US20060260194A1 - Process to prepare synthesis gas - Google Patents

Process to prepare synthesis gas Download PDF

Info

Publication number
US20060260194A1
US20060260194A1 US10/553,164 US55316404A US2006260194A1 US 20060260194 A1 US20060260194 A1 US 20060260194A1 US 55316404 A US55316404 A US 55316404A US 2006260194 A1 US2006260194 A1 US 2006260194A1
Authority
US
United States
Prior art keywords
steam
reactor
product
reforming
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/553,164
Other languages
English (en)
Inventor
Thian Tio
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell USA Inc
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Assigned to SHELL OIL COMPANY reassignment SHELL OIL COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TIO, THIAN HOEY
Publication of US20060260194A1 publication Critical patent/US20060260194A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • B01J8/06—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 in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • 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
    • 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
    • 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
    • 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
    • B01J8/04—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 passing successively through two or more beds
    • B01J8/0446—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 passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—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 passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • 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
    • 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
    • B01J8/04—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 passing successively through two or more beds
    • B01J8/0496—Heating or cooling the reactor
    • 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
    • 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
    • B01J8/06—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 in tube reactors; the solid particles being arranged in tubes
    • 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
    • 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
    • B01J8/06—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 in tube reactors; the solid particles being arranged in tubes
    • B01J8/062—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 in tube reactors; the solid particles being arranged in tubes being installed in a furnace
    • 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
    • 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
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
    • 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
    • B01J2208/00477—Controlling the temperature by thermal insulation means
    • B01J2208/00495—Controlling the temperature by thermal insulation means using insulating materials or refractories
    • 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
    • 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
    • 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
    • C01B2203/02—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
    • 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
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0255—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation 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
    • C01B2203/04—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
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • 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
    • C01B2203/10—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
    • 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
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel 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
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group 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
    • C01B2203/12—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
    • C01B2203/1241—Natural gas or methane
    • 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
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • 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
    • 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
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus

Definitions

  • the invention is directed to a process to prepare a mixture comprising carbon monoxide and hydrogen from a carbonaceous feed by performing a partial oxidation reaction and an endothermic steam reforming reaction.
  • EP-A-168892 describes an endothermic steam reforming reaction, which is carried out in a fixed bed situated in at least one pipe in which a temperature of between 800 and 950° C. is maintained by routing at least part of the hot product gas from a partial oxidation reaction along the pipe(s).
  • the combined partial oxidation and endothermic production of synthesis gas result in a better yield of synthesis gas, an increased H 2 /CO ratio, a lower usage of oxygen per m 3 of synthesis gas product obtained and a lower capital cost of the plant for the production of CO and H 2 -containing gas mixtures (as compared to partial oxidation).
  • a reactor and process for performing a steam reforming reaction is described in DE-A-3345088.
  • This publication describes a reactor vessel for performing a steam reforming reaction starting from a natural gas feedstock.
  • the vessel consisted of a tube sheet from which a plurality of tubes filled with a suitable catalyst extended into the vessel.
  • the required heat of reaction is provided by passing the hot effluent of a partial oxidation reaction of natural gas at the exterior of the reactor tubes in the vessel.
  • Such steam reformer reactors are also referred to as so-called convective steam reformer (CSR) reactors.
  • CSR convective steam reformer
  • EP-A-983964 describes a convective steam reforming reactor vessel, wherein the vessel is provided with a plurality of reactor tubes containing a catalyst bed. Around the reactor tubes an annular sleeve is provided to transport a hot effluent of an auto thermal reformer (ATR). By indirect heat exchange between this hot effluent and the reactants passing through the catalyst bed the steam reforming reaction can take place.
  • ATR auto thermal reformer
  • a disadvantage of the processes of the prior art is that the obtained synthesis gas, carbon monoxide and hydrogen mixture, comprises of a relatively high content of steam. This steam is not desired, especially when the synthesis gas is to be used in a Fischer-Tropsch synthesis. Operating a CSR at a lower steam to carbon ratio is possible. However this will result in that less methane will be converted in the CSR reactor resulting in a synthesis gas containing a high level of methane. Although such levels may be acceptable for some processes, if the synthesis gas is to be used as feed to a Fischer-Tropsch process the presence of methane is not desirable because it will be present as an inert occupying reactor space.
  • the object of the present invention is to provide a process wherein the CSR reactor can be operated at a lower steam to carbon ratio and wherein the methane content in the resulting synthesis gas is kept at a lower level such that the synthesis gas can be used for example advantageously as feed for a Fischer-Tropsch reaction.
  • step (b) catalytic steam reforming a carbonaceous feedstock in a Convective Steam Reformer comprising a tubular reactor provided with one or more tubes containing a reforming catalyst, wherein the steam to carbon molar ratio of the feed to step (b) is below 1, to obtain as separate product a steam reforming product,
  • step (c) feeding the steam reformer product to the upper end of the partial oxidation reactor to obtain a mixture of the effluent of step (a) and the steam reformer product, and
  • step (d) providing the required heat for the steam reforming reaction in step (b) by convective heat exchange between the mixture obtained in step (c) and the steam reformer reactor tubes thereby obtaining a hydrogen and carbon monoxide containing gas having a reduced temperature.
  • step (b) Applicants found that by feeding the steam reformer effluent obtained in step (b) to the upper part of the partial oxidation reactor vessel a large portion of the unconverted methane is converted to carbon monoxide and hydrogen due to the fact that methane will be partially oxidized by the burner also present in that part of the partial oxidation reactor vessel.
  • FIG. 1 illustrates a CSR reactor vessel which may be used in the present invention.
  • FIG. 2 illustrates the combination of the reactor vessel of FIG. 1 and a partial oxidation reactor vessel.
  • FIG. 3 illustrates an integrated process involving the installation of FIG. 2 , a Fischer-Tropsch synthesis and some of its downstream unit operations.
  • the carbonaceous feedstock in step (a) is preferably a gaseous hydrocarbon, suitably methane, natural gas, associated gas or a mixture of C 1-4 hydrocarbons.
  • gaseous hydrocarbons are natural gas, refinery gas, associated gas or (coal bed) methane and the like.
  • the gaseous hydrocarbons suitably comprises mainly, i.e. more than 90 v/v %, especially more than 94%, C 1-4 hydrocarbons, especially comprises at least 60 v/v percent methane, preferably at least 75 percent, more preferably 90 percent.
  • natural gas or associated gas is used.
  • any sulphur in the feedstock is removed.
  • the carbonaceous feed in both steps (a) and (b) is a gaseous feed as described above.
  • step (a) the partial oxidation may be performed according to well known principles as for example described for the Shell Gasification Process in the Oil and Gas Journal, Sep. 6, 1971, pp 85-90.
  • Publications describing examples of partial oxidation processes are EP-A-291111, WO-A- 9722547 , WO-A-9639354 and WO-A-9603345.
  • the feed is contacted with an oxygen containing gas under partial oxidation conditions preferably in the absence of a catalyst.
  • the oxygen containing gas may be air (containing about 21 percent of oxygen) and preferably oxygen enriched air, suitably containing up to 100 percent of oxygen, preferably containing at least 60 volume percent oxygen, more preferably at least 80 volume percent, more preferably at least 98 volume percent of oxygen.
  • oxygen enriched air may be produced via cryogenic techniques, but is preferably produced by a membrane based process, e.g. the process as described in WO 93/06041.
  • step (a) Contacting the feed with the oxygen containing gas in step (a) is preferably performed in a burner placed in a reactor vessel.
  • carbon dioxide and/or steam may be introduced into the feed.
  • water produced in an optional downstream hydrocarbon synthesis may be used.
  • the gaseous product of the partial oxidation reaction in step (a) typically has a temperature of between 1100 and 1500° C. and an H 2 /CO molar ratio of from 1.5 up to 2.6, preferably from 1.6 up to 2.2.
  • the resulting temperature in said upper region will be suitably from 800 up to 1050° C.
  • Step (b) may be performed by well-known steam reforming processes, wherein steam and the gaseous hydrocarbon feed are contacted with a suitable reforming catalyst in a CSR reactor.
  • the convective steam reactor preferably comprises of a tubular reactor vessel provided with one or more tubes containing a reforming catalyst.
  • Various designs for such a reactor are known and suited for the present invention. The design should be such that the steam reformer product and the synthesis gas used to provide heat are obtained as separate streams in such a reactor. Examples of such a reactor concept is described in U.S. Pat. No. 6,224,789. Alternatively a design such as illustrated in FIG. 1 may be applied.
  • FIG. 1 illustrates a CSR reactor.
  • the reactor space is defined by one or more parallel positioned reactor tubes ( 21 ) filled with a bed ( 22 ) of steam reforming catalyst, comprising a passageway ( 23 ) for hot gas.
  • a third tube sheet ( 32 ) is present at the lower end of the reactor vessel ( 44 ) defining a space ( 33 ) which fluidly connects the vessel inlet ( 38 ) for the mixture as obtained in step (c) with the inlet of the passageways ( 23 ) which penetrate the tube sheet ( 32 ) via openings ( 34 ) which are preferably larger than the passageway ( 23 ) itself.
  • the fact that the passageways are not fixed in the tube sheet ( 32 ) is advantageous because it allows the combined reactor tubes ( 21 ) and passageways ( 23 ) to freely thermally expand in the reactor vessel ( 44 ) at start-up and cool down situations.
  • the lower ends of the passageway which extends into the lower space ( 33 ) may preferably be made from heat resistant materials like for example ceramics because of the high temperatures present in said space due to the fact that here the hot gaseous medium enters the reactor via vessel inlet ( 38 ).
  • the outlet opening ( 35 ) of the reactor tubes ( 21 ) comprising the catalyst bed ( 22 ) are positioned just above said tube sheet ( 32 ).
  • the steam reforming product being discharged from said opening ( 35 ) will enter space ( 36 ) defined as the space between tube sheets ( 40 ) and ( 32 ).
  • This space ( 36 ) fluidly connects the vessel outlet ( 39 ) for the steam reforming product with the openings ( 35 ).
  • the space ( 36 ) may suitably be provided with flow directing baffles which will direct the flow of steam reforming product in a zig zag flow through said space thereby optimising the contact of the hot steam reformer product gas and the external surface of the reactor tubes ( 21 ) present in said space.
  • part of the steam reforming product being discharged from openings ( 35 ) will leave the reactor vessel via outlet ( 39 ) and part will leave space ( 36 ) via openings ( 34 ) to space ( 33 ) by operating the reactor such that the pressure in space ( 36 ) is higher than the pressure in space ( 33 ).
  • the pressure in space ( 36 ) is higher than the pressure in space ( 33 ).
  • preferably from 0 to 60 wt % and more preferably from 0 to 40 wt % of the steam reformer product, as being discharged from openings ( 35 ) may enter space ( 33 ) to be mixed with the hot gaseous medium. This is advantageous because the steam to carbon ratio of the gases flowing in the passageways ( 23 ) can be increased thereby limiting metal dusting within the passageways ( 23 ).
  • FIG. 1 further shows a vessel inlet ( 43 ) for natural gas and steam, a vessel inlet for a hot gaseous medium ( 38 ), a vessel outlet ( 39 ) for steam reforming product and a vessel outlet ( 42 ) for the gasses, which are emitted from the passageways ( 23 ).
  • Tube sheets ( 40 ) and ( 41 ) are present in order to fix the reactor tubes ( 21 ) and to define collecting space ( 45 ) for the gasses emitted by the passageways ( 23 ) and an inlet space ( 46 ) fluidly connecting the vessel inlet ( 43 ) for steam and natural gas and the reactor tubes ( 21 ) comprising the catalyst bed ( 22 ).
  • the catalyst and process conditions as applied in the steam reformer reactor tubes may be those known by the skilled person in the field of steam reforming.
  • Suitable catalysts comprise nickel optionally applied on a carrier, fro example alumina.
  • the space velocity of the gaseous feed is preferably from 700 to 1000 litre (S.T.P.)/litre catalyst/hour, wherein S.T.P. means Standard Temperature of 15° C. and pressure of 1 bar abs.
  • S.T.P. means Standard Temperature of 15° C. and pressure of 1 bar abs.
  • the steam to carbon (as hydrocarbon and CO) molar ratio is below 1 and preferably from 0.5 up to 0.9. If such low steam to carbon ratio's are applied in step (b) the catalyst preferably comprises a Group VIII metal.
  • the catalyst comprises (a) an oxidic support material and (b) a coating comprising between about 0.1 and about 7.0 wt % of at least one of the metals of the group consisting of Pt, Ni, Pd and Co, preferably platinum; said support material comprising: (i) at least 80 wt % of ZrO 2 which has been calcined at a temperature up to about 670° C. before the application of said coating; (ii) 0.5-10 mol % of at least one oxide selected from the group consisting of Y, La, Al, Ca, Ce and Si, preferably La 2 O 3 .
  • Examples of such catalysts are for example the catalyst described in EP-A-695279.
  • the feed also comprises an amount of CO 2 , wherein preferably the CO 2 over carbon (as hydrocarbon and CO) molar ratio is from 0.5 up to 2.
  • the product gas of step (b) preferably has a temperature of from 600 up to 1000° C. and an H 2 /CO molar ratio of from 0.5 up to 2.5.
  • the temperature of the hydrogen and carbon monoxide containing gas is preferably reduced in step (b) from a temperature of from 1000 up to 1500° C. after performing step (a) to a temperature of between 800 up to 1050° C. after performing step (c) to a temperature from 300 up to 750° C. after performing step (d).
  • the temperature of the metal wall surfaces of the materials of the internals in the CSR reactor are preferably maintained below 1100° C.
  • the mixture of the effluent of step (a) and the steam reformer product as obtained in step (c) may be subjected to a autothermal reformer step, also referred to as post catalytic reformer step, at the elevated temperatures of said mixture to convert the gaseous mixture obtained in step (c) to a mixture having a H 2 /CO molar ratio closer to the desired thermal equilibrium H 2 /CO molar ratio values valid for said operating temperatures.
  • the combined mixture optionally after performing such a post reforming step, is used in step (d).
  • FIG. 2 shows a CSR reactor vessel. For clarity reasons no internals of vessel ( 44 ) are shown in FIG. 2 . Also shown is a partial oxidation reactor ( 51 ) provided with a burner ( 52 ). A carbonaceous feed ( 50 ) and an oxygen containing gas ( 50 ′) is supplied to burner ( 52 ). Also shown is that the product gas ( 55 ) of step (b) is fed to the upper half of the reactor vessel ( 51 ).
  • the steam reformer product ( 55 ) is fed close, i.e. in the upper half of vessel ( 51 ), to the burner ( 52 ) in order to benefit the most of the resultant elevated temperatures of from 800 up to 1050° C. present in that region of the vessel ( 51 ).
  • the methane content in steam reformer product ( 55 ) may be between 5 and 30 mol % carbon relative to the carbon as hydrocarbon in the feed to step (b), ( 43 ). This relatively high methane content is a resultant when operating step (b) at low steam to carbon ratio as described before. Because a methane slip will be corrected by the process of the current invention a lower reaction temperature in the CSR reactor tubes may also be allowed.
  • step (b) A lower reaction temperature will also result in than more non-reacted methane will be part of product ( 55 ).
  • Low temperatures in step (b) are suitably between 700 and 800° C. as measured on steam reformer product ( 55 ) as it leaves the reactor ( 44 ).
  • a low temperature is desirable for material strength reasons for the internals used in reactor ( 44 ).
  • FIG. 2 also shows a preferred autothermal reformer or post catalytic reformer catalyst bed ( 53 ) as present in the lower half of reactor vessel ( 51 ).
  • the catalyst bed ( 53 ) may be any well-known reformer catalyst, for example a Ni-containing catalyst.
  • the effluent of optional catalyst bed ( 53 ) is subsequently fed to inlet ( 38 ) of vessel ( 44 ), wherein the gasses are cooled in the passageways ( 23 ) (not shown in this Figure) and obtained as the final synthesis gas product ( 63 ) via outlet ( 42 ).
  • the synthesis gas ( 63 ) as obtained by the above process may advantageously be used as feedstock for a Fischer-Tropsch synthesis process, methanol synthesis process, a di-methyl ether synthesis process, an acetic acid synthesis process, ammonia synthesis process or to other processes which use a synthesis gas mixture as feed such as for example processes involving carbonylation and hydroformylation reactions.
  • steps (a) and (b) preferably recycle gases are fed.
  • recycle gasses are obtained in, for example the above exemplified, processes which use the synthesis gas as prepared by the process according to the invention.
  • These recycle gasses may comprise C 1-5 hydrocarbons, preferably C 1-4 hydrocarbons, more preferably C 1-3 hydrocarbons. These hydrocarbons, or mixtures thereof, are gaseous at temperatures of 5-30° C. (1 bar), especially at 20° C. (1 bar).
  • oxygenated compounds e.g. methanol, dimethylether, acetic acid may be present.
  • the invention is especially directed to the above process for the preparation of hydrogen and carbon monoxide containing gas (synthesis gas), wherein additional steps (e) (f) and (g) are also performed.
  • the synthesis gas is catalytically converted using a Fischer-Tropsch catalyst into a hydrocarbons comprising stream.
  • the hydrocarbons comprising stream of step (e) is separated into a hydrocarbon product and a gaseous recycle stream.
  • the hydrocarbon product are those having 5 or more carbon atoms, preferably having 4 or more carbon atoms and more preferably having 3 or more carbon atoms.
  • the gaseous recycle stream may comprise normally gaseous hydrocarbons produced in the synthesis process, nitrogen, unconverted methane and other feedstock hydrocarbons, unconverted carbon monoxide, carbon dioxide, hydrogen and water.
  • step (f) the recycle stream is fed to step (a) and/or (b).
  • the recycle stream is supplied to the burner of step (a) or directly supplied to the interior of the partial oxidation reactor.
  • part or all of the carbon dioxide present in such a recycle stream is separated from said recycle stream before being fed to step (a).
  • Part of the carbon dioxide may suitably be fed to step (a).
  • Step (e) and (f) may be performed by the well known Fischer-Tropsch processes which are for example the Sasol process and the Shell Middle Distillate Process.
  • suitable catalysts are based on iron and cobalt.
  • Typical reactor configurations include slurry reactors and tubular reactors. These and other processes are for example described in more detail in EP-A-776959, EP-A-668342, U.S. Pat. No. 4,943,672, U.S. Pat. No. 5,059,299, WO-A-9934917 and WO-A-9920720.
  • FIG. 3 illustrates the configuration of FIG. 2 in combination with a Fischer-Tropsch synthesis process unit ( 64 ) and its downstream hydroconversion unit(s) ( 66 ), i.e. step (g).
  • FIG. 3 shows how the synthesis gas ( 63 ) is fed to Fischer-Tropsch synthesis process unit ( 64 ).
  • a gaseous recycle stream ( 54 ) is separated from the hydrocarbon product ( 65 ) and recycled to partial oxidation reactor ( 51 ).
  • part ( 60 ) of the steam reformer product ( 55 ) having a relatively high hydrogen over CO molar ratio is fed to a hydrogen recovery unit to obtain hydrogen ( 62 ) suitably for use in hydroprocessing unit(s) ( 66 ).
  • the hydrocarbon product present in ( 65 ) comprising typically a relatively large portion of compounds boiling above 370° C., is converted by well-known hydrocracking and hydroisomerisation processes to middle distillates. Any remaining residue may be further converted to base oils by catalytic dewaxing processes (not shown), which also require hydrogen. Examples of such downstream hydroprocessing units are described in for example WO-A-0107538, WO-02070631, WO-02070629 and WO-02070627 and in the references cited in these publications.
  • Example 1 is repeated except that the steam to carbon ratio of the feed to the CSR reactor of FIG. 3 was equal to 1.
  • EXAMPLE 3 Serial operation - steam to carbon ratio 0.75 Effluent of the partial oxidation Feed to reactor entering Steam reformer the partial Feed to the the reactor 44 product (55) in oxidation reactor CSR reactor of FIG. 2 via 56 flow rate flow rate flow rate flow rate Stream name mol % mol % mol % mol % Component kmol/h (dry) kmol/h (dry) kmol/h (dry) kmol/h (dry) Hexane 0 0.00 0 0.00 0 0.00 0 0.00 Pentane 0 0.00 0 0.00 0 0.00 0 0.00 Butane 38 0.10 17 0.13 0 0.00 0 0.00 Propane 161 0.44 73 0.55 0 0.00 0 0.00 Ethane 1,232 3.34 554 4.23 0 0.00 0 0.00 Methane 18,815 51.06 8,453 64.55 313 0.31 1,114 2.86 Hydrogen 531 1.44 239 1.82 63,382

Landscapes

  • 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)
US10/553,164 2003-04-15 2004-04-13 Process to prepare synthesis gas Abandoned US20060260194A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP03076114.2 2003-04-15
EP03076114 2003-04-15
PCT/EP2004/050504 WO2004092063A1 (en) 2003-04-15 2004-04-13 Process to prepare synthesis gas

Publications (1)

Publication Number Publication Date
US20060260194A1 true US20060260194A1 (en) 2006-11-23

Family

ID=33185905

Family Applications (5)

Application Number Title Priority Date Filing Date
US10/552,551 Abandoned US20080028680A1 (en) 2003-04-15 2004-04-13 Process to Prepare Synthesis Gas
US10/552,553 Expired - Fee Related US7462209B2 (en) 2003-04-15 2004-04-13 Reactor for performing a steam reforming reaction and a process to prepare synthesis gas
US10/552,854 Expired - Fee Related US7550635B2 (en) 2003-04-15 2004-04-13 Process for the preparation hydrogen and a mixture of hydrogen and carbon monoxide
US10/553,164 Abandoned US20060260194A1 (en) 2003-04-15 2004-04-13 Process to prepare synthesis gas
US12/264,121 Expired - Fee Related US8986631B2 (en) 2003-04-15 2008-11-03 Reactor vessel for performing a steam reforming reaction and a process to prepare synthesis gas

Family Applications Before (3)

Application Number Title Priority Date Filing Date
US10/552,551 Abandoned US20080028680A1 (en) 2003-04-15 2004-04-13 Process to Prepare Synthesis Gas
US10/552,553 Expired - Fee Related US7462209B2 (en) 2003-04-15 2004-04-13 Reactor for performing a steam reforming reaction and a process to prepare synthesis gas
US10/552,854 Expired - Fee Related US7550635B2 (en) 2003-04-15 2004-04-13 Process for the preparation hydrogen and a mixture of hydrogen and carbon monoxide

Family Applications After (1)

Application Number Title Priority Date Filing Date
US12/264,121 Expired - Fee Related US8986631B2 (en) 2003-04-15 2008-11-03 Reactor vessel for performing a steam reforming reaction and a process to prepare synthesis gas

Country Status (6)

Country Link
US (5) US20080028680A1 (da)
EP (4) EP1622829A1 (da)
JP (4) JP2006523595A (da)
KR (1) KR20050120719A (da)
CN (4) CN1774391A (da)
WO (4) WO2004092060A1 (da)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080241059A1 (en) * 2007-03-26 2008-10-02 Air Products And Chemicals, Inc. Catalytic Steam Reforming With Recycle
US9631285B2 (en) 2005-08-25 2017-04-25 Ceramatec, Inc. Electrochemical process for the production of synthesis gas using atmospheric air and water

Families Citing this family (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7642294B2 (en) 2004-10-08 2010-01-05 Shell Oil Company Process to prepare lower olefins from a carbon containing feedstock
WO2006045744A1 (en) * 2004-10-20 2006-05-04 Shell Internationale Research Maatschappij B.V. Process for steam and/or co2 reforming of a hydrocarbonaceous feedstock
FR2877939B1 (fr) * 2004-11-16 2007-02-02 Air Liquide Procede et installation pour la production combinee d'hydrogene et de dioxyde de carbone
KR101127688B1 (ko) * 2004-12-07 2012-03-23 에스케이이노베이션 주식회사 원통형 소형 개질 장치
DE102005021500A1 (de) * 2005-05-10 2006-11-16 Uhde Gmbh Verfahren zur Aufheizung eines Dampf-/Erdgasgemisches im Bereich eines Gassammelrohres nach einem Primärreformer
US7485767B2 (en) 2005-06-29 2009-02-03 Exxonmobil Chemical Patents Inc. Production of synthesis gas blends for conversion to methanol or Fischer-Tropsch liquids
EP1991639B1 (en) 2006-03-07 2015-04-22 Shell Internationale Research Maatschappij B.V. Process to prepare a fischer-tropsch synthesis product
FR2898518B1 (fr) * 2006-03-17 2009-01-16 Inst Francais Du Petrole Reacteur echangeur a combustion interne pour reaction endothermique en lit fixe
US7772292B2 (en) 2006-05-31 2010-08-10 Exxonmobil Chemical Patents Inc. Synthesis gas production and use
EP2049437A2 (en) 2006-07-11 2009-04-22 Shell Internationale Research Maatschappij B.V. Process to prepare a synthesis gas
AU2007290757B2 (en) * 2006-08-25 2011-05-26 Exxonmobil Chemical Patents Inc. Production of aromatics from methane
EP1916233A1 (en) * 2006-10-20 2008-04-30 BP Chemicals Limited Process for the conversion of hydrocarbons to alcohols
WO2008123337A1 (ja) * 2007-03-29 2008-10-16 Nippon Oil Corporation 水素製造および二酸化炭素回収方法ならびに装置
US9212059B2 (en) * 2007-12-13 2015-12-15 Gyco, Inc. Method and apparatus for improving the efficiency of an SMR process for producing syngas while reducing the CO2 in a gaseous stream
US7988948B2 (en) * 2008-03-17 2011-08-02 Air Products And Chemicals, Inc. Steam-hydrocarbon reforming method with limited steam export
US7850944B2 (en) * 2008-03-17 2010-12-14 Air Products And Chemicals, Inc. Steam-hydrocarbon reforming method with limited steam export
US8105402B1 (en) * 2008-07-30 2012-01-31 Bossard Peter R Micro-channel steam reformer and system for extracting ultra-pure hydrogen gas from a hydrocarbon fuel
WO2010022096A2 (en) * 2008-08-18 2010-02-25 Syngest, Inc. Method for converting biomass into synthesis gas using a pressurized multi-stage progressively expanding fluidized bed gasifier followed by an oxyblown autothermal reformer to reduce methane and tars
BRPI0904285B1 (pt) * 2009-10-30 2019-09-10 Petroleo Brasileiro Sa Petrobras dispositivo para resfriamento e distribuição de cargas mistas sobre leitos fixos de catalisador
CN101721957B (zh) * 2009-12-03 2011-08-31 太原理工大学 一种连续炭催化ch4-co2重整反应器
US9611437B2 (en) * 2010-01-12 2017-04-04 Lummus Technology Inc. Producing low methane syngas from a two-stage gasifier
US9227844B2 (en) * 2010-01-19 2016-01-05 Haldor Topsoe A/S Heat exchange reformer with double-tubes for reforming hydrocarbons
WO2011106895A1 (en) * 2010-03-01 2011-09-09 Plasco Energy Group Inc. Carbon conversion system with integrated processing zones
US9321641B1 (en) 2011-02-11 2016-04-26 Emerging Fuels Technology, Inc. Process to convert natural gas into liquid fuels and chemicals
US9034208B1 (en) 2011-02-11 2015-05-19 Emerging Fuels Technology, Inc. Process to convert natural gas into liquid fuels and chemicals
EP2740322B1 (en) 2011-08-04 2018-05-02 Stephen Lee Cunningham Plasma arc furnace and applications
EP2607301A1 (de) * 2011-12-20 2013-06-26 Karl-Heinz Tetzlaff Vorrichtung und Verfahren zur Erdgasreformierung
JP6002249B2 (ja) * 2012-02-06 2016-10-05 ヘルビオ ソシエテ アノニム ハイドロジェン アンド エナジー プロダクション システムズ 水素生成のための触媒燃焼式熱統合型改質器
EP2671842A1 (en) * 2012-06-06 2013-12-11 Ammonia Casale S.A. A process for gas-heated reforming of a hydrocarbon source and a related plant
CN104736472A (zh) * 2012-09-26 2015-06-24 埃讷肯公司 合成气分离与重整方法
US9452931B2 (en) * 2012-11-15 2016-09-27 Phillips 66 Company Process scheme for catalytic production of renewable hydrogen from oxygenate feedstocks
EP2801550A1 (en) * 2013-05-10 2014-11-12 Ammonia Casale S.A. A process for producing ammonia synthesis gas with high temperature shift and low steam-to-carbon ratio
CA2869645A1 (en) * 2013-11-04 2015-05-04 Me Resource Corp Method and apparatus for producing chemicals from a methane-containing gas
DE102014004264A1 (de) * 2014-03-14 2015-09-17 Universität Stuttgart Wärmeintegrierte Hochtemperatur-Reaktoren für die autotherme partielle Oxidation
EP3140601A4 (en) 2014-05-09 2017-11-08 Stephen Lee Cunningham Arc furnace smeltering system & method
WO2016016257A1 (en) 2014-07-29 2016-02-04 Eni S.P.A. Integrated sct-cpo/pox process for producing synthesis gas
WO2016016251A1 (en) 2014-07-29 2016-02-04 Eni S.P.A. Integrated sct-cpo/sr process for producing synthesis gas
US9840413B2 (en) 2015-05-18 2017-12-12 Energyield Llc Integrated reformer and syngas separator
US9843062B2 (en) 2016-03-23 2017-12-12 Energyield Llc Vortex tube reformer for hydrogen production, separation, and integrated use
FR3040313B1 (fr) * 2015-08-24 2017-08-25 Air Liquide Echangeur-reacteur integrant les reactions de vaporeformage et de gaz a l'eau pour la production d'hydrogene
DE102016212757A1 (de) * 2016-07-13 2018-01-18 Thyssenkrupp Ag Kompakter Methanolreformer für ein Unterseeboot
CN106082127B (zh) * 2016-08-25 2018-09-11 晋城市阿邦迪能源有限公司 选择性氧化净化co的甲醇重整反应器
CN106145036B (zh) * 2016-08-25 2018-12-04 晋城市阿邦迪能源有限公司 甲烷化反应净化co的甲醇重整反应器
EP3296255A1 (de) * 2016-09-14 2018-03-21 L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude Reformerrohr mit strukturiertem katalysator und verbessertem wärmehaushalt
DK3532430T3 (da) * 2016-10-25 2020-07-27 Technip France Katalysatorrør til reformering
EA039539B1 (ru) 2016-11-09 2022-02-08 8 Риверз Кэпитл, Ллк Способ выработки энергии с интегрированным производством водорода
GB201813431D0 (en) * 2018-08-17 2018-10-03 Weedon Geoffrey Gerald Process & apparatus for steam reforming
IT201900008280A1 (it) * 2019-06-06 2020-12-06 Amec Foster Wheeler Italiana S R L Reattore, in particolare reattore di reforming con vapore, e suo uso in un processo di reforming con vapore
AU2020292848A1 (en) 2019-06-13 2022-02-03 8 Rivers Capital, Llc Power production with cogeneration of further products
IT201900013239A1 (it) * 2019-07-29 2021-01-29 Milano Politecnico Impianto per la produzione di syngas a partire da polimeri plastici di recupero pretrattati
GB2593179B (en) * 2020-03-17 2022-04-27 Nordic Electrofuel As Production of hydrocarbons
CN112573482B (zh) * 2020-12-10 2022-07-08 洛阳沃达节能科技有限公司 一种制氢装置的制氢管以及制氢装置
WO2023089571A1 (en) 2021-11-18 2023-05-25 8 Rivers Capital, Llc Method for hydrogen production

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2324172A (en) * 1940-10-31 1943-07-13 Standard Oil Co Processing well fluids
US4650651A (en) * 1983-06-09 1987-03-17 Union Carbide Corporation Integrated process and apparatus for the primary and secondary catalytic steam reforming of hydrocarbons
US4943672A (en) * 1987-12-18 1990-07-24 Exxon Research And Engineering Company Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403)
US5059299A (en) * 1987-12-18 1991-10-22 Exxon Research And Engineering Company Method for isomerizing wax to lube base oils
US6224789B1 (en) * 1998-09-01 2001-05-01 Haldor Topsoe A/S Process and reactor system for preparation of synthesis gas
US20020006970A1 (en) * 1999-08-17 2002-01-17 Yong Wang Method and catalyst structure for steam reforming of a hydrocarbon

Family Cites Families (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1093943A (en) * 1963-10-07 1967-12-06 Ici Ltd Reforming hydrocarbons
US3549335A (en) * 1965-10-22 1970-12-22 Braun & Co C F Autothermal reactor
DE3244252A1 (de) * 1982-11-30 1984-05-30 Uhde Gmbh, 4600 Dortmund Verfahren und vorrichtung zur erzeugung von produktgas mit wasserstoff- und kohlenoxyde-gehalten
CN87100591A (zh) * 1983-06-09 1988-07-20 联合碳化公司 用于烃类一次及二次催化水蒸汽转化的联合方法及设备
DE3345088A1 (de) * 1983-12-13 1985-06-13 Linde Ag, 6200 Wiesbaden Verfahren zur erzeugung von synthesegas
GB2163449B (en) 1984-07-18 1988-06-02 Shell Int Research Production of gas mixtures containing hydrogen and carbon monoxide
NL8403144A (nl) * 1984-10-16 1986-05-16 Stamicarbon Werkwijze voor het bereiden van een synthesegas.
EP0194067B2 (en) 1985-03-05 1994-05-11 Imperial Chemical Industries Plc Steam reforming hydrocarbons
JPS62210047A (ja) * 1986-03-10 1987-09-16 Toyo Eng Corp 反応用装置
DE3750032D1 (de) * 1986-09-15 1994-07-14 Steinmueller Gmbh L & C Reformer für die katalytische spaltung gasförmiger kohlenwasserstoffe.
GB8711156D0 (en) 1987-05-12 1987-06-17 Shell Int Research Partial oxidation of hydrocarbon-containing fuel
JP2625443B2 (ja) * 1987-09-25 1997-07-02 三菱瓦斯化学株式会社 固定触媒層反応器
JPH01261201A (ja) * 1988-04-12 1989-10-18 Mitsubishi Gas Chem Co Inc 炭化水素改質反応器
DE3813863A1 (de) * 1988-04-23 1989-11-02 Uhde Gmbh Einrichtung zur aufnahme von katalysatoren, insbesondere bei der erzeugung von synthesegas
DK167864B1 (da) * 1990-02-02 1993-12-27 Topsoe Haldor As Fremgangsmaade og reaktorsystem til reforming af carbonhydrider under varmeveksling
US5029299A (en) 1990-05-09 1991-07-02 Altec Lansing Corporation Power amplifier with current limiting means
JPH0685866B2 (ja) * 1991-01-25 1994-11-02 株式会社日立製作所 触媒反応装置
US5245110A (en) 1991-09-19 1993-09-14 Starchem, Inc. Process for producing and utilizing an oxygen enriched gas
GB9203375D0 (en) * 1992-02-18 1992-04-01 Davy Mckee London Process
US5254318A (en) * 1992-07-20 1993-10-19 Stone & Webster Engineering Corporation Lined reformer tubes for high pressure reformer reactors
PL175047B1 (pl) 1993-04-22 1998-10-30 Kti Group Bv Sposób wytwarzania katalizatora do procesu wytwarzania gazu syntezowego
EP0668342B1 (en) 1994-02-08 1999-08-04 Shell Internationale Researchmaatschappij B.V. Lubricating base oil preparation process
MY115440A (en) 1994-07-22 2003-06-30 Shell Int Research A process for the manufacture of synthesis gas by partial oxidation of a gaseous hydrocarbon-containing fuel using a multi-orifice (co-annular)burner
EG20966A (en) 1995-06-06 2000-07-30 Shell Int Research A method for flame stabilization in a process for preparing synthesis gas
JP3734859B2 (ja) * 1995-07-31 2006-01-11 テキサコ・デベロップメント・コーポレーション 部分酸化装置ガス供給システムの熱含量連続制御方法
GB9516125D0 (en) * 1995-08-07 1995-10-04 Ici Plc Heat exchange apparatus and process
EP0776959B1 (en) 1995-11-28 2004-10-06 Shell Internationale Researchmaatschappij B.V. Process for producing lubricating base oils
US5931978A (en) 1995-12-18 1999-08-03 Shell Oil Company Process for preparing synthesis gas
JPH11106204A (ja) * 1997-10-01 1999-04-20 Sanyo Electric Co Ltd 水素製造装置及び水素製造方法
US6090989A (en) 1997-10-20 2000-07-18 Mobil Oil Corporation Isoparaffinic lube basestock compositions
WO1999034917A1 (en) 1997-12-30 1999-07-15 Shell Internationale Research Maatschappij B.V. Cobalt based fisher-tropsch catalyst
EP0983964A3 (de) 1998-09-04 2000-07-26 Linde Aktiengesellschaft Verfahren und Primärreformer zur Erzeugung von Synthesegas
DE60019935T2 (de) 1999-07-26 2006-02-16 Shell Internationale Research Maatschappij B.V. Verfahren zur herstellung eines grundschmieröls
DE19953641A1 (de) 1999-11-09 2001-06-07 Metallgesellschaft Ag Verfahren zur katalytischen Dehydrierung von Kohlenwasserstoffen im Röhrenreaktor
GB9927817D0 (en) 1999-11-26 2000-01-26 Ici Plc Steam reforming apparatus
GB0001540D0 (en) * 2000-01-25 2000-03-15 Gratwick Christopher Stream reforming
JP2001206702A (ja) * 2000-01-26 2001-07-31 Nissan Motor Co Ltd 燃料改質装置および燃料電池システム
US6521143B1 (en) 2000-04-13 2003-02-18 Air Products And Chemicals, Inc. Co-production of carbon monoxide-rich syngas wth high purity hydrogen
US6892225B1 (en) * 2000-07-19 2005-05-10 Fusionone, Inc. Agent system for a secure remote access system
AR032930A1 (es) 2001-03-05 2003-12-03 Shell Int Research Procedimiento para preparar un aceite de base lubricante y gas oil
MY137259A (en) 2001-03-05 2009-01-30 Shell Int Research Process to prepare a lubricating base oil and a gas oil.
AR032941A1 (es) 2001-03-05 2003-12-03 Shell Int Research Un procedimiento para preparar un aceite base lubricante y aceite base obtenido, con sus diversas utilizaciones
MY136087A (en) * 2001-10-22 2008-08-29 Shell Int Research Process to reduce the temperature of a hydrogen and carbon monoxide containing gas and heat exchanger for use in said process

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2324172A (en) * 1940-10-31 1943-07-13 Standard Oil Co Processing well fluids
US4650651A (en) * 1983-06-09 1987-03-17 Union Carbide Corporation Integrated process and apparatus for the primary and secondary catalytic steam reforming of hydrocarbons
US4943672A (en) * 1987-12-18 1990-07-24 Exxon Research And Engineering Company Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403)
US5059299A (en) * 1987-12-18 1991-10-22 Exxon Research And Engineering Company Method for isomerizing wax to lube base oils
US6224789B1 (en) * 1998-09-01 2001-05-01 Haldor Topsoe A/S Process and reactor system for preparation of synthesis gas
US20020006970A1 (en) * 1999-08-17 2002-01-17 Yong Wang Method and catalyst structure for steam reforming of a hydrocarbon

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9631285B2 (en) 2005-08-25 2017-04-25 Ceramatec, Inc. Electrochemical process for the production of synthesis gas using atmospheric air and water
US20080241059A1 (en) * 2007-03-26 2008-10-02 Air Products And Chemicals, Inc. Catalytic Steam Reforming With Recycle
US7695708B2 (en) 2007-03-26 2010-04-13 Air Products And Chemicals, Inc. Catalytic steam reforming with recycle

Also Published As

Publication number Publication date
US20060191201A1 (en) 2006-08-31
EP1622829A1 (en) 2006-02-08
JP2006523596A (ja) 2006-10-19
EP1622827A1 (en) 2006-02-08
WO2004092061A1 (en) 2004-10-28
US7462209B2 (en) 2008-12-09
WO2004092063A1 (en) 2004-10-28
EP1622828A1 (en) 2006-02-08
US7550635B2 (en) 2009-06-23
JP2006523595A (ja) 2006-10-19
CN100381353C (zh) 2008-04-16
US20080028680A1 (en) 2008-02-07
WO2004092062A1 (en) 2004-10-28
JP2006523597A (ja) 2006-10-19
CN1832900A (zh) 2006-09-13
US8986631B2 (en) 2015-03-24
EP1613552A1 (en) 2006-01-11
KR20050120719A (ko) 2005-12-22
CN1774392A (zh) 2006-05-17
US20070140954A1 (en) 2007-06-21
US20090126272A1 (en) 2009-05-21
CN1774391A (zh) 2006-05-17
WO2004092060A1 (en) 2004-10-28
JP2006523598A (ja) 2006-10-19
CN1774393A (zh) 2006-05-17

Similar Documents

Publication Publication Date Title
US20060260194A1 (en) Process to prepare synthesis gas
US6224789B1 (en) Process and reactor system for preparation of synthesis gas
US9434613B2 (en) Process for reforming hydrocarbons
US7074347B2 (en) Process for the preparation of synthesis gas
US9932229B2 (en) Method and system for production of hydrogen rich gas mixtures
EP0178007A2 (en) Process for the production of synthesis gas
AU2002317859B2 (en) Integrated process for hydrocarbon synthesis
WO2006045744A1 (en) Process for steam and/or co2 reforming of a hydrocarbonaceous feedstock
AU2002317859A1 (en) Integrated process for hydrocarbon synthesis
WO2004046022A2 (en) The production of synthesis gas from a feed stream comprising hydrogen
KR102668169B1 (ko) 합성 가스 제조를 위한 방법 및 시스템
KR20200096755A (ko) 합성 가스 제조를 위한 방법 및 시스템
EP3509985A1 (en) Process for the preparation of hydrogen

Legal Events

Date Code Title Description
AS Assignment

Owner name: SHELL OIL COMPANY, TEXAS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:TIO, THIAN HOEY;REEL/FRAME:018066/0599

Effective date: 20060301

STCB Information on status: application discontinuation

Free format text: ABANDONED -- AFTER EXAMINER'S ANSWER OR BOARD OF APPEALS DECISION