US20080260631A1 - Hydrogen production process - Google Patents

Hydrogen production process Download PDF

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Publication number
US20080260631A1
US20080260631A1 US12/029,826 US2982608A US2008260631A1 US 20080260631 A1 US20080260631 A1 US 20080260631A1 US 2982608 A US2982608 A US 2982608A US 2008260631 A1 US2008260631 A1 US 2008260631A1
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United States
Prior art keywords
production process
hydrogen production
feedstream
process according
catalyst
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Abandoned
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US12/029,826
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English (en)
Inventor
Franklin D. LOMAX
Maxim Lyubovsky
Rama Zakaria
Jon P. Wagner
Chandra Ratnasamy
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Sued Chemie Inc
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H2Gen Innovations Inc
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Priority to US12/029,826 priority Critical patent/US20080260631A1/en
Priority to US12/061,355 priority patent/US8591861B2/en
Assigned to H2GEN INNOVATIONS, INC. reassignment H2GEN INNOVATIONS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RATNASAMY, CHANDRA, WAGNER, JON P., LOMAX, FRANKLIN D., LYUBOVSKY, MAXIM, ZAKARIA, RAMA
Priority to EP08746040.8A priority patent/EP2137099B1/fr
Priority to PCT/US2008/060548 priority patent/WO2008131049A1/fr
Priority to CA002684252A priority patent/CA2684252A1/fr
Priority to JP2010504236A priority patent/JP2010524824A/ja
Priority to CN2008800166705A priority patent/CN101679027B/zh
Priority to AU2008242937A priority patent/AU2008242937A1/en
Publication of US20080260631A1 publication Critical patent/US20080260631A1/en
Priority to PCT/US2008/087110 priority patent/WO2009102383A1/fr
Assigned to SUED-CHEMIE, INC. (50%) reassignment SUED-CHEMIE, INC. (50%) ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: H2GEN INNOVATIONS, INC.
Assigned to AIR LIQUIDE PROCESS & CONSTRUCTION, INC. reassignment AIR LIQUIDE PROCESS & CONSTRUCTION, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: H2GEN INNOVATIONS, INC.
Assigned to L'AIR LIQUIDE SOCIETE ANONYME POUR L'ETUDE ET L'EXPLOITATION DES PROCEDES GEORGES CLAUDE reassignment L'AIR LIQUIDE SOCIETE ANONYME POUR L'ETUDE ET L'EXPLOITATION DES PROCEDES GEORGES CLAUDE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AIR LIQUIDE PROCESS & CONSTRUCTION, INC.
Abandoned legal-status Critical Current

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    • 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
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
    • C01B2203/1017—Packed bed of catalytic structures, e.g. particles, packing elements characterised by the form of the structure
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1023—Catalysts in the form of a monolith or honeycomb
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1247—Higher hydrocarbons
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation
    • 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

Definitions

  • the present invention relates to processes for producing hydrogen.
  • the present invention relates to processes for producing hydrogen through steam reforming.
  • Hydrogen production is typically performed through catalytic steam reforming.
  • the general reaction for catalytic steam reforming is as follows:
  • Steam reforming is an endothermic reaction carried out either in heat exchange reactors, or by other means where substantial heat may be transferred to the reacting fluid, such as in the case of autothermal reforming, where a portion of the feedstock is combusted inside the reactor to provide heat for steam reforming either subsequently or in the same location as the combustion.
  • hydrocarbon or alcohol feedstocks enriched in compounds with two or more carbon atoms per molecule C2+ hydrocarbons
  • existing hydrogen production processes employ at least one adiabatic catalytic reactor prior to the heated reactor. These adiabatic reactors are referred to as pre-reformers.
  • the hydrocarbon feedstock is mixed with 1 to 5% hydrogen by volume, then is subjected to a hydrodesulphurization (HDS) pre-treatment step to remove sulphur.
  • the feedstock hydrocarbons are then mixed with superheated steam in a ratio determined by the average molecular weight of the feedstock molecules.
  • Natural gas or other feedstocks where the average carbon number is less than two are processed with a molar steam to carbon ratio between 3:1 and 5:1.
  • Higher molecular weight feedstocks are often processed with steam to carbon ratios as much as twice as high. These high steam flowrates are used to suppress carbon formation, and enhance the steam reforming reaction.
  • High steam to carbon ratios disadvantageously increase energy usage in the hydrogen production process.
  • pre-reforming catalysts are prepared with very high metal loadings, above 10% by weight, and high metal surface areas. These high metal surface areas present several disadvantages. First, they are subject to rapid sintering and reduction of activity if feedstock temperature is not controlled very closely. Second, they present substantial safety risk due to their pyrophoric reaction with oxygen, especially when nickel metal is used, thus necessitating great care in handling the catalysts during reduction and subsequent operation. Further, even at the elevated steam to carbon ratios employed in existing hydrogen production processes using pre-reformers for C2+ feedstocks, deactivation by carbon deposition remains a problem.
  • volatile alkali or alkali-silicate promoters are added to suppress carbon deposition, as described by Twigg, et al. Catalyst Handbook: 2 nd Edition , Manson Publishing, Ltd. 1996, pp. 250-253, the contents of which are hereby incorporated by reference.
  • These promoters are very effective, but disadvantageously reduce catalyst reaction rate, necessitating larger pre-reforming reactors. Further, the promoters tend to volatilize and subsequently deposit on downstream catalysts and equipment. This causes deactivation of downstream catalysts and potential corrosion damage to equipment, both of which may lead to serious operation problems such as hot banding of reformer tubes, carbon deposition and eventual tube failure. Further, the protective effects of the alkali promoters are lost after they are volatilized, such that eventual catalyst failure is assured in existing pre-reformers. Upon failure, the highly-reactive catalyst must be safely removed from the reactor and replaced.
  • the present invention provides a catalytic steam reforming process for hydrogen production in which carbon deposition is reduced by adding more than 5 vol % hydrogen with the hydrocarbon feedstock gas.
  • the present invention provides an improved hydrogen production method, for processing feedstocks containing 20% or more of molecules having at least two carbon atoms each, which is not deactivated by carbon deposition.
  • FIG. 1 is a schematic diagram of a hydrogen production process
  • FIG. 2 is a propane conversion versus time plot for catalysts according to the present invention.
  • the present invention relates to a hydrogen production process comprising combining a first feedstream and a second feedstream to produce, in a pre-reforming reactor, a first product stream comprising CH 4 and H 2 O.
  • the first feedstream comprises a mixture of H 2 and at least one member selected from the group consisting of hydrocarbons having two or more carbon atoms and alcohols having two or more carbon atoms, the mixture having a hydrogen stoichiometric ratio ( ⁇ ) of at least 0.1.
  • the first product stream is fed into a reforming reactor and reacted in the reforming reactor to produce a second product stream comprising CO and H 2 .
  • first feedstream and “second feedstream” are used to distinguish the two feedstreams, but does not designate their order of addition into the pre-reforming reactor.
  • first feedstream can be introduced into the pre-reforming reactor either before, after or simultaneously with the “second feedstream” or the first and second feedstreams can be combined prior to introduction into the pre-reforming reactor as a single combined feed.
  • FIG. 1 shows a typical hydrogen production process 1 , in which feedstock gas 2 (the first feedstream of the present invention) is co-fed to pre-reforming reactor 3 with steam 4 (the second feedstream of the present invention).
  • feedstock gas 2 the first feedstream of the present invention
  • steam 4 the second feedstream of the present invention
  • the product from the pre-reforming reactor (first product stream of the present invention) is subsequently fed to the reforming reactor 5 , with or without the additional feed 6 .
  • Additional feed 6 may include further steam injection, air or other non-air oxidant injection, mixtures of desulphurized gases such as hydrocarbons, carbon oxides, inerts, etc., for instance as is practiced in reforming for the production of synthesis gas.
  • the product from the reformer then exits the reforming reactor 5 to the balance of the plant.
  • the feedstock gas 2 can be treated in a desulphurizing process 7 . If the feedgas possesses bound organic sulphur compounds such as mercaptans, thiols, etc. then the desulphurizing process 7 usually includes a hydrogenation step, and a hydrogen-containing gas 8 is added to the feedgas to facilitate sulphur removal.
  • the generalized hydrogen production process 1 illustrated in FIG. 1 can be used to describe both the prior art hydrogen production process for C2+ feedstocks and the present invention.
  • the pre-reforming reactor 3 is operated at temperatures from 350° C. to 600° C. inlet temperature both in the present invention and in the prior art.
  • the pre-reformer of the present invention may be operated at temperatures of 400° C. or higher.
  • the reactor may be operated at or below 550° C.
  • Operating pressures for pre-reforming reactors in the prior art and the present invention may be between atmospheric pressure and 50 MPa. Common industrial embodiments are operated between essentially atmospheric pressure and 5 MPa. These typical operating conditions are recited in Twigg, supra, and Rostrup-Nielsen, J. R., Catalytic Steam Reforming , Reprint from Catalysis - Science and Technology , Springer-Verlag, 1984, hereby incorporated by reference, among other sources.
  • the amount of hydrogen contained in the feedstock gas 2 is increased compared to prior-art processes.
  • the proportion of hydrogen employed in the feedstock 2 can be best described by a hydrogenation stoichiometric ratio, or hydrogen stoichiometric ratio, or hydrogen stoichiometry (hereafter “hydrogen stoichiometry”), ⁇ , for the hydrogenation reaction of a given hydrocarbon to methane.
  • ⁇ it is convenient to represent the average chemical composition of the feedstock molecules in a feed mixture containing hydrocarbons and oxygenated species as C x H y O z , where
  • ⁇ is then defined in terms of molar flow rates, F, to the hydrogen production process as follows:
  • the hydrogen stoichiometry, ⁇ is preferably at least 0.1. In another embodiment of the present invention, ⁇ is greater than or equal to 0.2, and also less than or equal to 1.5. In another embodiment of the present invention, ⁇ is greater than or equal to 0.25, and also less than or equal to 1.
  • the increased amount of hydrogen in the method of the present invention may be added prior to the desulphurizing process 7 as part of hydrogen-containing gas 8 , or it may be added prior to the pre-reforming reactor 3 as stream 10 . Further, distributed injection of the hydrogen may be practiced through the pre-reformer 3 . The relative amounts of hydrogen added at any of these locations does not limit the application of the present invention.
  • the addition of hydrogen in the amounts of the present invention advantageously promotes the hydrogenation reaction.
  • This reaction is exothermic, whereas the steam reforming reaction is endothermic.
  • the method of the present invention advantageously compensates for the usual drop in temperature, and thus reaction rate, observed in traditional methods.
  • the method of the present invention can advantageously be employed to obtain a temperature increase in the pre-reforming reactor 3 . This temperature increase promotes both the hydrogenation reaction rate and both the rate and equilibrium limits to the steam reforming reaction.
  • the present method advantageously increases conversion of C2+ hydrocarbons and alcohols via hydrogenation while also enhancing the rate and extent of conversion possible through the steam reforming reaction in the same reactor.
  • the method of this invention is not catalyst specific and can be applied to various reforming catalyst normally used in the art.
  • the catalyst used in the present process is a catalyst having an active component supported on a non-reducible oxide support.
  • Suitable active components include, but are not limited to, Pt, Rh, Ru, Ni, Co, Pd, Ir and any combination thereof.
  • Suitable supports include, but are not limited to, TiO 2 , ZrO 2 , alkaline-earth metal hexaaluminates (preferably barium hexaaluminate), monoclinic zirconia or alumina.
  • the support of the preferred catalyst has a preferred surface area of from 10 to 250 m 2 /g, preferably from 80 to 180 m 2 /g.
  • One preferred catalyst formulation is described in U.S. Patent Application Publication No. US 2005/0232857, the contents of which is incorporated by reference herein in its entirety, and contain as active metal at least one of Ir, Pt and Pd, on a support of monoclinic zirconia or an alkaline-earth metal hexaaluminate.
  • the oxide support of the preferred catalyst can optionally include one or more surface area stabilizers.
  • Suitable surface area stabilizers include, but are not limited to, REO (La, Ce, Pr, Nd, Sm), Zr, Y, Ti, Sc and combinations thereof.
  • Such stabilizers can be present in the support in an amount from 0 to 30% by weight, preferably from 5 to 20% by weight, based on amount of support.
  • the preferred catalyst formulation can be provided in any desired physical form.
  • the supported catalyst is in a form selected from the group consisting of powders, granulates, tablets, extrudates, and washcoats on ceramic or metallic monoliths or tubular structures.
  • the present process is performed with a molar ratio of steam per carbon atom in the first feedstream, S:C, that is less than 5, preferably less than 4, more preferably between 3 and 4.
  • S:C a molar ratio of steam per carbon atom in the first feedstream
  • Propane was used as hydrocarbon feedstock having three carbon atoms.
  • a reactor vessel having 1.4′′ ID was loaded with 10 g of catalyst having 1 wt % Ir deposited on a non-reducible oxide support comprising barium hexaaluminate, making an approximately 1 cm deep catalyst bed.
  • the pre-reforming reaction was conducted under nearly adiabatic conditions.
  • Two ⁇ 2 cm deep layers of 3 mm glass beads were placed below and above the catalyst bed to provide uniform flow of reacting gas through the bed.
  • Two thermocouples were installed just below and above the catalyst bed to measure the temperature differential across the catalyst.
  • Table 1 shows conversion of C 3 H 8 into C 1 species (CH 4 and CO 2 , below detectable amounts of CO were observed for all samples) and ⁇ T between inlet and outlet (T in ⁇ T out ) of the catalyst (negative sign indicates temperature increase over the catalyst).
  • Increasing negative values of ⁇ T indicate a high degree of the exothermic methanation reaction according to the present invention, whereas high positive values of ⁇ T indicate endothermic steam reforming reaction dominates the observed conversion of the propane feedstock.
  • Example 1 The catalyst of Example 1 was aged for about 1500 hrs in the steam methane reforming (SMR) reaction. The catalyst was then removed and loaded into the reactor of Example 1. The same testing procedure was used as described above. Table 2 shows the results for the second catalyst testing.
  • SMR steam methane reforming
  • the method of the present invention yields a surprising increase in C2+ hydrocarbon conversion with increasing hydrogen stoichiometry, ⁇ . Furthermore, the exothermic temperature change increases with increased hydrogen stoichiometry within the inventive range.
  • This catalyst has a metal loading of approximately 4 wt % Iridum on an alumina carrier promoted with a mixture of rare earth oxides, namely, CeO 2 at 14-20 wt %, La 2 O 3 at 1-5 wt %, and Y 2 O 3 at 1-5 wt %, based on amount of catalyst.
  • FCR-69-1 Ten grams of fresh FCR-69-1 catalyst obtained from Sud-Chemie Corporation was loaded into the same test vessel.
  • FCR-69-1 has active metal loading of 1 wt % but is otherwise identical to the FCR-69-4 catalyst of the Example 3.
  • the same testing procedure was used as described above testing, and the results are shown in Table 4. Even with a reduction in metal loading to 1 ⁇ 4 of the value in Example 3, extensive conversion of feed was achieved in proportion to the hydrogen stoichiometry.
  • FIG. 2 shows the relative conversion C 3 H 8 versus time for the rare earth oxide promoted catalyst of Example 3 and 4 versus the unpromoted catalyst of Examples 1 and 2.
  • the rare earth oxide promoted catalyst shows a surprising advantage in deactivation rate compared to the unpromoted catalyst.
  • the hydrogen stoichiometry ⁇ for the promoted catalysts was uniformly higher than that for the unpromoted catalyst, such that the effects of increased hydrogen stoichiometry and catalyst composition can not be readily separated.
  • Both the promoted and unpromoted catalysts possess substantially lower active metal loadings than prior art pre-reforming catalysts. Further, neither catalyst is promoted with alkaline earth promoters with their attendant disadvantages.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US12/029,826 2007-04-18 2008-02-12 Hydrogen production process Abandoned US20080260631A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US12/029,826 US20080260631A1 (en) 2007-04-18 2008-02-12 Hydrogen production process
US12/061,355 US8591861B2 (en) 2007-04-18 2008-04-02 Hydrogenating pre-reformer in synthesis gas production processes
AU2008242937A AU2008242937A1 (en) 2007-04-18 2008-04-17 Hydrogen production process
CN2008800166705A CN101679027B (zh) 2007-04-18 2008-04-17 氢气生产方法
PCT/US2008/060548 WO2008131049A1 (fr) 2007-04-18 2008-04-17 Procédé de production d'hydrogène
CA002684252A CA2684252A1 (fr) 2007-04-18 2008-04-17 Procede de production d'hydrogene
JP2010504236A JP2010524824A (ja) 2007-04-18 2008-04-17 水素製造方法
EP08746040.8A EP2137099B1 (fr) 2007-04-18 2008-04-17 Procédé de production d'hydrogène
PCT/US2008/087110 WO2009102383A1 (fr) 2008-02-12 2008-12-17 Unité de pré-reformage d'hydrogénation dans des procédés de production de gaz de synthèse

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US91249507P 2007-04-18 2007-04-18
US12/029,826 US20080260631A1 (en) 2007-04-18 2008-02-12 Hydrogen production process

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Cited By (1)

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US8591861B2 (en) 2007-04-18 2013-11-26 Schlumberger Technology Corporation Hydrogenating pre-reformer in synthesis gas production processes

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US8293805B2 (en) * 2008-05-29 2012-10-23 Schlumberger Technology Corporation Tracking feedstock production with micro scale gas-to-liquid units
WO2013015687A1 (fr) * 2011-07-26 2013-01-31 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center Procédé et système pour la production de mélanges de gaz riches en hydrogène
US9199888B2 (en) 2012-01-24 2015-12-01 Sge Scandgreen Energy Ab Combined processes for utilizing synthesis gas with low CO2 emission and high energy output
GB2507042B (en) 2012-10-16 2018-07-11 Schlumberger Holdings Electrochemical hydrogen sensor
MX2015003867A (es) * 2012-10-23 2015-07-17 Haldor Topsøe As Proceso para la preparacion de hidrocarburos.
US9181148B2 (en) 2013-05-22 2015-11-10 Saudi Arabian Oil Company Ni/CGO and Ni-Ru/CGO based pre-reforming catalysts formulation for methane rich gas production from diesel processing for fuel cell applications
EP2886514A1 (fr) * 2013-12-20 2015-06-24 Basf Se Procédé de reformage de mélanges à partir d'hydrocarbures et de dioxyde de carbone
EP2762442A1 (fr) 2014-04-23 2014-08-06 Air Products And Chemicals, Inc. Procédé de reformage d'hydrocarbures lourds
US9409773B2 (en) 2014-11-10 2016-08-09 Air Products And Chemicals, Inc. Steam-hydrocarbon reforming process
US9933408B2 (en) 2014-11-10 2018-04-03 Air Products And Chemicals, Inc. Method for characterizing the hydrocarbon content of a reformate stream
CN105154125A (zh) * 2015-07-10 2015-12-16 北京宝塔三聚能源科技有限公司 一种由合成气联产甲烷、石蜡和高碳烯烃的转化工艺
WO2017085594A2 (fr) * 2015-11-16 2017-05-26 Sabic Global Technologies B.V. Procédé et catalyseur pour la conversion de co2 en gaz de synthèse pour une production simultanée d'oléfines et de méthanol
US10953388B1 (en) 2019-12-27 2021-03-23 Saudi Arabian Oil Company Ni—Ru—CgO based pre-reforming catalyst for liquid hydrocarbons

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