WO2010045516A2 - Procédés et appareil pour la synthèse d'alcools à partir de gaz de synthèse - Google Patents

Procédés et appareil pour la synthèse d'alcools à partir de gaz de synthèse Download PDF

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WO2010045516A2
WO2010045516A2 PCT/US2009/060935 US2009060935W WO2010045516A2 WO 2010045516 A2 WO2010045516 A2 WO 2010045516A2 US 2009060935 W US2009060935 W US 2009060935W WO 2010045516 A2 WO2010045516 A2 WO 2010045516A2
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hydration
propanol
zone
ethanol
methanol
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PCT/US2009/060935
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WO2010045516A3 (fr
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Karl Kharas
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Range Fuels, Inc.
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Priority claimed from US12/579,950 external-priority patent/US8354563B2/en
Application filed by Range Fuels, Inc. filed Critical Range Fuels, Inc.
Publication of WO2010045516A2 publication Critical patent/WO2010045516A2/fr
Publication of WO2010045516A3 publication Critical patent/WO2010045516A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C07C29/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds with formation of absorption products in mineral acids and their hydrolysis
    • C07C29/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds with formation of absorption products in mineral acids and their hydrolysis the acid being phosphoric acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • 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
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • 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
    • 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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • 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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • Patent App. No. 61/105,858 for "METHODS FOR SYNTHESIS OF ALCOHOLS FROM SYNGAS," filed October 16, 2008, and of U.S. Patent App. Nos. 12/579,950, 12/579,991, and 12/580,022 each for "METHODS AND APPARATUS FOR SYNTHESIS OF ALCOHOLS FROM SYNGAS," each filed October 15, 2009.
  • the present invention generally relates to the field of processes for the chemical conversion of synthesis gas to alcohols, such as ethanol.
  • Synthesis gas (hereinafter referred to as syngas) is a mixture of hydrogen (H 2 ) and carbon monoxide (CO). Syngas can be produced, in principle, from virtually any material containing carbon. Carbonaceous materials commonly include fossil resources such as natural gas, petroleum, coal, and lignite; and renewable resources such as lignocellulosic biomass and various carbon-rich waste materials. It is preferable to utilize a renewable resource to produce syngas because of the rising economic, environmental, and social costs associated with fossil resources.
  • Syngas is a platform intermediate in the chemical and biorefming industries and has a vast number of uses. Syngas can be converted into alkanes, olefins, oxygenates, and alcohols. These chemicals can be blended into, or used directly as, diesel fuel, gasoline, and other liquid fuels. Syngas can also be directly combusted to produce heat and power.
  • Syngas conversion to methanol is well-known.
  • syngas (usually derived from natural gas) can be catalytically converted to methanol at very high selectivities using a mixture of copper, zinc oxide, and alumina at a temperature of 25O 0 C and pressures of 750-1500 psi.
  • other catalyst systems suitable for methanol synthesis include Zn(VCr 2 O 3 , Cu/ZnO, Cu/ZnO/ Cr 2 O 3 , Cu/ThO 2 , Co/S, Mo/S, Co/Mo/S, Ni/S, Ni/Mo/S, and Ni/Co/Mo/S.
  • methanol can be combusted to produce energy
  • methanol is not currently acceptable as a liquid transportation fuel except in small quantities, e.g. as a minor additive to gasoline.
  • Methanol can, however, be converted to many other fuels and chemicals.
  • methanol can be considered a platform intermediate for producing gasoline and biodiesel. It would be useful to convert methanol to specific oxygenates, such as ethanol, for addition to gasoline. Heavier alcohols can also be valuable for chemical applications, as is known.
  • Ci-C 4 alcohols such as ethanol and/or 2-propanol
  • syngas or methanol it is sought to overcome the poor selectivities associated with alcohol-synthesis catalysts.
  • this invention addresses the problems in the art by providing methods capable of producing high selectivities to desired alcohols. [0011] In some embodiments, this invention provides a method for producing ethanol and 2-propanol from syngas, the method comprising:
  • step (b) converting at least some of the methanol from step (a) into a composition including ethylene and propylene in the presence of a methanol-to-olefms catalyst;
  • the syngas is derived from biomass.
  • the syngas can be derived, however, from any carbon-containing source.
  • the methanol-to-olefms catalyst can comprise an aluminosilicate zeolite such as one selected from the group consisting of ZSM-5, ZSM-11, ZSM- 12,
  • ZSM-23, ZSM-35, and ZSM-48 are examples of ZSM-23, ZSM-35, and ZSM-48.
  • the methanol-to-olef ⁇ ns catalyst can comprise a silicoaluminophosphate such as one selected from the group consisting of SAPO-5,
  • SAPO-8 SAPO-I l
  • SAPO-16 SAPO-17
  • SAPO-18 SAPO-20
  • SAPO-31 SAPO- 34
  • SAPO-35 SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-
  • SAPO-34 is a preferred methanol-to-olefms catalyst.
  • the silicoaluminophosphate further includes one or more transition metals, such as (but not limited to) one or more transition metals is selected from the group consisting of Mn, Ni, and Co. Nickel is a preferred transition metal, and a preferred methanol-to-olefms catalyst is Ni-SAPO-34. In some embodiments, the ratio of silicon to the transition metal is selected from about 1 to about 500, such as about 10 to about 200.
  • step (c) is conducted in the presence of one or more olefin-hydration catalysts, such as one or more olefin-hydration catalysts selected from zeolites, supported acids, acidic resins, and heteropoly acids.
  • one or more olefin-hydration catalysts includes sulfuric acid.
  • one or more olefin-hydration catalysts includes a catalyst selected for ethylene hydration, such as phosphoric acid.
  • one or more olefin-hydration catalysts includes a catalyst selected for propylene hydration.
  • the hydrating of ethylene and propylene is conducted substantially simultaneously.
  • the method further includes separating the ethylene from the propylene generated in step (b) and then separately hydrating the ethylene and the propylene during step (c).
  • step (c) hydrating of the propylene is substantially conducted prior to hydrating of the ethylene.
  • hydrating is conducted in a first reaction zone for converting propylene into 2- propanol and a second reaction zone for converting ethylene into ethanol.
  • Step (b) can further generate butenes which can be hydrated to 2-butanol during step (c).
  • the first reaction zone can be located in a first reactor and the second reaction zone can be located in a second reactor. Or, both of the reaction zones can be located in a single reactor.
  • the temperature within the first reaction zone is lower than the temperature within the second reaction zone.
  • the temperature within the first reaction zone can be selected from about 125-200 0 C and the temperature within the second reaction zone can be independently selected from about 200-250 0 C.
  • step (c) At least a portion of water produced from reactions during step (b) is used for the hydrating during step (c). In certain embodiments, all or substantially all of the water produced during step (b) is fed for the hydrating during step (c).
  • step (c) one or more dialkyl ethers are generated, and wherein the method further comprises removing at least a portion of the dialkyl ethers during or after step (c).
  • Methods of the invention can further comprise the step of separating unhydrated olefins from alcohols by distillation. Methods can additionally, or alternatively, comprise the step of separating unhydrated olefins from alcohols by absorption of the alcohols into water.
  • the method further comprises the step of separating unhydrated olefins from alcohols by absorption of the alcohols into dimethyl ether.
  • ethanol and/or the 2-propanol are separated
  • ethanol is separated from the 2- propanol.
  • Some variations of the invention provide a method for producing ethanol and 2-propanol from biomass, the method comprising:
  • step (c) converting at least some of the methanol from step (b) into a composition including ethylene and propylene in the presence of SAPO-34 or Ni-SAPO-34;
  • Variations of the present invention also provide a method of separating one or more olefins from one or more alcohols, the method comprising:
  • step (c) removing dimethyl ether from the solution from step (b), to generate a purified alcohol stream comprising the at least one alcohol.
  • the one or more olefins can include ethylene, propylene, or another olefin.
  • the one or more alcohols can include ethanol, 2-propanol, or another alcohol.
  • ethanol and 2-propanol absorb into the dimethyl ether and wherein ethylene and propylene do not substantially absorb into the dimethyl ether.
  • step (c) can include evaporation of dimethyl ether.
  • the olefins can be derived from methanol, and the alcohols can be generated from hydration of the olefins.
  • the dimethyl ether can be derived from the methanol, which can be the same source of methanol as that for generating the olefins.
  • the molar ratio of ethylene to propylene can be greater than about 2, 5, or 10 in various embodiments.
  • the combined yield of the ethanol and the 2-propanol from the biomass can be at least 70 gallons per dry ton biomass, at least 100 gallons per dry ton biomass, or at least 120 gallons per dry ton biomass.
  • the yield of ethanol is at least 100 gallons per dry ton biomass.
  • the yield of 2-propanol is at least 50 gallons per dry ton biomass.
  • the alcohols produced by this invention can be used directly as liquid fuels, or blended into various fuel mixtures.
  • 2-propanol is blended into gasoline.
  • ethanol and 2-propanol are blended into gasoline, which can be beneficial to decrease Reid vapor pressure versus a gasoline/ethanol blend because 2-propanol is less volatile than ethanol.
  • Some variations of the invention convert methanol (from any source) to higher alcohols such as ethanol and 2-propanol.
  • a method is provided for producing ethanol and 2-propanol from methanol, the method comprising:
  • step (b) feeding the stream from step (a) and water to a first hydration zone under suitable conditions for hydration of propylene to 2-propanol;
  • the invention provides a method for producing ethanol and 2-propanol from methanol, the method comprising:
  • step (a) converting methanol, in the presence of SAPO-34 or Ni-SAPO-34, into a stream including ethylene and propylene; (b) feeding the stream from step (a) and water to a first hydration zone under suitable conditions for catalytic hydration of propylene to 2-propanol; and
  • This invention also provides, in some variations, an apparatus for producing ethanol and 2-propanol from methanol, the apparatus comprising:
  • a first hydration zone optionally containing a first hydration catalyst, and configured for hydrating propylene to 2-propanol
  • a second hydration zone optionally containing a second hydration catalyst, and configured for hydrating ethylene to ethanol
  • (h) means for collecting the ethanol and 2-propanol.
  • the first hydration zone can located in a first reactor and the second hydration zone can located in a second reactor. Or, both of the hydration zones can be located in a single reactor.
  • the temperature within the first hydration zone is lower than the temperature within the second hydration zone.
  • the temperature within the first hydration zone can be selected from about 125-200 0 C and the temperature within the second hydration zone can be independently selected from about 200-250 0 C.
  • the apparatus of some variations of the invention further includes means for separating unhydrated olefins from alcohols.
  • One such means for separating unhydrated olefins from alcohols comprises absorption into dimethyl ether.
  • the apparatus includes means for separating the ethanol and/or the 2-propanol from water and/or means for separating the ethanol from the 2- propanol.
  • step (b) feeding the stream from step (a) and water to a reactive-distillation unit including a first zone containing an propylene-hydration catalyst, a second zone containing a ethylene-hydration catalyst, an overhead stream, and a bottoms stream;
  • the methanol can be derived from syngas, which can in turn be derived from biomass or another carbonaceous feedstock.
  • the overhead stream includes ethanol and 2- propanol.
  • the bottoms stream includes 2-propanol and water.
  • the reactive-distillation unit e.g., distillation column
  • the reactive-distillation unit can include at least one side- draw stream for removing ethanol, 2-propanol, or both ethanol and 2-propanol.
  • the reactive-distillation unit can include at least two side-draw streams.
  • the reactive-distillation unit in some embodiments, operates with a temperature profile from about 25O 0 C or less at the reboiler to about 100 0 C or greater at the condenser. In certain embodiments, the reactive-distillation unit operates with a temperature profile from about 235 0 C or less at the reboiler to about 125 0 C or greater at the condenser.
  • At least one olefin and water are preferably in countercurrent flow within the reactive-distillation unit.
  • hydration is rate-limited by water in the first zone and/or the second zone.
  • the first zone is preferably above the second zone so that the first zone for ethylene hydration is at a higher temperature than the second zone for propylene hydration.
  • a stream including ethylene and propylene is preferably introduced to a zone for propylene hydration before contacting a zone for ethylene hydration.
  • the feed location to the distillation column is between the first zone and the second zone. Water from the bottoms stream can be recycled to one or more feed locations. A portion of the overhead stream can be refluxed back to the distillation column at a position below the second zone.
  • the column can include trays, packing, or different column internals. In some embodiments, a portion of the packing comprises an ethylene-hydration catalyst and/or a propylene- hydration catalyst.
  • This invention further includes an apparatus for producing ethanol and
  • a reactive-distillation unit including a first zone containing an propylene- hydration catalyst and a second zone containing a ethylene -hydration catalyst;
  • FIG. 1 is a simplified block-flow diagram depicting variations of the invention converting syngas into ethanol and 2-propanol.
  • FIG. 2 is a simplified block-flow diagram of some variations wherein propylene hydration is followed by ethylene hydration.
  • FIG. 3 is a sketch of a reactive-distillation unit according to some embodiments of the invention.
  • FIG. 4 is a sketch of a reactive-distillation unit according to some embodiments of the invention. DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
  • Biomass for the purposes of the present invention is any material not derived from fossil resources and comprising at least carbon, hydrogen, and oxygen. Biomass includes, for example, plant and plant-derived material, vegetation, agricultural waste, wood waste, paper waste, animal-derived waste, and municipal solid waste.
  • the present invention can also be used for carbon-containing feedstocks other than biomass, such as a fossil fuel (e.g., coal or petroleum).
  • a fossil fuel e.g., coal or petroleum
  • any method or system described herein in reference to biomass can alternatively be used with any other carbon-containing feed material.
  • the methods and systems of the invention can accommodate a wide range of feedstocks of various types, sizes, and moisture contents.
  • carbon-containing feedstocks can include one or more materials selected from timber harvesting residues, softwood chips, hardwood chips, tree branches, tree stumps, leaves, bark, sawdust, paper pulp, corn stover, wheat straw, rice straw, sugarcane bagasse, switchgrass, miscanthus, animal manure, municipal solid waste, municipal sewage, commercial waste, used tires, grape pumice, almond shells, pecan shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets, cardboard, paper, plastic, rubber, cloth, coal, lignite, coke, lignin, and/or petroleum.
  • Mixtures of any of these feedstocks can be used. Mixtures can be accomplished by blending prior to feeding, co-feeding several feedstocks, or by some other means. A person of ordinary skill in the art will readily appreciate that the feedstock options are virtually unlimited.
  • syngas passes through a reactor for producing methanol.
  • methanol can be made at high productivity (such as ⁇ 1 kg methanol/kg-catalyst-hr) and these reactors can work at very high syngas conversions.
  • the catalyst could be, for example, a Cu/Zn/Al-based catalyst or another commercial methanol catalyst, including (but not limited to) selection from Cu/ZnO/Al 2 O 3 , Zn(VCr 2 O 3 , Cu/ZnO, Cu/ZnO/ Cr 2 O 3 , Cu/ZrO 2 , Cu/ThO 2 , Co/S, Mo/S, Co/Mo/S, Ni/S, Ni/Mo/S, and Ni/Co/Mo/S.
  • this step employs a low-temperature Cu/Zn/alumina methanol- synthesis catalyst.
  • the temperature of this reactor could be, for example, 230-250 0 C and the pressure could be, for example, 750-1000 psi.
  • syngas is provided according to methods described in Klepper et al., "Methods and apparatus for producing syngas," U.S. Patent App. No. 12/166,167 (filed July 1, 2008); or “Methods and apparatus for producing syngas and alcohols," U.S. Patent App. No. 12/166,194 (filed July 1, 2008).
  • U.S. Patent App. Nos. 12/166,167 and 12/166,194 are hereby incorporated by reference herein in their entireties.
  • the syngas entering the methanol reactor is compressed.
  • Conditions effective for producing methanol from syngas include reactor pressures from about 20-500 atm, preferably about 50-200 atm or higher. Generally, productivity increases with increasing reactor pressure, and pressures outside of these ranges can be employed with varying effectiveness.
  • the methanol stream produced from syngas (or a portion of the methanol-containing stream, or another source of methanol) can be passed over a methanol-to-olefin catalyst to generate a mixture of ethylene and propylene.
  • a methanol-to-olefin catalyst Any suitable methanol-to-olefm catalyst can be employed. That is, any material exhibiting activity for converting methanol to one or more olefins can be employed.
  • the methanol-to-olefin catalyst comprises an aluminosilicate zeolite, such as one selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, and ZSM-48.
  • the methanol-to-olefin catalyst comprises a silicoaluminophosphate ("SAPO"), such as a SAPO selected from the group consisting of SAPO-5, SAPO-8, SAPO-I l, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO- 34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO- 41, SAPO-42, SAPO-44, SAPO-47, and SAPO-56.
  • SAPO silicoaluminophosphate
  • SAPOs can be synthesized by forming a mixture containing sources of silicon, aluminum, and phosphorus mixed with an organic template, and then crystallizing the molecular sieve at reaction conditions. Many factors affect the form the molecular sieve takes, including the relative amounts of the different components, the order of mixing, the reaction conditions (e.g. temperature and pressure) and the choice of organic template.
  • a preferred methanol-to-olefm catalyst that can be used is SAPO-34
  • the framework structure can trap organic intermediates (such as ethylbenzenes) deriving from methanol. These organic intermediates act as organic reaction centers that catalyze the olefm-forming reactions in cooperation with active sites over the surface of the catalyst. Olefins, such as ethylene and propylene, are small enough to exit the micropores of SAPO-34.
  • SAPO-34 offers a good combination of catalyst activity, selectivity, and durability. Ethylene/propylene ratios in H-SAPO-34 may be driven by increased temperatures; at higher temperatures ethylene selectivities increase. At higher temperatures, coking rates are higher so more frequent regeneration is typically needed.
  • the methanol-to-olefm catalyst can employ silicoaluminophosphates that also include at least one transition metal.
  • the transition metal is selected from manganese, nickel, or cobalt.
  • the process of incorporating the transition metal may be accomplished through any one of the standard methods well known to those skilled in the art.
  • a solution of the desired metal is first made by dissolving the desired amount of the metal-containing compound in water under mild conditions. The temperature of mixing is dependent upon the solubility of the metal compound in water, or another medium.
  • the amount of metal which is incorporated may vary over a wide range depending, at least in part, on the selected silicoaluminophosphate (or other material) and on the incorporation method.
  • the amount of metal incorporated is measured on an atomic metal basis in terms of silicon-to-metal ratio.
  • the silicon-to- metal atomic ratios are in the range from about 0.1 :1 to about 1000:1, preferably from about 1 :1 to about 500:1, and most preferably from about 10:1 to about 200:1.
  • high methanol-to-olefm conversion can be accomplished by using Ni-SAPO-34.
  • Ni-SAPO-34 is described in Inui and Kang, "Reliable procedure for the synthesis of Ni-SAPO-34 as a highly selective catalyst for methanol to ethylene conversion," Applied Catalysis A: General, vol. 164, 211-223, 1997. As taught therein, ethylene selectivity is 88% over Ni-SAPO-34, at 425-450 0 C and close to atmospheric pressure.
  • ethylene is the preferred olefin.
  • propylene is the preferred olefin.
  • process conditions and catalysts can be selected to optimize selectivity to one particular olefin, which can be ethylene or propylene in particular embodiments.
  • process conditions and catalysts can be selected to optimize selectivity to total olefins rather than non-olefins (e.g., alkanes, aromatics, and CO 2 ).
  • Process conditions and catalysts can also be selected to maximize methanol conversion, maximize yield of total olefins, maximize yield of C2-C3 olefins, or maximize yield of a specific olefin such as ethylene or propylene.
  • methanol is completely or nearly completely converted in the olefin- forming process step.
  • selectivities to ethylene are in the 50-75 mol% range, while selectivities to propylene are in the 25-50 mol% range.
  • negligible quantities of methane and carbon dioxide are produced during olefin formation. Production of carbon dioxide can occur, however, in the gas phase away from catalyst surfaces, or possibly catalyzed by other non-selective surfaces present, such as walls of the reactor.
  • the olefin- forming reaction is exothermic.
  • the catalyst can produce coke, and if that occurs, the catalyst can be periodically regenerated by hot air or oxygen.
  • a plurality of reactors can be employed, so that when one is being regenerated, the other reactors can continue operation.
  • the temperature for the olefm-forming step(s) can be 375-425°C, for example. Higher temperatures will generally lead to higher selectivity to ethylene relative to propylene, but the choice of catalyst will also dictate product distribution. Any pressure can be employed, and selection of pressure will typically be dictated by economics and integration with an overall process. Reactor configurations are further discussed below.
  • the olefins produced from methanol can be passed through a catalyst to hydrate the olefins, by water addition across the double bonds.
  • Acid catalysts such as phosphoric acid, can be effective for olefin hydration. Hydration will proceed without any catalyst, but olefin hydration is preferably catalyzed to increase rates, maximize alcohol yield, and minimize olefin polymerization or other undesirable side reactions.
  • the temperature for this third step can be 100-250 0 C, for example. In some embodiments, ethylene is hydrated at about 240 0 C while propylene is hydrated at about 195°C. At excessively high temperatures, olefin polymers have a tendency to form.
  • the process generally produces a composition comprising ethanol and propanol.
  • the propanol can include both 1-propanol and 2- propanol, although hydration of propylene typically generates 2-propanol in accordance with Markovnikov's rule.
  • the secondary alcohol 2-propanol is also known as propan-2-ol, isopropyl alcohol, isopropanol, or IPA.
  • the product distribution can be adjusted to favor ethanol or to favor propanol, depending on what is desired.
  • ethanol is the dominant product of the overall process.
  • 2-propanol is the dominant product of the overall process.
  • Methanol-to-olefin catalysts such as H-SAPO-34
  • H-SAPO-34 will generally make a small amount of linear butenes that will hydrate to 2-butanol.
  • the range of temperatures of these hydration reactions, for direct hydration processes utilizing heterogeneous catalysts, is typically from about 100-250 0 C with heavier olefins (e.g., propylene and butenes) being hydrated at lower temperatures.
  • olefins e.g., propylene and butenes
  • two or three hydration reactors are contemplated (see, for example, FIG. 2).
  • Alcohols can be isolated by condensation or by scrubbing into a suitable solvent, which can be water, DME, or propane (U.S. Patent No. 4,469,903).
  • a hydration reaction produces an alcohol, or a product mixture comprising an alcohol and an ether, the alcohol and the ether each having the same carbon chain length as the olefin, in equilibrium with the olefin and water.
  • the thermodynamics and hence the equilibrium of the hydration reaction is such that formation of the alcohol is more favorable at low temperatures and high pressures.
  • at least a portion of the water necessary for hydration of ethylene (or other olefins) is supplied from the methanol-to-olefms step, which produces water during dehydration.
  • such water is supplied while substantially still hot, thereby improving overall thermal efficiency.
  • olefin-hydration catalysts are selected from zeolites, supported acids (e.g., phosphoric acid on silica), acidic resins, and heteropoly acids.
  • the ethylene-hydration catalyst can be the same as, or different from, the propylene-hydration catalyst.
  • Various heterogeneous catalysts may be used for hydration of olefins.
  • Ethylene may be hydrated, typically at temperatures above 200 0 C, by H 3 PO 4 ZSiO 2 catalysts.
  • This type of catalyst is the basis of the Shell ethylene-hydration process, the first direct catalytic hydration process known commercially.
  • Carbons may be used instead of silica as a support for phosphoric acid.
  • Alumina is less preferred as a support for phosphoric acid since relatively inert AlPO 4 will tend to form.
  • Zeolites such as H-ZSM-5, H-mordenite, H-Beta, or H-Y, may also be used as hydration catalysts in some embodiments.
  • H-Y When H-Y is used, preferably its Si/ Al is preferably greater than 10 and preferably at least 25% of Al is associated with a Br ⁇ nsted acid site.
  • H-ZSM-5 or H-mordenite are preferable. Si/ Al ratios can be in the range of 50-100, in some embodiments.
  • a mild dealumination is preferable in order to generate a suitable fraction of strongly acidic sites. Dealumination may be conducted by various means, such as treatment with steam, leaching with mineral acid or organic acids such as oxalic acid, or treatment with SiCl 4 and the like.
  • medium-pore zeolites such as ZSM-5, H- mordenite, and the like
  • ZSM-5, H- mordenite, and the like An advantage of medium-pore zeolites is that the pores are large enough to accommodate reactant olefins and water, as well as product alcohols, but small enough to prevent ethers from forming.
  • Acidic resins based on polysiloxane can be used in some embodiments.
  • thermally durable silica-Nafion® composite resins are employed.
  • Supported heteropoly acid catalysts may also be used.
  • Aqueous solutions of heteropoly acids also may be used in some embodiments.
  • Zeolites may be used to catalyze these hydration reactions.
  • More reactive olefins such as propene and butenes, may be hydrated over strong acid organic resins such as Nafion resins. These resins are unstable above about 15O 0 C, so they are not preferred for ethylene hydration. Ethylene, propene, and butenes may be hydrated by aqueous mixtures of suitable polytungate acids, such as (but by no means limited to) H3PW12O40, H 4 SiWi 2 O 4 O, or by their molybdenum analogues.
  • suitable polytungate acids such as (but by no means limited to) H3PW12O40, H 4 SiWi 2 O 4 O, or by their molybdenum analogues.
  • indirect hydration of olefins is employed.
  • a mixture of olefins (mainly ethylene and propylene, but also small amounts of butenes will typically be present) may hydrated indirectly by initial absorption into sulfuric acid and subsequent hydrolysis of the resultant sulfate esters.
  • This indirect hydration method has been practiced for ethylene hydration (e.g., Carle and Stewart, "Synthetic Ethanol Production," Chemistry and Industry, pp. 830-839, 1962).
  • indirect hydration has been used to make isopropanol from propene (e.g., U.S. Patent No. 3,352,930).
  • Advantages of this approach include the following: a mixture of olefins may be hydrated more or less simultaneously; and thermodynamic limitations associated with direct hydration are avoided, allowing very high conversion of olefins.
  • reaction temperature is too high, olefin polymers may form.
  • Ethers both symmetrical and nonsymmetrical also may form. Also, SO 2 can form to a limited extent. Dilute sulfuric acid that is formed must be reconcentrated.
  • alcohols formed from olefins are isolated and purified. Alcohols can be separated from unreacted olefin streams by selective absorption of alcohol into water. The aqueous alcoholic mixture is then separated in a series of distillation columns, often including an azeotropic distillation. A similar approach may be used to separate the mixture of product alcohols from unreacted olefins from the sulfuric acid/water indirect-hydration reactor.
  • alcohols can be absorbed into a dialkyl ether such as dimethyl ether.
  • Dimethyl ether is conveniently available in a methanol-based biorefmery, since methanol is readily dehydrated selectively, under mild conditions, over catalysts such as H-ZSM-5, Na,H- ZSM-5, or ⁇ -Al 2 ⁇ 3 to dimethyl ether (DME).
  • the absorption can be done under moderate pressure and low temperature, conditions under which dimethyl ether is a liquid. Purification of the resultant mixtures is straightforward since DME may be removed by volatilization, resulting in a non-aqueous mixture of alcohols more amenable to separation by distillation.
  • reaction and separation are carried out simultaneously in a reactive-distillation unit, such as a column.
  • Reactive distillation can reduce energy costs and is especially useful for equilibrium-limited reactions due to continuous removal of products from the reaction zone.
  • a reactive-distillation unit employs one or more acid catalysts deployed in at least two separate beds, to hydrate mixtures of olefins whose hydration catalysis preferably proceeds at different temperatures.
  • Use of more active acid catalysts may allow ethylene hydration to proceed at considerably lower temperatures. Decreasing the temperatures of ethylene hydration decreases the severity of thermodynamic limitations which should enable higher levels of ethylene conversion.
  • the ethylene conversion bed is preferably below the propylene conversion bed.
  • Makeup olefins i.e., from column reflux, plant recycle, or fresh feed
  • Olefins can be purified, at least in part, prior to being fed back into the unit.
  • Water is preferably introduced near the top of one or both of the olefin-hydration beds. In some embodiments, the unit is operated so that essentially all water is consumed in hydration reactions.
  • the reactive-distillation unit can be operated at sufficient pressure to encourage forward reaction (hydration) by Le Chatlier's principle and also permit product alcohols to exist as both liquid and vapor.
  • olefins and water are fed countercurrently in each reaction zone and reactions are performed under water-limiting conditions in order to keep the bulk of the reactor essentially anhydrous.
  • alcohols are collected from the bottoms stream, while unreacted olefins are collected from the overhead stream.
  • there is a split of alcohols e.g., ethanol is collected in the overhead stream and 2-propanol is collected from the bottoms stream. Water is expected to collect in the bottoms stream.
  • FIG. 3 is an exemplary (and non- limiting) reactive-distillation unit wherein ethylene and propylene are introduced below the propylene-hydration zone (upper shaded portion). Water is introduced above each of the hydration zones in FIG. 3. In other embodiments, water is fed to only one of these locations; in still other embodiments, water is fed to additional locations beyond the two feed locations depicted in FIG. 3.
  • the liquid phase comprises ethanol and can be recovered, while the vapor phase comprises unreacted olefins which can be fed back into the column below the ethylene-hydration zone (lower shaded portion). In the bottoms, the liquid stream comprises 2-propanol which can be recovered. Due to the chemical kinetics involved, the vapor recycle from the condenser can be enriched in ethylene which is why it can be preferred to feed this vapor reflux at or below the ethylene-hydration zone.
  • FIG. 4 is another exemplary (and non-limiting) reactive-distillation unit wherein ethylene and propylene are introduced below the propylene-hydration zone (upper shaded portion). Water is introduced above each of the hydration zones in FIG. 4.
  • the vapor stream from the condenser can be recycled in a similar manner as described above for FIG. 3. Water in the bottoms can be recycled to one or more water-feed locations.
  • two side-draw streams are included: a 2- propanol-containing side draw stream that withdraws material between the propylene- hydration zone and the condenser; and an ethanol-containing side-draw stream that withdraws material between the two hydration zones.
  • 2- propanol-containing side draw stream that withdraws material between the propylene- hydration zone and the condenser
  • an ethanol-containing side-draw stream that withdraws material between the two hydration zones.
  • other locations for side-draw streams are possible.
  • the reactive-distillation unit can contain packing in addition to one or more catalysts.
  • column packing is coated, or impregnated, with hydration catalysts.
  • Catalysts can be wrapped in fabric and inserted into the column internals. Or, catalysts can be placed on one or more trays within a distillation column.
  • a “reactor” is any apparatus capable of being effective for catalyzing the conversion of reactants to products.
  • a reactor can be a single vessel or a plurality of vessels, i.e. a network of several reactors in various arrangements.
  • the reactors employed herein can be engineered and operated in a wide variety of ways. Reactor operation can be continuous, semicontinuous, or batch. Operation that is substantially continuous and at steady state is preferable.
  • the flow pattern can be substantially plug flow, substantially well-mixed, or a flow pattern between these extremes.
  • the flow direction can be vertical-upflow, vertical- do wnflow, or horizontal.
  • the catalyst phase within each reactor can be a packed bed or a fluidized bed.
  • the methanol-to-olefm reactor employs a fluidized bed.
  • the hydration reactor can also employ a fluidized bed if suitable catalyst materials are utilized. That is, fluidized beds are not particularly suitable for acidic resins or for phosphoric acid catalysts.
  • the catalyst particles can be sized and configured such that the chemistry is, in some embodiments, mass-transfer-limited or kinetically limited.
  • the catalyst can take the form of a powder, pellets, granules, beads, extrudates, and so on.
  • the support may assume any physical form such as pellets, spheres, monolithic channels, etc.
  • the supports may be coprecipitated with active metal species; or the support may be treated with the catalytic metal species and then used as is or formed into the aforementioned shapes; or the support may be formed into the aforementioned shapes and then treated with the catalytic species.
  • Some embodiments employ heat integration such that process heat from one or more exothermic steps is used to provide heat for distillation (or other purification) of the desired final products.
  • heat can supply energy for the conversion of a carbon-containing feedstock into syngas, such as in gasification.
  • the specific selection of reactor configuration, feed compositions, temperatures, pressures, and residence times (or feed rates) for each reactor, reaction zone, or distillation column will be selected to provide an economically optimized process.
  • the plurality of reactor variables and other system parameters can be optimized, in whole or in part, by a variety of means.
  • the quantity of liquid alcohols that can be generated from a given amount of biomass (or other carbonaceous feedstock) will depend on the syngas- generation process selected, the specific feedstock, the selection of process conditions and catalysts for the methods of the present invention, and various engineering and economic considerations relating to the overall process and biorefmery site (e.g., utilities available).
  • the feedstock is wood which is typically about 50 wt% carbon.
  • the present invention can be carried out to generate C2-C3 alcohol yields of at least about 50, 60, 70, 75, or more gallons per dry ton of feedstock.
  • the present invention can be carried out to generate C2-C3 alcohol yields of at least about 100, 110, 120, 125, or more gallons per dry ton of feedstock.
  • the distribution of alcohols produced can be adjusted to favor ethanol or to favor 2-propanol, as taught hereinabove.
  • a SAPO-34 catalyst can generate C 2 and C3 olefins at selectivities described in Wilson and Barger, Microporous and Mesoporous Materials, vol. 29, pp. 117-126, 1999.
  • the expected products from 1 dry ton include about 35 gallons ethanol, 30 gallons 2-propanol, and 7 gallons 2-butanol when the methanol-to-olef ⁇ ns step is conducted at about 375 0 C.
  • the expected products from 1 dry ton include about 50 gallons ethanol, 20 gallons 2-propanol, and 4 gallons 2-butanol. These yields assume that 40% of the starting biomass is used for energy production.
  • a SAPO-34 catalyst can generate C 2 and C 3 olefins at selectivities described in Wilson and Barger, Microporous and Mesoporous Materials, vol. 29, pp. 117-126, 1999. After effective hydration, the expected products from 1 dry ton include about 60 gallons ethanol, 50 gallons 2-propanol, and 12 gallons 2-butanol when the methanol-to-olef ⁇ ns step is conducted at about 375 0 C.
  • the expected products from 1 dry ton include about 85 gallons ethanol, 33 gallons 2-propanol, and 6 gallons 2-butanol.
  • the ethanol yield from 1 dry ton of biomass is expected to be about 70 gallons in the energy self-sufficient mode of operation (assuming 40% of the starting biomass is used for energy production).
  • the ethanol yield from 1 dry ton of biomass is expected to be about 115 gallons along with 5 gallons of 2-propanol.
  • distillation methods can be used to distill the final product. Any number of distillation columns may be employed, depending on the desired overall separation.
  • a purified ethanol product can be made to meet the ASTM D4806-07a specification for fuel ethanol, or some other fuel-grade specification as will be appreciated.
  • a purified 2-propanol product is produced.
  • the purified alcohol product can be used to power an internal combustion engine to power a transportation vehicle.
  • the purified alcohol(s) product can be combined (blended) with at least one other hydrocarbon, or multiple hydrocarbons such as gasoline, to create a liquid- fuel blend.
  • a mixture of ethanol and 2-propanol is produced as an alcohol product.
  • This biofuel mixture can be blended into gasoline to meet oxygenate requirements, while decreasing the Reid vapor pressure of the liquid fuel relative to gasoline blends with ethanol as the primary oxygenate.
  • 2-Propanol can also counteract water problems in fuel tanks that can accompany ethanol/gasoline blends (2-propanol is able to dissolve small quantities of water in fuel tanks).
  • one or more alcohols produced, such as 2- propanol can be sold into the chemical markets. For example, 2-propanol is used widely as in solvent, cleaning, and drying applications.

Abstract

Cette invention porte sur un procédé de production d'éthanol et de 2-propanol à partir de gaz de synthèse. Ce procédé comprend les opérations consistant à : (a) convertir le gaz de synthèse en méthanol à l'aide d'un catalyseur de synthèse de méthanol; (b) convertir le méthanol en éthylène et propylène à l'aide d'un catalyseur de conversion de méthanol en oléfines; et (c) hydrater l'éthylène en éthanol et le propylène en 2-propanol. Comme enseigné ici, le rendement combiné de l'éthanol et du 2-propanol à partir d'une biomasse peut être d'au moins 100 gallons par tonne sèche de biomasse. Dans certains modes de réalisation, le rendement d'éthanol est d'au moins de 100 gallons par biomasse. Dans certains modes de réalisation, le rendement de 2-propanol est d'au moins 50 gallons par tonne sèche de biomasse.
PCT/US2009/060935 2008-10-16 2009-10-16 Procédés et appareil pour la synthèse d'alcools à partir de gaz de synthèse WO2010045516A2 (fr)

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US12/579,991 US8357826B2 (en) 2008-10-16 2009-10-15 Methods and apparatus for synthesis of alcohols from syngas
US12/579,991 2009-10-15
US12/580,022 2009-10-15
US12/580,022 US8344188B2 (en) 2008-10-16 2009-10-15 Methods and apparatus for synthesis of alcohols from syngas
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CN109647503A (zh) * 2017-10-10 2019-04-19 中国石油化工股份有限公司 一种由合成气制备低碳烯烃的复合催化剂及其制备方法和由合成气制备低碳烯烃的方法
CN111569784A (zh) * 2020-03-25 2020-08-25 南京延长反应技术研究院有限公司 一种分段式丙烯水合制备异丙醇的强化反应系统及工艺
CN111569785A (zh) * 2020-03-25 2020-08-25 南京延长反应技术研究院有限公司 一种浸没式丙烯水合微界面强化反应系统及工艺

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EP0955284A1 (fr) * 1998-04-29 1999-11-10 BP Chemicals Limited Procédé pour l'hydration des oléfines
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EP0955284A1 (fr) * 1998-04-29 1999-11-10 BP Chemicals Limited Procédé pour l'hydration des oléfines
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CN109647503A (zh) * 2017-10-10 2019-04-19 中国石油化工股份有限公司 一种由合成气制备低碳烯烃的复合催化剂及其制备方法和由合成气制备低碳烯烃的方法
CN109647503B (zh) * 2017-10-10 2021-11-16 中国石油化工股份有限公司 一种由合成气制备低碳烯烃的复合催化剂及其制备方法和由合成气制备低碳烯烃的方法
CN111569784A (zh) * 2020-03-25 2020-08-25 南京延长反应技术研究院有限公司 一种分段式丙烯水合制备异丙醇的强化反应系统及工艺
CN111569785A (zh) * 2020-03-25 2020-08-25 南京延长反应技术研究院有限公司 一种浸没式丙烯水合微界面强化反应系统及工艺

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