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METHANOL PRODUCTION USING VULCAN SYSTEMS COMBINED REFORMING TECHNOLOGY (ATR) AUTO THERMAL REFORMING AND (AGHR) ADVANCED GAS HEATED REFORING
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GBH Enterprises, Ltd.
METHANOL PRODUCTION USING VULCAN SYSTEMS
COMBINED REFORMING TECHNOLOGY
(ATR) AUTO THERMAL REFORMING AND
(AGHR) ADVANCED GAS HEATED REFORING
CASE STUDY#08270414
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Contents
Section
1 Introduction
2 Autothermal Reforming
2.1 Process Description
3 Gas Heated Reforming (GHR)
CASE STUDY #08270414
4 Plant Equipment List
5 Combined Reforming – ATR / AGHR PFD’s
6 Process Stream Descriptions
7 Combined Reforming Simulation Results*
8 AGHR Output Simulation Results
9 Single Column – Distillation
10 Distillation Column Profiles
Hysys Output*
Aspen Output
11 Scrubbers Simulation Results
12 ATR / AGHR Design Considerations
*400% PDF Magnification Required
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Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
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APPENDIX
FIGURES
Figure 1 Conventional Small Scale Steam Methane Reformer Design
Figure 2 Compact, Tubular, Small Scale Steam Methane
Reformer Designed for Fuel Cell Applications, with
Convective Heat Transfer
TABLES
Table I Comparison between Different Reformer Concepts
Table 2 Advantages and Disadvantages for Different
Synthesis Gas Technologies
Table 3: Small-Scale Steam Methane Reforming for Syn Gas Generation
Table 4: Small-Scale Autothermal Reformers for SynGas Generation
Table 5: Small-Scale Partial Oxidation for SynGas Generation
Table 6: Small-Scale Methanol Steam Reforming for SynGas Generation
Table 7: Small-Scale [Ammonia Cracking, Sorbent Enhanced
Reforming, Ion Transport Membranes, Catalytic Cracking of
Methane, Plasma Reformer] for SynGas Generation
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Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
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1 INTRODUCTION
For heavy natural gas and oil-associated gases, the required stoichiometric
number cannot be obtained by pure autothermal reforming, even if all hydrogen
available is recycled.
For these applications, the VULCAN SYSTEMS COMBINED REFORMING
concept, proposes autothermal and advanced gas heated reforming as an
economically and technically viable option, in generating synthesis gas for
methanol plants.
A methanol plant with natural gas feed can be divided into three main sections. In
the first part of the plant natural gas is converted into synthesis gas. The
synthesis gas reacts to produce methanol in the second section, and methanol is
purified to the desired purity in the tail-end of the plant.
The capital cost of large scale methanol plants is substantial. The synthesis gas
production including compression and oxygen production when required may
account for 60% or more of the investment. In many plants today either tubular
steam reforming or two-step reforming (tubular steam reforming followed by
autothermal or oxygen blown secondary reforming) is used for the production of
synthesis gas.
Stand-alone Autothermal Reforming (ATR) at low steam to carbon (S/C) ratio is
reportedly the preferred technology for large scale plants by maximizing the
single line capacity and minimizing the investment.
ATR combines substoichiometric combustion and catalytic steam reforming in
one compact refractory lined reactor to produce synthesis gas for production of
more than 10,000 MTPD of methanol. The ATR operates at low S/C ratio, thus
reducing the flow through the plant and minimizing the investment. The ATR
produces a synthesis gas well suited for production of both fuel grade and high
purity methanol.
This case study describes the benefits of using ATR and AGHR for synthesis gas
production for large scale production of methanol; (ATR) Autothermal Reforming
with (AGHR) Advanced Gas Heated Reforming, with emphasis on performance
simulation, of a single line capacity.
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2 Autothermal Reforming (ATR)
2.1. Process Description
This process combines partial oxidation and steam reforming in one vessel,
where the hydrocarbon conversion is driven by heat released in the POX
reaction. Developed in the late1950’s by Haldor Topsøe and Société Belge de
l’Azote the process is used for methanol and ammonia production. Both light and
heavy hydrocarbon feed stocks can be converted. In the latter case, an adiabatic
pre-reformer is required. In this process a preheated mixture of natural gas,
steam and oxygen is fed through the top of the reactor. In the upper zone, partial
oxidation proceeds at a temperature of around 1200°C. After that, the mixture is
passed through a catalyst bed, where final reforming reaction takes place. The
catalyst destroys any carbon formed at the top of the reactor. The outlet
temperature of the catalyst bed is between 850 and 1050°C.
In autothermal reforming, a hydrocarbon feed (methane or a liquid fuel) is
reacted with both steam and air to produce a hydrogen-rich gas. Both the steam
reforming and partial oxidation reactions take place. For example, with methane
CH4 + H2O ↔ CO + 3 H2 Δh = +206.16 kJ/mol CH4 (1)
CH4 + 1/2 O2 -> CO + 2 H2 Δh° = -36 MJ/kmol CH4
With the right mixture of input fuel, air and steam, the partial oxidation reaction
supplies all the heat needed to drive the catalytic steam reforming reaction.
Unlike the steam methane reformer, the autothermal reformer requires no
external heat source and no indirect heat exchangers. This makes autothermal
reformers simpler and more compact than steam reformers, and it is likely that
autothermal reformers will have a lower capital cost. In an autothermal reformer
all the heat generated by the partial oxidation reaction is fully utilized to drive the
steam reforming reaction. Thus, autothermal reformers typically offer higher
system efficiency than partial oxidation systems, where excess heat is not easily
recovered.
The main advantages of ATR are a favorable H2/CO ratio (1.6 to 2.6), reduction
of emissions due to internal heat supply, a high methane conversion, and the
possibility to adjust the syngas composition by changing the temperature of the
reaction. However, it requires an oxygen source.
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The capital costs for autothermal reforming are lower than those of the SMR
plant by 25%, as reported by Haldor Topsøe. Operational costs, however, are the
same or even higher due to the need to produce oxygen.
A recent study reported a capital-cost reduction of 35%, but an 8%-increase in
operational costs for the ATR technology in comparison to the SMR process.
ATR technology is commercially available, but still has limited commercial
experience. The main licensors are Haldor Topsøe, Lurgi, Johnson Matthey,
Foster Wheeler.
The heat transfer to the catalyst bed is more favorable in an autothermal
reformer than in the externally heated tubular reformers, since in the former case
the heat in the gas is supplied directly to the catalyst bed.
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This means that a high temperature in the catalyst bed can be achieved by
burning only a small portion of the product gas. The quantity of the gas to be
burned will be dependant to the inlet concentration of the methane and other
“reformable” compounds (such as tars) in the gas. It is more likely that the initial
temperature increase in the combustion zone will reduce the concentration of the
tars and other hydrocarbons sharply. However it must be taken to account that
the combustion reaction will consume a part of the hydrogen that is present in
product gas.
As with a steam reformer or partial oxidation system, water gas shift reactors and
a hydrogen purification stage are needed.
Autothermal reformers (ATRs) combine some of the best features of steam
reforming and partial oxidation systems. Several companies are developing small
autothermal reformers for converting liquid hydrocarbon fuels to hydrogen in fuel
cell systems. (See Appendix Tables 3 – 7)
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3 Gas Heated Reforming (GHR)
In the gas heated reformer (GHR) concept the heat for the endothermic reaction
is supplied by cooling down the reformed gas from the secondary reformer. This
technology, originally developed in the 1960s by ICI, was first demonstrated
during 1988 at two ammonia plants in Severnside, UK.
The feed in the gas-heated reformer is passed first to the primary reformer where
about 25% of reforming takes place. The partially reformed gas is then passed to
a secondary oxygen-fired reformer. The effluent of the latter is used to heat up
the feed in the primary reformer. For start-up, an auxiliary burner is employed.
Gas Heated Reformer
The volume of a GHR is typically 15 times smaller than the volume of a fired
reformer (SMR or CO2) for the same output (51). Overheating of hot metal parts
and a poor temperature control can lead to problems concerning the reliable
operation of heat exchange reformers. To overcome these problems, reformers
usually use counter-current flows in the low-temperature part with effective heat
transfer and co-current flows in the hot section for a better temperature control.
Sogge et al estimated that the GHR plant would cost about 40% less to build
than a comparable SMR plant, while operational costs would be about the same.
According to Abbott, the GHR scheme requires 33% less oxygen than the ATR
plant. The main developer of GHR technology is Johnson Matthey.
(See Appendix Table 1 Comparison between different reformer concepts)
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(AGHR) Advanced Gas Heated Reformer
• The original GHR was a complex device to fabricate.
• Desire to simplify the design:
• eliminate the bayonet tubes
• simplify the upper (triple) tubesheet
• In 1998, BHPP replaced the original GHR with the new AGHR.
The objective of this case study was to examine the flowsheet performance
implications of combining (ATR) Autothermal Reforming with (AGHR) Advanced
Gas Heated Reforming in the production of synthesis gas for methanol plants.
(See Appendix for a Comparison of Reformer Types / Configurations)
25. Purge Gas Scrubber 2 ft diameter based on 1.5" metal Pall rings and 3 te/hr of scrubbing water
Vapor to:
Tray Mass Flow [kg/h] Gas Flow
[ACT_m3/h]
Mole Wt. Temperature [C] Density [kg/m3] Viscosity [cP]
1 5249.3 1000.3 26.20 66.5 5.25 1.67E-02
2 5299.8 985.3 26.26 66.5 5.38 1.66E-02
3 5350.2 958.6 26.40 63.2 5.58 1.64E-02
4 5488.1 914.7 26.84 52.4 6.00 1.58E-02
Liquid from:
Tray Mass Flow [kg/h] Liq Flow [m3/s] Mole Wt. Temperature [C] Density [kg/m3] Viscosity [cP] Surf Ten [dyne/cm]
1 3084.9 8.80E-04 18.17 62.4 974.13 0.476 65.1
2 3135.3 9.01E-04 18.30 66.5 966.37 0.446 63.9
3 3185.7 9.22E-04 18.51 66.5 959.99 0.444 63.3
4 3323.6 9.77E-04 19.11 63.2 944.52 0.459 62.1
Vent & Flash Gas Scrubber 3 ft diameter based on 1.5" metal Pall rings and 4 te/hr of scrubbing water
Vapor to:
Tray Mass Flow [kg/h] Gas Flow [ACT_mMole Wt. Temperature [C] Density [kg/m3] Viscosity [cP]
1 9886.5 2172.7 30.91 60.4 4.55 1.59E-02
2 10017.8 2137.8 31.08 56.8 4.69 1.56E-02
3 10296.5 2099.3 31.59 47.9 4.90 1.50E-02
Liquid from:
Tray Mass Flow [kg/h] Liq Flow [m3/s] Mole Wt. Temperature [C] Density [kg/m3] Viscosity [cP] Surf Ten [dyne/cm]
1 4140.9 1.18E-03 18.29 59.5 972.42 0.494 65.3
2 4272.2 1.24E-03 18.67 60.4 960.02 0.481 64.0
3 4551.0 1.35E-03 19.58 56.8 937.25 0.493 62.1
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CASE STUDY#08270414
26. VULCAN SYSTEMS METHANOL PLANT
TECHNOLOGY
(ATR) AUTO THERMAL REFORMING AND
(AGHR) ADVANCED GAS HEATED REFORING
CASE STUDY#08270414
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27. Process Concept for Synthesis Gas Production by
Adiabatic Prereforming and Autothermal Reforming
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35. • Part of major component
combined with the sheath
tubeplate
• Low alloy plate P4 group
materials
• Machined Fabrication
• Weight 28 tonnes
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36. Part of major component
combined with catalyst
tubeplate sub-assembly
Low alloy plate P4 group
materials
Machined Fabrication
Weight 17 tonnes
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37. Major element of the AGHR
Large Fabrication, critical
machined features
Support platform for the bundle
Key item with two tiers of close
tolerance tube hole arrays.
Weight 45 tonnes
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38. Fabricated tube component
with laser welded fins.
High tolerance required, needs
to fit precisely with
corresponding components
Relatively flimsy assembly
careful handling required
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39. Fabricated tube
component
High tolerance required
on outside & inside
diameters to achieve fit
with corresponding
components
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APPENDIX
METHANOL PRODUCTION USING VULCAN SYSTEMS
COMBINED REFORMING TECHNOLOGY
(ATR) AUTO THERMAL REFORMING AND
(AGHR) ADVANCED GAS HEATED REFORING
CASE STUDY#08270414
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Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
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Figure 1
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Figure 2
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Table I Comparison between Different Reformer Concepts
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Table 2 Advantages and Disadvantages for Different
Synthesis Gas Technologies
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Table 3: Small-Scale Reformers for Syn Gas Generation (Con’t)
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Table 4: Small-Scale Autothermal Reformers for SynGas Generation
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Table 5: Small-Scale Partial Oxidation for SynGas Generation
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Table 6: Small-Scale Methanol Steam Reforming for SynGas
Generation
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Table 7: Small-Scale [Ammonia Cracking, Sorbent Enhanced
Reforming, Ion Transport Membranes, Catalytic Cracking of
Methane, Plasma Reformer] for SynGas Generation
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