Process Description and Features of Toyo ’s Hydrogen Plant

1. Process Description of Toyo’s Technology for Hydrogen Production Unit

1.1 Feed Gas Preparation

The natural gas from OSBL is mixed with recycle hydrogen which is compressed by
Recycle Hydrogen Compressor (GB101) and then heated by the Feedstock Heater
(EC204).

The natural gas contains organic sulfur and H2S. These are removed by two steps of
catalytic reactions. The natural gas is mixed with recycle hydrogen from a part of
product hydrogen, the ratio of which is adjusted to maintain about 2-3 vol.% of hydrogen
content in natural gas.

The Feedstock Heater is located in the reformer convection section. After preheating up
to 380°C, the feed gas flows to the Hydrotreater (DC101) which contains Nickel-
Molybdenum catalyst to decompose organic sulfur to H 2S as the first step. Then the
feed gas leads to the Desulfurizer (DC102A,B) which contains Zinc Oxide catalyst and
Ultra Purification catalyst to remove all sulfur by the main reaction with packed ZnO
forming ZnS as the second step. The H 2S reacts with ZnO according to the following
reaction.

ZnO + H2S ⇒ ZnS + H2O

1.2 Steam Reforming and Heat Recovery

The feed gas is mixed with process steam in an amount equivalent to a steam-carbon
ratio of 3.0 to 1.0. The sources of process steam is middle pressure superheated steam
from M.P. steam header (35.0 bar(A)) and the middle pressure saturated steam from
Condensate Stripper (DA601).

The gas steam mixture flows to the Mixed Gas Heater for Reformer (EC201) located in
the reformer convection section and reheated to about 500℃ and distributed to catalyst
tubes installed in the radiant section of the Reformer (BA201). This mixed feed gas
passes down in the reformer tubes and contacts with nickel reforming catalyst.

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Steam reforming takes place in the catalyst tube by following reaction.

CH4 + H2O ⇔ CO + 3H2

CO + H2O ⇔ CO2 + H2

The Reformer (BA201) operates with down-firing of fuel gas between the rows of tubes
to develop the process gas temperature to about 875°C at the outlet of the catalyst
tubes. Under this condition, the unconverted methane content will be about 3.1vol% as
dry basis. The pressure at the outlet of catalyst tubes is about 21 bar(G).

The Reformer is designed to attain maximum thermal efficiency by recovering heat in

the convection section from the flue gas.

The convection heat is used for the following services:

(1) To preheat feed gas/steam feed for reformer

(2) To superheat middle pressure steam
(3) To preheat feed gas
(4) To vaporize boiler water
(5) To preheat combustion air

The flue gas leaves the base of the furnace and the heat in this gas is utilized for steam
superheating and reactants heating before being discharged to the Chimney Stack
(BI201) by the Induced Draft Fan (GB201).

The flue gas first enters the Mixed Gas Heater for Reformer (EC201) which heats the
feed gas and steam mixture gas entering the Reformer. The flue gas then passes to the
Steam Superheater (EC203) in which the steam is superheated and passes to the
steam turbine for Off Gas Compressor (GT301). Then the flue gas enters to the
Feedstock Heater (EC204) in which the feed gas is heated and introduced to the
Hydrotreater (DC101).

The flue gas passes the Flue Gas Waste Heat Boiler (EC205) to vaporize the boiler
water and then passes the Combustion Air Preheater (EC206). The combustion air is
introduced to the Combustion Air Heater by Forced Draft Fan (GB202) through Steam
Air Heater (EC207), and is preheated to about 223°C by the Combustion Air Preheater
(EC206).

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The endothermic reforming reaction occurs in the tubes over nickel reforming catalyst,
and the heat of reaction is provided by downward firing burners arranged in the furnace
roof.

For firing the reformer furnace, the design is based on utilization of fuel gas provided
from the plant network.

The reformed gas is collected in the outlet header and transferred to the Heat Recovery
Section through the transfer line.

Firstly the reformed gas enters the No.1 Reformed Gas Waste Heat Boiler (EB201) and
it is used to generate middle pressure steam at about 36 bar(G).

1.3 Shift Conversion and Heat Recovery

The shift reaction is as follows:

CO + H2O ⇔ CO2 + H2

The reaction is exothermic and limited by the chemical equilibrium. The reaction takes
place in Shift Converter (DC201), which contains copper promoted iron catalyst. The
temperature is 350°C at the converter inlet and 430°C at the outlet. Some of reformed
gas bypasses Shift Converter to adjust the carbon monoxide content at the outlet of
Shift Converter. The carbon monoxide content of the process gas is reduced to about
6.6 vol% on a dry basis after bypass flow is combined to Shift Converter outlet.

Then process gas enters the No.2 Reformed Gas Economizer (EB202) and Reformed
Gas Economizer (EA201) in which the heat is used to preheat boiler feed water before
entering the Steam Drum (FA601).

Then the process gas passes through the following heat exchangers:

(1) BFW Heater (EA202)

(2) Process Gas Cooler (EA203)

In the BFW Heater (EA202), the process gas heats the feed water to the Deaerator
(EG601) and then passes to the No.1 Process Condensate K.O. Drum (FA201) and the
condensate is separated and delivered to the Condensate Stripper (DA601) by the No.1
Process Condensate Pump (GA201A,B).

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The process gas from the No.1 Process Condensate K.O. Drum (FA201) is cooled to
40°C in the Process Gas Cooler (EA203) and passes to the No.2 Process Condensate
K.O. Drum (FA202) and the gas finally passes to PSA Unit (CT301). Process
condensate separated in the K.O. drums is delivered to the Condensate Stripper
(DA601) by the No.2 Process Condensate Pump (GA202A,B)

1.4 PSA Unit

The hydrogen rich gas from shift converter through heat recovery train enters the
Process Gas K.O Drum (FA202) where condensed water is separated. The hydrogen
rich gas is then introduced to the PSA unit (CT301).

The PSA unit uses several adsorbent beds on an alternating cycle of adsorption and
regeneration to provide a continuous and constant product flow of purified hydrogen
with the optimized hydrogen recovery ratio.

Operation of the unit is completely automatic with all control valve actuated by a central
microprocessor (PLC) based control system.

The regeneration gas is sent to Reformer burners and burnt in the fire box.

A part of purified hydrogen is recycled back to desulfurization section for hydrogenating

the organic sulfur in the feed. Purified hydrogen is sent to the suction of Recycle
Hydrogen Compressor (GB101).

1.5 Steam System

The middle pressure steam (36 bar(G)) is generated in the Steam Drum (FA601) which
is connected to the No.1 Reformed Gas Waste Heat Boiler (EB201), the No.2 Reformed
gas Waste Heat Boiler (EB202) and the Flue Gas Waste Heat boiler (EC205). The
generated steam is fed and heated up to 380°C in the Steam Superheater (EC203)
located in the reformer convection section.

The low pressure steam from OSBL flows to the low pressure steam header and most
of low pressure steam is used for deaeration steam and Steam Air Heater (EC207).

The boiler blow down from the Steam Drum (FA601) is introduced to Flash Vessel
(FA602) to recover the low pressure steam. The water from the Flash Vessel is cooled

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in the Blow down Cooler (M-EA603) and flows to OSBL.

The deaerator feed water from OSBL is heated in the BFW Heater (EA202) and is fed to
Deaerator (EG601). After deaeration with oxygen scavenger and low pressure steam,
the boiler feed water at about 130°C is delivered to the Steam Drum (FA601) by the
Boiler Feed Water Pump (GA601A,B) through the Reformed Gas Economizer (EA201)
located in the shift converter heat recovery section.

1.6 Condensate Recovery System

The process condensate from the shift converter heat recovery section is stripped by
stripping system and then sent to Deaerator (EG601).

The process condensate from the No.1 Process Condensate K.O. Drum (FA201) and
the No.2 Process Condensate K.O. Drum (FA202) which contains slight amount of CO2
and other gas dissolved from the process gas are pumped by the No.1 Process
Condensate Pump (GA201A,B) and the No.2 Process Condensate Pump (GA202A,B)
and fed to the Condensate Stripper (DA601) after preheated through the Process
Condensate Exchanger (EA601A,B,C).

The stripped process condensate from the Condensate Stripper (DA601) is delivered to
the Process Condensate Exchanger (EA601A,B,C) and then sent to Deaerator
(EG601).

2. Features of Toyo’s Technology for Hydrogen Production Unit

The features of Toyo’s technology for Hydrogen Production Unit are described
hereunder.

2.1 Reforming System

a) Toyo’s Experience of Steam Reforming

Toyo has carried out design and construction many Steam Reformers for ammonia,
methanol and hydrogen plants since 1964. The total number of Steam Reformers
designed and constructed by Toyo is 43. The Reformers are all top-fired type. The
capacity, the customer, the location and of each Reformer is listed in Table 1 attached
hereto.

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Toyo's Steam Reformer is still in operation for over 23 years at Trinidad and Tobago
Methanol Co., Ltd. and the capacity is equivalent to 1,380 t/d refined methanol
production. Three (3) Toyo Steam Reformers designed and constructed for S-Oil
Corporation in Korea are processing naphtha feed and producing H 2 of 90 MMSCFD in
each unit. These Reformers are the largest steam reformers in the world processing
naphtha feed. The largest Toyo Steam Reformer currently in operation is at Oman
Methanol Company with the capacity equivalent to 3,000 t/d refined methanol
production.

Fig. 1 TOYO Steam Reformer at TTMC 1,380 t/d Methanol Plant, Trinidad

Fig. 2 TOYO Steam Reformer at 90MM SCFD Hydrogen Plant of S-Oil, Korea

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 Fig. 3 TOYO Steam Reformer at 3,000 t/d Methanol Plant
of Oman Methanol Company L.L.C.

Table 1 Toyo’s Experience of Steam Reformer

A: Ammonia M: Methanol H: Hydrogen G:GTL

Feedstock / C
Client Location Capacity (MMSCFD) Start Up

MitsuiToatsuChemicals Japan C4 / 30 1965 A

GSFC India Naphtha / 27 1966 A

Korea Fertilizer Co., Ltd. Korea Naphtha / 36 1967 A

Mitsui Toatsu Chemicals Japan C4 / 54 1969 A

Bangladesh Industries Bangladesh NG / 39 1970 A

Nishi Nihon Methanol Japan C4 / 85 1971 M

V/O Techmachimport CIS(Ex-USSR) NG / 86 1972 A

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 A: Ammonia M: Methanol H: Hydrogen G:GTL
Feedstock / C
Client Location Capacity (MMSCFD) Start Up

V/O Techmachimport CIS(Ex-USSR) NG / 86 1972 A

Industrieanlagen-Import FRG(Ex-GDR) NG / 86 1973 A

Zuari Agro Chemicals India Naphtha / 41 1974 A

V/O Techmachimport CIS(Ex-USSR) NG / 86 1974 A

V/O Techmachimport CIS(Ex-USSR) NG / 86 1975 A

V/O Techmachimport CIS(Ex-USSR) NG / 86 1975 A

Industrieanlagen-Import FRG(Ex-GDR) NG / 86 1975 A

CNTIC P.R.C NG / 62 1976 A

CNTIC P.R.C NG / 62 1976 A

V/O Techmachimport CIS(Ex-USSR) NG / 86 1979 A

V/O Techmachimport CIS(Ex-USSR) NG / 86 1979 A

V/O Techmachimport CIS(Ex-USSR) NG / 86 1979 A

V/O Techmachimport CIS(Ex-USSR) NG / 86 1979 A

V/O Techmachimport CIS(Ex-USSR) NG / 86 1979 A

V/O Techmachimport CIS(Ex-USSR) NG / 86 1979 A

V/O Techmachimport CIS(Ex-USSR) NG / 86 1980 A

V/O Techmachimport CIS(Ex-USSR) NG / 86 1981 A

V/O Techmachimport CIS(Ex-USSR) NG / 86 1981 A

V/O Techmachimport CIS(Ex-USSR) Naphtha / 86 1983 A

ASEAN Aceh Fertilizer Indonesia NG / 59 1983 A

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 A: Ammonia M: Methanol H: Hydrogen G:GTL
Feedstock / C
Client Location Capacity (MMSCFD) Start Up

Pupuk Iskandar Muda Indonesia NG / 59 1984 A

National Energy Corp. Trinidad and NG / 94 1984 M

Tobago
Industrienanlagen-Import FRG(Ex-GDR) OG/C4 / 7 1984 H

National Chemical Fert. Saudi Arabia NG / 77 1987 A

Chittagong Urea Fert. Bangladesh NG / 75 1987 A

GNFC India NG/Naphtha / 24 1990 M

Ssangyong Oil Korea OG/Naphtha / 90 1995 H

Ssangyong Oil Korea OG/Naphtha / 90 1996 H

PAK-American Fert. Pakistan NG / 34 1997 A

CFCL India NG/Naphtha / 76 1999 A

Pupuk Iskandar Muda Indonesia NG / 59 2003 A

S-Oil Corporation Korea OG/Naphtha / 90 2003 H

Pupuk Kujang Indonesia NG / 52 2005 A

National Petrochemical Iran NG / 110 2006 A

Company
National Petrochemical Iran NG / 110 2007 A
Company
Oman Methanol Company Oman NG / 295 2007 M

Qatar Shell GTL Ltd Qatar NG / 220 Under G

Commissioning

Note: The above reformers such as Methanol, Ammonia, GTL are converted to the
equivalent capacity as H2 plant.

b) Features of Toyo Steam Reformer

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The heat required for the radiant coil is supplied by Arch Burners, and additional heat is
supplied by Duct Burners for the convection coil where Mixed Gas Heater, Economizer
and Steam Superheater are located in the hot flue gas stream. Additionally, in order to
enhance the thermal efficiency to above 92%, an Air Preheater is installed at the outlet
of the convection section. Air after being preheated in the Air Preheater is supplied to
the Arch and Duct Burners via Air Ducts.

The configuration of the radiant coils includes transfer line(s), inlet headers, inlet pigtails
and catalyst tubes. The recent radiant coils of Toyo Steam Reformers have the
following features.

(1) Catalyst tubes are directly welded on the bottom manifold.

(2) The heavy transfer line is located under the radiant floor.
(3) Bottom manifolds are supported by roller supports.

Thermal expansion of the catalyst tube is absorbed by the spring hangers and the
pigtails.

Some of Toyo Steam Reformers were designed without outlet pigtails and have been or
are still running satisfactorily without serious maintenance problem.

c) Improved Steam Reforming Catalyst (ISOP catalyst)

Toyo has patents of a very unique concept, so-called “ISOP catalyst”, in the field of
steam reforming catalyst. As the capacity of methanol plant becomes larger, the ISOP
catalyst brings more reduction of expenditure of plant operation.

ISOP catalyst is a revolutionary improved catalyst for steam reforming and exhibits four
(4) times higher activity than the conventional steam reforming catalysts for natural gas.
This can be achieved by advanced catalyst manufacturing techniques, which produce a
high porosity support matrix combined with small finely dispersed nickel particles. Such
combination of properties produces a finished product, which enhances the steam
reforming reaction rate by reducing diffusion resistance at the molecular level and
providing an increased number of available active sites for subsequent reaction. ISOP
catalyst utilizes the same basic components (nickel, aluminum and calcium) used as
conventional steam reforming catalysts. The ISOP catalyst exhibits also equivalent to,
or higher in mechanical strength than, the conventional catalysts.

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- Catalyst Shape and size
Catalyst shape of high geometric surface area, seven-spoked “EW” wheels and “LDP”,
are available, which provides optimal active surface area, heat transfer efficiency and
pressure drop properties for all applications. Typical properties of “EW” shape are as
follows.
Diameter: 17.0 +- 1.5 mm
Height: 8.5 +- 0.5 mm

- Bulk Density
Typical value is 850 +- 100 Kg/m3

- Side Crush Strength

Minimum average of the EW shape is 34Kg

- Nickel Content
Typical Ni content is 14 +- 1.5wt%

ISOP catalyst has larger coking resistance under commercial operating conditions. The
coking resistance was proven in a steam reformer of a 1,650 t/d ammonia plant with
four (4) years continuous operation, where ISOP catalyst had only 1/3 of deposited
carbon compared with that by conventional catalysts in two (2) years operation. The
larger coking resistance is realized with faster reaction rate of the steam reforming
against the rate of coking.

The features of ISOP catalyst are summarized as below.

1) Four times higher activity

2) Longer catalyst life
3) High mechanical strength properties
4) Availability in shapes
5) Successful commercial experience

Application for Conventional Steam Reformer

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Tube wall temperature profiles vary relatively with operating conditions as well as the
steam reformer design. ISOP catalyst decreases peak temperatures by about 25 C
compared with the case using conventional catalyst. The temperature decrease is
because of the higher activity and the faster rate of the steam reforming reaction. The
reaction heat is absorbed from the tube surface more rapidly.

The decrease of the tube wall temperature gives an impact to the overall profitability of
operating plant very significantly. As for new reformer design, this could give a higher
throughput by decreasing number of reformer tubes, which leads to economical design.

Application for Pre-reformer

The conventional pre-reformer catalyst is limited to use in the range of 380-520C due
to weakness of heat resistance. Although with the feature stated above, high activity
and low coking tendency, ISOP catalyst has more resistance to high temperature than
conventional one. It is, therefore much more beneficial if the catalyst is used in the
range of 550-650C, by which more reforming load is shifted from radiant to convection
zone of reformer than that with conventional catalyst, resulting in low capital cost and
high efficiency.

2.2 Top-Fired Reformer Design

Steam Reforming is a reliable and experienced technology to produce synthesis gas

from natural gas and naphtha. The steam reforming reaction is endothermic reaction
between methane and excess steam over a nickel catalyst in principle loaded in tubular
reactors which are installed in the radiant zone of a fired heated furnace. There are
options of the furnace, either top fired or side fired.

The top fired furnace can provide heating load to each reformer tubes uniformly
because burners are mounted at the furnace ceiling between the tube rows and
arranged uniformly. Even in case of large reformer design only the reformer tube rows
can be increased easily pursuing scale merit.

In case of side fired type, tubes are mounted in a single row along the centerline of the
furnace. Burners are mounted in several levels in furnace walls. Therefore, tube skin
temperature can be controlled well, which is one of the advantages from the operation
point of view. However, in a large reformer design, two or more of such furnaces are

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required to be installed side by side. It requires larger plot area and the cost of
construction will be also increased compared to the top fired furnace scale up.

This would conclude that the top fired furnace is preferable for a large plant having
hundreds number of catalyst tubes to be bared with even heat load.
Table 2 shows comparison of top-firing and side-firing type reformer.

Table 2 Comparison of Reformer Type

Top-Firing type Reformer Side-Firing type Reformer
Heater
Arrangement

Burner - Burners are located on radiant - -Burners are located on both

Arrangement arch.
- Zone control of heating along
reformer tube is not possible, the
tube can be heated properly as
follows.
 Burner flame heats reformer
tube upper part where requires
heat for reforming process.
 Flue gas of lower temperature
at lower part of radiant tube
prevents the tube from
overheating.
Coil Many tube rows, i.e. 15 rows, can
Arrangement be arranged between both side of
radiant walls.
Features This type of reformer is suitable for
larger capacity reformer because
tubes can be arranged in many
rows and it allows compact design
of reformer.
side of radiant walls.
Consequently.
- Zone control of heating along
reformer tube is possible
because burners are located at
different level (2-3 stages).
Maximum number of tube rows
between both side of radiant walls
is two.
This type of reformer is not suitable
for larger capacity reformer
because tubes can not be arranged
in multiple rows.

3. Better than Other Licensers

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The strongest characteristics of Toyo hydrogen technology can be summarized as
follows;

- Toyo’s own steam reformer that is technically capable of achieving the most efficient
overall optimization of the hydrogen plant.
- Coverage of a full scope of the Process Design Package.
- Feedback of a full scope of service up to a commercial operation of plant.

1) Steam Reformer

Toyo has an own steam reformer for designing the Reforming Section which requires
the most of the capital investment in a hydrogen plant. This technical capability can
achieve the most efficient overall optimization of the hydrogen plant.

2) Process Design Package

One of the most important expertise for Toyo is its capability to be able to provide with a
full scope of Process Design Package for a hydrogen plant without using any design
furnished by a third party for any parts.

3) Full Scope of Service

Among the major process licensors for the full scope of a hydrogen plant, Toyo is one of
the few licensers to be able to provide a full-scope services and guarantees comprised
of the Technology Licensing such as;

- Basic Design and Supply of Process Design Package

- Engineering
- Procurement
- Construction
- Technical Assistant Services

Toyo is confident to render all necessary technical services and assistance from the
beginning up to the commercial operation of Project smoothly, utilizing knowledge and
know-how in the point of “Constructability”, “Operability” and “Maintenability”
accumulated in a lot of turn-key lump-sum type contract projects.

The comparison with other licensers is summarized in Table 3.

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Table 3 Comparison of Steam Methane Reformer Licensers

Manufacturers Topsoe Technip (KTI) Toyo

Type of Reformer Side-Firing Top-Firing Top-Firing
Max. Experienced Approx. 130 624 840
Tube No. per Single fire box (QSGTL, Qatar) (Oman MeOH plant)
Max. Reformer
Approx. 150 MM Approx. 230 MM Approx. 290 MM
Design Equivalent to
SCFD (double box) SCFD SCFD
H2 production
Experience Many Many Many
Most Suitable Mid Scale Large Scale Large Scale
Capacity < 50 MM SCFD > 50 MM SCFD > 50 MM SCFD
Total Investment Cost
Highest Slightly Higher Base
For Large Scale plant

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