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WO2007031713A1 - Procede de production d'hydrogene - Google Patents

Procede de production d'hydrogene Download PDF

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Publication number
WO2007031713A1
WO2007031713A1 PCT/GB2006/003305 GB2006003305W WO2007031713A1 WO 2007031713 A1 WO2007031713 A1 WO 2007031713A1 GB 2006003305 W GB2006003305 W GB 2006003305W WO 2007031713 A1 WO2007031713 A1 WO 2007031713A1
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Prior art keywords
hydrogen
reactor
hydrocarbon
zone
catalyst
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PCT/GB2006/003305
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English (en)
Inventor
Yazhong Chen
Yuzhong Wang
Hengyong Xu
Original Assignee
Bp P.L.C.
Dalian Institute Of Chemical Physics
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Filing date
Publication date
Priority claimed from CNB200510086418XA external-priority patent/CN100417588C/zh
Priority claimed from GB0616301A external-priority patent/GB0616301D0/en
Application filed by Bp P.L.C., Dalian Institute Of Chemical Physics filed Critical Bp P.L.C.
Publication of WO2007031713A1 publication Critical patent/WO2007031713A1/fr

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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
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    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
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    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
    • B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
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    • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
    • B01J8/0257—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical annular shaped bed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0278—Feeding reactive fluids
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • C01B3/505—Membranes containing palladium
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    • 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
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    • 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
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C01B2203/041—In-situ membrane purification during hydrogen production
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/048—Composition of the impurity the impurity being an organic compound
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    • 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
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
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    • 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
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    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
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    • 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
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/86—Carbon dioxide sequestration
    • 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
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry

Definitions

  • This invention relates to the production of hydrogen, more specifically to the conversion of hydrocarbons into hydrogen in a reactor comprising a palladium membrane.
  • Hydrogen is increasingly being studied as an energy source, as it produces a large amount of energy per unit mass, and emits only water when combusted.
  • hydrogen can be used in small-scale energy devices, such as proton membrane fuel cells, which combine the benefits of energy efficiency and clean emissions with flexibility.
  • Activity has also been directed towards extracting hydrogen from hydrocarbon fossil fuels, through processes such as steam reforming, and capturing the resulting CO 2 for sequestration in order to make the fuel effectively greenhouse gas neutral.
  • the hydrogen produced by such processes can ultimately be used as an energy source for a number of applications, for example as a fuel for a fuel cell-powered vehicle, or as a combustible fuel in a power station.
  • US 5,525,322 describes the recovery of hydrogen from water and hydrocarbons and an isotope method for the same, using a palladium membrane and nickel-based catalyst.
  • the following equilibria can be shifted to the right; CO + H 2 O ⁇ CO 2 + H 2 , CH 4 + H 2 O ⁇ CO + 3H 2 , and CH 4 ⁇ C + 2H 2 , thus realising high conversions and hydrogen yields at relatively low starting material space velocity.
  • there is a marked fall in the hydrogen recovery rate severely limiting the hydrogen-producing capacity of the device.
  • Higher hydrocarbons for example liquid fuels such as liquefied petroleum gas (LPG), gasoline, diesel, kerosene and the like, have a high energy density and are easily transported and stored, and can potentially be used in low-scale production of hydrogen.
  • LPG liquefied petroleum gas
  • the steam reforming of such hydrocarbons or the catalytic partial oxidation needs to be carried out at temperatures in excess of 800°C to obtain acceptable hydrocarbon conversions and hydrogen yields.
  • methane which needs to be separated and recycled in order to improve the hydrogen yields. Therefore, there remains a need for a process to convert higher hydrocarbons into hydrogen at lower temperatures, and with reduced production of methane.
  • a process for producing hydrogen from a hydrocarbon in a reactor having a first and a second zone separated by a selective hydrogen-permeable membrane which process comprises contacting the hydrocarbon with water in the first zone of the reactor, in the presence of a catalyst and under conditions that allow a reaction to occur to produce hydrogen, which hydrogen permeates through the selective hydrogen-permeable membrane to the second zone of.the reactor, characterised in that the gas hourly space velocity of hydrocarbon over the catalyst, when multiplied by the number of carbon atoms in the hydrocarbon, is maintained at a value of greater than 2000 h "1 .
  • a hydrocarbon is reacted with steam in the first zone of the reactor, optionally in the presence of oxygen.
  • the reactor has a selective hydrogen- permeable membrane that separates the first zone from a second zone. Hydrogen produced in the reaction permeates through " the membrane, reducing the hydrogen partial pressure in the first zone and hence shifting the equilibrium therein to allow further production of hydrogen. By such means, reduced reaction temperatures are necessary, typically below temperatures of 800 0 C often employed for steam reforming reactions.
  • the molar ratio of water (or steam) to carbon is selected so that sufficient water is present to minimise catalyst coking, while simultaneously minimising any excess to maintain energy efficiency.
  • the molar steam to carbon ratio is typically in the range of from 50 : 1 to 1 : 50, such as in the range of from 10 : 1 to 1 : 10.
  • the steam to "carbon" molar ratio is in the range of 1.8 : 1 to 4 : 1.
  • decane was used as the hydrocarbon
  • a molar ratio of steam to decane of 20 : 1 was used, this would equate to a steam to carbon molar ratio of 2 : 1.
  • oxygen is also fed to the first zone.
  • This allows a combined steam reforming and partial oxidation reaction to occur therein.
  • Heat released by the exothermic partial oxidation reaction can reduce the amount of heat that need to be otherwise supplied to the reactor to compensate for that absorbed during the endothermic steam reforming reaction, and hence improves the energy efficiency of the process.
  • Both partial oxidation and steam reforming reactions result in the formation of hydrogen and oxides of carbon (CO x ) from the hydrocarbon.
  • the temperature in the first zone of the reactor is below 800 0 C, such as in the range from 300 to 600 0 C.
  • Pressures in the first zone of the reactor are typically maintained so as to maximise hydrogen yields, which are improved at lower pressures, while maintaining a sufficient hydrogen pressure so that a sufficient gradient exists across the selective hydrogen-permeable membrane.
  • the pressure is typically up to 10 MPa, preferably 0.5 MPa or more, such as in the range of from 1 to 10 MPa.
  • GHSV gas hourly space velocity
  • this val ⁇ e is then simply multiplied by the number of carbon atoms in the hydrocarbon.
  • the C- GHSV of hydrocarbon is 5 000 h '1 or more, more preferably is 10 000 h "1 or more, and yet more preferably is 15 000 h "1 or more.
  • the process of the present invention is particularly suitable for producing hydrogen from hydrocarbons having two or more carbon atoms, such as those found in or derived from liquefied hydrocarbons such as natural gas liquids (NGL) or liquefied petroleum gases (LPG), or the hydrocarbon can comprise one or more liquid hydrocarbons with in the range of, for example, from 6 to 30 carbon atoms, such as those present in naphtha, middle distillate, kerosene or atmospheric gas oil fractions of a refinery crude distillation unit, or products derived from the fractions such as gasoline, diesel, aviation fuel, heating oil and the like.
  • NNL natural gas liquids
  • LPG liquefied petroleum gases
  • the hydrocarbon is a hydrocarbon having in the range of from 4 to 16 carbon atoms, or a mixture of hydrocarbons having in the range of from 4 to 16 carbon atoms.
  • the reactor has two zones which are separated by a selective hydrogen-permeable membrane. Hydrogen is produced from the hydrocarbon in the first zone, and the hydrogen permeates through the membrane into the second zone of the reactor. By constantly removing hydrogen selectively from the first zone of the reactor, the extent of methanation is reduced, and the yield of hydrogen is improved.
  • a concentration gradient such that it flows from a region of high hydrogen concentration or partial pressure to a region of low hydrogen concentration of partial pressure.
  • Hydrogen permeates the membrane in response to a concentration gradient, such that it flows from a region of high hydrogen concentration or partial pressure to a region of low hydrogen concentration of partial pressure.
  • to remove hydrogen from the first zone of the reactor where it is generated requires a lower partial pressure to be maintained in the second zone of the reactor. This is achieved by maintaining a reduced total pressure in the second zone of the reactor and/or by diluting any hydrogen that permeates, for example with a gas that is inert to hydrogen under conditions in the second zone such as one or more of nitrogen, steam or argon.
  • the diluent gas can also be used to flush hydrogen from the second zone of the reactor.
  • the membrane is a palladium membrane, optionally in
  • the catalyst of the present invention is capable of catalysing the conversion of the hydrocarbon to oxides of carbon (CO x ) and hydrogen under the low temperature conditions in the first zone of the reactor.
  • the catalyst will comprise one or more of the metals nickel, ruthenium, platinum, palladium, rhodium, rhenium and iridium.
  • the catalyst can be supported on an inert support, typically a refractory oxide.
  • the refractory oxide is suitably selected from one or more of magnesia, alumina, silica and zirconia.
  • the catalyst may also comprise additional components that can promote activity, or improve selectivity, such as alkaline earth elements and lanthanide elements.
  • nickel is used due to its low cost, and is supported on an alumina support, preferably with a nickel loading in the range of from 25 to 70% by weight, based on NiO, and is preferably in the range of from 30 to 50% by weight, based on NiO.
  • the catalyst additionally comprises magnesium and lanthanum as promoters.
  • the catalyst can be prepared by deposition techniques, where the catalyst and/or any promoters are deposited on the oxide support, or using co-precipitation techniques wherein a precipitate comprising the various constituents of the catalyst is obtained from a solution comprising soluble compounds of the various constituents, typically achieved by adding a base such as an alkali metal hydroxide, an alkaline earth metal hydroxide or ' ammonium hydroxide.
  • a base such as an alkali metal hydroxide, an alkaline earth metal hydroxide or ' ammonium hydroxide.
  • FIG. 1 shows a plan view of a steam reforming process in accordance with the present invention.
  • a hydrocarbon (such as iso-octane) and steam reactants 1 are fed into the first zone 2 of reactor 3, which reactor comprises a closed end ceramic alumina tube 4 supporting a palladium membrane 5 that separates the first zone from a second zone 6 on the permeate side of the palladium membrane.
  • the reactants pass over a steam reforming catalyst 7 in the first zone of the reactor, where the iso-octane and steam react to form CO x and hydrogen.
  • Methane selectivity 100 x [Product methane flow rate x 2 / (product methane flow rate x 2 + product hydrogen flow rate)]
  • Hydrogen selectivity 100 x [Product hydrogen flow rate / (product methane flow rate x 2 + product hydrogen flow rate)]
  • Example 1 A catalyst was prepared by adding (MLi) 2 CO 3 (as a precipitating agent) to an aqueous solution of Ni(NO 3 ) 2 .6H 2 O and A1(NO 3 ) 3 .9H 2 O. A pH of 8.0 - 8.5 was maintained, and the precipitate was aged in the supernatant solution for 2 h at room temperature. The precipitate was separated, washed with water, and dried at 12O 0 C before being calcined at 600°C for 4 h. The NiO content of the catalyst was 40 wt%, and the Al 2 O 3 content was 60 wt%.
  • 5.5 g of the catalyst was diluted with quartz sand and placed in the first zone of the palladium membrane reactor with a bed layer height of 100 mm.
  • the hydrogen permeation rate of the membrane was 52 m 3 m "2 bar "1 h "1 , and the H 2 /N 2 separation coefficient was over 10,000.
  • a Daqing 6 # solvent oil comprising a mixture of C 5 to C 7 hydrocarbons, was then fed to the catalyst-containing zone of the reactor at a rate of 0.34 ml/min of liquid, and liquid water was also fed at a rate of 0.80 ml/min.
  • the reaction was conducted at 550 0 C and 1.1 MPa, and an Ar flushing gas was injected into the second (hydrogen permeate) zone of the reactor.
  • the molar feed rate of argon fed to the second reactor in unit time was 1.8 times that of the molar rate of feeding carbon atoms to the first reactor zone.
  • a catalyst was prepared by adding ammonium hydroxide (as a precipitating agent) to an aqueous solution of Ni(NO 3 ) 2 .6H 2 O and A1(NO 3 ) 3 .9H 2 O and La(NO 3 ) 3 .6H 2 O at room temperature. A pH of 8.0 was maintained, and the precipitate was aged in the supernatant solution for 1 h at room temperature. The precipitate was separated, washed with water, and dried at 120°C before being calcined at 600°C for 4 h. The catalyst obtained had a composition of 50 wt% NiO, 42 wt% Al 2 O 3 and 8 wt% La 2 O 3 .
  • Catalyst performance was measured in a conventional fixed bed reactor with isp- octane as the starting material at a pressure of 0.8 MPa 5 and at temperatures of 450°C, 500°C and 550°C respectively. A steam to carbon ratio of 2.73 was used in the reactions. The results are shown in Table 1.
  • the molar feed rate ratio of Ar flushing gas fed to the second (hydrogen permeate) zone of the reactor to the carbon fed to the first zone of the reactor was 1.8.
  • Selectivity to methane was 2.3%, and the hydrogen selectivity was 97.7%.
  • the purity of the hydrogen having passed through the membrane was greater than 99.9%.
  • a catalyst was prepared by adding (NH 4 ) 2 CO 3 (as a precipitating agent) to an aqueous solution of Ni(NO 3 ) 2 .6H 2 O and A1(NO 3 ) 3 .9H 2 O and Mg(NO 3 ) 2 .6H 2 O at room temperature. A pH of 8.0 - 8.5 was maintained, and the precipitate was aged in the supernatant solution for 2 h at room temperature. The precipitate was separated, washed with water, and dried at 120°C before being calcined at 700°C for 4 h.
  • the catalyst obtained had a composition of 36 wt% NiO, 12 wt% MgO and 52 wt% Al 2 O 3 .
  • the prepared catalyst was pressed and crushed into particle sizes having a diameter of 420-630 ⁇ m. 5.5 g of the catalyst were diluted with quartz sand and placed in the first zone of the palladium membrane reactor to a bed layer height of 100 mm. The hydrogen permeation rate of the membrane was 65 m m " bar " h " , and the H 2 /N 2 separation coefficient was greater than 10 000. With iso-octane as the hydrocarbon feed, the reaction was conducted with a C-GHSV of 2000 h '1 , a reaction temperature 550°C, a H 2 O/C ratio 2.73 and a pressure 1.7 MPa. The molar feed rate ratio of Argon flush gas fed to the second reactor zone to carbon fed to the first reaction zone was 1.8. The product methane selectivity was 1.8%, and the hydrogen selectivity was
  • Example 4 5.5 g of the Ni/MgO-Al 2 O 3 catalyst from Example 3 was used and placed in the first zone of a palladium membrane reactor. The permeation rate of the membrane was 68

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Abstract

Procédé servant à produire de l'hydrogène à partir d'un hydrocarbure dans un réacteur possédant une membrane sélective perméable à l'hydrogène, ce qui consiste à effectuer la réaction de l'hydrocarbure et d'eau en présence d'un catalyseur afin de produire l'hydrogène qui traverse la membrane sélective par perméabilité, la vitesse spatiale horaire gazeuse de l'hydrocarbure par rapport au catalyseur, quand elle est multipliée par le nombre d'atomes de carbone de l'hydrocarbure, étant maintenue à une valeur supérieure à 2000 h-1.
PCT/GB2006/003305 2005-09-14 2006-09-07 Procede de production d'hydrogene WO2007031713A1 (fr)

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WO2010100432A2 (fr) 2009-03-06 2010-09-10 Institute Of Metal Research, Chinese Academy Of Sciences Technologie de scellement
WO2010099635A1 (fr) * 2009-03-06 2010-09-10 Institute Of Metal Research, Chinese Academy Of Sciences Composition d'alliage et appareil comprenant celle-ci
WO2011016030A1 (fr) 2009-08-03 2011-02-10 Technion Research & Development Foundation Ltd. Production d'hydrogène par un reformeur de gaz autotherme avec échangeurs de chaleur, lits de garnissage et membranes de séparation
WO2012072199A1 (fr) * 2010-12-02 2012-06-07 Linde Aktiengesellschaft Procédé et dispositif de production d'hydrogène à partir de glycérine
US8597383B2 (en) 2011-04-11 2013-12-03 Saudi Arabian Oil Company Metal supported silica based catalytic membrane reactor assembly
ITUA20151262A1 (it) * 2015-12-28 2017-06-28 Grazia Leonzio Reazione di sabatier catalizzata da terre rare in reattori a membrana
US9745191B2 (en) 2011-04-11 2017-08-29 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic structures
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US11492254B2 (en) 2020-06-18 2022-11-08 Saudi Arabian Oil Company Hydrogen production with membrane reformer
US11578016B1 (en) 2021-08-12 2023-02-14 Saudi Arabian Oil Company Olefin production via dry reforming and olefin synthesis in a vessel
US11583824B2 (en) 2020-06-18 2023-02-21 Saudi Arabian Oil Company Hydrogen production with membrane reformer
US11617981B1 (en) 2022-01-03 2023-04-04 Saudi Arabian Oil Company Method for capturing CO2 with assisted vapor compression
US11639290B2 (en) 2020-06-04 2023-05-02 Saudi Arabian Oil Company Dry reforming of methane with carbon dioxide at elevated pressure
US11718575B2 (en) 2021-08-12 2023-08-08 Saudi Arabian Oil Company Methanol production via dry reforming and methanol synthesis in a vessel
US11787759B2 (en) 2021-08-12 2023-10-17 Saudi Arabian Oil Company Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel
US11999619B2 (en) 2020-06-18 2024-06-04 Saudi Arabian Oil Company Hydrogen production with membrane reactor
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US12258272B2 (en) 2021-08-12 2025-03-25 Saudi Arabian Oil Company Dry reforming of methane using a nickel-based bi-metallic catalyst

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US8486367B2 (en) 2008-07-01 2013-07-16 Linde Ag Method and device for generating hydrogen
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WO2010000375A1 (fr) * 2008-07-01 2010-01-07 Linde Aktiengesellschaft Procédé et dispositif pour la production d'hydrogène
WO2010100432A2 (fr) 2009-03-06 2010-09-10 Institute Of Metal Research, Chinese Academy Of Sciences Technologie de scellement
WO2010099635A1 (fr) * 2009-03-06 2010-09-10 Institute Of Metal Research, Chinese Academy Of Sciences Composition d'alliage et appareil comprenant celle-ci
US9359201B2 (en) 2009-08-03 2016-06-07 Technion Research & Development Foundation Ltd. Hydrogen production by an autothermal heat exchanger packed-bed membrane gas reformer
WO2011016030A1 (fr) 2009-08-03 2011-02-10 Technion Research & Development Foundation Ltd. Production d'hydrogène par un reformeur de gaz autotherme avec échangeurs de chaleur, lits de garnissage et membranes de séparation
WO2012072199A1 (fr) * 2010-12-02 2012-06-07 Linde Aktiengesellschaft Procédé et dispositif de production d'hydrogène à partir de glycérine
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