WO2014174107A1 - Production d'hydrocarbures à partir d'un gaz de synthèse - Google Patents

Production d'hydrocarbures à partir d'un gaz de synthèse Download PDF

Info

Publication number
WO2014174107A1
WO2014174107A1 PCT/EP2014/058529 EP2014058529W WO2014174107A1 WO 2014174107 A1 WO2014174107 A1 WO 2014174107A1 EP 2014058529 W EP2014058529 W EP 2014058529W WO 2014174107 A1 WO2014174107 A1 WO 2014174107A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
zeolite
stage
bed
conversion
Prior art date
Application number
PCT/EP2014/058529
Other languages
English (en)
Inventor
Qingjie Ge
Chun Wang
Xiangang MA
Hengyong Xu
Original Assignee
Bp P.L.C.
Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences
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
Priority claimed from CN201310149855.6A external-priority patent/CN104117380B/zh
Application filed by Bp P.L.C., Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences filed Critical Bp P.L.C.
Publication of WO2014174107A1 publication Critical patent/WO2014174107A1/fr

Links

Classifications

    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/068—Noble metals
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/072—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Definitions

  • This invention relates to the production of hydrocarbons from synthesis gas.
  • Examples of the invention relate to the production of saturated hydrocarbons from synthesis gas. Aspects of the invention relate to the production of saturated C 5 and higher hydrocarbons, in some examples in addition to the production of aromatic hydrocarbons for example being C9 or higher hydrocarbons. Aspects of the invention relate to the co- production of saturated C 5 to C 8 hydrocarbons and C9 - Cn aromatic hydrocarbons.
  • the saturated C 5 and higher hydrocarbons include branched alkanes (iso-paraffins).
  • a two-stage catalyst bed reaction scheme is used.
  • the Fischer-Tropsch (FT) process for conversion of syngas to hydrocarbons was first developed in the 1920s.
  • the catalysts used in such processes conventionally contain active metals of the transition elements group VIII.
  • metals such as Fe, Co, Ni and Ru.
  • the distribution of the produced hydrocarbons when these traditional FT catalysts are used follows the Anderson-Schulz-Flory law (ASF), according to which some types of product within a narrow range of number of carbon atoms cannot be obtained with high selectivity.
  • modified FT process in which a traditional FT catalyst is supported or mixed with zeolites.
  • a modified catalyst has been seen in some cases to exhibit a higher selectivity for the C 5 -C 12 hydrocarbon product fraction.
  • shape-selectivity of the zeolites plays a key role in hydrocarbon product distribution; Jincan Kang, et al.
  • the conversion of methanol to hydrocarbons is also known, including the methanol to olefins (MTO) process, methanol to gasoline (MTG), and methanol to aromatics (MTA) processes.
  • MTO methanol to olefins
  • MTA methanol to aromatics
  • the methanol is first synthesized and separated from the other components before being fed to the methanol conversion process.
  • the catalyst bed may be composed of methanol synthesis catalyst and metal-modified zeolite.
  • co-production of light iso-paraffins (C 5 -C ) and heavy aromatics (C 9 -Cn) from syngas can be realized in a two catalyst bed reaction system.
  • the catalyst may be preferentially active to produce methanol in the first catalyst bed.
  • the catalyst in the first catalyst bed may include a methanol synthesis catalyst.
  • the intermediate product may therefore include methanol.
  • the catalyst may produce dimethyl ether (DME) in the first catalyst bed.
  • both methanol and DME are produced in the first stage.
  • the intermediate product stream may include DME and/or methanol.
  • the catalyst of the second catalyst bed preferentially includes a dehydration catalyst.
  • the catalyst might be modified by some metals in the second catalyst bed.
  • the second catalyst bed may have dehydration and hydrogenation activity.
  • aspects of the present invention seek to provide a method for the production of hydrocarbons from syngas.
  • the invention seeks to provide high selectivity to branched alkanes (iso-paraffins), in particular C 5+ alkanes.
  • the invention seeks to provide selectivity to heavy aromatics, in particular C 9+ aromatics.
  • the invention seeks to provide low selectivity to C 5 to C 8 aromatics.
  • a catalyst composition for use as a dehydration/ hydrogenation catalyst in a multi-stage catalyst system for the catalysed production of saturated hydrocarbons from carbon oxide(s) and hydrogen comprising: an acidic substrate comprising a zeolite, or an M-zeolite catalyst, where M comprises a metal, wherein the Si0 2 /Al 2 0 3 molar ratio of the zeolite or the zeolite of the M-zeolite catalyst is 100 or more.
  • Si0 2 /Al 2 0 3 ratio can be beneficial, for example in the production of a product stream including C 5 - C 8 having a high iso-paraffinic content as well as a low olefin and aromatic content.
  • the heavy C 9 - Cn fraction contains mainly trimethylbenzenes and
  • the Si0 2 /Al 2 0 3 molar ratio of the zeolite or M-zeolite catalyst is 100 or more, or 120 or more, or 140 or more, or 200 or more, or 250 or more, or 300 or more.
  • the zeolite composition having a high Si0 2 /Al 2 0 3 ratio has a reduced number of acid sites compared with conventional, lower Si0 2 /Al 2 0 3 ratio, zeolites. It is thought that this reduced number of acid sites in the second stage catalyst improves the selectivity to iso-paraffins in the formation of the hydrocarbon product.
  • the Si0 2 Al 2 0 3 molar ratio of the zeolite of the catalyst composition may be 120 or more, or 140 or more. In some examples, the Si0 2 /Al 2 0 3 molar ratio may be 200 or more, or 250 or more, or 300 or more, or 350 or more. In examples given herein, the Si0 2 /Al 2 0 3 molar ratio is 360.
  • the Si0 2 /Al 2 0 3 molar ratio of the zeolites of the second stage catalyst composition of the present invention is significantly higher than for conventional zeolites which may have for example a Si0 2 /Al 2 0 3 molar ratio of about 20.
  • the Si0 2 /Al 2 0 3 ratio of a particular zeolite sample may be measured by any appropriate method, for example by a ICP-MS technique (inductively coupled plasma mass spectrometry),, or XRF technique (X-ray Fluroscene technique).
  • ICP-MS technique inductively coupled plasma mass spectrometry
  • XRF technique X-ray Fluroscene technique
  • dehydration/ hydrogenation for example to a component or catalyst being used for dehydration/ hydrogenation, preferably it will be understood that the reference is to dehydration, hydrogenation or to both dehydration and hydrogenation as appropriate in the context.
  • the catalyst composition may have been prepared for example by a method described herein. However, some aspects of the invention extend to the case in which is obtained by other methods or from other sources. Thus aspects of the invention extend to such catalyst compositions irrespective of their source or method of preparation.
  • the zeolite catalyst may comprise one or more from the group comprising Y zeolite, ⁇ zeolite, and ZSM-5.
  • the acidic substrate may comprise two or more such components from the group.
  • the zeolite catalyst may comprise ZSM-5.
  • M comprises a hydrogenation metal.
  • M preferably comprises a metal chosen from the group comprising Pd, Pt, Rh, Ru, Cu and Zn, preferably M comprises Pd and/or Cu.
  • the weight percent of metal M in the M-zeolite may be for example from about 0.1 wt% to about 20 wt%. In examples, the weight percent M in the M-zeolite is from about 0.1 wt% to about 2wt%, for example from about 0.5 wt% to about 1 wt%.
  • the hydrogenation catalyst is used in combination with an additional catalyst, for example a carbon oxide(s) conversion catalyst.
  • an additional catalyst for example a carbon oxide(s) conversion catalyst.
  • the catalyst system may comprise a two-stage catalyst system, for example in which the two stages of the system are separate.
  • the two-stage catalyst system may be a part of a multi-stage catalyst system.
  • the two catalysts may be mixed together, or may be provided having a direct interface between them, or spaced apart by a spacer element.
  • the two catalyst stages may be separate.
  • a further aspect of the invention provides a multi-stage catalyst system for use in the catalysed production of saturated hydrocarbons from carbon oxides and hydrogen, the catalyst system comprising a first stage comprising a carbon oxide(s) conversion catalyst, and a second stage comprising a hydrogenation catalyst comprising: an acidic substrate comprising a zeolite, or an M-zeolite catalyst, where M comprises a metal, wherein the Si0 2 /Al 2 0 3 molar ratio of the zeolite or of the zeolite of the M-zeolite catalyst is 100 or more.
  • the multi-stage catalyst system may be used as physically separate stages, or physically segmented stages, or the stages may be physically mixed, and other options are possible.
  • the carbon oxides conversion catalyst may be active to produce methanol and/or may be active to produce dimethyl ether (DME), for example to produce DME in the first stage where a two-stage or multi-stage system is used, or for a hybrid catalyst, to produce DME in the catalysed conversion process.
  • DME dimethyl ether
  • both methanol and DME may be produced in the process.
  • Improved catalysts have allowed viable rates of methanol formation to be achieved at relatively low reaction temperatures, and hence allow commercial operation at lower reaction pressures.
  • a CuO/ZnO/Al 2 0 3 conversion catalyst may be operated at a nominal pressure of 5-10 MPa and at temperatures ranging from approximately 150 degrees C to 300 degrees C.
  • a low-pressure, copper- based methanol synthesis catalyst is commercially available from suppliers such as BASF and Haldor-Topsoe. Methanol yields from copper-based catalysts are generally over 99.5% of the converted carbon oxide(s) present.
  • Water is a by-product of the conversion of C0 2 to methanol and the conversion of synthesis gas to C 2 and C 2+ oxygenates.
  • an active water gas-shift catalyst such as a methanol catalyst or a cobalt molybdenum catalyst, the water equilibrates with the carbon monoxide to give C0 2 and hydrogen.
  • the carbon oxide(s) conversion catalyst may be provided together with the dehydration/hydrogenation catalyst in a mixed catalyst.
  • a methanol synthesis catalyst, and/or DME synthesis catalyst and the dehydration/hydrogenation catalyst will be present together in a mixed catalyst.
  • the mixed catalyst may for example include a mechanical mixture of the hydrogenation catalyst and a methanol synthesis catalyst and/or DME synthesis catalyst.
  • a further aspect of the invention provides a mixed catalyst for the catalysed production of saturated hydrocarbons from carbon oxides and hydrogen, mixed catalyst including: a carbon oxide(s) conversion catalyst, and a hydrogenation catalyst comprising an acidic substrate comprising a zeolite, or an M-zeolite catalyst, where M comprises a metal, wherein the Si0 2 /Al 2 03 molar ratio of the zeolite or the zeolite of the M-zeolite catalyst is 100 or more.
  • the carbon oxide(s) conversion catalyst comprises a methanol synthesis catalyst and/or DME synthesis catalyst.
  • the carbon oxide(s) conversion catalyst may comprise a copper oxide.
  • the carbon oxide(s) conversion catalyst may comprise a zeolite and/or ⁇ - ⁇ 1- 2 0 3 .
  • the carbon oxide(s) conversion catalyst may for example comprise a methanol synthesis catalyst.
  • the methanol synthesis catalyst may be any appropriate composition.
  • the catalyst includes Cu-ZnO-[Sup], Pd-[Sup] and Zn-Cr-[Sup], where [Sup] is preferably a support composition for example including A1 2 0 3 , Si0 2 , and/or zeolite.
  • the carbon oxide(s) conversion catalyst comprises Cu-ZnO-Al 2 0 3 .
  • the carbon oxides(s) conversion catalyst may for example comprise a DME synthesis catalyst.
  • the DME synthesis catalyst may comprise for example Cu-ZnO [Sup], Cu-Pd/Ce0 2 -[Sup], where [Sup] may be as described above, together with for example ZSM-5 or ⁇ - ⁇ 1 2 0 3 and/or ZSM-5.
  • [Sup] comprises A1 2 0 3 for the DME synthesis catalyst.
  • the carbon oxide(s) conversion catalyst may comprise Cu-ZnO- Al 2 0 3 /ZSM-5 Cu-ZnO-Al 2 0 3 /y-Al 2 0 3.
  • the carbon oxide(s) conversion catalyst may comprise a hybrid catalyst.
  • the hybrid catalyst may be prepared by any appropriate method.
  • the first stage or carbon oxide(s) conversion catalyst composition may also comprise a zeolite. It has been identified by the inventors that the Si0 2 /Al 2 0 3 molar ratio of zeolite of the first stage catalyst composition is of less importance in some examples than for that of the second stage catalyst. Thus in some examples, the
  • Si0 2 /Al 2 0 3 molar ratio of zeolite of the first stage catalyst composition is less than that of the zeolite of the second stage composition.
  • the Si0 2 /Al 2 0 3 molar ratio of zeolite of the first stage composition may be less than 100, for example less than 70, for example less than 50.
  • a catalyst for use in the catalysed production of saturated hydrocarbons from carbon oxides and hydrogen comprising:
  • an acidic substrate comprising a zeolite, or an M-zeolite catalyst, where M comprises a metal, wherein the Si0 2 /Al 2 0 3 molar ratio of the zeolite or M-zeolite catalyst is 100 or more.
  • the method includes producing a mixed catalyst, the method further including the step of mixing the dehydration/hydrogenation catalyst and a carbon oxide(s) conversion catalyst, for example a methanol synthesis catalyst.
  • a mixed catalyst is adapted for the conversion of carbon oxide(s) and hydrogen to form saturated hydrocarbons, in particular C 3 and higher saturated hydrocarbons.
  • the invention further provides the use of a catalyst as described herein in the catalysed conversion of carbon oxide(s) and hydrogen to form saturated hydrocarbons.
  • a process for the catalysed production of saturated hydrocarbons using a dehydration/hydrogenation catalyst comprising:
  • a zeolite or M-zeolite composition where M comprises a metal, wherein the Si0 2 /Al 2 0 3 molar ratio of the zeolite is 100 or more.
  • the dehydration/hydrogenation catalyst is exposed to a source of a gas including methanol and/or DME and hydrogen.
  • the catalyst may comprise the
  • dehydration/hydrogenation catalyst and a further catalyst, for example a carbon oxide(s) conversion catalyst, for example a methanol synthesis catalyst.
  • a further catalyst for example a carbon oxide(s) conversion catalyst, for example a methanol synthesis catalyst.
  • the reactants may for example comprise syngas.
  • the process includes feeding syngas to the dehydration/hydrogenation catalyst.
  • the process is preferably in gas phase.
  • the reaction temperature may be between from about 260 to 400 degrees C, for example from about 290 to 335 degrees C.
  • the reaction pressure may be between from about 0.5 to 6.0MPa, for examples from 2.0 to 3.0MPa.
  • the gas space velocity may be from about 500 to 6000h _1 , and for example about 1000 to 1500h ' ⁇
  • Preferably the gas space velocity is defined as the hourly volume of gas flow in standard units divided by the catalyst volume.
  • the carbon oxide(s) conversion catalyst may be in a first stage with a second stage including the dehydration/hydrogenation catalyst.
  • the first and second stages may be physically separate, may be spaced apart from each other, or may have a direct interface, or may be spaced using a physical spacer, or other method.
  • the catalyst may be non-homogeneous in that there are carbon oxide(s) conversion catalyst rich regions (or region) and dehydration/ hydrogenation catalyst rich regions (or region).
  • the carbon oxide(s) conversion catalyst region(s) will normally be arranged upstream of the dehydration/hydrogenation catalyst region(s).
  • the process may include an upstream catalyst bed including the carbon oxide(s) conversion catalyst, for example for the production of DME and/or methanol from carbon oxides and hydrogen.
  • the process may be carried out in a multiple stage system.
  • a carbon oxide(s) conversion catalyst for example a methanol synthesis catalyst and/or DME synthesis catalyst may be provided in a first stage and the hydrogenation catalyst in a second stage.
  • the two stages will be separated. By separating the stages of the reaction system, it is possible to independently optimize the two stages.
  • a significant advantage of this for some examples is that the methanol- and/or DME-generating catalyst can be run at conditions more suitable for improved conversion, selectivity, and/or longer catalyst life.
  • Also provided by an aspect of the invention is an integrated process for the generation of saturated C 3 and higher hydrocarbons from carbon oxide(s) and hydrogen, the process comprising the steps of: (a) feeding a gas stream including carbon oxide(s) and hydrogen to a reaction system comprising a catalyst system including a first stage catalyst composition, and a second stage catalyst composition, and (b) removing a product stream from the reaction system, the product stream including saturated C 3 and higher
  • the first stage catalyst composition comprises a dimethyl ether (DME) synthesis catalyst and/or a methanol synthesis catalyst
  • the second stage catalyst composition comprises a zeolite or M-zeolite composition, where M comprises a metal, wherein the Si0 2 /Al 2 0 3 molar ratio of the zeolite is 100 or more.
  • the apparatus may comprise a one-stage reaction system and therefore the method may include the step of feeding the gas to a one-bed system comprising the first stage catalyst composition and the second stage catalyst composition.
  • the one bed may include a mixture of the carbon oxide(s) conversion catalyst and the
  • the temperature of the bed is more than 300 degrees C.
  • the carbon oxide(s) conversion catalyst may be active to produce methanol and/or active to produce DME.
  • the dehydration/hydrogenation catalyst may include a source of Pd and/or Cu.
  • the dehydration/hydrogenation catalyst may include ZSM-5.
  • the method may include feeding the gas stream to a two-bed reaction system comprising a first bed including the first stage catalyst composition wherein the gas stream is at least partly converted in the first bed to form an intermediate product stream, and feeding at least a part of the intermediate product stream to a second bed including the second stage catalyst composition.
  • the first reaction stage temperature is lower than the second stage temperature, for example at least 20 degrees or at least 50 degrees lower.
  • the temperature of the first stage may be less than 300 degrees C.
  • the temperature of the first stage is less than 295 degrees C, for example not more than 280 degrees C, for example not more than 250 degrees C.
  • the temperature of the first stage may be between from about 190 to 250 degrees C, for example between from about 210 to 230 degrees C. In practical systems, it is likely that the temperature will vary across the reaction stage.
  • the temperature of the stage is measured as an average temperature across a reaction region.
  • the temperature of the second stage may be more than 300 degrees C.
  • the temperature of the second stage will be 320 degrees C or more. In some examples, a temperature of 340 degrees C or more will be preferred. In some examples the temperature of the second stage will be between from about 330 to 360 degrees C. In many cases it will be preferable for the temperature of the second stage to be less than 450 degrees C, for example less than 420 degrees C, or for example less than 400 degrees C which may prolong the life of the catalyst. Depending on the target products, other temperatures may be used for the second stage.
  • the first and second stages may be operated at the same or at different pressures. Both stages may be operated for example at a pressure less than 40 bar. In some examples, it will be preferable for the second stage to be operated at a pressure lower than that of the first stage, for example at least 5 bar lower, for example at least 10 bar lower.
  • the first stage may be operated at a pressure of less than 40 bar, less than 20 bar, or less than 10 bar. In some examples, a significantly higher pressure may be desirable.
  • the second stage may be operated at a pressure of less than 20 bar, less than 10 bar, or less than 5 bar. In some examples, a significantly higher pressure may be desirable.
  • the gas hourly space velocity of the first stage may be for example between about 500 and 6000, for example between about 500 and 3000.
  • the gas hourly space velocity of the second stage may be for example between about 500 and 20000, for example between about 1000- 10000.
  • the gas hourly space velocity is defined as the number of bed volumes of gas passing over the catalyst bed per hour at standard temperature and pressure.
  • a more flexible system provides the two stages in separate vessels. At least a portion of the intermediate product stream (or effluent) exiting the first stage preferably passes directly to the second stage. In some examples, substantially the entire intermediate product stream passes to the second stage.
  • additional second stage influent components can be added to the intermediate stream upstream of the second stage.
  • addition of hydrogen and/or DME may be carried out.
  • the intermediate stream may be subject to operations for example heat exchange upstream of the second stage and/or pressure adjustment, for example pressure reduction.
  • Each of the stages may include any appropriate catalyst bed type, for example fixed bed, fluidized bed, moving bed.
  • the bed type of the first and second stages may be the same or different.
  • Potential application for example for the second stage is the use of a moving bed or paired bed system, for example a swing bed system, in particular where catalyst regeneration is desirable.
  • the feed to the process includes carbon oxide(s) and hydrogen.
  • Any appropriate source of carbon oxides for example carbon monoxide and/or carbon dioxide
  • Processes for producing mixtures of carbon oxide(s) and hydrogen are well known. Each method has its advantages and disadvantages, and the choice of using a particular reforming process over another is normally governed by economic and available feed stream considerations, as well as by the desire to obtain the desired (3 ⁇ 4- C0 2 ):(CO+C0 2 ) molar ratio in the resulting gas mixture, that is suitable for further processing.
  • Synthesis gas as used herein preferably refers to mixtures containing carbon dioxide and/or carbon monoxide with hydrogen.
  • Synthesis gas may for example be a combination of hydrogen and carbon oxides produced in a synthesis gas plant from a carbon source such as natural gas, petroleum liquids, biomass and carbonaceous materials including coal, recycled plastics, municipal wastes, or any organic material.
  • the synthesis gas may be prepared using any appropriate process for example partial oxidation of hydrocarbons (POX), steam reforming (SR), advanced gas heated reforming (AGHR), microchannel reforming (as described in, for example, US Patent No. 6,284,217), plasma reforming, autothermal reforming (ATR) and any combination thereof.
  • the synthesis gas source used in the present invention preferably contains a molar ratio of (H 2 -C0 2 ): (CO+C0 2 ) ranging from 0.6 to 2.5.
  • the gas composition which the catalyst is exposed to will generally differ from such a range due to for example gas recycling occurring within the reaction system.
  • a syngas feed molar ratio (as defined above) of 2:1 is commonly used, whereas the catalyst may experience a molar ratio of greater than 5:1 due to recycle.
  • the gas composition experienced by the catalyst in the first stage where a two-stage process is used may initially be for example between from about 0.8 to 7, for example from about 2 to 3.
  • Carbon oxide(s) conversion catalysts for example methanol synthesis catalysts are commonly water gas shift active.
  • the water gas shift reaction is the equilibrium of H 2 and C0 2 with CO and H 2 0.
  • the reaction conditions for the methanol synthesis catalyst (for example in the first stage) preferably favour the formation of H 2 and C0 2.
  • the reaction stoichiometry requires a synthesis gas molar ratio of 2:1.
  • the reaction coproduces water which is shifted with CO according to the water gas shift reaction to C0 2 and hydrogen.
  • the synthesis gas molar ratio (as defined above) requirement is also 2:1 but here a reaction product is C0 2 .
  • the second part of the reaction for example the second stage reaction in the case of methanol synthesis in the first stage is thought to comprise initial conversion to DME and water, and subsequent conversion of DME to C 3 and higher saturated hydrocarbons and water.
  • the second stage reaction in the case of DME synthesis in the first stage is thought to comprise only the stages of DME conversion to C 3 and higher saturated hydrocarbons and water.
  • the product mixture additionally includes carbon dioxide. Where a hybrid catalyst is used, these two stages will be in the same reactor.
  • the catalysts of the methods may comprise any of the catalyst compositions described herein as appropriate.
  • the carbon oxide(s) conversion catalyst may be active to produce methanol in the first bed and or dimethyl ether (DME) in the first bed.
  • DME dimethyl ether
  • the temperature of the second bed may be more than 300 degrees C.
  • the carbon oxide(s) conversion catalyst may comprise a copper oxide and/or may include a zeolite and/or ⁇ - ⁇ 1 2 0 3 .
  • the dehydration/hydrogenation catalyst may include a source of Pd and/or Cu.
  • the second bed may include ZSM-5.
  • a further aspect of the invention provides an apparatus for carrying out a method as defined herein.
  • Also provided by the invention is apparatus for use in a process as described herein and a dehydration/hydrogenation catalyst obtained or obtainable by a method described herein.
  • the invention extends to methods and/or apparatus and/or catalyst composition substantially as herein described with reference to the accompanying drawings.
  • Figure 1 shows schematically an example of a two-stage reactor system used in a process for the conversion of syngas to saturated hydrocarbons in an example of the invention.
  • FIG. 1 shows schematically an example of a two-stage test reactor system 1 for saturated hydrocarbon synthesis from syngas.
  • the system 1 includes two reaction stages 3, 5 arranged in series.
  • Each reaction stage 3, 5 includes a reaction vessel containing a fixed bed catalyst system. The reactions were carried out under pressurized conditions in these examples.
  • Each stage 3, 5 was equipped with an electronic temperature controller for a furnace, a tubular reactor with an inner diameter of 12mm, and a back pressure valve 21, 21 ' downstream of the reactor.
  • a back pressure valve 21, 21 ' downstream of the reactor When carrying out examples including a one catalyst stage, only the reactor of the first stage 3 was used.
  • the upstream reaction stage 3 includes a first catalyst composition including a methanol synthesis catalyst; the downstream reactor vessel 5 contains a second catalyst composition including a dehydration/hydrogenation catalyst.
  • a syngas feed line 7 feeds syngas via a first pressure test point PI, a pressure reducing valve 9, a second pressure test point P2, a globe valve system including a mass flowmeter 11, and a third pressure test point P3 to the first reaction stage 3.
  • a nitrogen feed line 13 is provided for feeding N 2 to a point at the first pressure test point PI .
  • a hydrogen feed line 15 and vent 17 is provided upstream of the pressure reducing valve 9.
  • Intermediate product stream leaving the first reaction stage 3 via line 19 passes through a back pressure valve to a fourth pressure test point P4 before passing to the second reaction stage 5.
  • a product stream passes from the second reaction stage 5 via line 23 through a further back pressure valve 2 .
  • the system further includes gas chromatography (GC) apparatus 25 arranged to receive intermediate product stream from line 19 and/or product stream from line 23.
  • the gas chromatography apparatus 25 in this example includes a flame ionization detector (FID) and a thermal conductivity detector (TCD).
  • the catalyst was first activated at 250 degrees C for 2 hours in a pure hydrogen flow. Subsequently, syngas was fed to the reaction vessels and the reaction was carried out using different reaction conditions as described below. All the products from the reactor were formed in the gaseous phase and analysed by gas chromatography on-line. The components CO, C0 2 , CH 4 and N 2 were analysed using a GC equipped with a TCD and organic compounds were analyzed by another GC apparatus equipped with a FID.
  • a commercial Cu-ZnO-Al 2 0 3 (Cu-Zn-Al) methanol synthesis catalyst (from Shenyang Catalyst Corp.) was crushed into particles of size 20-40 mesh.
  • a commercial Cu-ZnO-A ⁇ Cb (Cu-Zn-Al) methanol synthesis catalyst was crushed into particles of size 20-40 mesh.
  • ZSM-5 was pelletized and crushed into particles of size 20-40 mesh. 0.35g Cu-Zn-Al methanol synthesis catalyst and 0.45g ZSM-5
  • a commercial Cu-ZnO-Al 2 0 3 (Cu-Zn-Al) methanol synthesis catalyst and ⁇ - ⁇ 1 2 0 3 were powder mixed at the weight of 9/5, pelletized and crushed into particles of size 20-40 mesh.
  • This catalyst was denoted as hybrid catalyst I.
  • Pd modified ZSM-5 was prepared by the following ion-exchange method. lOg ZSM-5 was added to a 200ml solution of PdCl 2 at 60 degrees C with stirring, maintained for 8h, washed with water, dried at 120 degrees C, calcined at 550 degrees C and then pelletized and crushed into particles of size 20-40 mesh. The catalyst was denoted as 0.5%Pd-ZSM-5.
  • the reaction temperature for the first catalyst bed was 282 degrees C
  • the reaction temperature for the second catalyst bed was 320 degrees C.
  • the reaction pressure was 3.0MPa
  • CO conversion was 62.5%.
  • the selectivity of C0 2 was 34.6%.
  • the selectivity of hydrocarbons was 65.1%.
  • the sum selectivity of methanol and DME was 0.3%.
  • the hydrocarbon distribution is shown in Table 5.
  • the reaction temperature for the first catalyst bed was 294 degrees C, and the reaction temperature for the second catalyst bed was 330 degrees C.
  • the selectivity of C0 2 was 34.4%.
  • the selectivity of hydrocarbons was 63.9%.
  • the sum selectivity of methanol and DME was 1.7%.
  • the hydrocarbon distribution is shown in Table 6.
  • the reaction temperature for the first catalyst bed was 282 degrees C and the reaction temperature for the second catalyst bed was 321 degrees C.
  • a commercial Cu-ZnO-Al 2 0 3 (Cu-Zn-Al) methanol synthesis catalyst and ZSM-5 (SiO 2 /Al 2 O 3 140) were powder mixed at the weight of 9/5, pelletized and crushed into particles of size 20-40 mesh. This catalyst is denoted as hybrid catalyst III.
  • the selectivity of C0 2 was 48.2%.
  • the sum selectivity of methanol and DME was 0.4%.
  • the selectivity of hydrocarbons was 51.4%.
  • the hydrocarbon distribution is shown in Table 11.
  • Cu modified ZSM-5 was prepared by an incipient- wetness impregnation method.
  • the Cu(N0 3 ) 2 3H 2 0 as the precursors of Cu was dissolved in water. About a 10ml solution was added to lOg ZSM-5 zeolite drop by drop in 5min, maintained for 24 h at room temperature, and then dried at 90 degrees C and calcined at 400 degrees C for 4 h.
  • the resulting product is denoted herein as xCu-ZSM-5, where x stands for the weight content ofCu.
  • the reaction temperature for the first catalyst bed was 282 degrees C and the reaction temperature for the second catalyst bed was 320 degrees C.
  • the reaction temperature for the first catalyst bed was 282 degrees C and the reaction temperature for the second catalyst bed was 320 degrees C.
  • the reaction temperature for the first catalyst bed was 294 degrees C and the reaction temperature for the second catalyst bed was 330 degrees C.
  • hybrid catalyst I 0.6 of hybrid catalyst I was in the first catalyst bed and 0.45g 0.5%Pd-ZSM-5 was in the second catalyst bed. There was no direct contact between the two components.
  • the reaction temperature for the first catalyst bed was 282 degrees C and the reaction temperature for the second catalyst bed was 320 degrees C.
  • the selectivity of methanol and DME increased with time on stream. It may have been caused by the decreased dehydration ability of the catalyst.
  • the content of olefins in the hydrocarbons increased and it may have been the result of the decreased hydrogenation ability of catalyst.
  • the reaction temperature for the first catalyst bed was 282 degrees C and the reaction temperature for the second catalyst bed was 320 degrees C.
  • the selectivity of C0 2 was 35.6%.
  • the selectivity of hydrocarbons was 62. %.
  • the sum selectivity of methanol and DME was 1.6%.
  • the hydrocarbon distribution is shown in Table 16.
  • the catalyst bed was 0.5g H-ZSM-5.
  • the reaction temperature was 400 degrees C.
  • the reaction pressure was atmospheric pressure and the flow rate of N 2 was 25ml/min.
  • the conversion of methanol was 100%.
  • the selectivity of C 2- 4 olefins in e f fraction was about 66%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé destiné à la synthèse d'hydrocarbures saturés à partir d'un gaz de synthèse. Le procédé contient un système catalytique à un étage et/ou un système catalytique à plusieurs étages devant être utilisés dans la production catalysée d'hydrocarbures saturés à partir d'oxydes de carbone et d'hydrogène. Le procédé diminue les quantités d'hydrocarbures non souhaités à faible indice de carbone, tels que C3 et moins, puis fournit des hydrocarbures à indice d'octane élevé entrant en ébullition dans la plage de l'essence.
PCT/EP2014/058529 2013-04-26 2014-04-25 Production d'hydrocarbures à partir d'un gaz de synthèse WO2014174107A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CNPCT/CN2013/074777 2013-04-26
CN2013074777 2013-04-26
CN201310149855.6 2013-04-26
CN201310149855.6A CN104117380B (zh) 2013-04-26 2013-04-26 合成气转化生产烃类化合物的工艺及所用催化剂

Publications (1)

Publication Number Publication Date
WO2014174107A1 true WO2014174107A1 (fr) 2014-10-30

Family

ID=50588705

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/058529 WO2014174107A1 (fr) 2013-04-26 2014-04-25 Production d'hydrocarbures à partir d'un gaz de synthèse

Country Status (1)

Country Link
WO (1) WO2014174107A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019122078A1 (fr) * 2017-12-20 2019-06-27 Basf Se Système catalyseur et processus de préparation d'éther diméthylique
WO2019122075A1 (fr) * 2017-12-20 2019-06-27 Basf Se Catalyseur et processus de préparation d'éther diméthylique
WO2020168548A1 (fr) * 2019-02-22 2020-08-27 Bp P.L.C. Procédé
WO2020168539A1 (fr) * 2019-02-22 2020-08-27 Bp P.L.C. Procédé
CN115340435A (zh) * 2021-05-13 2022-11-15 中国科学院大连化学物理研究所 一种丙烷的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4340503A (en) * 1980-08-15 1982-07-20 The United States Of America As Represented By The United States Department Of Energy Catalyst for converting synthesis gas to light olefins
EP0154063A1 (fr) * 1984-03-01 1985-09-11 The Standard Oil Company Catalyseur silicalite modifié, sa préparation et procédé pour son utilisation
US20100261940A1 (en) * 2007-10-26 2010-10-14 Ki-Won Jun Process for producing light olefins from synthesis gas using dual sequential bed reactor
US20110124750A1 (en) * 2009-11-20 2011-05-26 Chevron U.S.A., Inc. Zeolite supported cobalt hybrid fischer-tropsch catalyst
WO2012142725A1 (fr) * 2011-04-21 2012-10-26 Dalian Institute Of Chemical Physics Chinese Academy Of Sciences Production d'hydrocarbures saturés à partir d'un gaz de synthèse

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4340503A (en) * 1980-08-15 1982-07-20 The United States Of America As Represented By The United States Department Of Energy Catalyst for converting synthesis gas to light olefins
EP0154063A1 (fr) * 1984-03-01 1985-09-11 The Standard Oil Company Catalyseur silicalite modifié, sa préparation et procédé pour son utilisation
US20100261940A1 (en) * 2007-10-26 2010-10-14 Ki-Won Jun Process for producing light olefins from synthesis gas using dual sequential bed reactor
US20110124750A1 (en) * 2009-11-20 2011-05-26 Chevron U.S.A., Inc. Zeolite supported cobalt hybrid fischer-tropsch catalyst
WO2012142725A1 (fr) * 2011-04-21 2012-10-26 Dalian Institute Of Chemical Physics Chinese Academy Of Sciences Production d'hydrocarbures saturés à partir d'un gaz de synthèse

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021508286A (ja) * 2017-12-20 2021-03-04 ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ ジメチルエーテルを製造するための触媒システムおよび方法
WO2019122078A1 (fr) * 2017-12-20 2019-06-27 Basf Se Système catalyseur et processus de préparation d'éther diméthylique
CN111491732A (zh) * 2017-12-20 2020-08-04 巴斯夫欧洲公司 用于制备二甲醚的催化剂系统和方法
CN111556785A (zh) * 2017-12-20 2020-08-18 巴斯夫欧洲公司 用于制备二甲醚的催化剂和方法
CN111556785B (zh) * 2017-12-20 2023-11-03 巴斯夫欧洲公司 用于制备二甲醚的催化剂和方法
US11529616B2 (en) * 2017-12-20 2022-12-20 Basf Se Catalyst system and process for preparing dimethyl ether
WO2019122075A1 (fr) * 2017-12-20 2019-06-27 Basf Se Catalyseur et processus de préparation d'éther diméthylique
US11452995B2 (en) 2017-12-20 2022-09-27 Basf Se Catalyst and process for preparing dimethyl ether
CN113677655A (zh) * 2019-02-22 2021-11-19 英国石油有限公司 方法
CN113677654A (zh) * 2019-02-22 2021-11-19 英国石油有限公司 方法
WO2020168539A1 (fr) * 2019-02-22 2020-08-27 Bp P.L.C. Procédé
CN113677654B (zh) * 2019-02-22 2023-10-10 英国石油有限公司 方法
WO2020168548A1 (fr) * 2019-02-22 2020-08-27 Bp P.L.C. Procédé
CN113677655B (zh) * 2019-02-22 2024-03-19 英国石油有限公司 一种二甲醚的生产方法
CN115340435A (zh) * 2021-05-13 2022-11-15 中国科学院大连化学物理研究所 一种丙烷的制备方法

Similar Documents

Publication Publication Date Title
Guo et al. Recent advances in direct catalytic hydrogenation of carbon dioxide to valuable C 2+ hydrocarbons
Bao et al. Significant advances in C1 catalysis: highly efficient catalysts and catalytic reactions
CN108137431B (zh) 使用双官能氧化铬/氧化锌-sapo-34催化剂将合成气体转化为烯烃的方法
Jin et al. Indirect coal to liquid technologies
KR100903439B1 (ko) 천연가스로부터 경질탄화수소의 직접 제조방법
Fierro Catalysis in C 1 chemistry: Future and prospect
CN109701602B (zh) 用于生产烃类的催化剂体系及其使用方法
US20090255171A1 (en) Single-reactor process for producing liquid-phase organic compounds from biomass
Bae et al. Coproduction of methanol and dimethyl ether from biomass-derived syngas on a Cu− ZnO− Al2O3/γ-Al2O3 hybrid catalyst
CN104117380B (zh) 合成气转化生产烃类化合物的工艺及所用催化剂
US11660587B2 (en) Catalysts and process for liquid hydrocarbon fuel production
WO2014174107A1 (fr) Production d'hydrocarbures à partir d'un gaz de synthèse
JP2009179801A (ja) 液化石油ガスの製造方法
US20140316177A1 (en) Catalyst for use in production of hydrocarbons
CA2973638C (fr) Rejet d'hydrogene dans procede de conversion de methanol en hydrocarbure
TW201429941A (zh) 用於製造甲醇及乙酸甲酯之整合方法（二）
US20140163122A1 (en) Production of saturated hydrocarbons from synthesis gas
Sibi et al. Direct conversion of CO2 into aromatics over multifunctional heterogeneous catalysts
JP2007181755A (ja) 液化石油ガス製造用触媒、および、この触媒を用いた液化石油ガスの製造方法
EP2103584A1 (fr) Procédé de fabrication d'un composé aromatique alkylé et procédé de fabrication de phénol
CN101460438A (zh) 用于将合成气转化为含氧物的方法
CN109694306B (zh) 甲醇高效转化制二甲苯的方法
US9073804B2 (en) Enhanced conversion of syngas to propylene
Coffano et al. One-pot lower olefins production from CO2 hydrogenation
CN101460439B (zh) 用于将合成气转化为氧化物的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14719759

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14719759

Country of ref document: EP

Kind code of ref document: A1