-K-4021) following the instructions provided by the
supplier.
Open all low point drains downstream of the air compressor to drain trapped
condensate.
Establish a pressure upstream of the flow control valve 10-FV-2016

approximately 2 bar higher than the downstream pressure, measured by local
gauges 10-PI-2516 and 10-PI-2520.
Make sure that the temperature outlet of the secondary reformer 10-TI-2076
exceeds 700C.
Switch 10-FIC-2016 into automatic mode and increase the set point to admit a
process air flow of approximately 1000 Nm 3/h. The flow of protection steam feed
to the air preheater coil 10-E-2002-1 should be controlled to maintain an
air/steam temperature at the inlet of 10-R-2003 of 500 - 550C.
Carefully monitor the temperature at the outlet of the secondary reformer 10-TI-
2076 during this operation. If ignition occurs, there will be an increase in
temperature. If no temperature increase has been observed within 5 minutes,
stop the air flow for 5 minutes. If the temperature at the secondary reformer outlet
decreases by less than 5C, let the outlet temperature stabilize and try again to
ignite; but now with a larger air flow. There must be an interval of 15-20 minutes
between each ignition attempt. If an attempt results in a temperature decrease of
more than 5C, wait until catalyst temperatures have returned to the original
value before making another attempt.
After ignition of the secondary reformer, await stabilization of the outlet

temperature before gradually increasing the air flow rate. The rate of temperature
increase should be kept below 30C/h. While increasing process air flow,
decrease the protection steam flow using 10-FIC-2017, in order to keep the outlet
temperature of the process air preheater 10-E-2002-1 at 500-550C.
When protection steam has been stopped, gradually close bypass valve 10-HV-
2011 over process air preheater 10-E-2002-2 to maintain constant the outlet
temperature of the process air preheater 10-E-2002-1 as the process air flow
increases.
At this point, a set point should be entered to protection steam flow controller 10-
FIC-2017, in case of emergency shut down of the secondary reformer, i.e. IS-2 or
IS-3. Enter a flow approximately equal to the amount of protection steam used
before process air was introduced.
Proj. 2098
Pag. 5-28
Adjust the air flow to give a hydrogen/nitrogen ratio of about 3.0 in the process
gas downstream of the CO 2 absorber, i.e. approximately 22,000 Nm 3/h at 40 %
load.
During ignition of the secondary reformer and when increasing air flow, the level
10-LIC-2056 and 10-LI-2057B in the steam drum should be observed carefully.
Also, continuously check that the temperature controller of process gas to HT CO
converter is well within controlling range, since 10-E-2008 bypass will close to
maintain the steam temperature outlet 10-E-2009. The steam production in 10-E-
2008 will increase when the secondary reformer is ignited, but the duty in the
WHS steam superheaters 10-E-2003-1/2 will remain the same; consequently it
will be necessary to increase the set point of temperature controller 10-TIC-2080,
to maintain a superheated steam temperature of 515C outlet 10-E-2003-1. The
steam drum pressure controller 10-PIC-2029 set point must be increased before
the capacity limit of the vent 10-SL-2002 is approached.
5.3.14. Taking LT CO Converter into Operation
It is assumed that the reactor has been tested for leaks as described in the
preparatory procedures in Section 4.
The LT CO converter 10-R-2005 must be isolated by closing motorized block

valves 10-HV-2081 and 10-HV-2082, manual block valves with associated 2"
bypasses and blinds at inlet and outlet of the reactor. Bleed valves located
between manual block valves and blinds must be open.
The converter bypass valve 10-HV-2083 must be open.
The LT CO converter must be purged and pressurized with nitrogen to 5 bar g in

order to bring down the oxygen concentration to less than 0.1% by volume.
When reduced, the LT CO converter is heated up with circulating nitrogen using

the nitrogen start-up circuit. If the catalyst is new, it must first be reduced as
described in para. 5.7.2.
The maximum allowable heating rate is 50C/h. If some of the temperature

indicators in the catalyst bed behave strangely at approximately 100C, this may
be due to the presence of water in the thermowells; the thermowells should then
be blown with nitrogen. When a temperature of 200-220C has been reached at
the inlet of the reactor (10-TIC-2111), this temperature should be maintained until
the outlet temperature from the converter has stabilized. It is important to
ascertain that the catalyst temperatures throughout the bed are at least 20C
above the dew point of the process gas.
When the LT CO converter is taken into operation, the S/C-ratio at the inlet of the
primary reformer should have been reduced to 3.5-4.5, in order to have a
sufficiently low dew point of the process gas when admitted to the LT CO
converter.
Make sure that the boiler feed water outlet temperature (10-TI-2099) from the
BFW pre-heater no. 1 10-E-2012-A is above the dew point of the process gas to
Proj. 2098
Pag. 5-29
the LT CO converter, and adjust the process gas temperature at the LT CO

converter outlet 10-TI-2122 to 20C above the dew point of the process gas.
If the HT CO catalyst is new, confirm that the H 2S concentration in the dry gas
exit the HT CO converter is below 0.05 vol. ppm.
The low temperature shift converter is now ready to be taken into operation:
Stop the nitrogen circulation and isolate the nitrogen start-up circuit completely by
closing the isolation valves and turning the spectacle blinds to closed position.
Turn the spectacle blinds in 20" lines upstream of 10-HV-2081 and downstream
of 10-HV-2082 to open position.
Open the 2" bypass valve across the 20" isolation valve upstream of 10-HV-2081
completely. Then open the 2" bypass valve across 10-HV-2081 slightly and
pressurize 10-R-2005 slowly. Open the 2" bypass valve across the 20" isolation
valve downstream of 10-HV-2082 completely.
During introduction of process gas, condensation will take place in the cold part
of the piping. In order to avoid that condensate accumulated upstream of the LT
CO converter enters the converter, the 2" low point drain valve must be opened
regularly during the pressurization.
When the pressure has been equalized and condensate is no longer present,
close the 2" drain valve and open the 20" isolation valves at 10-HV-2081 and 10-
HV-2082, respectively. Close all the 2" bypass valves.
Take the LT CO converter into operation by first resetting I-2005 and then
activating I-2006. Check proper function of the motorized valve actions.
The low temperature shift converter is now in operation.
NOTE! If new catalyst is installed in the LT CO converter, and if the CO 2 removal

is already in operation, the venting point of process gas should be moved
upstream the CO2 absorber to 10-PV-2076/10-HV-3022 before taking the
converter in operation. Close 10-PV-3036 on manual. This is to avoid catalyst
dust from entering the CO2 removal. Vent the gas upstream for 2-3 hours before
sending the process gas back through the CO2 absorber.
It should be noted that when process gas is admitted to the converter after
reduction or during restart after shut-down, a sudden temperature increase of 50-
100C may be observed in the catalyst bed. This is due to chemisorption of
reactants on the catalyst surface. A short exposure to such temperatures will
have no adverse effect on the catalyst. It may take about half an hour for this
"heat wave" to travel through the catalyst bed after the full process gas flow has
been established, which should take place as quickly as possible. When
temperatures in the catalyst bed have stabilized, the outlet gas is analyzed for
CO and CO2.
Proj. 2098
Pag. 5-30
It should be noted that when taking the low temperature CO converter into
operation, the CO content in the methanator feed will drop sharply and
adjustments of valve 10-TV-3039A positions around 10-E-3011 A/B will be
required if the methanator is in operation.
5.3.15. Taking Methanator into Operation
It is assumed that the methanation section has been tested for leaks and purged
as de-scribed in the preparatory procedures in Section 4.
The methanation section is isolated before pressurization with nitrogen by:
- closing 10-XV-3036 upstream isolation valve and its 2" bypass valve
- 10-PIC-3037 in manual mode to close 10-PV-3037 to flare.
- isolation valve and his 1” bypass upstream 10-XV-4002 at synthesis gas to
10-K-4031
- isolation valves in other adjoining piping.
Pressurize with nitrogen to 5 bar g using the line 2"-N2-1305306 connected with
flexible hose to downstream of the methanator.
Before heating up the methanator, check that the control valves 10-PIC-3037 and
10-LIC-3039 are in manual mode and closed position and open all block valves
around the control valves.
Check that butterfly valves on 18"-GP-1305001 and 12"-GP-1305008, (process

gas to and from 10-E-2011) are open. Switch temperature controller 10-TIC-
3039 into manual mode with an output of 0% and check that 10-TV-3039-A is
fully open and 10-TV-3039-B is fully closed (minimum stop).
Open drain upstream of 10-XV-3036 and drain trapped condensate by opening

the 2" bypass valve upstream as well.
Reset IS-6 to energize the trip valve 10-XYS-3036.
Establish normal flow of cooling water to the final cooler 10-E-3012.
The methanator is now ready to be heated up and taken into operation.
The methanation catalyst is prereduced and does not have to be reduced at the
initial start-up.
The CO and CO2 content in the gas to the methanator should be as low as
possible to prevent overheating of the catalyst. (The maximum recommended hot
spot temperature for continuous operation is 400C). The temperature
increments for 1 mole % CO and 1 mole % CO 2 are 73C and 60C respectively.
Confirm by analysis that the process gas is free of sulphur, i.e. contains less than
0.05 vol. ppm.
Proj. 2098
Pag. 5-31
Equalize the pressure by slowly opening the 2" bypass valve over the inlet
isolation valve. Upon equalization open the isolation valve and close the 2"
bypass again.
Establish flow by slowly opening 10-PV-3037 on manual.
To start heating up the methanator increase output from 10-TIC-3039 to 100%

and check that 10-TV-3039-A is fully open and 10-TV-3039-B is fully close.
Switch controller 10-TIC-3039 into automatic mode with a set point of
approximately 100C. Only a small flow will pass through the trim heater 10-E-
2011, so initially 10-TV-3039-B will stay fully open trying to maintain the desired
inlet temperature of 100C. To divert more flow to the trim heater and get the
temperature controller within controlling range, gradually close the butterfly valve
on 18"-GP-1305001 (by pass of 10-E.2011) . Increase 10-TIC-3039 set point to
maintain a heating rate of maximum 50C per hour and close the 18" butterfly
valve more, if required.
When the methanator inlet temperature has reached 220-240C, the methanation
reaction starts. When observing an increase in temperature difference between
the inlet and the outlet of the methanator, check that 10-TIC-3039 starts to
reduce the flow to the trim heater 10-E-2011 and, if required, opens the bypass
10-TV-3039-A, to control the inlet temperature.
Attention should be paid to the differential temperature across 10-E-2011 (10-

TDI-2085). 10-TDI-2085 is equipped with a high alarm in order to alert the
operators in case of a too high differential temperature on the tube side of 10-E-
2011 during start-up of the methanator.
Continue to heat up to the normal operating temperature of 300C at the reactor

inlet. If 10-TV-3039-B remains closed, and no duty is likely to be required from
the trim heater, the 18" butterfly valve may be opened completely, to avoid
unnecessary pressure drop.
When the level in the final gas separator 10-V-3011 has reached its normal
value, start the condensate pump 10-P-7005 A and check that the level controller
10-LIC-3039 is functioning properly. Open 10-HV-3531 to establish a minimum
return flow.
When the LT CO converter has been taken into operation, it is recommended to

bring the inlet temperature up to 320-330C for a few hours in order to obtain full
activity also for the top layer of catalyst. Afterwards, the inlet temperature is
reduced to the normal level of 300C.
Transfer the full process gas flow from vent 10-PV-3036 to vent 10-PV-3037 by
gradually increasing the output from 10-PIC-3037 and thereby opening the vent
valve. At the same time, check that the vent 10-PV-3036 closes. Switch the
pressure controller 10-PIC-3037 into automatic mode. Increase set point of 10-
PIC-3036 to about 2 bar above the actual.
Proj. 2098
Pag. 5-32
The optimum reaction temperature can be determined from the effluent gas
stream analysis as indicated on the analyser 10-AI-3033.
The CO + CO2 content measured is to be less than 10 vol. ppm.
When determining the operating temperature, it should be taken into account that
the catalyst lifetime is shorter at higher temperature and that temperature rise
due to breakthrough of CO2 is more dangerous at higher catalyst temperatures.
Adjust the process air flow to the secondary reformer to obtain a H2/N2 ratio of 3.0
in the process gas outlet the final gas separator 10-V-3011.
The recycle gas flow should now be taken downstream of the final gas separator
10-V-3011 instead of downstream of the CO 2 absorber 10-T-3002, to avoid CO
and CO2 in the recycle gas, as it affects the equilibrium of the zinc oxide
absorption reaction.
5.3.16. Taking the Process Condensate Stripper into Operation
Establish normal flow of cooling water to the stripped condensate cooler 10-E-
7002.
Check that the controllers 10-FIC-7010 and 10-LIC-7012 are in manual mode and
closed position. Open all block valves around the control valves. Check that the
isolation valve on 6"-SP-1701008 1 at addition point to process steam to primary
reformer is closed.
Close isolation valve on 4"-WCP-1701006 to battery limit (30-PK-1001). Turn

blind and open isolating valves downstream 10-HV-7011-B and open 4” drain
downstream 10-E-7002.
Fill up the process condensate stripper 10-T-7001 to normal level with process
condensate by opening 10-HV-7011-A. Switch the level controller 10-LIC-7012
into automatic mode. Reset interlock group I-7002. Open 10-HV-7011-A fully and
close 10-HV-7011-B.
Before admitting heating steam to the process condensate stripper, switch

flow controller 10-FIC-2030 for steam to primary reformer into manual mode
and maintain the output. This will ensure that the steam flow to the primary
reformer does not change when steam is admitted to the process condensate
stripper.
Open the 2" manual vent upstream of the process steam mixing point to lower
the pressure to close to atmospheric to purge out air from the equipment, when
heating steam is introduced.
Slowly introduce steam to the stripper by increasing the output of flow controller
10-FIC-7010 on manual. Gradually increase the flow to about 5000 kg/h and
switch the controller into automatic mode. Simultaneously, check that flow
measurement of steam to reformer 10-FIC-2030 increases by approximately the
Proj. 2098
Pag. 5-33
same amount. This will confirm that the steam flow to the reformer has not
changed.
Adjust the steam flow until the condensate quality is as specified. The pressure in
the stripper is increased to the normal operating value, which must be higher than
the pressure at the addition point to process steam.
When the quality of the condensate is acceptable the stripped condensate may
be routed to the demineralization unit. Open isolation valve on 4"-WCP-1701006
to battery limit (30-PK-1001) and close isolating valves downstream 10-HV-7011-
B and close 4”drain downstream 10-E-7002.
The steam which has until now been vented is added to the process steam by
slowly opening the manual block valve in line 6"-SP-1701008 until it is fully open.
Closely watch the process steam flow to the reformer 10-FIC-2030, which must
still be approximately the original flow plus the flow to the stripper. A minor
decrease, due to the increased back-pressure when stripper steam is added to
the process steam, is to be expected.
Switch flow controller for process steam 10-FIC-2030 back into automatic mode
and gradually reduce the flow to the desired S/C ratio, observing reformer
temperatures.
In case the process condensate stripper has an emergency shut down, the steam
flow to the stripper will automatically be stopped. Steam flow controller 10-FIC-
2030 will increase the flow through 10-FV-2030 to compensate for the steam flow
previously coming from the stripper.
5.3.17 Hydrogen recovery unit.
For detailed instructions see section 11 item 11.17

Proj. 2098
Pag. 5-34
5.4. Start of Ammonia Refrigeration System
Purge the refrigeration section with nitrogen and test for tightness at the same
time as the ammonia loop is purged.
Check that all relevant control valves are closed and the associated block valves
all are open.
Fill up the ammonia accumulator 10-V-5004 with ammonia from storage through
line 2"-HNL-1506012 and fill up all chillers with liquid ammonia to the normal
level. Switch all level controllers to automatic mode.
Take the ammonia condensers 10-E-5010 A/B into operation, opening C.W. lines
and purging off inerts. If it is suspected that inerts are present in the condensers,
open the vent lines 2"-NHG-1506020 and 1506022 as required.
Check that all block valves in the connecting lines to the ammonia refrigeration
compressor are open, and that all anti-surge control valves are opened in
accordance with the supplier's instructions. Start the ammonia compressor 10-K-
4041 and the ammonia booster compressor 10-K-4051 in accordance with the
supplier's instructions.
If the refrigeration system has been purged, vent the nitrogen to the ammonia
vent drum by opening the manual 2" vent valves at 10-E-5010 A/B and 10-V-
5004, until the pressure at 10-PI-5031 is 0.5-1 bar above the equilibrium pressure
corresponding to the temperature in the accumulator (10-TI-5067).
When circulation and heating is started in the synthesis loop, take the 1st and
2nd ammonia chiller 10-E-5006 and 10-E-5008 and the make-up gas chiller 10-E-
5009 into operation by gradually lowering the pressure in the 2nd chiller to
approximately 2.0 bar g, controlled by 10-PIC-5014 acting on the speed governor
of the ammonia compressor turbine 10-STK-4041. Bring the purge gas chiller 10-
E-5014 and the inert vent gas chiller 10-E-5011 online when necessary by
admitting gas to the chillers. At the initial start-up, the ammonia temperature in
the 2nd ammonia chiller must never be below 5C until the ammonia
concentration in the ammonia separator 10-V-5001 is at least 25%.
Once there is a normal level of liquid ammonia in the ammonia separator, start to
route the ammonia to the let down vessel 10-V-5002 by opening 10-LV-5010-A
and B. Keep the pressure in the let-down vessel at approximately 25 bar g
controlled by 10-PIC-5021. Vent the let-down gas and inert vent gas to the
ammonia vent drum 10-V-5011 via the 2" bypass across the off-gas absorber 10-
T-5052 and through 10-PV-5043, until the ammonia recovery section has been
taken into operation. (Before admitting flow to the off-gas header, check that
block valves on off-gas to reformer fuel line are closed).
Proj. 2098
Pag. 5-35
Route product ammonia from let-down vessel to flash vessel 10-V-5003 when
level is adequate. Hand controllers 10-LIC-5021-must both be given an output of
0 %. By handwhel close 10-LV-5021-A and let it blocked. Let 10-LIC-5021 to
control only 10-LV-5021-B.
During reduction of the synthesis catalyst, when the level of water and impurities
(catalyst dust) in the ammonia is too high, the ammonia product from the let down
vessel 10-V-5002 must be transferred to the ammonia vent drum 10-V-5011 via
the 3" drain. When the ammonia quality is acceptable, the ammonia is transferred
to the flash vessel as described above.
Open the vent 10-PIC-5023 for a few seconds to purge the flash vessel. Switch
pressure controller 10-PIC-5022 to manual and gradually lower the pressure in
the flash vessel to approximately 0.05 bar g by increasing the controller output to
the ammonia booster compressor 10-K-4051 capacity control system. Switch to
automatic suction pressure control when conditions have stabilized.
Switch 10-LIC-5023 into manual mode in closed position and start the ammonia
product pumps 10-P-5001 A/B and the sealing system in accordance with
supplier's instructions. By his handwhhel crack open 10-LV-5023 and send a
small flow of liquid ammonia through the product line to ammonia storage 6"-
NHL-1505007 to cool down the pipe. Open 10-LV-5023 to transfer liquid
ammonia to storage and switch to automatic level control.
Ammonia is transferred to the urea plant, when required, through the ammonia
product heater (10-E-5012). Assuming 10-LIC-5021 is in automatic mode,
gradually,with the handweel, open 10-LV-5021-A. When 10-LV-5021-A begins to
open, 10-LV-5021-B will begin to close. In case it closes completely, use the
handwheel of 10-LV-5021-B to maintain a certain minimum flow to the flash
vessel to keep product pumps and booster compressor running in case the urea
plant has an emergency shut down. Adjust 10-TIC-5066 at 10-E-5012 bypass to
approximately 25C in order to cool liquid ammonia from the accumulator to the
1st chiller further.
When the level in the ammonia accumulator 10-V-5004 starts to increase, switch
level controller 10-LIC-5031 into automatic mode and flow controller 10-FIC-5012
into remote mode from 10-LIC-5031. Keep the pressure in the ammonia
accumulator at approximately 16.6 bar g controlled by 10-PIC-5032. The exact
pressure set point depends on the cooling water temperature (daily and seasonal
variations) to the ammonia condenser, as this determines the temperature and
equilibrium pressure of ammonia in the accumulator. By keeping a set pressure
equal to the vapour pressure, inerts will continuously be vented, and pressure
build-up in the refrigeration system is avoided. Secondly, adjust the inert vent gas
flow rate from the ammonia accumulator using 10-FIC-5031 to avoid overloading
the inert vent gas chiller.
When the level in the inert vent gas separator 10-V-5005 has reached its normal
value, line up liquid ammonia to 10-E-5008/10-E-5014, and check the function of
the level controller 10-LIC-5033.
Proj. 2098
Pag. 5-36
5.5. Start of Ammonia Synthesis Loop
5.5.1. General Remarks
If required, the synthesis loop must be purged and tested for leaks as described
in the preparatory procedures in Section 4.
During the heating-up process, a high linear gas velocity will favour a uniform
heating of the ammonia synthesis converter.
When the heater load has been increased to its maximum, it should be kept at
that level; any further temperature changes should be effected by adjusting the
gas circulation rate. This will assure the maximum possible circulation rate.
During the heating-up process, it is preferable to maintain a low loop pressure to

provide a high linear velocity and to control the ammonia synthesis reaction rate.
While the exact pressure is not very important, it is important that the level
chosen is kept as constant as possible to facilitate temperature control.
When the loop has been pressurised and gas circulation is about to start, verify
the tightness of the Steam Generation waste heat boiler 10-E-5001 and the
Steam Generation BFW preheater 10-E-5002 by water analysis of the reduction
gas. If the waste heat boilers are leaking, it is likely that the boiler water has
entered the synthesis loop and is contaminating the reduction gas.
5.5.2. Starting the Synthesis Gas Compressor, 10-K-4031
Once the process conditions specified above in the previous sections have been
obtained, pressurize all process stages of the synthesis gas compressor 10-K-
4031 with synthesis gas and start the compressor at minimum governor speed
with 100 % kick-back (or Antisurge) for all process stages; follow the supplier’s
instructions.
An increase of the throughput of the gas preparation section to approximately 70

% may be necessary to generate enough KS ( High-High Pressure) steam to run
the synthesis gas compressor 10-K-4031 above the minimum governor speed.
5.5.3. Heating Up the Ammonia Synthesis Loop
The following procedure should be followed:
1. Initially, check that the cold-shot valve 10-TV-5011 is closed by 10-TIC-

5011 in manual mode. The main inlet valve 10-HV-5002 must be partly
open, by means of 10-HIC-5002, to allow sufficient cooling of the converter
shell.
2. Check that the 6” manual gear operated inlet valve to the start-up heater
10-H-5001 is fully open and that the heater is ready for ignition.
Proj. 2098
Pag. 5-37
3. Check that the bypass valve 10-TV-5003 over the BFW preheater 10-E-
5002 is closed and that the butterfly valve at the gas outlet of the
exchanger is open.
4. Establish a flow of BFW to 10-E-5002 by opening 10-HV-2071-B. The BFW

temperature (10-TI-5032) outlet 10-E-5002 must be monitored continuously
and the flow adjusted to avoid boiling in the exchanger.
5. Introduce cooling water to the water cooler 10-E-5004 to decrease the

process side outlet temperature as much as possible, thus lowering the
ammonia concentration inlet the converter.
6. Establish the maximum possible circulation rate by closing the kick-back

valve for the recirculator 10-K-4031 and opening the suction valve fully.
7. Ignite the start-up heater 10-H-5001, following the recommendations of the

supplier.
8. Start the ammonia compressor 10-K-4041 and the ammonia booster

compressor 10-K-4051 in accordance with supplier's recommendations and
establish a flow of cooling water to the ammonia condensers 10-E-5010
A/B, if not already in operation (cf. para. 5.4). The pressure in the 2nd
ammonia chiller 10-E-5008 is kept at approximately 2.0 bar g by the
controller 10-PIC-5014, controlling the speed of the ammonia compressor
turbine 10-STK-4041.
9. Increase the start-up heater load to maximum and start heating up the
catalyst. Stay below the maximum heating-up rates and within a maximum
temperature difference of 150C between the start-up heater outlet and the
first catalyst bed outlet. Furthermore, stay within a maximum temperature
difference of 200C between start-up heater outlet and converter outlet.
10. Keep the start-up heater at the highest possible load, and control the
temperature by adjusting the circulation rate.
11. Bring the inlet temperature of the first catalyst bed up to approximately
400C at a maximum rate of 50C/h.
If significant differences occur between individual readings of the outlet

temperature of the first bed, and if these differences tend to increase,
reduce the heating rate by raising the circulation rate and/or lowering the
operating pressure to boost the actual gas velocity further.
12. Monitor the temperature increase across the first bed and when there are
evident signs of reaction, gradually increase the circulation rate to obtain a
temperature increase of not more than 50C/h at the outlet of the first bed.
The outlet temperature from the first bed should not exceed 480C.
Proj. 2098
Pag. 5-38
Start ammonia analysis of the synthesis gas at the shell-side inlet and tube-
side outlet of the hot heat exchanger 10-E-5003 at the sign of reaction.
Increase the make-up gas flow to the loop to maintain a constant loop
pressure of 85-100 bar g.
13. Establish a purge gas flow controlled by 10-FIC-5011 to maintain a

constant level of inert gases in the synthesis loop.
14. Increase the inlet temperature of the second catalyst bed until a
temperature of approximately 380C is reached. The maximum heating rate
should be 50C/h.
The temperature at the inlet to the second bed is basically controlled by the
circulation rate, i.e. the flow through both the main inlet and the start-up
heater.
To increase the second bed inlet temperature, it may also be necessary to

change the distribution between main flow and start-up heater flow.
Throttling the main valve will increase the flow to the start-up heater and
decrease the start-up heater outlet temperature. This will give a lower inlet
temperature to the first bed, which should minimum be about 370C, and
probably increase the temperature difference across the first bed.
Furthermore, the duty transferred in the interbed exchanger will be lower.
Consequently the inlet temperature to the second bed will increase.
17. Running at maximum circulation rate a temperature of about 370-390C at

the inlet of the first catalyst bed should be maintained. The start-up heater
load should be reduced when required and in small steps allowing
converter temperatures to stabilize in between.
While reducing the heater load, keep the first bed inlet temperature
somewhat on the high side: this reduces the risk of losing the reaction in
the converter. The following steps may be taken to compensate for each
reduction of the heater load, thus keeping the variations in catalyst
temperatures at a minimum:
- Change the distribution of flow between the inlets, namely in the

direction of more flow through the main inlet and less flow via the
heater through the cold-shot inlet, i.e. by opening the main valve
more.
- Increase the pressure if necessary and permissible.
- Gradually decrease the ammonia concentration at the converter inlet

by decreasing the pressure in the chillers.
- If necessary, reduce the circulation flow by opening the recirculator

bypass.
Proj. 2098
Pag. 5-39
- Increase the purge gas flow if necessary.
18. After some time, the outlet temperature of the start-up heater will drop
below the inlet temperature to the first bed, at which point the heater gas
begins to function as cold shot.
When the heater load is reduced to a minimum, the outlet temperature of

the heater approaches the normal inlet temperature of the ammonia
converter, and the start-up heater can then be stopped. This ensures a
slow cooling of the heater, the connecting piping and the converter bottom
part. Furthermore, temperature shocks are avoided when the normal cold
shot is introduced.
Introduce the normal cold shot flow shortly after stopping the heater, as
follows.
Verify that the bottom forging of the converter has cooled down, open the
cold shot valve slowly (small steps) while keeping the first bed inlet
temperature constant by opening the main valve correspondingly.
If the first bed inlet temperature has a tendency to decrease, reduce the
circulation slightly. Once a reasonable amount of flow through the cold shot
valve has been reached, isolate the start-up heater by closing the manual
inlet valve.
When the main valve is fully open (or almost fully open), the cold shot valve
10-TV-5011 should be within the range for automatic control, and can be
switched over to automatic.
Switch the synthesis gas compressor to normal make-up gas suction

pressure control, following the recommendations of the compressor
supplier.
Proj. 2098
Pag. 5-40
5.6. Start of Ammonia Recovery Unit
It is assumed that the system has been flushed and purged with N 2 as described
in the preparatory procedures in Section 4.
Check that all relevant control valves are in manual mode in closed position and
the associated block valves are all open.
Reset interlock groups as required to open control valves and start pumps.
Start the ammonia recovery section as follows:
Admit demineralized water to off-gas absorber 10-T-5052 via 2"-WD-1508303.

Once normal level is established, start LP circulation pump 10-P-5052 A/B
according to supplier's instructions. Switch 10-LIC-5044 to automatic mode.
Establish level in purge gas absorber 10-T-5051 by opening 10-LV-5041 to

obtain a back flow to the absorber. Close the valve when the level is inside
normal range and switch the controller to automatic mode.
Continue to add demineralized water to the off-gas absorber as required. The

water will flow through the rich/lean solution exchanger 10-E-5051 A/B to fill up
the distillation column 10-T-5053 and reboiler 10-E-5053.
When the level in the distillation column is within normal range, pressurize the
column to 25 bar g 10-PI-5051 using gas from the let down vessel. Open the 2"
bypass valve around the non-return valve on 2"-NHG-1510010 inlet the let-down
vessel to pressurize the system. Close the 2" bypass. By pressurizing the
column, the rest of the ammonia water system can be filled with water.
The purge gas absorber 10-T-5051 is pressurized to 123 bar g with purge gas via
bypass valve 10-HV-5502 and 1” bypass valve inlet absorber.
Start HP circulation pump 10-P-5051 A/B, according to supplier's instructions,

and 10-FIC-5041 in manual mode set to get 10-FV-5041 full open.
Stop the admission of demineralized water from header.
Adjust the flow through 10-FV-5042 to normal value and switch the controller into
automatic mode.
Adjust the flow to purge gas absorber through 10-FIC-5041 to normal value.
Circulation has now been fully established.
Pressurize the off-gas absorber to 14.7 bar g (10-PG-5548) with off-gas by
opening gate valve on
2"-NHG-1505004.
Proj. 2098
Pag. 5-41
It will not be possible to admit demineralized water when the system is

pressurized. After pressurizing the system, make-up water required in the
ammonia recovery unit will be added by injection of HP steam to the distillation
column via 1" steam bypass of 10-E-5053.
Take the lean solution cooler 10-E-5054 and ammonia OH condenser 10-E-5052
into operation.
Take the reboiler 10-E-5053 into operation by slowly admitting steam through
flow controller 10-FIC-5053. Increase flow to normal operating value of
approximately 2000 kg/h and adjust quench temperature at 10-TIC-5095 to
270C. Aim at a bottom outlet temperature from the distillation column 10-TI-5094
of approximately 226C.
Open the gate valve inlet purge gas absorber and close the 1" bypass valve.
Switch pressure controller 10-PIC-5042 into automatic mode with a set pressure
of 123 bar g. Check that pressure controller 10-PIC-5043 is in automatic mode
with a set point of 14.7 bar g.
Transfer all vented purge gas from 10-V-5014 to purge gas absorber by
gradually resetting 10-FIC-5011. This will open flow control valve 10-FV-5011-A
and at the same time close 10-FV-5011-B. Check that the pressure controllers
10-PIC-5042 and 10-PIC-5043 are functioning properly while transferring flow.
Admit let down and inert vent gas to the off-gas absorber by opening gate valve
on 2"-NHG-1506011 outlet absorber and closing the 2” gate valve on the
absorber bypass line.
Normal flows of purge, let-down and inert vent gas are now passing through the
absorbers and being vented to the flare. To avoid overloading the absorbers,
ensure that levels in purge and inert vent gas chillers, 10-E-5014 and 10-E-5011,
are kept above tube bundles (may be checked by confirming that gas outlet
temperature is maximum 5C above liquid ammonia temperature in chiller).
Adjust the flow of ammonia water to the absorber to obtain gas outlet
temperatures of approx. 42°C and 4°C respectively.
Keep levels evolution under observation.
Start to inject direct steam to the distillation column by opening the manual 1”
globe valve on by-pass of 10-E-5053. This will make up for the water lost in liquid
ammonia to storage and off-gases from the absorbers.
When the level in the ammonia OH drum 10-V-5051 has reached the normal
value, start the ammonia reflux pump 10-P-5053A or B following Supplier
instructions.
Initially temperature control valve 10-TV-5088 must be fully open and 10-LV-5053
must be fully close to obtain total reflux.
Proj. 2098
Pag. 5-42
When the ammonia concentration in the reflux product increases, adjust the
reflux flow until the desired concentration is obtained. Then switch the
temperature controller 10-TIC-5088 to auto mode with set point equal to the
actually observed temperature.
The water content of the overhead product is checked by analysis. When the
water content is below 1 % the product may be sent to storage under control of
10-LIC-5053.
When the hydrogen recovery unit 10-PK-5001 has been taken into operation and
the ammonia recovery unit is operating in steady conditions, off-gas should be
introduced as fuel at the primary reformer burners as described in para. 5.3.3.5.
Proj. 2098
Pag. 5-43
5.7. Special Procedures During Initial Start-up
5.7.1. Reduction of High Temperature CO Converter Catalyst
The HT CO converter has been taken online as described previously.
The catalyst will be reduced by hydrogen and carbon monoxide generated in the
primary reformer. The reduction of Fe2O3 by CO is fast and exothermic, so in
order to ensure a moderate reduction rate and easy temperature control,
maintain a S/C ratio of 8 or more. This will reduce the content of carbon
monoxide in the primary reformer effluent.
After introduction of process gas and stabilization of catalyst temperatures, the

inlet temperature ,indicated by 10-TI-2086, is increased at a rate of 25C per hour
until normal operating temperatures have been reached.
As the reduction process begins, a temperature increase at the bottom of the

catalyst bed will probably be observed. The rate of increase must not be allowed
to exceed 50C per hour, nor should the outlet temperature of the HT CO
converter exceed the inlet temperature by more than 50C at any time. If any of
the catalyst temperatures show a tendency to increase by more than 50C/h,
stop the natural gas flow to the primary reformer.
The HTAS catalyst contains less than 150 ppm vol. sulphur in the form of
sulphate. Due to the low sulphur content, the conventional desulphurization
period is not required.
Analyze samples of the process gas taken both upstream by 10-AI-5001-1 and
downstream by 10-AI-5001-8 of the HT CO converter during the reduction period.
During the HT shift catalyst reduction and capacity increase, the pressure drop
across the catalyst bed in the HT CO converter should not exceed 0.5 bar. The
system pressure at 10-PIC-2076 must be increased accordingly.
5.7.2. Reduction of Low Temperature CO Converter Catalyst
5.7.2.1 Prior to Activation of Catalyst
The LK-821-2 catalysts are activated by reducing the copper oxide to copper
using hydrogen as reducing agent. Carbon monoxide will also reduce the catalyst
and it must be kept in mind that the reduction heat for this reaction is
approximately twice as high. The amount of heat evolved by the reduction is very
large compared to that of the normal shift reaction, and great care has to be
taken when the unreduced catalyst is exposed to a reducing gas.
Proj. 2098
Pag. 5-44
During the reduction, some carbon dioxide is released from the LK-821-2
catalyst. In addition, if the reducing gas contains carbon monoxide, carbon
dioxide is produced. A suitable purge, taken from the vent on 10-V-2002, should
be established from the reduction loop in order to keep the partial pressure of
carbon dioxide (plus carbon monoxide) below 1 bar since it could react with the
catalyst under formation of carbonates, which may weaken the structure of the
catalyst.
Prepare the start-up blower 10-K-2003 in accordance with supplier's detailed

instructions.
Open all valves and blinds in the nitrogen start-up circuit:
10-K-2003  10-E-2015  10-R-2005 

10-E-2014  10-V-2002  10-K-2003
All isolation valves in the branches connected to the above loop are closed.
5.7.2.2 Activation Procedure
Reduction is now performed in the following sequence:
Take the start-up cooler 10-E-2014 into operation by opening the 2" bypass valve
at the cooling water inlet, pressurize and then open the main FCS inlet 8" block
valve. Slowly open the main outlet 8" block valve. In case the pressure in the
cooling water header is higher than normal, due to lower circulation rate, keep the
main outlet valve partly closed to avoid vibrations in the exchanger.
The circulating nitrogen pressure should be as high as possible to obtain a high

circulation rate and a high space velocity, speeding up the reduction.
Start the nitrogen blower 10-K-2003 in accordance with supplier's detailed

instructions. The flow should be as high as possible.
Hydrogen Analysis:
It is imperative that hydrogen analyses at reactor inlet and outlet, measured

before and after the hydrogen addition point (10-AP-2566 and 10-AP-2577), are
made right from the start of establishing the nitrogen circulation, at half-hourly
intervals, also to check for possible leaks of process gas or hydrogen into the
circuit.
Hydrogen Flow meter Calibration:
It is strongly recommended that calibration of the hydrogen flow meter 10-FI-2577

is performed before heating up is commenced, at latest when 120C at the inlet is
reached.
Proj. 2098
Pag. 5-45
Admit steam to the start-up nitrogen heater 10-E-2015 and initiate heating up of
the catalyst bed from ambient to 170C, measured at the reactor inlet by 10-TIC-
2111. The temperature can be brought up as fast as allowable out of regard for
the capabilities of the heater, the piping and the vessel.
If some of the temperature indicators show heavy fluctuations when approaching

100C, this may be due to the presence of water in the thermowells, and blowing
of the thermowells with nitrogen is recommended.
After reaching 170C at the inlet of the reactor, maintain this inlet temperature
and let all converter bed temperatures stabilize.
When all temperatures have stabilized, add an amount of hydrogen

corresponding to 0.3 - 0.5 mole % to the nitrogen recycle gas. The hydrogen-rich
gas (recycle gas from header) is added to the nitrogen start-up circuit
downstream of 10-V-2002 using 10-HV-2576. The temperature at the top of the
catalyst bed should be watched very closely : 0.5 mole % hydrogen in the
nitrogen results in a temperature increase over the bed of approximately 17C.
After stabilization of the catalyst bed temperatures and verification by analysis of

hydrogen consumption, increase the hydrogen flow gradually (maximum 0.5 mole
% steps) and adjust it to give a temperature increase across the bed of
approximately 60C, i.e. about 170C inlet and about 230C hot spot and,
eventually, exit converter. The inlet hydrogen concentration should not be
allowed to exceed 2.5 mole % at this stage.
As the hydrogen containing recycle gas also contains other gases, mostly
nitrogen, which are inert the pressure in the nitrogen circuit will increase. A small
purge flow may be established by opening the manual globe valve on the 2" vent
line in the overhead line of 10-V-2002, to maintain the pressure.
The reduction now proceeds at the above converter feed conditions for several
hours and the reduction zone moves downwards through the bed.
If the catalyst hot spot exceeds 250C, the hydrogen flow must be stopped
immediately.
If the catalyst hot spot tends to increase above 230C, decrease hydrogen flow
as required to control the temperature.
If the catalyst temperatures appear to be completely out of control (fast

increasing hot spot temperature), hydrogen addition and nitrogen circulation must
be stopped immediately and the converter depressurized and, then after
depressurization, purged with nitrogen.
Proj. 2098
Pag. 5-46
When the reduction zone approaches the bottom catalyst layer, hydrogen
breakthrough can be expected soon, resulting in hydrogen build-up in the circuit if
the recycle gas make-up flow is not reduced. Since it is not recommended to
exceed 2.5 mole % hydrogen at the converter inlet at this stage, the recycle gas
make-up flow must be reduced accordingly.
At the first sign of a decrease in the reduction rate, as indicated by decreasing

hot spot temperature at the bottom of the catalyst bed and/or the converter outlet,
it is recommended to slowly increase the top bed temperature towards 220C at
a rate of 15 - 20C/h. The hot spot temperature must be below 230C.
When a temperature of 220C has been obtained at converter inlet and the
temperature profile has stabilized, the hydrogen concentration may slowly be
increased to about 4 mole %, provided this does not give rise to temperatures
higher than 230C anywhere in the bed or at the converter outlet.
Continue to recycle at the above conditions, i.e. about 4 mole % hydrogen and
220C, until hydrogen consumption has ceased. The reduction is considered
complete when hydrogen consumption has not exceeded 0.2 mole % for 2 hours.
When the reduction procedure has been completed, continue the recirculation in
order to keep the catalyst temperature 20C above the dew point of the process
gas. Maintain the circulation until a few hours before introduction of process gas
is foreseen.
It is essential to stop the flow of hydrogen containing recycle gas immediately

whenever the nitrogen circulation is stopped during the reduction period, by
closing hand control valve 10-HV-2576.
5.7.3. Reduction of Ammonia Synthesis Catalyst
5.7.3.1 Gas Composition and use of Refrigeration Chillers
A hydrogen/nitrogen mixture with an approximate ratio of 3 to 1 should be used.

Activation with normal ammonia synthesis gas at a pressure which is not too low
means that the ammonia synthesis reaction will take place somewhat before the
activation is completed, which presents two important advantages.
The heat produced makes it possible to increase the gas circulation rate above
the rate that can be supported by the start-up heater alone, and this means that
the last part of the activation process will take less time than would otherwise
have been the case. Also, a gradual transition from activation to normal operation
is achieved.
The co-condensation of the ammonia produced and the water, i.e. water released
during catalyst activation, results in a more efficient removal of water from the
synthesis gas before the gas is recycled back to the synthesis converter. This is
especially important because water is poisonous to the activated catalyst. Water
removal is improved for two reasons:
Proj. 2098
Pag. 5-47
The water vapour pressure above liquid mixed ammonia and water is lower than
above pure water.
The freezing point of the mixed liquid phase is lower than that of pure water, and
a lower condensation temperature can be used.
To remove the water, take water cooler 10-E-5004 into operation the moment
circulation is started.
Better removal of water vapour from the circulating gas is obtained when
refrigeration chillers 10-E-5006, 10-E-5008 and 10-E-5009 are brought online. It
is therefore important that the gas is cooled down in the refrigeration chillers as
soon as this can be done without any risk of ice formation.
Ice may be formed even if the temperature of the gas leaving the second chiller is
above 0C, because the surface of the tubes submerged in liquid ammonia will
be colder than the gas and may be sufficiently cold to cause freezing. Particularly
for this reason, and because some cooling tubes may freeze without anyone
noticing and then later break at full system pressure, it is advisable to work with a
broad safety margin.
When the ammonia water contains about 190 g NH3 per litre of solution, its
freezing point is below the boiling point of pure liquid ammonia at atmospheric
pressure. The refrigeration chillers should not be operated at such a low
pressure, but as soon as analysis of the ammonia water in the separator shows
more than 250 g NH3 per litre, the refrigeration chiller gas outlet temperature may
be decreased to -5C.
The thermodynamic properties of aqueous ammonia, including its freezing point

as a function of ammonia concentration from 0 to 100% by weight, are included
in the appendix to this chapter.
With an ammonia pressure of more than 4 bar g in the chillers, there is no risk of
ice formation in the tubes. The pressure in the second ammonia chiller 10-E-5008
is controlled by 10-PIC-5014, which controls the speed of the ammonia
compressor driver.
It is assumed that the catalyst is activated by circulating synthesis gas, with a

constant addition of synthesis gas to the loop and an equivalent amount of purge
to obtain steady conditions when the ammonia synthesis reaction begins after
catalyst activation. Furthermore, the hydrogen/nitrogen ratio is to be kept
constant during the activation process, which consumes hydrogen only; this
ensures a smooth transition from catalyst activation to normal operation.
When the loop has been pressurized and gas circulation is about to start, test the
tightness of the waste heat boiler 10-E-5001 by analyzing samples of the
synthesis gas in the loop to determine the water content. If the waste heat boiler
is leaking, boiler water will enter the synthesis loop and contaminate the
synthesis gas.
Proj. 2098
Pag. 5-48
5.7.3.2 Heater Load and Gas Distribution
Throughout the activation process, it is best to keep the circulation rate at the
highest possible level. A high linear gas velocity during the heating-up process
will promote a uniform heating up of the ammonia converter. In the later stages of
catalyst activation, a high circulation rate helps keep the water content of the
synthesis gas at a low level. It has also been found that a high circulation rate
leads to the highest catalyst activity.
During the first part of the heating-up period, when the catalyst temperatures in
10-R-5001 are low, the outlet temperature of the start-up heater should be kept at
a level not more than 125-175C above the highest temperature in the first
catalyst bed of 10-R-5001. The gas flow through the start-up heater should be
fairly high. Control the heating rate by increasing the load of the start-up heater.
When the heater load is at its maximum, it should be kept at that level: any
further temperature changes should be effected by adjusting the gas circulation
rate. This will ensure that the maximum circulation rate is maintained throughout
the catalyst activation process. The minimum circulation rate will therefore be
achieved when the inlet temperature of the first catalyst bed is at its maximum,
approximately 410-415C, and the ammonia synthesis reaction is about to start.
The circulation rate should at this point in time correspond to a space velocity of
at least 1000 Nm3/h per m3 of catalyst, preferably higher.
From the very beginning of the heating-up process, part of the synthesis gas,
controlled by 10-HIC-5002, should be routed to the converter main inlet, from
where it flows through the annulus and cools the pressure shell. The cold-shot
valve 10-TV-5011 should be closed, routing the remaining synthesis gas through
the start-up heater. While the converter is being heated up, the maximum rate of
temperature increase at the bottom of the converter should be 50C/h. The
temperature at the bottom of the converter depends on the outlet temperature of
the start-up heater and the total circulation rate.
5.7.3.3 Operating Pressure
During the initial period of activation, operate at a pressure of about 85 bar g if

possible, considering the operating limitations of the recirculation compressor.
The exact value is not critical, but to keep the linear velocity high, do not operate
above 100 bar g. Too high a pressure is also undesirable when the ammonia
synthesis reaction starts. In addition, to remove as much as possible of the water
from the circulating gas when the catalyst starts releasing water, the pressure
should not be much below 85 bar g. While the exact pressure is not very
important, it is quite important that the pressure level chosen is kept as constant
as possible to facilitate temperature control.
Proj. 2098
Pag. 5-49
5.7.3.4 Operating Temperature
Throughout the entire activation process, it is important that all thermocouples be

read continuously to ensure that temperatures are developing uniformly and
symmetrically. Careful monitoring is especially vital when production starts and
when the pressure is slowly increased.
If significant differences occur between the individual readings of the outlet

temperature of the first bed, and if these differences show a tendency to
increase, this is probably due to an unsymmetrical activation of the catalyst, with
the result that the ammonia synthesis takes place faster in one part of the bed
than in another part.
Reduce the heating rate by increasing the circulation rate and maintain these
conditions for a few hours. This will even out the temperatures. If additional
correction is needed, lower the pressure to increase the actual gas velocity still
further. These steps will cause the reaction in the already activated part of the
bed to decrease, and the catalyst reduction in the inactivated part to progress
faster.
5.7.3.5 Water Formation
During the entire catalyst activation process, temperatures should be controlled in

such a way that the water concentration does not exceed 3000 ppm vol. in the
effluent gas.
Methods for determination of water vapour concentration at the converter outlet

are described in Section 11.
With prereduced KM1R catalyst, about 20 litres of water will be formed per tonne
of catalyst; with unreduced KM1 catalyst, about 280 litres of water per tonne.
With 26.9 m3 of prereduced catalyst in the first bed and 70.7 m3 unreduced
catalyst in the second bed of 10-R-5001, approximately 57 tons of water will be
formed during the activation process.
The amount and concentration of the aqueous ammonia formed depends to

some extent on the pressure and temperature conditions present during the
activation. Assuming a normal activation schedule is performed, the water will
settle out as:
 1% of the water appears as 0-20% aqueous NH3

 16% of the water appears as 90-99.5% aqueous NH3
 65% of the water appears as >99.5% aqueous NH3
Proj. 2098
Pag. 5-50
5.7.3.6 Catalyst Activation Schedule
In the following, the activation procedure is described for a combined charge with
prereduced KM1R in the upper bed and unreduced KM1 in the lower bed.
It is assumed that the synthesis loop has been purged and tested for tightness as
described in the preparatory procedures in Section 4.
Before the circulation of synthesis gas is commenced, the following points must
be fulfilled:
1. Purge the four thermowells in the ammonia converter 10-R-5001 with dry
nitrogen for at least 30 minutes in order to remove any water, which might
have condensed. Dry instrument air could also be used for this procedure.
Note: Please note that the nitrogen purge should not be used during normal
operation, as this may cause faulty readings.
2. Take the water cooler 10-E-5004 into operation.
3. Check that the refrigeration system is ready, i.e. fill up ammonia

accumulator and all chillers with liquid ammonia to normal level. Establish a
flow of cooling water to the ammonia condensers 10-E-5010 A/B if not
already done .
The ammonia temperature in the 2nd ammonia chiller must never be below
5C until the ammonia concentration in the ammonia separator 10-V-5001
is at least 25 wt%.
4. The ammonia compressor 10-K-4041 and the ammonia booster

compressor 10-K-4051 A/B must be ready to start.
5. The cold-shot, which is controlled by 10-TIC-5011, must be completely

closed during the entire catalyst activation.
6. Open the main inlet valve 10-HV-5002 partly, to allow sufficient cooling of
the converter shell.
7. Open the 18” butterfly valve at the gas outlet of the exchanger 10-E-5002
and close the bypass valve 10-TV-5003.
Establish a flow of BFW by opening 10-HV-2071-B. The BFW outlet

temperature 10-TI-5032 must be monitored continuously and the flow
adjusted accordingly, to avoid boiling in the exchanger.
8. Open the 10” manual valve inlet the start-up heater 10-H-5001 and prepare
the burners for ignition following the recommendations of the supplier.
Proj. 2098
Pag. 5-51
9. During activation, the following temperatures must be monitored and

logged on separate trends in the DCS system:
Instrument Description
10-TIC-5003 Main inlet

10-TIC-5011 Inlet 1st bed
10-TI-5004 Inlet 1st bed
10-TI-5005 Outlet 1st bed
10-TI-5007 Inlet 2nd bed
10-TI-5010 Inlet 2nd bed
10-TI-5026 Outlet 2nd bed
The following schedule for the activation should be considered as guidelines,

indicating reasonable times, temperatures and pressures during the various
stages of activation.
The activation procedure is divided into four periods as tabulated below:
Period Hot spot Rate of temp. Pressure App. length

temp. increase of period
C C/h bar g hours
1 Amb-250 30-50 85 6
2 250-400 15-25 85 10
3 400-480 Top bed: max. 10 85-120 60
Bottom bed: 2-3
4 Heater is taken off - 4
5.7.3.7 Period 1
During this period, the inlet temperature to the first catalyst bed is increased to
250C. Initially, increase the temperature at a rate of 30-50C/h, but allow this
rate to level off at about 30C/h towards the end of the period. At about 225C the
prereduced catalyst starts giving off water. Keep the pressure at about 85 bar g.
Establish the maximum possible circulation rate by closing the bypass valve of
the recirculator 10-K-4031 and opening the suction valve fully.
Increase the start-up heater load to the maximum load as quickly as possible, to
provide the highest possible space velocity. Then reduce the circulation rate by
increasing the recirculator bypass, to provide the desired temperature rise per
hour. Besides, a maximum temperature difference between the start-up heater
outlet and converter outlet of 200C should be observed.
Proj. 2098
Pag. 5-52
When approaching the maximum heater load, check that the butterfly valves are
not passing substantial amounts of gas, when they appear to be closed, or nearly
closed.
The converter main inlet valve 10-HV-5002 must be slightly open and should be
operated in such a way that the converter pressure shell temperatures are kept
below the design temperature of 370C. The cold shot valve 10-TV-5011 must be
closed throughout the activation.
The reduction water collected in the ammonia separator 10-V-5001 will in the
beginning probably be contaminated with catalyst dust, and it is recommended to
drain the first 500-1000 kg into waste liquid drums or tank car, using the flanged
spool, and then transfer it to the neutralization basin in the effluent treatment unit.
If at that time the ammonia content of the liquid is already too high for safe
handling, disconnect the flanged spool and transfer the liquid to the ammonia
vent drum 10-V-5011 and let the ammonia evaporate before final disposal.
The flanged spool during normal operation shall be disconnected.
5.7.3.8 Period 2
During this period the inlet temperature to the first bed is raised from 250C to
about 400C. Initially, increase the temperature at a rate of 25C/h, but allow this
rate to level off at about 15C/h towards the end of the period.
When the inlet temperature of the first bed approaches 360-375C, signs of
reaction in the first bed will probably appear, as evidenced by a small
temperature increase across the bed. Increase first bed inlet temperature to
about 400C to increase activity further. Preferably, the temperature should not
be increased beyond 400C to ensure that the reaction does not run away and
cause the reduction of the 2nd bed to progress too fast.
Nevertheless, if the reaction has not started when the inlet temperature to the
first bed has reached 400C (i.e. absence of increasing temperatures in the gas
flow direction), gradually increase the temperature further, e.g. to 420C. This will
probably not be necessary, and possibly the inlet temperature even has to be
decreased to limit the temperature increase across the first catalyst bed. If the
inlet temperature has to be adjusted, it should rather be managed by changing
the circulation rate than the heater load. If additional correction should be
needed, the pressure can be changed.
During activation, the outlet temperature of the first bed should not exceed
480C. The first bed inlet temperature should not be below 360-370C. If the
outlet temperature is still too high, a further reduction may be achieved by
increasing the ammonia content inlet the converter, i.e. by increasing the
pressure in the 2nd chiller 10-E-5008.
Proj. 2098
Pag. 5-53
The heating rate during this period is determined, besides the heater capacity, by
the desire of keeping the water concentration at converter outlet below 3000 ppm
volume and obtaining uniform catalyst temperatures. If the water vapour
concentrations exceed 3000 ppm, although it is unlikely, the rate of heating up
should be reduced by increasing the circulation rate.
It is strongly recommended that the development of the reduction is followed by

means of water analyses of the converter outlet gas. These analyses should be
initiated at the beginning of period 2 and should be continued throughout period
3. The analysis should be made every hour and every 4-8 hours at the inlet.
The unreduced catalyst in the 2nd bed does not start to reduce at an appreciable
rate until it has reached a temperature of about 390C.
When sign of reaction in the first bed is evident, begin ammonia analysis of the
gas inlet and outlet of the converter.
5.7.3.9 Period 3
At the beginning of period 3, the activation of the pre-reduced catalyst in the first
bed is far advanced, whereas the catalyst in the second bed has only been
slightly reduced. The inlet temperature to the first bed is probably about 400C
and the outlet temperature from this bed is increasing slowly at a maximum rate
of 10-15C/h.
The pressure may be brought up to 100 bar g (if not already done) or more, over
a couple of hours during the first part of period 3.
Refrigeration chilling has probably been established in the last part of period 2,
but if not, it should be established now. The precautions discussed previously
should be observed, e.g. ammonia concentration of 25 wt.% or more.
Throughout period 3, the water vapour analysis of the converter outlet gas should
be continued. If the concentration exceeds 3000 ppm by volume, the rate of
reduction should be lowered by increasing the space velocity.
The increase of the first bed outlet temperature causes the temperature in the
second bed to increase. The inlet temperature to the second bed should be
allowed to rise to 410-420C, and should be maintained at that level for 10-15
hours.
The pressure may be raised to 120 bar g or more, provided that the temperatures
are developing fairly symmetrically in the catalyst beds.
The inlet temperature to the second bed is basically controlled by the circulation
rate, i.e. the flow through both main inlet and start-up heater.
Increasing the circulation rate will also decrease the temperature rise outlet of the
second bed, where temperatures should be allowed to rise at a maximum rate of
2-3C/h.
Proj. 2098
Pag. 5-54
To increase the second bed inlet temperature to 410-425C, it may also be

necessary to change the distribution between main flow and start-up heater flow.
Throttling the main valve will increase the flow to the start-up heater and
decrease start-up heater outlet temperature. Furthermore, the duty transferred in
the interbed exchanger will be lower. This will give a lower inlet temperature to
the first bed which should minimum be about 370C. As a result, the temperature
rise across the first bed and consequently the inlet temperature to the second
bed will both increase.
While throttling the main valve, monitor the pressure shell temperatures carefully.
Also the start-up heater pressure drop should be monitored. If the start-up heater
pressure drop becomes too high, it may be necessary to lower the circulation rate
and heater load to obtain the desired temperature levels.
The outlet temperatures from the first bed should not exceed 470-475C during
period 3.
At the end of period 3, the activity of the catalyst should have reached a level at
which the space velocity is close to the level for normal operation.
5.7.3.10 Period 4
When the process of decreasing the heater load is about to begin, the
recirculator bypass should be nearly closed and the circulation rate should have
reached an almost normal level, provided that the pressure is close to the normal
level for fresh catalyst. Whether it is desirable or not to increase the pressure
somewhat while the heater is being taken off-line is a decision to be made on the
basis of the actual conditions. It may be an advantage to keep the pressure
constant to avoid too many overlapping effects. Under certain circumstances,
however, it may be preferable to increase the rate of reaction by raising the
pressure or, on the other hand, it may be necessary to decrease the pressure if
the temperatures tend to run away.
While decreasing the heater load, keep the inlet temperature of the first bed a
little on the high side (say 400-410C): this reduces the risk of losing the reaction.
The heater load should be decreased stepwise in small steps. Reduction of the
heater load requires other adjustments to be performed so that catalyst
temperatures can be controlled. Variations in catalyst temperatures should be
kept to a minimum. The following steps may be taken to compensate for each
decrease in heater load:
1. Change the distribution of flow between the inlets, namely in the direction of
more flow through the main inlet and less flow via the heater through the
cold-shot inlet, i.e. by opening the main valve more.
2. Increase the pressure if necessary and permissible.
3. Gradually decrease the ammonia concentration at the converter inlet by

decreasing the pressure in the chillers.
Proj. 2098
Pag. 5-55
4. If necessary, reduce the circulation flow by opening the recirculator bypass.
5. Increase the purge gas flow if necessary.
No heater load reduction step should be carried out until the converter conditions
have been stabilized after the preceding step.
The heater load should be lowered before the gas distribution is changed (1). In
this way a gradual decrease of the heater outlet temperature is obtained.
Please note that while the heater load is being reduced, the second bed inlet
temperature will have a tendency to decrease, and thus approach normal
operating conditions for the second bed.
When the heater load is slowly reduced, the heater outlet temperature will, after
some time, become lower than the inlet temperature to the first bed, from which
time the heater gas acts as a "hot" cold shot. When heater load is reduced
further, the temperature of this "hot" cold shot slowly approaches the temperature
of the normal cold shot gas, i.e. the converter feed inlet temperature. During
these steps, care should be taken not to trip the start-up heater interlock group
due to low pressure drop (low flow).
Once firing has been reduced to a minimum, the heater outlet temperature has
almost reached the normal converter inlet temperature, and the start-up heater
interlock group can be tripped. This ensures a slow cooling of the heater, the
connecting piping and the converter bottom part. Furthermore, temperature
shocks are avoided when the normal cold shot is introduced shortly after the
heater has been taken off.
The normal cold shot is introduced in the following way:
After ensuring that the bottom forging of the converter has cooled down, open the
cold shot valve slowly (small steps) while keeping the first bed inlet temperature
constant by opening the main valve correspondingly. If the first bed inlet
temperature has a tendency to decrease, reduce the circulation slightly. Once a
reasonable amount of normal cold shot flow through the cold shot valve is
reached, isolate the start-up heater by closing the manual inlet valve.
When the main valve is fully open (or almost fully open), the cold shot valve
should be within the range for automatic control, and should be switched over to
automatic control.
Finally, increase circulation to maximum by completely opening the suction

isolation valve and closing the recirculator bypass, if not already closed. Switch
the synthesis gas compressor to normal make-up gas suction pressure control
(speed control) following the compressor vendor's instructions.
This ensures a smooth transition to normal operating conditions.

Proj. 2098
Pag. 5-56
At the end of this period, the catalyst activity has not yet reached the maximum
value, nor will it do so until after several days of operation. During this period in
which the pressure may slowly be raised to the normal operating value, it is
particularly important to avoid excessive temperatures, i.e. the outlet
temperatures from the two catalyst beds should not exceed 500C/450C
respectively.
5.7.3.11 Special Measures
We wish to emphasize that from the time when the catalyst starts giving off water
vapour and until it has been completely activated, it is extremely important to
avoid a stagnant synthesis gas atmosphere in the hot converter. In such an
atmosphere the reduction process will continue, and a fairly high concentration of
water vapour would poison the catalyst already activated. For this reason it is
vital to maintain a continuous gas flow through the converter during the entire
activation.
If the circulation has to be interrupted for a while, lower the temperature of the
catalyst to about 50C below the actual operating temperature level. This will stop
the activation of the catalyst very quickly and allow a safe interruption of the
circulation. If a sudden interruption of the circulation causes the gas flow through
the converter to stop before the temperature has been lowered as mentioned
above, establish a flow of purge gas through 10-FV-5011-B depressurizing the
loop to the ammonia vent through 10-V-5014. This will create a low gas flow
through the catalyst beds of the converter in the normal direction to remove the
water.
Proj. 2098
Pag. 5-57
5.8. Start-Up After Shutdown
5.8.1. Introduction
The start-up procedure to be used after a shut-down will, of course, depend on

the extent to which the units were taken out of operation during the shut-down
process. For the ammonia loop in a short period of down time, it is always an
advantage to keep the units upstream the loop operating at a reduced load (60%)
and to vent the treated gas. The gas can be vented at different points:
- Downstream from the desulphurization section through 10-PV-2027

- Downstream from the LT CO converter through 10-PV-2076
- Upstream from the CO2 absorber through the manual vent 10-HV-3022
- Downstream from the CO2 absorber through 10-PV-3036
- Downstream from the final gas separator through 10-PV-3037
5.8.2. Desulphurization Section
Heat the natural gas to its normal operating temperature in the natural gas
preheater coils 10-E-2004-2/1, send it through the desulphurization section and
then vent it through 10-PV-2027. Refer to initial start-up procedures.
If no recycle hydrogen is available, the temperature should be kept below 300 °C

due to the risk of cracking of higher hydrocarbons and carbon laydown on the
catalyst in the absence of hydrogen.
When the natural gas downstream from the sulphur absorber 10-R-2002 B has a
sulphur content of 0.05 ppm by volume or lower, then it may be introduced into
the primary reformer. As an extra precaution, if steam is not admitted to the
primary reformer, the pressure in the desulphurization section should be kept as
low as possible, preferably below the downstream pressure in the reforming
section.
Always check to make sure that the process natural gas supply to the primary
reformer is completely closed off by double block and bleed until the natural gas
is allowed to enter the primary reformer.
5.8.3. Reforming Section
5.8.3.1 Restart with Reduced Catalyst
If the system only will be shut down for a short time (a few hours), keep the
primary reformer hot and the catalyst reduced with a flow of approximately 30 t/h
of steam and about 1500 Nm 3/h of synthesis gas from the ammonia synthesis
loop.
Proj. 2098
Pag. 5-58
Add natural gas to the process steam, which is then routed to the primary
reformer in accordance with the start-up procedure. Once the natural gas has
been admitted into the primary reformer, increase the capacity and ignite the
secondary reformer as described in start-up procedure.
If the reforming section will be down anywhere from a few hours to, say, two
days, depressurize the reforming section to approximately 4 bar g, purge it with
nitrogen and maintain an internal nitrogen pressure slightly above atmospheric. In
order to restart the section, follow the normal start-up procedure.
Normally the catalyst in the primary reformer is kept in its reduced state during a
shut down, and the reforming section can be restarted using the procedure
described in start-up procedure.
For shut downs of short duration the reformer should be kept as warm as
possible to enable a fast restart. This means that prolonged steaming after stop
(trip) of the reformer should be avoided. Also long term operation of the flue gas
blower, beyond the time required for purging the furnace, should be avoided.
5.8.3.2 Restart with Oxidised Catalyst
During a shut down the primary reformer catalyst may accidentally be oxidized
through exposure to steam without a reducing agent present, although the
reforming catalyst is not oxidized easily. In this case an activation stage should be
incorporated in the start-up procedure.
5.8.3.2.1. Hydrogen-assisted Activation
Heat the catalyst in a stagnant atmosphere and introduce steam as described in

start-up procedure.
If hydrogen is available from the loop, it is introduced shortly after the steam at the
maximum available flow. The pressure is kept as low as possible. Hydrocarbon feed
corresponding to a steam/carbon ratio of 6-8 is introduced at an outlet temperature
of 600-650 °C.
If only a limited quantity of hydrogen is available, hydrocarbon feed is introduced as

stipulated above, and the available hydrogen is used only when the reformer inlet
temperature is close to that of normal operation.
The temperatures are increased to those of normal operation, with relatively more
firing applied around the top of the tubes. The pressure is kept as low as possible,
until the temperatures in the reformer are close to normal operating temperatures.
With hydrogen or a mixture of hydrogen and gas, the activation of the catalyst is
considered complete 4-8 hours after the normal operating temperature level has
been obtained depending on the degree of oxidation. After the activation period, the
normal operating conditions can be established gradually.
Proj. 2098
Pag. 5-59
5.8.3.2.2. No Hydrogen Available
If hydrogen is not available, and the natural gas is free from sulphur, the catalyst
can be activated by a steam/gas mixture corresponding to a molar steam/carbon
ratio of 6-8 introduced at an outlet temperature of 600-650 °C at the exit of the
reformer.
The temperature is increased gradually to normal operating level and the

pressure is kept below 10 bar g for 6-12 hours. The reduction will be more
effective if the reformed gas is recycled back to the suction side of the natural gas
compressor 10-K-4011.
If the natural gas contains sulphur compounds, the primary reformer must be
started up by cracking ammonia. Establish a flow of recycle hydrogen to the
hydrogenator via the connection at the suction side of 10-K-4011 and replace liquid
ammonia by desulphurized natural gas when it has been verified by analysis that
the total sulphur content of the exit gas from 10-R-2002 B is below 0.05 ppm. Follow
the procedures described in normal start-up procedure.
5.8.3.2.3. Carbon Laydown
Carbon deposit on the reforming catalyst may take place for various reasons, such
as:
1. Operating at normal process conditions on an insufficiently active catalyst,

due to
a) Insufficient reduction (activation)

b) Poisoning (normally by sulphur)
c) Ageing
2. Operation at abnormal process conditions, such as:
a) Too low steam to carbon ratio (or in extreme cases, exposure of the
catalyst to hydrocarbon in the absence of steam).
b) Too high preheat temperature or too violent firing at the top part of the
reformer, implying high radial and axial temperature gradients, which
will tend to favour thermal cracking reactions.
c) Excessive load (the higher the load, the higher the partial pressure of
the higher hydrocarbon will be at a given temperature level, and
consequently the risk of thermal cracking).
Proj. 2098
Pag. 5-60
It is extremely difficult to give limits for each of the parameters mentioned, as they
are all interrelated. Up to a certain activity of the catalyst, a certain range of
operating conditions can be tolerated, and it is thus possible that operating
conditions which could be used without difficulty in the early age of the catalyst, may
involve carbon deposit after some years of operation, when the catalyst activity has
decreased.
Carbon deposit is normally identified by an increasing pressure drop across the

primary reformer, indicated on 10-PDI-2052, and by the appearance of hot patches
on tubes when operating at constant and normal process conditions. Carbon
deposit is, however, more likely to be encountered in connection with changes of
operating conditions, such as an increase in the capacity or a lowering in the steam-
to-carbon ratio.
5.8.3.2.4. Recommended Actions to Take
In any case of carbon lay-down as indicated by a gradual increase in the pressure

drop, it is recommended that action should be taken as soon as possible, either in
order to stop further carbon build-up by changing operating conditions towards less
tendency to carbon formation, or preferably to remove the carbon deposited by
establishing a steam-to-carbon ratio of 10-15 (moles per atom) at a pressure as low
as possible, e.g. 3-5 bar g and at normal process temperatures. This treatment will,
within a few hours, remove freshly deposited carbon at conditions where the
catalyst is kept reduced, and normal operating conditions may be re-established
within a short period of time.
If the reason for the carbon lay-down is accidental operation at abnormal process
conditions, no further action should be required.
If the reason is low catalyst activity, the difficulties are likely to arise again when the
process conditions involving carbon deposit are re-established, unless the activity of
the catalyst is restored.
In that case, attempts should be made to judge whether the reduced activity is due
to insufficient reduction or to poisoning.
The remedy is either a re-reduction as described in section 5.8.3.3, or a sulphur

regeneration as described in section 5.8.3.4.
5.8.3.2.5. Removal of Larger Amounts of Carbon
If the process conditions, at which carbon formation is encountered, are not

changed as described in the previous section, the increase in pressure drop will
continue. The flow through the tubes may be restricted and some tubes may
become hotter than the average. In extreme cases, tubes may be completely
blocked by carbon and the catalyst may break down mechanically. Regeneration of
catalyst in blocked tubes is not possible.
Proj. 2098
Pag. 5-61
Substantial amounts of carbon or carbon which has been allowed to stay in the
catalyst bed for more than a few days, cannot be removed by the "mild
regeneration" described in the previously, but will require an oxidizing treatment,
either by steam or by steam plus air.
The steam plus air treatment is preferred, because it can be carried out successfully
at relatively low temperatures, whereas steaming is effective only at high tempera-
tures, which can hardly be obtained in the top part of the reformer where carbon is
most likely to be deposited.
The recommended procedure is as follows:
1. Gradually cut off the hydrocarbon feed flow and adjust the steam flow to
about 30 t/h. The vent valve 10-PV-2076 downstream from the LT CO
converter 10-R-2005 is opened to keep the pressure in the reforming system
as low as possible.
2. The LT CO converter is isolated from the reforming section.
3. Simultaneously adjust the firing pattern to obtain 450C inlet the catalyst
tubes and 650C outlet the catalyst tubes. The inlet temperature at the HT CO
converter (10-TI-2086) should be kept at least 15 °C above the dew point
4. Establish a temporary connection between the process air bypass line

downstream the process air flow control valve 10-FV-2016, and the liquid
ammonia line 2"-NHL-1203020, downstream the control valve 10-FV-2025.
5. Admit air gradually (over four hours), to obtain 2-4 % by volume of air in the
steam. Maintain this condition until the CO 2 concentration in the reformer
effluent has decreased below 0.1 % (approximately 6 hours). The
temperature exit the primary reformer should not be allowed to exceed 650C
in order to facilitate the subsequent re-reduction of the catalyst. Check also
the reformer effluent for SO2 if sulphur poisoning is suspected.
6. To check whether carbon removal is complete, increase the air flow gradually
to 8-10 % by volume of the steam flow. The CO 2 content of the reformer
effluent should increase only slightly or decrease.
7. When carbon removal has been completed, cut off air flow and maintain
steaming for about half an hour in order to purge the reformer for air.
8. Shut down the reformer, purge the reforming section with nitrogen and
remove the temporary connection between the process air line and the liquid
ammonia line.
9. The regeneration is now over. The catalyst is oxidized and must be re-
reduced following the procedure described in para 5.8.3.2.
Proj. 2098
Pag. 5-62
5.8.3.3 Sulphur Poisoning
5.8.3.3.1. General
The first indication of sulphur poisoning will normally be a change in the catalyst
temperature profile (increasing temperatures, particularly in the upper half of the
catalyst bed). If the poisoning is allowed to proceed, hot spots will appear on the
upper half of the tubes (typically 3-4 m from the top) and the pressure drop will
increase.
As for possible regeneration, it is important that the sulphur poisoning is identified in

an early phase. Regeneration is necessary when the reduced activity and
subsequent carbon lay-down lead to excessive tube skin temperature and/or
increasing pressure drops across the primary reformer, indicated on 10-PDI-2052.
The first step of a sulphur removal will therefore be removal of the carbon deposits.
5.8.3.3.2. Regeneration Procedure
1 The steps 1) to 6) of the carbon removal procedure described above in

section 5.8.3.3.3 are carried out.
During an oxidation of the catalyst, the SO2 content in the reformer effluent is
monitored. Part of the sulphur in the catalyst will be oxidized to SO 2, but the
main part will stay on the catalyst in the form of sulphate.
2. Synthesis gas from the loop is added to the steam corresponding to a H2O/H2
molar ratio of about 50, i.e. 30 t/h of steam and 1000 Nm3/h of synthesis gas.
The temperatures are essentially maintained the same as during the

oxidation. At these conditions, sulphur in the form of sulphates will be reduced
to H2S, whereas nickel oxide will not be reduced. The H 2S content of the
reformer effluent is monitored as soon as the hydrogen has been added and
can be expected to reach several hundreds of ppm volume.
3. When the sulphur concentration exit the reformer has decreased to below 100
ppm (this could last many hours depending on the degree of sulphur
poisoning), the hydrogen flow is gradually increased over a period of 2-4
hours corresponding to a decrease of the H2O/H2 ratio from 50 towards 10.
When the H2O/H2 ratio of 10 has been reached, the primary reformer
temperatures are increased to approximately 450C in the top, 650C in the
middle and 700-750C at the outlet of the catalyst.
During the first part of this period, reduction of sulphate still progresses, but
reduction of nickel will start mainly in the lower (and hotter) part of the tubes
and the nickel will absorb the H 2S. Therefore, the H2S concentration in the
reformer effluent will drop fast. As long as reduction of nickel oxide has not
started in the upper part of the tubes, sulphur will, however, be transferred
downwards in the tubes, i.e. into the part where it is less harmful.
Proj. 2098
Pag. 5-63
4. When a H2O/H2 ratio of 10 has been obtained, the catalyst could either be re-
reduced as described in para 5.8.3.2 or the sulphur removal could be re-
peated by once more oxidizing and reducing as described above.
A repeat of the regeneration would remove most of the sulphur "pushed

downwards" during the later part of the first regeneration. A single oxidation-
reduction cycle is, however, considered sufficient for restoring the original
activity of the catalyst.
5.8.4. CO Conversion Section
5.8.4.1 HT CO Converter, 10-R-2004
If catalyst temperatures are above the dew point of the process gas, then keep
the catalyst in an atmosphere of process gas. It can then be restarted
immediately when process gas is available.
Heat up the HT CO converter 10-R-2004 together with the reforming section.
5.8.4.2 LT CO Converter, 10-R-2005
Heat the LT CO converter 10-R-2005 to normal operating temperature using the

nitrogen start-up circuit at a pressure of about 7 bar g.
Add process gas to the converter after the heating process is completed.
It should be noted that when process gas is admitted after a shut-down, a sudden
temperature increase (up to 50C) may be observed. This is due to the
chemisorption of reactants on the surface of the catalyst. It may take about half
an hour for this "heat wave" to move down through the bed. In any case,
condensing of process gas must be avoided in the LT CO converter 10-R-2005.
Similarly, care must be taken to remove any condensate in the system before
admitting process gas to the converter by using the low point drains.
If any of the catalyst temperatures approaches the dew point of the process gas,
the partial pressure of the steam can be reduced by reducing the pressure in the
converter. Alternatively, purge the converter with nitrogen.
5.8.5. CO2 Removal Section
If the shut-down is for a short period of time, maintain the heat input to the CO 2
stripper reboiler 10-E-3002 and keep the MDEA solution circulating. The heat
input to 10-E-3002 is maintained by opening the manual vent 10-HV-3022, thus
allowing a process gas flow through 10-E-3002.
Carry out the restart procedure as described in start-up procedure.
Solvent circulation and process parameters must stabilize by the end of the
restart period.
Proj. 2098
Pag. 5-64
Take special care to ensure that a stable and sufficiently low figure (below 0.1
vol.%) is obtained for CO2 leaving the top of 10-T-3002. There must be a steady
flow of lean solution for at least 15 minutes before the methanation section can
be restarted.
After a complete shut down where the circulation has been stopped and the solution
has cooled down, heat up the CO2 section and take it into operation as described in
start-up procedure.
5.8.6. Methanation Section
If the system is only going to be shut down for a short period of time (a few
hours), keep the catalyst in the methanator 10-R-3001 in an atmosphere of
process gas. It can then be restarted immediately when process gas is available.
In case of a longer shut-down period and if catalyst temperatures drop below

approximately 200C, then there is a risk that nickel carbonyl [Ni(CO)4, very toxic]
will form, and the methanator must therefore be purged with nitrogen.
Heat up the methanator 10-R-3001 with process gas until the operating
temperature has been reached.
5.8.7. Ammonia Synthesis Section
5.8.7.1 General Information
Follow the below procedure for starting up the ammonia synthesis loop with
activated catalyst.
If the temperatures in the first catalyst bed are sufficiently high, it is possible to
start this section up without using the start-up heater. The minimum temperature
at which this is possible depends on the prevailing conditions, particularly catalyst
activity. It is normally necessary to use the start-up heater if catalyst
temperatures are below 340C.
The start-up procedure should be carried out at a relatively low pressure: about
85-100 bar g. This will facilitate control of catalyst temperatures when the
ammonia reaction starts.
Probably the easiest method - at least until operators gain a certain amount of
experience in operating the converter - is to keep the pressure constant until the
converter is online and conditions are stable. When the converter operation is
stable with a normal-type temperature profile (although not normal operating
temperatures), the pressure can be raised to the normal level fairly rapidly, e.g.
10-20 bar per hour.
Proj. 2098
Pag. 5-65
After short system down times (e.g. 2 to 5 minutes), it is normally possible to re-
establish operating conditions by restarting the synthesis gas compressor 10-K-
4031. The control valves in the loop should remain in the same positions as
before the shut-down. During the start-up procedure, monitor the temperatures in
the ammonia synthesis converter closely and stop the make-up gas flow
immediately if the situation begins to run out of control.
5.8.7.2 Start-up Without Using the Start-up Heater
1. Open the converter main inlet valve 10-HV-5002, close the cold-shot valve
10-TV-5011, and check to make sure that the start-up heater inlet valve is
closed. Open the tube side bypass across the BFW preheater 10-E-5002 to
increase the converter inlet temperature if necessary.
2. Open the block valves on the level control valve 10-LV-5010-A/B

downstream from the ammonia separator 10-V-5001 and check the
operation of the level controller 10-LIC-5010.
3. Stop any flow of BFW to 10-E-5002 by closing 10-HV-2071B.
4. Put the water cooler 10-E-5004 online; then put the refrigeration
compressor 10-K-4041 and the ammonia chillers 10-E-5006, 10-E-5008,
10-E-5009, 10-E-5011 and 10-E-5014 online as well, particularly if catalyst
temperatures and the loop pressure are low (the initial ammonia reaction
will be slow).
5. Start the synthesis gas compressor 10-K-4031 with all antisurge valves and
the suction valve wide open and the block valves on the discharge side
closed. The balancing valve between the main compressor and the
recirculator should be open.
6. Adjust the loop pressure to correspond to the start-up pressure desired by

purging through purge valve 10-FV-5011B . Increase the discharge
pressure from the synthesis gas compressor 10-K-4031 to match loop
pressure by controlling the antisurge valves, and when the pressures are
about the same, open the discharge valve (continue to operate the
recirculator with closed block valves and an open bypass). The pressure in
the loop is now controlled by the synthesis gas compressor.
Establish a small purge gas flow (approximately 2000 Nm 3/h) to maintain a

constant level of inerts and adjust the pressure as required (about 85-100
bar g).
7. Now start the recirculation. This is a difficult procedure, and catalyst

temperatures and operating conditions in the loop should be monitored
closely.
Proj. 2098
Pag. 5-66
First open the suction block valve, then open the discharge valve slightly.
This will establish a small recirculation, and the ammonia reaction may
start. Establish the recirculation to provide constant or slowly increasing
temperatures in the catalyst.
If the ammonia reaction does not start, then reduce the recirculation slightly
and observe the exit temperature from the first catalyst bed. If no ammonia
reaction is observed at this point - i.e. if temperatures continue to drop
slowly - then the ammonia synthesis section must be restarted using the
start-up heater as described .
When the synthesis reaction starts, increase the flow of make-up gas to
maintain the loop pressure. When the circulation has been started, and the
gas temperature inlet 10-E-5002 has stabilized, carefully establish a flow of
boiler feed water through 10-E-5002 and switch the temperature controller 10-
TIC-5003 into automatic mode. Gradually increase the purge gas flow along
with the make-up gas flow.
8. Keep the loop pressure constant until operations are stable, the
recirculation rate is high, and catalyst temperatures are close to normal.
Then increase the loop pressure by 10-20 bar per hour while controlling the
catalyst temperatures with the cold-shot flow through 10-TV-5011 and the
temperature at the inlet of 10-R-5001 (10-TIC-5003).
9. Switch level controller 10-LIC-5010, which controls the level in the

ammonia separator 10-V-5001, into automatic mode when the normal liquid
level is reached.
10. At the same time, start the let-down section and the ammonia product
pump 10-P-5001 A/B to transfer product ammonia to storage.
5.8.7.3 Start-up Using the Start-up Heater
The procedure for using the start-up heater to restart the ammonia synthesis loop
is described in start-up procedure.
Refrigeration Circuit
When required, the refrigeration circuit is taken into operation following the
procedure described in start-up procedure.
Proj. 2098
Pag. 5-67
Appendix 1
A1 – A3 SHIFT REACTION EQUILIBRIUM TABLES
A4 – A6 METHANE REFORMING REACTION EQUILIBRIUM TABLES
A7 – A13 METHANE LEAKAGE CURVES
A14 AMMONIA CONVERSION PROFILE

Proj. 2098
Pag. 5-68
Appendix 2
- STEAM TABLES

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5.8. Start-Up After Shutdown

5.1. General Information

This chapter consists of three main sections:

- an outline of the start-up sequence

- a detailed description of a normal start-up

- special procedures required during initial start-up

During start-up, regularly check the surface temperatures of brick-lined

All recommendations given by equipment suppliers (particularly of valves,

5.2. Start-up Sequence Survey

The start-up of the plant is to some extent depending on the availability of

2. Bypass, isolate and pressurise the LT CO converter with nitrogen to 5 bar g

7. While heating the primary reformer in stagnant atmosphere, begin heating

16. Start the process air compressor 10-K-4021, following supplier's

17. Ignite the secondary reformer 10-R-2003 (cf. para. 5.3.13).

19. Heating up of the LT CO converter 10-R-2005 in circulating nitrogen, by

5.3. Detailed Start-up Description of Syngas Production

5.3.1. Preparing Plant Start-up

Check the availability of feedstock and utilities.

Confirm the completion of the preparatory work as described in Section 4 Plant

Confirm the operability of the:

 Emergency power system

5.3.3. Heating up the Reforming Section

5.3.3.1 Preparatory Steps

It is assumed that the reforming section including the HT CO converter 10-R-

Bypass valves 10-TV-2079 in waste heat boiler 10-E-2008 and 10-TV-2080 in

Switch the controllers 10-FIC-2046, 10-FIC-2047 and 10-PIC-2047 to manual

Open the control valve 10-FV-2047 slightly by increasing 10-PIC-2047 output.

It is important to fire symmetrically in both chambers and on both sides of

The endothermic reforming reaction begins when natural gas or ammonia is

5.3.3.3 Protection of Coils in the Waste Heat Section

Item no. Hot end / cold end (C)

Item no. Inlet / Outlet (C)

Note:Heating any coil above the design temperature must be avoided.

Overheating of the coils (especially during start-up) can be avoided by routing a

When heating in stagnant atmosphere, protection of 10-E-2001 is not required.

flow must be by-pass 10-E-2002-2, by means of 10-HIC/HV-2011, to maintain the

5.3.3.4 Control of Heat Distribution in the Primary Reformer

 the firing profile in the radiant section

 the excess combustion air to the radiant section

5.3.3.5 Taking Off-gas Fuel into Operation at Primary Reformer Burners

Introduction of off-gas from PGRU PK-5002

1. The reformer duty controller 10-FIC-2047 should be in operation (automatic

2. Check that the controllers 10-FIC-2052 and 10-PIC-2049 are switched to

4. Select the type of off-gas on 10-HS-2052; treated if the hydrogen recovery

6. The off-gas fuel header isolation valves 10-XV-2038-A/B and 10-XV-2039

7. Open fully the off-gas isolation valve to all burners in operation.

8. Slowly introduce the off-gas fuel by increasing the output of 10-FIC-2052 on

9. When the flow is sufficient (about 30% of range) switch 10-FIC-2052 to

Introduction of flash gas fuel:

Introduction of process gas fuel:

5.3.4. Heating Up the Desulphurization Section with Natural Gas

The desulphurizer catalyst beds are heated up at a maximum heating rate of

If no hydrogen gas is available, the hydrogenator catalyst temperature must be

The absorption capacity of the ZnO catalyst is optimal at temperatures close to

5.3.5. Introduction of Steam to Primary Reformer

Establish a flow of approximately 30 t/h steam by opening 10-FV-2033. The full