DESCRIPTION

PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 1/16
Ref. FEED DOC. No. : S-00781-4343219

PROCESS DESCRIPTION

FOR

UNIT 13 – HYDROGEN PRODUCT UNIT – Train 1

UNIT 14 – HYDROGEN PRODUCT UNIT – Train 2

UNIT 15 – HYDROGEN PRODUCT UNIT – Common Parts

PROJECT : KARBALA REFINERY PROJECT

LOCATION : KARBALA, IRAQ

EMPLOYER : STATE COMPANY FOR OIL PROJECTS (SCOP)

ISSUE FOR
0 29 APR 15
CONSTRUCTION
J.N.Park S.J.Seong K.D.Ko J.B.Kim -

A 29 OCT 14 ISSUE FOR REVIEW J.N.Park S.J.Seong K.D.Ko J.B.Kim -

REV. DATE DESCRIPTION PRPD CHKD REVD APPRD CONFD

Joint Venture of Hyundai Engineering & Construction Co., Ltd., GS Engineering & Construction Co., Ltd., SK Engineering

& Construction Co., Ltd., and Hyundai Engineering Co., Ltd.,

Note :

a) Revision bar(vertical line) shall be placed in the right hand margin to indicate where the changes has been made

b) PRPD = Prepared by, CHKD = Checked by, REVD = Reviewed by, APPRD = Approved by, CONFD = Confirmed by

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 2/16
Ref. FEED DOC. No. : S-00781-4343219

REVISION HISTORY

Rev Date Description Page

A 29 OCT 14 Drawing numbers were revised. 4
A Equipment number was changed to 13-E-111A/B 15,16
29 OCT 14
from 13-E-111
A Equipment number was changed to 13-E-115A/B 16
29 OCT 14
from 13-E-115
0 29 APR 15 The sentence is added as “Refinery fuel gas is not 4
considered to design but will be remain in this
document as future installation case”.
0 29 APR 15 BR naphtha is deleted in the sentence “in natural 6
gas/BR naphtha and hydrogen.” as per KRP-C-
MOM-N-0060-attachment 7_TQ.No.: TQ-PR-E-
056, BR naphtha line from BL is deleted.

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 3/16
Ref. FEED DOC. No. : S-00781-4343219

TABLE OF CONTENTS

1. GENERAL INFORMATION .......................................................................................... 4

2. DESULPHURIZATION SECTION ................................................................................. 4

2.1. Processes ......................................................................................................................4

2.2. Hydrogenation ..............................................................................................................6

2.3. Absorption of chlorine and sulphur ............................................................................7

3. REFORMING SECTION ............................................................................................... 8

3.1. Processes ......................................................................................................................8

3.2. Adiabatic prereforming.................................................................................................9

3.3. Tubular reforming .........................................................................................................9
3.4. Prereforming catalyst RKNGR and reforming catalyst R-67-7H ..............................10
3.5. Flue gas waste heat recovery section .......................................................................12

4. CO CONVERSION SECTION..................................................................................... 13
4.1. Chemical reaction .......................................................................................................13
4.2. MT CO shift catalyst LK-813/LK-817 ..........................................................................13

5. WASTE HEAT RECOVERY / STEAM PRODUCTION ............................................... 14

5.1. Cooling of process gas ..............................................................................................14
5.2. Steam production .......................................................................................................15

7. PSA UNIT ................................................................................................................... 16

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 4/16
Ref. FEED DOC. No. : S-00781-4343219

1. GENERAL INFORMATION
The hydrogen plant, which is designed for production of 36,000 Nm3/h of pure H2 will be laid out
as shown on the following flow sheets (for heavy naphtha feed):

Description Drawing no.

- Feed preparation IONE-AA13-PFD-0010-001-01
- Desulphurization and reforming IONE-AA13-PFD-0010-001-02
- CO conversion and PSA IONE-AA13-PFD-0010-001-03

The hydrogen plant has been designed for operation on the following feedstocks:
- Heavy naphtha
- Light naphtha
- Natural gas
- Refinery fuel gas
(Refinery fuel gas case is not considered to design in the Karbala Project but it will
be remain in this document as only future installation case)
- LPG
- C4

The fuel for the reformer furnace is off-gas from the PSA Unit, supplemented with natural gas or
refinery fuel gas.

Besides H2, the plant also generates superheated high pressure steam at 44 kg/cm² g pressure
for export.

This document deals with the chemical reactors and catalysts in each of the main sections:

- Desulphurization
- Reforming
- CO conversion

2. DESULPHURIZATION SECTION
2.1. Processes

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 5/16
Ref. FEED DOC. No. : S-00781-4343219

The desulphurization section removes sulphur from the feed as the catalysts in the reforming
section are sensitive to sulphur compounds, sulphur will cause deactivation and poisoning.
Similarly, the MT shift catalyst in the CO conversion section is sensitive to sulphur and chlorine
compounds.

The desulphurization section contains four reactors, two hydrogenation reactors are loaded with
nickel-molybdenum-oxide catalyst (TK-261) and two sulphur/chlorine absorbers loaded with
chlorine absorption catalyst (HTG-1) and zinc-oxide sulphur absorption catalyst (HTZ-3). The
feed contains max. total S of 50 wt ppm, max. Cl of 0.5 wt ppm and max. heavy metals of 120
wt ppb.

When operating with heavy or light naphtha, the feed is at first sent to the Naphtha Surge Drum,
13-V-101. The naphtha feed stocks are fed directly from the upstream refinery process unit or
blanketed storage tanks and is free from oxygen. The naphtha is pumped to approx. 41.4
kg/cm² g by the Naphtha Feed Pump, 13-P-101 A/B.
When operating with LPG or C4, the feed is at first sent to the LPG/C4 Surge Drum, 13-V-102.
The LPG/C4 is pumped to approx. 41.4 kg/cm² g by the LPG/C4 Feed Pump, 13-P-102 A/B.

When operating with refinery fuel gas or natural gas it is compressed to approx. 41.4 kg/cm² g
by the Refinery Fuel Gas Compressor, 13-K-104 or the Natural Gas Booster Compressor, 13-K-
105 respectively. The natural gas booster compressor is bypassed if the natural gas pressure at
BL is above 41.4 kg/cm2 g.

The hydrocarbon feedstock is mixed with H2 from the PSA Unit prior to desulphurization. The
mixture is evaporated / heated to 261°C in the Feed Preheater/Vaporizer, 13-E-101 A/B.

Since the refinery fuel gas feed contains a large amount of olefins and LPG and C4 feeds
contain diolefins, a dual reactor layout has been chosen. The Pre-Hydrogenator, 13-R-101 A, is
designed for hydrogenation of olefins and diolefins and removal of heavy metals. It will act as a
guard reactor and the catalyst may be replaced during operation. The Hydrogenator, 13-R-101
B, is designed for hydrogenation of the organic sulphur compounds in the feed. The
hydrogenators are equipped with a recycle stream using an ejector, 13-J-101, and an air cooler,
13-EA-122 in order to limit the temperature increase in 13-R-101 A to maximum 100°C while
processing feeds with high olefinic content.

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 6/16
Ref. FEED DOC. No. : S-00781-4343219

2.2. Hydrogenation

The first catalyst in the desulphurization section is a nickel-molybdenum hydrogenation catalyst

(TK-261) placed in a single bed in the reactors, 13-R-101 A and B. The catalyst TK-261 is
delivered as 5 mm rings. It catalyses the following reactions:

RSH + H2 → RH + H2S
R1SSR2 + 3H2 → R1H + R2H + 2H2S
R1SR2 + 2H2 → R1H + R2H + H2S
(CH)4S + 4H2 → C4H10 + H2S
COS + H2 → CO + H2S
Where, R is a radical of hydrocarbon.

Besides the above mentioned hydrogenation of sulphur compounds, the catalyst also
hydrogenates olefines to saturated hydrocarbons. The hydrogenation of olefins is an exothermic
reaction.

For any given feedstock a certain hydrogen flow is required for the hydrogenation and to keep
the top layer of the downstream prereformer catalyst RKNGR in its reduced state. Sufficient
hydrogen for the hydrogenation must always be added, since the result would otherwise be a
poor conversion of organic sulphur compounds, giving an increased sulphur slip to the reformer
section. The hydrogen recycle flow is adjusted to obtain 0.3 Nm3 H2 per kg hydrocarbon feed for
all operating cases. No hydrogen recycle is required for refinery fuel gas feed since it already
contains sufficient hydrogen

The maximum activity of the hydrogenation catalyst depends on the concentration of hydrogen
and the inlet temperature to the reactor. The recommended operating peak temperature for the
catalyst is approximately 380°C. At temperatures above 400°C, coke could be formed on the
surface of the catalyst and thus decrease the activity
During start-up, the catalyst is heated with recirculating nitrogen from the start-up loop for HDS
section and afterwards in natural gas and hydrogen. The catalyst must not be operated above
300C with hydrocarbon without hydrogen, because carbon lay-down may otherwise take place
and thereby block the catalyst surface with insufficient hydrogenation as a result. However
naphtha feedstock can only be initiated when the catalyst temperature throughout the HDS
section is safely above the naphtha dew point. Condensation of naphtha will not harm the
catalyst, but the flow control will be difficult.

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 7/16
Ref. FEED DOC. No. : S-00781-4343219

The TK-261 catalyst is oxidised as delivered and obtains its activity when sulphided. The activity
is obtained from the start by pre-sulphiding of the catalyst. The higher activity is necessary in
order to hydrogenate all organic sulphur compounds and olefins. If the catalyst is not pre-
sulphided, there is a risk of hydro-cracking with severe temperature excursions as a result.

In order to maintain the catalyst’s hydrogenation activity, and to prevent side reactions, it is
essential that it remains in its sulphided state. If the sulphur content in the feedstock is below 5
wt. ppm for a prolonged period of time, sulphur may be stripped off the catalyst and an injection
of sulphur will be necessary. It is therefore foreseen that sulphur in the form of
dimethyldisulphide, DMDS, can be doped to the feed before the process gas enters the Pre-
Hydrogenator, 13-R-101 A.

After the catalyst has been in operation, the catalyst is pyrophoric and must not be exposed to
air at temperatures above 70°C.

2.3. Absorption of chlorine and sulphur

Having passed the hydrogenation catalyst in the first reactors, the chlorine is absorbed in a
potassium-based dechlorination catalyst (HTG-1) loaded in the top part of the second and third
reactors in this section, 13-R-102 A/B, and the hydrogen sulphide is absorbed in a zinc oxide
catalyst (HTZ-3) loaded in the bottom part of the reactors. The two reactors, 13-R-102 A/B
located in series are identical. 13-R-102 B is acting as guard vessel in case of breakthrough
from 13-R-102 A or in case 13-R-102 A is taken out of service for replacing the catalyst.

The catalyst HTG-1 for chlorine absorption is delivered as 5 mm rings. The catalyst will absorb
HCl according to the following reaction:

K 2 CO 3  2HCl  KCl  KHCO 3  HCl  2 KCl  H2 O  CO 2

The catalyst HTZ-3 consists of activated zinc oxide. The zinc oxide is delivered as 4 mm
diameter extrusions. The zinc oxide reacts with H2S according to the following equation:
ZnO + H2S ⇄ ZnS + H2O
ZnO + COS ⇄ ZnS + CO2

If the process gas contains CO2 formation of water will occur according to:
CO2 + H2 → CO + H2O (Reverse Shift)
The inlet temperature to the hydrogenation catalyst varies from 280°C to 385C depending on

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 8/16
Ref. FEED DOC. No. : S-00781-4343219

the concentration of olefins and diolefins in the feed gas in order to reach the same outlet
temperature for all feeds.

Fresh or sulphided catalyst reacts neither with oxygen nor with hydrogen at practically any
temperature. Zinc sulphide is not pyrophoric and no special care during unloading is required. It
is however recommended to cool the catalyst to ambient temperature before unloading since
possible carbon deposits on the catalyst might heat up at elevated temperature.

Steaming operations should not be carried out in connection with systems containing zinc oxide.
The fresh zinc oxide will hydrate if it is exposed to condensing steam, and in case of zinc
sulphide, the absorbed sulphur will be stripped off at high temperatures (150 to 200C).

3. REFORMING SECTION
3.1. Processes
The gas from the desulphurization section is mixed with steam and sent to the reforming section
where hydrocarbons are reacted over nickel catalysts with steam in two steps. First in the
adiabatic prereformer, 13-R-103, and then in the Tubular Reformer, 13-H-101.
The steam reforming of hydrocarbons can be described by the following reactions:
 m
1. CnHm + nH2O → nCO +  n   H2 – Heat
 2
2. CO + 3H2 ⇄ CH4 + H2O + Heat

3. CO + H2O ⇄ CO2 + H2 + Heat

Reaction 1 is endothermic while reactions 2 and 3 are exothermic.

In the Prereformer, 13-R-103, all higher hydrocarbons will be completely converted by rea
ction 1 while reactions 2 and 3 will be almost equilibrated.

In the operation of the reformer system, carbon formation outside and/or inside the catalyst
particles is possible. Carbon deposits outside the particles will increase the pressure drop over
the catalyst bed, and deposits inside the particles reduce the mechanical strength and activity.
In operation of the adiabatic prereformer, carbon deposition is only possible in case of very low
steam/carbon ratios or in case of overheating of the feed.

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 9/16
Ref. FEED DOC. No. : S-00781-4343219

In the Tubular Reformer, carbon formation is thermodynamically not possible under the
conditions foreseen - i.e. close to equilibrium. However, if the catalyst is poisoned, for instance
by sulphur, it will lose its activity and carbon formation may occur.

3.2. Adiabatic prereforming

After mixing with steam, the feedstock from the desulphurization section is preheated to 490°C
by heat exchange with the hot flue gas from the reformer in the Prereformer feed preheat coil,
13-E-104. From 13-E-104 the reaction mixture continues to the prereformer, 13-R-103, where
all the higher hydrocarbons are decomposed into hydrogen, carbon monoxide, carbon dioxide
and methane corresponding to the reaction schemes 1, 2 and 3.

The Prereformer, 13-R-103, contains RKNGR catalyst, size 4.5 × 4.5 mm, which is a
prereduced naphtha reforming catalyst, specially treated for low temperature operation.

As higher hydrocarbons are no more present in the gas leaving 13-R-103, it can now be heated
up to 650°C without risk of carbon formation due to thermal cracking.

3.3. Tubular reforming

The prereformed gas is preheated by heat exchange with the hot flue gas from the Tubular
Reformer in the Reformer Feed Preheat Coil, 13-E-103, and sent to the Tubular Reformer, 13-
H-101, where most of the methane reforming takes place. The reaction is strongly endothermic
and the heat of reaction is supplied indirectly by firing.

The Tubular reformer, 13-H-101 is constructed as a radiant chamber divided into four sections.
The chamber contains a single row of 100 centrifugally cast tubes fabricated of high alloy Cr-Ni
steel (25 Cr 35 NiNbTi).

The 100 tubes contain a total of 11.3 m3 R-67-7H reforming catalyst, size 20 × 18 mm.

The process gas flows downwards with the gas entering the top of the vertically mounted tubes
from a header through "hairpins" at a temperature of about 600-650°C depending on the feed
stock and plant load. The gas leaves the tubes at about 915°C and enters directly into a
refractory lined collector.

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 10/16
Ref. FEED DOC. No. : S-00781-4343219

The tubes in the furnace are heated by a total of 144 burners arranged in 6 rows on each side
of the chamber to provide easy control and a uniform temperature profile along the length of the
catalyst tubes.

The tube arrangement permits easy visual inspection of all tubes during operation through the
peep holes in the ends and sides of the reformer casing.

Flue gas flow is upward with an outlet near the top of the radiant chamber. The flue gas outlet
temperature is about 1030-1070°C. Off-gas from the PSA Unit and refinery fuel gas or natural
gas are used as fuel for the reformer, and the combustion air is supplied by the Combustion Air
Blower, 13-FA-102, and is preheated to about 245°C in the Combustion Air Preheater, 13-E-120,
in the flue gas waste heat recovery section.

To ensure a complete combustion of the fuel gas, the burners must operate with excess air. A
reducing atmosphere should always be avoided, since it might be harmful to the catalyst tube
material. 10% excess air corresponding to approximately 1.8% (dry basis) oxygen in the flue
gas has been foreseen for normal operation.

3.4. Prereforming catalyst RKNGR and reforming catalyst R-67-7H

Two types of reforming catalyst are employed in the reforming system. The Prereformer,
13-R-103, is charged with pre-reforming catalyst, RKNGR and the Tubular Reformer, 13-H-101,
is charged with reforming catalyst, R-67-7H.

The catalysts are supplied in rings of the following nominal dimensions:

13-R-103
Catalyst RKNGR
Diameter 4.5 mm
Height 4.5 mm
Shape Tablets

13-H-101
Catalyst R-67-7H
Diameter 20 mm
Height 18 mm
Shape Cylinder with 7 holes

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 11/16
Ref. FEED DOC. No. : S-00781-4343219

The RKNGR catalyst is supplied in prereduced form. It is not pyrophoric at temperatures below
60°C, i.e. it may be handled without any difficulties in atmospheric air during loading of the
catalyst. RKNGR needs no special activation at the start-up of the unit.

Reducing gases coming from the RKNGR catalyst in 13-R-103 at the start-up of the unit
activates the R-67-7H catalyst in Tubular Reformer, 13-H-101. During start-up, great care
should be taken always to maintain a reducing atmosphere in order to avoid oxidation of the
reforming catalyst, which would necessitate a re-activation, if at all possible.

The RKNGR catalyst contains magnesia, which under certain conditions may react with st
eam to form magnesium hydroxide according to the hydration reaction:

MgO + H2O → Mg(OH)2

Hydration may mechanically destroy the catalyst cylinders. It must be ensured that the cat
alyst is heated up to a temperature above the hydration temperature before steam is add
ed during start-up, and that steam is cut off and purged out before the temperature has
dropped too much during shut-down.

The decrease in activity will be a slow process under normal operation and reducing conditions.
The catalyst may, however, be poisoned by a variety of compounds that may be introduced with
the process feedstock or the steam. The catalyst poisons most frequently encountered are
sulphur and silica.
In principle, it is immaterial to the catalysts whether the catalyst poisons are introduced with the
process feedstock or the process steam, so each feed stream should consequently be as free
of poisons as possible. It should be noticed that the amount of process steam by weight is about
three times larger than the amount of process feedstock, and the poisoning effect for the same
concentration of catalyst poisons will be correspondingly worse.

In order to check that sulphur does not enter with the process steam analysis should be made
of the boiler feed water, the boiler water and the steam.

Trouble arising from impure boiler feed water may be further aggravated by insufficient blow-
down from the steam drum or excessive liquid entrainment in the steam.

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 12/16
Ref. FEED DOC. No. : S-00781-4343219

Poisoning will result in loss of activity of the catalyst in the Prereformer, 13-R-103, which will be
noticed by downward movement of the temperature profile at constant operating conditions
(load, temperature, pressure and steam to carbon ratio).

Towards the end of the RKNGR catalyst life, higher hydrocarbons will be observed at the outlet
of 13-R-103, due to reduced activity of the RKNGR catalyst. This will give risk of coke formation
in the Reformer Feed Preheat Coil, 13-E-103, due to thermal cracking. Higher hydrocarbons will
also lead to carbon formation on the catalyst in the Tubular Reformer, 13-H-101, due to the high
inlet temperature.

Since the feed to the Prereformer, 13-R-103, will always contain minor amounts of sulphur (ppb
level), a progressive poisoning of the catalyst during the life time of the catalyst will be
experienced. However, with the expected sulphur leakage to the reforming section, the rate of
progress of de-activation of the RKNGR catalyst due to sulphur poisoning is very low.

If the hydrogen flow to the desulphurization section is interrupted, breakthrough of large

amounts of organic sulphur will poison the prereforming catalyst.

If the steam to carbon ratio drops to very low levels, and especially if the steam flow stops
completely, even for some seconds, a heavy carbon lay-down on the catalyst must be expected.

If the catalyst is exposed to steam alone, it will be oxidised. In order to avoid oxidation, steam
must always be mixed with hydrogen or another reducing agent like methanol.

The R-67-7H catalyst is very temperature-resistant and will not be harmed by the temperatures
normally obtained in tubular reformers.

3.5. Flue gas waste heat recovery section

The flue gas collector passes the flue gas from the radiant chamber to the flue gas waste heat
recovery section where the sensible heat of the flue gas is used for:

- Preheating of reformer feed 13-E-103

- Preheating of prereformer feed 13-E-104

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 13/16
Ref. FEED DOC. No. : S-00781-4343219

- Superheating of HHP steam 13-E-105

- Generation of steam 13-E-106

- Preheating of combustion air 13-E-120

In the waste heat recovery section the temperature of the flue gas is decreased to about 160-
165°C, and finally the flue gas leaving the waste heat recovery section is passed to the stack by
the Flue Gas Fan, 13-FA-101.

4. CO CONVERSION SECTION
4.1. Chemical reaction
The previously mentioned reaction 3 is also taking place in the MT Shift Converter, 13-R-104.

CO + H2O ⇄ CO2 + H2 + Heat

where it proceeds very close to equilibrium. A low equilibrium content of CO is favoured by

lower temperatures and more steam, while the reaction rate will be higher at higher
temperatures.

More steam in the process gas can result in an apparently lower reaction rate due to the higher
space velocity, giving a shorter contact time. The maximum conversion reflected by maximum
temperature rise across the reactor is obtained at an optimum temperature, which depends on
the actual activity of the shift catalyst.

4.2. MT CO shift catalyst LK-813/LK-817

The MT Shift Converter, 13-R-104, is filled with a top layer of LK-817, a middle layer of LK-813
and a bottom layer of LK-817. LK-813 and LK-817 consists of oxides of copper, zinc and
aluminum. The LK-817 catalyst is delivered as 4.5 × 4.5 mm cylinders and LK-813 is delivered
as 4.5 x 3.4 mm cylinders.

Since the LK-813/LK-817 catalyst is delivered in its oxidised state, it is necessary to reduce the
catalyst before taking it into operation.

The LK-813/LK-817 catalyst is extremely sensitive to sulphur poisoning. Chlorides and silica are
also strong poisons. Sulphur compounds not absorbed in the desulphurization section are,

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 14/16
Ref. FEED DOC. No. : S-00781-4343219

however, quantitatively absorbed on the prereformer catalyst. Only chlorides present in the
process feed or the process steam will reach the MT shift catalyst. The result is that during the
life of the catalyst, the active volume is only diminishing slowly.

The catalyst is activated by reduction at 170-230°C with nitrogen gas containing 0.2-6% of
hydrogen. During the reduction the copper oxide reacts with the hydrogen under formation of
free copper.

The catalyst, LK-813/LK-817 is active between 190°C and 340°C, with a normal inlet
temperature of approximately 200-210°C. The outlet temperature should normally be kept below
330°C to extend the catalyst lifetime. At temperatures near the dew point, the activity will
decrease due to capillary condensation of water inside the catalyst, thus reducing the free area.
During operation the inlet temperature should therefore be kept at least 15°C above the dew
point of the process gas.
The reduced MT catalyst is pyrophoric and must not be exposed to air while it is inside the
reactor.

5. WASTE HEAT RECOVERY / STEAM PRODUCTION

5.1. Cooling of process gas
The process gas leaving the tubular reformer will pass through the Waste Heat Boiler, 13-E-108,
producing saturated steam at 71.5 kg/cm2g. In 13-E-108, the temperature of the process gas is
brought down to 317°C.

The process gas from the Waste Heat Boiler, 13-E-108, is cooled to about 200-210°C in the 1st
BFW Preheater, 13-E-109. The gas then enters the MT Shift Converter, 13-R-104, where the
previously mentioned exothermic reaction 3. takes place. The temperature is hereby raised to
about 330°C. Then CO2 and H2 rich gas is sent through the 2nd BFW Preheater, 13-E-110 and
cooled down about 250°C. The gas is further cooled to about 150°C in 3rd BFW Preheater, 13-
E-111A/B, and sent to Process Air Cooler 13-EA-112 cooling to 65°C, and Water Cooler, 13-E-
113 cooling to 37°C, before it is sent to Process Condensate Separator, 13-V-108, where
process condensate is separated from the gas. The gas is sent to the PSA Unit, 13-PK-101.

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 15/16
Ref. FEED DOC. No. : S-00781-4343219

5.2. Steam production

BFW water from battery limit is mixed with stripped process condensate form Stripped Process
Condensate Pump 13-P-104 A/B and sent to the Steam Drum, 13-V-103, after preheating in the
3rd BFW Preheater, 13-E-111A/B, the 2nd BFW Preheater, 13-E-110, and the 1st BFW Preheater,
13-E-109.
The boiler water from the Steam Drum, 13-V-103, is used for production of steam in the two
waste heat boilers: Convection Section Boiler Coil, 13-E-106, located in the flue gas section,
and the Process Gas Boiler, 13-E-108. Phosphate is added just upstream the steam drum to
adjust the pH in the steam drum and for precipitation of hardness builders (Ca2+, Mg2+).
In order to check that poisons do not reach the catalysts with the process steam, analyse
s should be made of the boiler feed water, the boiler water and the steam.

In order to ensure the quality of boiler water, a continuous blow down is maintained by a special
blow down valve. A rate of 1% is foreseen to be adequate.
Trouble arising from impure boiler feed water may be further aggravated by insufficient bl
ow-down from the steam drum or excessive liquid entrainment in the steam.

The major part of steam produced is superheated to about 440C in 13-E-105, in the flue
gas waste heat section and used as process steam and export steam. Steam is exporte
d at 44 kg/cm2 g and 405°C.

6. CONDENSATE STRIPPER SECTION

Process condensate from the Process Condensate Separator, 13-V-108, is pumped by the
Process Condensate pump, 13-P-103 A/B, and preheated in the Process Condensate
Feed/Effluent Exchanger, 13-E-115A/B, before it is treated in a Process Condensate Stripper,
13-T-101. Dissolved gases, methanol and ammonia are stripped off by counter current contact
with steam. The steam from the top of 13-T-101 is mixed with process gas and steam at the mix
point upstream the Prereformer, 13-R-103.
Stripped condensate from 13-T-101 is cooled in the Process Condensate Feed/Effluent
Exchanger, 13-E-115A/B, before it is mixed with BFW from battery limit and sent to the BFW
exchangers.

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea

 DESCRIPTION
PROCESS DESCRIPTION
FOR UNIT 13 14 15
DOC. NO. : IONE-1A13-SP-PR-0002
KARBALA REFINERY PROJECT Rev. 0 Page 16/16
Ref. FEED DOC. No. : S-00781-4343219

7. PSA UNIT
The process gas produced in the reforming and shift section contains about 73–76 mole%(dry)
hydrogen depending upon the feedstock. The PSA (pressure swing adsorption) unit, 13-PK-101,
is installed to clean up the hydrogen in order to obtain a purity of 99.9 mole % hydrogen.
The basic principle of pressure swing adsorption is to adsorb the impurities in the hydrogen
stream at high pressure while the hydrogen passes through the adsorbent and then releases
the impurities again at low pressure and in this way regenerate the adsorbent.

The PSA unit is controlled by a separate PLC.

For details, refer to PSA vendor documentation.

Part of the hydrogen product from the PSA unit is recycled to the desulphurization section by
the Hydrogen Recycle Compressor, 15-K-103 A/B.

Product hydrogen is exported to battery limit at a pressure of 25 kg/cm2 g.

HDGSK JV  Gran Seoul Tower 1, 33, Jong-ro, Jongno-gu, Seoul, Korea