CA2227598C - Synthesis gas production by steam reforming using catalyzed hardware - Google Patents

Synthesis gas production by steam reforming using catalyzed hardware Download PDF

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CA2227598C
CA2227598C CA002227598A CA2227598A CA2227598C CA 2227598 C CA2227598 C CA 2227598C CA 002227598 A CA002227598 A CA 002227598A CA 2227598 A CA2227598 A CA 2227598A CA 2227598 C CA2227598 C CA 2227598C
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steam reforming
steam
gas
reforming catalyst
hydrogen
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CA2227598A1 (en
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Jens Rostrup-Nielsen
Peter Seier Christensen
Viggo Lucassen Hansen
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Topsoe AS
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Haldor Topsoe AS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J15/00—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor
    • B01J15/005—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00504—Controlling the temperature by means of a burner
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0866—Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C01B2203/143—Three or more reforming, decomposition or partial oxidation steps in series
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention provides an improvement in a process for the preparation of hydrogen and a carbon monoxide-rich gas by steam reforming of a hydrogen-rich gas in the presence of a steam reforming catalyst. The improvement comprising the essential steps of passing a heated, prereformed hydrogen feedstock through a second tubular reactor which is provided with a thin film of the steam reforming catalyst, and which is heated by the burning of fuel, thereby to obtain a partially-steam-reformed gas effluent and hot flue gas, passing the partially-steam-reformed gas effluent through a fixed bed, steam reforming catalyst, and withdrawing a product gas stream comprising hydrogen and a carbon monoxide- rich gas from the fixed bed.

Description

(a) TITLE OF THE INVENTION
Synthesis Gas Production By Steam Reforming Using Catalyzed Hardware (b) TECHNICAL FIELD TO WHICH THE INVENTION BELONGS
The present invention relates to the production of synthesis gas by steam reforming of a hydrocarbon feedstock in contact with catalyzed hardware.
(c) BACKGROUND ART
The term catalyzed hardware is used for a catalyst system where a layer of catalyst is fixed on a surface of another material, e.g. metallic surfaces. The other mateerial serves as the supporting structure giving strength to t:he system. This allows to design catalyst shapes which wou::d not have sufficient mechanical strength in itself.
The system herein consists of tubes on which a thin layer of reforming catalyst is placed on the inner wall.
Synthesis gas is produced from hydrocarbons by steiam reforming by the reactions (1) -(3) :

CnHm + n H20 n CO + (n + 2) H2 -,,H2 9 6 < 0) (1) C:O + H20 CO2 + H2 (-dH298 = 41 kJ/mole) (2) CH4 + H20 CO + 3 H2 ( -1~i298 = -206 kJ/mole) (3) State of the art steam reforming technology makes use of reforming catalyst in the form of pellets of various sizes and shapes. The catalyst pellets are placed in fixed bed. reactors (reformer tubes). The reforming reaction is endothermic. In conventional reformers, the necessary heat for the reaction is supplied from the environment outside the tubes usually by a combination of radiation and convec-tion to the outer side of the reformer tube. The heat is traLnsferred to the inner side of the tube by heat conduc-tic>n through the tube wall, and is transferred to the gas phase by convection. Finally, the heat is transferred from the gas phase to the catalyst pellet by convection. The catalyst temperature can be more than 100 C lower than the inner tube wall temperature at the same axial position of the reformer tube.
(d) DESCRIPTION OF THE INVENTION
By one broad aspect, the present invention provides an improvement in a process for the preparation of hydrogen and a carbon monoxide-rich gas by steam reforming of a hydrogen-rich gas in the presence of a steam reforming catalyst, the improvement comprising the essential steps of passing a heated, prereformed hydrogen feedstock through a second tubular reactor which is provided with a thin film of the steam reforming catalyst, and which is heated by the burning of fuel, thereby to obtain a partially-steam-reformed gas effluent and hot flue gas, passing the partially-steam-reformed gas effluent through a fixed bed, steam reforming catalyst, and withdrawing a product gas stream comprising hydrogen and a carbon monoxide-rich gas from the fixed bed.

By another broad aspect, the present invention provides a process for the preparation of hydrogen and a carbon monoxide-rich gas by steam reforming of a hydrogen-rich gas in the presence of a steam reforming catalyst, the essential steps of passing a process gas of prereformed hydrocarbon feedstock through a first tubular reactor which is provided with a thin film of the steam reforming catalyst which is supported on walls of the reactor in heat-conducting relationship with hot flue gas which has been recycled from a downstream second tubular steam reforming reactor, thereby to obtain a heated, prereformed hydrogen feedstock gas effluent, passing the heated, prereformed hydrogen feedstock from the first tubular reactor through a second tubular reactor which is provided with a thin film of the steam reforming catalyst, and which is heated by the burning of fuel, thereby to obtain a partiatly-steam-reformed gas effluent and the hot flue gas, passing the partially-steam-reformed gas effluent from the second tubular reactor to a fixed bed, steam reforming catalyst, and withdrawing a product gas stream comprising hydrogen and a carbon monoxide-rich gas from the fixed bed.
By one variant thereof, the fixed bed reforming catalyst is operated at adiabatic conditions. The fixed bed stream reforming catalyst may be arranged within the second tubular reactor.
By another variant thereof, the fixed bed steam reforming catalyst is arranged within the second tubular reactor.
By yet another variant thereof the steam reforming catalyst comprises at least one of nickel and ruthenium.

It has been found that heat transport is more efficient when catalyzed hardware is used in the steam reforming process. The heat transport to the catalyst occurs by conduction from the inner tube wall. This is a much more efficient transport mechanism than the transport by convection via the gas phase. The result is that the temperatures of the inner tube wall and the catalyst are almost identical (the difference below S C). Furthermore, the tube thickness can be reduced, see below, which makes the temperature difference between the inner and outer side of the reformer tube smaller. It is hence possible to have both. a higher catalyst temperature and a lower tube tem-perature, all other conditions being the same when replac-ing the conventional reformer tubes with catalyzed hardware tubes. A low outer tube wall temperature is desirable since it prolongs the lifetime of the tube. A high catalyst temperature is advantageous since the reaction rate increases with temperature and since the equilibrium of reaction (3) is shifted to the right hand side resulting in a better utilisation of the feed.
Pressure drop in the catalyzed reformer tube is much. lower than in the conventional case for the same tube diameter. This enables the use of reactor tubes with a smaller diameter and still maintaining an acceptable pres-sure: drop. Smaller tube diameter results in an increased tube lifetime, tolerates higher temperatures and reduces the tube material consumption.
Finally, the catalyst amount is reduced when using catalyzed hardware reformer tubes compared to the conven-tional reformer with a fixed bed of reforming catalyst.
(e) DESCRIPTION OF THE FIGURES
In the accompanying drawings;
Fig. 1 is a schematic representation of the front end of a plant producing according to one aspect of the present invention;
Fig. 2 is a representation of process gas flow inside tubes showing the layout of one tube according to one aspect of the present invention; and Fig. 3 is a flow scheme of a prices according to one aspect of the present invention.
(f) AT LEAST ONE MODE FOR CARRYING OUT THE INVENTION

Fig. 1 shows the front-end of a plant producing syngas. Feed 2 is preheated, desulphurized in unit 4, mixed with process steam 6, and further heated before entering an adiabatic prereformer B. The effluent stream from prere-former 8 is further heated in loop arranged in flue gas channel 12 and send to the tubular reformer 14, where conv-ersion of methane to hydrogen, carbon monoxide, and carbon dioxide occurs. The processing of effluent gas dowr.Lstream from the tubular reformer depends on the use of the product.
Catalyzed hardware can be used in two of the units shown in Fig. 1:

1. In the preheater coil 10 for heating the prerefor-mer,effluent gas before entering the tubular reformer 14.
2. In the tubular reformer 14.

Below is presented the results obtained for the plant in Fig. 1 when catalyzed hardware is used in the above two units. The catalyst used for the catalyzed hard-ware is the R-67R nickel steam reforming catalyst available from Haldor Topsoe A/S. The results are compared with the conventional case.
The purpose of the preheater coil is to use the heat content in the flue gas for preheating of the process gas before it enters the tubular reformer. The flue gas is used for preheating of process gas and for preheating of the combustion air for the tubular reformer (not shown in Fig. 1). However, the heat content of the flue gas is larger than what can be used for these purposes and the remaining heat is used for steam production. It will be an advantage, if a larger amount of the heat content in the flue gas can be transferred to the process gas. This will reduce the necessary amount of fuel in the tubular reformer, and it will reduce the size of the reformer since a smaller amount of heat is to be transferred in the unit.
The conventional preheater is limited by the risk of carbon formation by decomposition of methane. This sets an upper limit for the tube wall temperature, which can be accepted. Fixing a layer of catalyzed hardware on the inner tube wa1116 of the preheater coil 10 (as shown in Fig. 2) results in a decrease of both the tube wall temperature and the process gas temperature. This enables the transfer of a higher duty in the coil without having a higher tube tem-perature.
The preheater coil used in the calculation consists of 8 tubes in which the process gas flow inside the tubes.
The flue gas flows on the outer side. The flow pattern is cross flow/co-current. Fig. 2 shows the layout for one tube. The two cases with and without catalyzed hardware are summarised in Table 1. It is apparent that the transferred duty (heat energy) is 49% higher in the catalyzed hardware case compared to the conventional case. The catalyst layer thickness in the catalyst hardware case is 1.0 mm.

Table 1 Conventional case Catalyzed hard-ware case Number of 8 8 tubes Total effec- 51.6 m 76.2 m tive tube length Flue gas in/- 1057 C/964 C 1057 C/912 C
out tempera-ture Proces gas 512 C/650 C 512 C/631 C
in/out tem-perature Methane con- 0% 8.70 version Tra:nsferred 9.69*106 kcal/h 1.44*107 kcal/h duty The effective tube length is the length of the tube inside the flue gas channel.
The conventional tubular reformer consists of a number of tubes which is filled with catalyst pellets. The process gas flows inside the tubes. The tubes are placed in a furnace which is heated by combustion of a fuel.
In the catalyzed hardware case the catalyst pellet filled tubes are replaced with a number of tubes with a layer of catalyzed hardware on the inner tube wall. The catalyst layer thickness is 0.25 mm. An additional adiabatic reforming fixed bed reactor is placed downstream from the tubular reactor since the conversion of methane in the catalyzed hardware tubular reformer is inferior to the conventional case. This reactor is called post reformer.
The catalyst used in the post reformer is the RKS-2 nickel steam reforming catalyst available from Haldor Topsoe A/S.
The two cases are summarised below in Table 2. It is seen that catalyst consumption is decreased by a factor 11.5, and that material consumption for the tubes in the tubular reformer is decreased 24% in the catalyzed hardware case compared to the conventional case.

Table 2 Conventional Catalyzed Catalyzed hard-case hardware ware case +
reformer post reformer Number of 276 187 tubes Tube length 13 m 55 m Catalyst con- 31.0 t 0.63 t 2.70 t sumption Tube material 153.6 t 116.0 t consumption for tubular reformer Methane con- 89.0 o 80.7 0 90.2 0 version A flow scheme of a process according to the inven-tion is shown in Fig. 3. The numbers in the triangles refer to the table below in which the overall figures for the procE=_ss are compared. The fuel consumption is decreased by 7.4% in the catalyzed hardware case compared to the conven-tional case.

Table 3 Posi- Conventional Catalysed hard-tion. case ware case 1 T ( C) 512 512 P (kg/cm'- g) 28.5 28.5 Total dry flow (Nm3/h) 57851 57851 Total flow (Nm3/h) 143168 143168 Composition (dry mole e) 23.78 23.78 H2 0.74 0.74 CO 21.14 21.14 COZ 54.34 54.34 CHy 2 T ( C) 650 631 P (kg/cm2 g) 27.5 27.4 Total dry flow (Nm3/h) 57851 67397 Total flow (Nm3/h) 143168 148720 Composition (dry mole g) 23.78 34.58 H2 0.74 2.67 CO 21.14 20.16 CO2 54.34 42.59 CHa 3 T ( C) 925 1015 P (kg/cm' g) 24.1 26.0 Total dry flow (Nm3/h) 141533 132653 Total flow (Nm3/h) 199121 194106 Composition (dry mole a) 68.85 66.76 H2 20.24 20.42 CO 8.47 8.24 COZ 2.44 4.57 CHa 4 T( C) No post reformer 930 P(kg/cm' g) in this case 24.4 Total dry flow (Nm3/h) 142580 Total flow (Nm3/h) 200003 Composition (dry mole o) 69.08 H2 20.35 CO 8.40 CO2 2.17 CHa T ( C) 1057 1057 Total flow (Nm3/h) 244672 234677 6 T ( C) 964 912 7 Total flow (Nm3/h) 9524 8820

Claims (5)

1. In a process for the preparation of hydrogen and a carbon monoxide-rich gas by steam reforming of a hydrocarbon feedstock in the presence of a steam reforming catalyst, the essential steps of:
passing a heated, prereformed hydrocarbon feedstock through a tubular reactor which is provided with a thin film of said steam reforming catalyst, and which is heated by the burning of fuel, thereby to obtain a partially-steam-reformed gas effluent and hot flue gas;
passing said partially-steam-reformed gas effluent through a fixed bed, steam reforming catalyst; and withdrawing a product gas stream comprising hydrogen and a carbon monoxide-rich gas from said fixed bed.
2. A process for the preparation of hydrogen and a carbon monoxide-rich gas by steam reforming of a hydrocarbon feedstock in the presence of a steam reforming catalyst, the essential steps of:
passing a process gas of prereformed hydrocarbon feedstock through a first tubular reactor which is provided with a thin film of said steam, reforming catalyst supported on walls of said reactor in heat-conducting relationship with hot flue gas which has been recycled from a downstream second tubular steam reforming reactor, thereby to obtain a heated, prereformed hydrogen feedstock gas effluent;
passing said heated, prereformed hydrogen feedstock from said first reactor through the second tubular reactor which is provided with a thin film of said steam reforming catalyst, and which is heated by the burning of fuel, thereby to obtain a partially-steam-reformed gas effluent and said hot flue gas;

passing said partially-steam-reformed gas effluent from said second tubular reactor to a fixed bed, steam reforming catalyst; and withdrawing a product gas stream comprising hydrogen and a carbon monoxide-rich gas from said fixed bed.
3. The process according to claim 1 or claim 2, wherein said fixed bed reforming catalyst is operated at adiabatic conditions.
4. The process according to claim 1, claim 2 or claim 3, wherein said fixed bed steam reforming catalyst is arranged within said second tubular reactor.
5. The process according to any one or more of claims 1 to 4, inclusive, wherein said steam reforming catalyst comprises at least one of nickel and ruthenium.
CA002227598A 1997-01-22 1998-01-21 Synthesis gas production by steam reforming using catalyzed hardware Expired - Fee Related CA2227598C (en)

Applications Claiming Priority (2)

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US3539697P 1997-01-22 1997-01-22
US60/035,396 1997-01-22

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CA2227598C true CA2227598C (en) 2007-09-11

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EP (1) EP0855366B1 (en)
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KR (1) KR100547540B1 (en)
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Families Citing this family (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK173496B1 (en) * 1998-07-16 2001-01-02 Topsoe Haldor As Process for producing synthesis gas by steam vapor reforming using a catalyzed metal surface
KR100401369B1 (en) 1998-07-21 2003-10-17 할도르 토프쉐 에이/에스 Synthesis gas production by steam reforming
DK173742B1 (en) * 1998-09-01 2001-08-27 Topsoe Haldor As Process and reactor system for producing synthesis gas
DK173897B1 (en) 1998-09-25 2002-02-04 Topsoe Haldor As Process for autothermal reforming of a hydrocarbon feed containing higher hydrocarbons
EP1584603A3 (en) * 1999-05-27 2007-06-13 Haldor Topsoe A/S Steam reforming reactor for synthesis gas production
EP1055637B1 (en) 1999-05-27 2005-11-02 Haldor Topsoe A/S Synthesis gas production by steam reforming
EP1069070B1 (en) * 1999-07-15 2011-11-30 Haldor Topsoe A/S Process for the catalytic steam reforming of a hydrocarbon feedstock
US20040161381A1 (en) * 1999-12-02 2004-08-19 Thomsen Soren Gyde Process and reactor for carrying out non-adiabatic catalytic reactions
PT1106570E (en) * 1999-12-02 2013-10-15 Haldor Topsoe As Process for carrying out non-adiabatic catalytic reactions
AU2002211388A1 (en) 2000-10-02 2002-04-15 Chevron U.S.A. Inc. Process for reducing coke formation in hydrocarbon processing by application of radio frequency electromagnetic radiation
RU2167808C1 (en) * 2000-10-09 2001-05-27 Пискунов Семен Евсеевич Synthetic gas generation process
US6890672B2 (en) 2001-06-26 2005-05-10 Idatech, Llc Fuel processor feedstock delivery system
US6818028B2 (en) * 2001-07-18 2004-11-16 Kellogg Brown & Root, Inc. Steam-methane reformer furnace with convection-heated pre-reformer
AU2003219821A1 (en) * 2002-02-22 2003-09-09 Chevron U.S.A. Inc. Process for reducing metal catalyzed coke formation in hydrocarbon processing
US20030223926A1 (en) 2002-04-14 2003-12-04 Edlund David J. Steam reforming fuel processor, burner assembly, and methods of operating the same
EP1403217A1 (en) 2002-09-26 2004-03-31 Haldor Topsoe A/S Process and apparatus for the preparation of synthesis gas
ES2405587T3 (en) * 2002-09-26 2013-05-31 Haldor Topsoe A/S Procedure and apparatus for the preparation of synthesis gas
EP1413547A1 (en) 2002-09-26 2004-04-28 Haldor Topsoe A/S Process for the production of synthesis gas
CA2410927A1 (en) * 2002-11-05 2004-05-05 Michel Petitclerc Electrically heated reactor for reforming in gaseous phase
EP1445235B1 (en) * 2003-02-05 2012-03-07 Haldor Topsoe A/S Process for treatment of synthesis gas
CA2516355A1 (en) * 2003-02-24 2004-09-10 Texaco Development Corporation Diesel steam reforming with co2 fixing
US7427388B2 (en) * 2004-03-19 2008-09-23 Air Products And Chemicals, Inc. Process for improving prereforming and reforming of natural gas containing higher hydrocarbons along with methane
US7892511B2 (en) 2004-07-02 2011-02-22 Kellogg Brown & Root Llc Pseudoisothermal ammonia process
US7320778B2 (en) * 2004-07-21 2008-01-22 Catacel Corp. High-performance catalyst support
US7472936B2 (en) * 2005-04-14 2009-01-06 Catacel Corp. Tool for insertion and removal of a catalytic reactor cartridge
US20060230613A1 (en) * 2005-04-14 2006-10-19 Catacel Corporation Catalytic reactor cartridge
US7565743B2 (en) * 2005-04-14 2009-07-28 Catacel Corp. Method for insertion and removal of a catalytic reactor cartridge
US7682580B2 (en) * 2005-05-19 2010-03-23 Catacel Corp. Catalytic reactor having radial leaves
US7632322B2 (en) * 2005-06-07 2009-12-15 Idatech, Llc Hydrogen-producing fuel processing assemblies, heating assemblies, and methods of operating the same
US7504048B2 (en) * 2005-06-14 2009-03-17 Air Products And Chemicals, Inc. Axial convective reformer
US7501102B2 (en) * 2005-07-28 2009-03-10 Catacel Corp. Reactor having improved heat transfer
US7588738B2 (en) * 2005-08-23 2009-09-15 Exxonmobil Chemical Patents Inc. Series catalyst beds
JP4724029B2 (en) * 2006-03-27 2011-07-13 アイシン精機株式会社 Method for shutting down reformer
US7629067B2 (en) 2006-05-22 2009-12-08 Idatech, Llc Hydrogen-producing fuel processing systems and fuel cell systems with a liquid leak detection system
US7501078B2 (en) * 2007-01-10 2009-03-10 Air Products And Chemicals, Inc. Process for generating synthesis gas using catalyzed structured packing
US7771585B2 (en) 2007-03-09 2010-08-10 Southern Company Method and apparatus for the separation of a gas-solids mixture in a circulating fluidized bed reactor
US7850944B2 (en) * 2008-03-17 2010-12-14 Air Products And Chemicals, Inc. Steam-hydrocarbon reforming method with limited steam export
US20100147749A1 (en) * 2008-12-11 2010-06-17 American Air Liquide, Inc. Multi-Metallic Catalysts For Pre-Reforming Reactions
US9561476B2 (en) 2010-12-15 2017-02-07 Praxair Technology, Inc. Catalyst containing oxygen transport membrane
CN103011077B (en) * 2011-09-27 2016-04-06 中国科学院宁波材料技术与工程研究所 A kind of catalytically reforming hydrogen producing method and catalytic unit
US9486735B2 (en) 2011-12-15 2016-11-08 Praxair Technology, Inc. Composite oxygen transport membrane
WO2013089895A1 (en) 2011-12-15 2013-06-20 Praxair Technology, Inc. Composite oxygen transport membrane
US9969645B2 (en) 2012-12-19 2018-05-15 Praxair Technology, Inc. Method for sealing an oxygen transport membrane assembly
US9453644B2 (en) 2012-12-28 2016-09-27 Praxair Technology, Inc. Oxygen transport membrane based advanced power cycle with low pressure synthesis gas slip stream
US9938145B2 (en) 2013-04-26 2018-04-10 Praxair Technology, Inc. Method and system for adjusting synthesis gas module in an oxygen transport membrane based reforming system
US9212113B2 (en) 2013-04-26 2015-12-15 Praxair Technology, Inc. Method and system for producing a synthesis gas using an oxygen transport membrane based reforming system with secondary reforming and auxiliary heat source
US9611144B2 (en) 2013-04-26 2017-04-04 Praxair Technology, Inc. Method and system for producing a synthesis gas in an oxygen transport membrane based reforming system that is free of metal dusting corrosion
US9296671B2 (en) 2013-04-26 2016-03-29 Praxair Technology, Inc. Method and system for producing methanol using an integrated oxygen transport membrane based reforming system
EP3055054A2 (en) 2013-10-07 2016-08-17 Praxair Technology Inc. Ceramic oxygen transport membrane array reactor and reforming method
US9573094B2 (en) 2013-10-08 2017-02-21 Praxair Technology, Inc. System and method for temperature control in an oxygen transport membrane based reactor
CA2926757C (en) 2013-12-02 2020-02-25 Praxair Technology, Inc. Method and system for producing hydrogen using an oxygen transport membrane based reforming system with secondary reforming
CN105980666B (en) 2014-02-12 2019-04-09 普莱克斯技术有限公司 For generating the method and system based on oxygen transport membrane reactor of electric power
US20170021322A1 (en) 2014-04-02 2017-01-26 Haldor Topsøes A/S Pseudo-isothermal reactor
US10822234B2 (en) 2014-04-16 2020-11-03 Praxair Technology, Inc. Method and system for oxygen transport membrane enhanced integrated gasifier combined cycle (IGCC)
US9789445B2 (en) 2014-10-07 2017-10-17 Praxair Technology, Inc. Composite oxygen ion transport membrane
US10441922B2 (en) 2015-06-29 2019-10-15 Praxair Technology, Inc. Dual function composite oxygen transport membrane
US10118823B2 (en) 2015-12-15 2018-11-06 Praxair Technology, Inc. Method of thermally-stabilizing an oxygen transport membrane-based reforming system
US9938146B2 (en) 2015-12-28 2018-04-10 Praxair Technology, Inc. High aspect ratio catalytic reactor and catalyst inserts therefor
KR102154420B1 (en) 2016-04-01 2020-09-10 프랙스에어 테크놀로지, 인코포레이티드 Catalyst-containing oxygen transport membrane
WO2018208373A1 (en) * 2017-05-09 2018-11-15 Exxonmobil Chemical Patents Inc. Linear alpha olefin process using temperature control in oligomerization reactor
WO2019226435A1 (en) 2018-05-21 2019-11-28 Praxair Technology, Inc. Otm syngas panel with gas heated reformer
EP4247533A1 (en) 2020-11-19 2023-09-27 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Reforming reactor comprising reformer tubes with enlarged outer surface area and structured catalyst
EP4155259A1 (en) 2021-09-22 2023-03-29 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Method for producing synthesis gas with reduced steam export

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1008667A (en) * 1972-06-30 1977-04-19 Foster Wheeler Corporation Catalytic steam reforming
US4079017A (en) * 1976-11-19 1978-03-14 Pullman Incorporated Parallel steam reformers to provide low energy process
EP0049967A1 (en) * 1980-10-14 1982-04-21 Imperial Chemical Industries Plc Ammonia production process
US4844837A (en) * 1982-09-30 1989-07-04 Engelhard Corporation Catalytic partial oxidation process
DE3480192D1 (en) * 1983-03-25 1989-11-23 Ici Plc Steam reforming
GB8308343D0 (en) * 1983-03-25 1983-05-05 Ici Plc Steam reforming
GB8309359D0 (en) * 1983-04-06 1983-05-11 Ici Plc Synthesis gas
DK165946C (en) * 1985-03-21 1993-07-05 Haldor Topsoe As REFORMING PROCESS DURING HEAT EXCHANGE AND REACTOR THEREOF
GB8728882D0 (en) * 1987-12-10 1988-01-27 Ici Plc Hydrogen
EP0334540B1 (en) * 1988-03-24 1993-10-20 Imperial Chemical Industries Plc Two-step steam-reforming process
JP2607644B2 (en) * 1988-10-27 1997-05-07 三菱重工業株式会社 Methanol reforming method
GB9000389D0 (en) * 1990-01-08 1990-03-07 Ici Plc Steam reforming
DK167864B1 (en) * 1990-02-02 1993-12-27 Topsoe Haldor As PROCEDURE AND REACTOR SYSTEM FOR REFORMING CARBON HYDROIDS DURING HEAT EXCHANGE
ATE156778T1 (en) * 1991-07-09 1997-08-15 Ici Plc SYNTHESIS GAS GENERATION
US5429809A (en) * 1991-09-23 1995-07-04 Haldor Topsoe A/S Process and reactor for carrying out non-adiabatic catalytic reactions
JPH05155602A (en) * 1991-12-09 1993-06-22 Sekiyu Sangyo Kasseika Center Thin type steam reforming reactor
JPH05186203A (en) * 1992-01-07 1993-07-27 Toshiba Corp Catalytic element for steam reforming
FR2696168B1 (en) * 1992-09-25 1994-12-09 Inst Francais Du Petrole Process and device for the production of synthesis gas and associated use.
JPH06219705A (en) * 1993-01-22 1994-08-09 Mitsubishi Electric Corp Fuel reformer
MY131526A (en) * 1993-12-27 2007-08-30 Shell Int Research A process for the preparation of carbon monoxide and/or hydrogen

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AU728728B2 (en) 2001-01-18
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US5932141A (en) 1999-08-03
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CN1196330A (en) 1998-10-21
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