WO2015089703A1 - Procédé destiné à être utilisé dans la production de méthanol et la coproduction d'alcools en c2-c4 - Google Patents

Procédé destiné à être utilisé dans la production de méthanol et la coproduction d'alcools en c2-c4 Download PDF

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WO2015089703A1
WO2015089703A1 PCT/CN2013/089536 CN2013089536W WO2015089703A1 WO 2015089703 A1 WO2015089703 A1 WO 2015089703A1 CN 2013089536 W CN2013089536 W CN 2013089536W WO 2015089703 A1 WO2015089703 A1 WO 2015089703A1
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catalyst
carbon
methanol
synthesis gas
low
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PCT/CN2013/089536
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Chinese (zh)
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刘勇
朱文良
刘红超
倪友明
刘中民
孟霜鹤
李利娜
刘世平
周慧
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中国科学院大连化学物理研究所
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    • 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
    • B01J23/72—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
    • 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
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/868—Chromium copper and chromium
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8878—Chromium
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • C07C29/132—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 an oxygen containing functional group
    • C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • 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
    • C07C29/153—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 characterised by the catalyst used
    • C07C29/154—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 characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8873—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
    • B01J2523/00—Constitutive chemical elements of heterogeneous 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • 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

Definitions

  • the present invention is in the field of catalytic chemistry and relates to a process for producing methanol in parallel to produce lower alcohols. Background technique
  • Methanol is an important chemical raw material and clean liquid fuel, mainly used as a solvent and raw materials for the preparation of formaldehyde, acetic acid, dimethyl ether, and MTG, MTO and other processes.
  • the production capacity of methanol at home and abroad has grown rapidly. From 2000 to 2008, the world's methanol production capacity increased by about 10% annually. Among them, China's methanol production capacity grew at an average annual rate of 23.5%. In 2011, China's methanol production reached 20.35 million tons. With the promotion of MTO and other technologies, it is expected that methanol production will increase in the future.
  • the medium and low pressure methanol synthesis process has been developed successively by the companies represented by British ICI Company and German Lurgi Company.
  • the medium and low pressure method can achieve high activity and high selectivity synthesis of methanol at a lower temperature (200-290 ° C) and a lower pressure (5 MPa).
  • the catalyst used is a copper catalyst (CuO/ZnO/Al 2 ). 0 3 , CuO/ZnO/Cr 2 0 3 , CuO/ZnO/MnO). Since the mid-1970s, almost all new and expanded methanol synthesis plants in the world have adopted medium and low pressure synthesis processes.
  • Low-carbon alcohol also known as C 2+ OH
  • C 2+ OH generally refers to a fatty alcohol with a carbon number of 2-6.
  • it can also be used as a gasoline additive to increase the bismuth value.
  • It is also an important basic raw material in the chemical industry.
  • One of them has a wide range of applications [Li Debao et al., Progress in Chemistry, 2004 (16) 584-592; Ge Qingjie et al., Chemical Progress, 2009 (28;) 917-921].
  • relatively concentrated systems for the synthesis of low-carbon alcohol catalysts mainly include modified methanol synthesis catalysts, Cu-Co groups and MoS 2 based catalysts [Forzatti P etc. Catal. Rev. 1991 (33) 109-168; Mahdavi V etc. Appl. Catal. A 2005 (281) 259-265].
  • An object of the present invention is to provide a process for synthesizing methanol to produce other lower alcohols (C2-C4 alcohols) by using a mixture of a lower carbon ester and a synthesis gas as a reaction material.
  • the present invention provides a process for producing methanol in parallel to produce C2-C4 alcohol, characterized in that a feed gas containing a lower carbon ester and a synthesis gas is passed through a reactor equipped with a catalyst at a reaction temperature of 150.
  • a feed gas containing a lower carbon ester and a synthesis gas is passed through a reactor equipped with a catalyst at a reaction temperature of 150.
  • the active component is copper and optionally zinc and/or aluminum.
  • the lower alcohol ester is one or more of an aliphatic ester having a total carbon number of not more than 8 (ie, a carbon number of 8 or less);
  • the polyhydric alcohol is ethanol, propanol, and butyl.
  • the active component copper is 50.0-100.0% by weight of the total weight of the catalyst in terms of CuO; zinc is 0-35.0% by weight of the total weight of the catalyst in terms of ZnO; Aluminum accounts for 0-10.0% by weight of the total weight of the catalyst in terms of A1 2 0 3 .
  • the catalyst further contains one or more of manganese, molybdenum, zirconium, chromium, iron, cerium, magnesium, nickel, calcium as an auxiliary. More preferably, the auxiliaries are manganese, chromium, iron, magnesium, nickel, most preferably manganese, iron, chromium.
  • the adjuvant is from 0 to 5.0% by weight based on the total weight of the catalyst, based on its metal oxide.
  • the catalyst is reduced with H 2 and / or synthesis gas prior to use.
  • the synthesis gas/low carbon ester molar ratio is 9 to: 1000/1 in the raw material gas, and the hydrogen/carbon monoxide molar ratio in the synthesis gas is 0.06 to 300/1.
  • the synthesis gas / lower carbon ester molar ratio is 40 to 560/1, and the hydrogen/carbon monoxide molar ratio of the synthesis gas is 0.3 to ⁇ 1.
  • the syngas also contains carbon dioxide, nitrogen and formamidine, and carbon dioxide, nitrogen and formamidine comprise from 3 to 13% by mole of the synthesis gas.
  • the reaction temperature is 180 to 300 ° C
  • the reaction pressure is 1.0 to 10.0 MPa
  • the reaction volume space velocity is 400-30000 mlg - 1
  • the lower ester Mass airspeed is 0.1 ⁇ 1.0h—
  • Advantageous effects of the present invention include, but are not limited to: providing a new reaction process for synthesizing methanol in parallel with a catalyst of a low-carbon ester and syngas to produce ethanol, propanol,
  • the addition of butanol, a lower ester promotes catalytic activity and does not affect catalyst life.
  • the ratio of each lower alcohol can be adjusted by changing the reaction conditions, which greatly improves product flexibility and market adaptability.
  • the method of the invention utilizes a co-feed of a low-carbon ester and a syngas as a reaction raw material to synthesize methanol to produce another low-carbon alcohol in parallel, wherein a raw material gas containing a lower-carbon ester and a synthesis gas is passed through a reactor equipped with a catalyst in the reaction.
  • the active component in the catalyst is copper, and may also contain zinc and/or aluminum.
  • the lower carbon ester is one or a mixture of any of several aliphatic esters having a total carbon number of not more than 8.
  • the lower carbon ester is ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate.
  • Butyl propionate a mixture of ester, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate or a mixture of any of the following;
  • the lower alcohol is one of methanol, ethanol, propanol, butanol or A variety.
  • the active component copper is 50.0-100.0% by weight based on the total weight of the catalyst, and the promoter zinc is 0-35.0% by weight based on the total weight of the catalyst;
  • the aluminum agent is 0-10.0% by weight based on the total weight of the catalyst, based on the metal oxide.
  • the catalyst may further contain a composition of one or any of manganese, molybdenum, zirconium, chromium, iron, cerium, magnesium, nickel, calcium, and more preferably, the auxiliary agent is manganese. Chromium, iron, magnesium, and nickel are most preferably manganese, iron, and chromium. It is 0-5.0 wt% based on the total weight of the catalyst, based on the metal oxide (e.g., MnO, Cr 2 O 3 , Fe 2 O 3 , MgO, NiO, etc.).
  • the metal oxide e.g., MnO, Cr 2 O 3 , Fe 2 O 3 , MgO, NiO, etc.
  • the synthesis gas/low carbon ester molar ratio is 9 to 1000/1, and the hydrogen/carbon monoxide molar ratio in the synthesis gas is 0.06 to 300/1.
  • the syngas may also contain carbon dioxide, nitrogen and formamidine, which may comprise from 3 to 13% by mole of the synthesis gas.
  • the synthesis gas/low carbon ester molar ratio is 40 to 560/1, and the hydrogen/carbon monoxide molar ratio in the synthesis gas is 0.3 to: 100/1.
  • the reaction conditions are: a reaction temperature of 180 to 300 ° C, a reaction pressure of 1.0 to 10.0 MPa, a reaction volume space velocity of 400 to 30 000 mlg 1 ⁇ 1 , and a low carbon ester mass space velocity of 0.1 to: 1.Oh-
  • the catalyst of the present invention (also referred to as a copper-based catalyst) is preferably prepared by a coprecipitation method, and includes the following steps:
  • step a) adding a solution containing Cu 2+ and optionally Zn 2+ and/or Al 3+ ions to a precipitant solution at 25-60 ° C, stirring the resulting precipitate to homogeneity, and obtaining a precipitate having a pH of 7.0- 1); b) the precipitate obtained in step a) is aged for 5 to 60 hours, dried at 80-160 ° C and calcined at 240-500 ° C to obtain a calcined sample;
  • step b) optionally, the calcined sample obtained in step b) is placed in a salt solution containing one or more of the components manganese, molybdenum, zirconium, chromium, iron, strontium, magnesium, nickel, calcium
  • the catalyst is obtained by dipping one or more times, drying after drying at 80-160 ° C, and calcination at 240-500 ° C.
  • the main advantages of the present invention are mainly: under the condition of co-feeding of low-carbon ester and syngas, in one One reactor synthesizes methanol to produce low-carbon alcohol in parallel (the ratio of methanol and low-carbon alcohol is adjustable), the addition of low-carbon ester promotes catalytic activity and does not affect the life of the catalyst, greatly improving product flexibility and Market adaptability.
  • the invention is described in detail below by way of examples, but the invention is not limited to the examples.
  • the obtained precipitate was dried in an oven at 120 ° C for 24 hours. After drying, the sample was placed in a muffle furnace, heated to 400 ° C at a heating rate of rC / mm, and calcined for 5 hours to obtain a calcined sample.
  • This catalyst is referred to as CAT1.
  • the water was diluted with 72.52 g of concentrated ammonia (25-28%).
  • the aqueous ammonia solution was vigorously stirred at room temperature, and then the mixed metal nitrate aqueous solution was slowly added to the aqueous ammonia solution for about 60 minutes.
  • the pH of the precipitate was adjusted to 10.0 with an aqueous ammonia solution, and after stirring for 200 mm, it was aged for 36 hours.
  • the precipitate was washed with deionized water to neutrality and centrifuged.
  • the obtained precipitate was dried in an oven at 120 ° C for 24 hours. After drying, the sample was placed in a muffle furnace, heated to 400 ° C at a heating rate of rC / mm, and calcined for 5 hours to obtain a calcined sample.
  • This catalyst is referred to as CAT3.
  • Adjusting the precipitation with aqueous ammonia solution The pH was adjusted to 10.0, and after stirring for 200 mm, it was aged for 36 hours. The precipitate was washed with deionized water to neutrality and centrifuged. The obtained precipitate was dried in an oven at 120 ° C for 24 hours. After drying, the sample was placed in a muffle furnace, heated to 400 ° C at a heating rate of rC / mm, and calcined for 5 hours to obtain a calcined sample.
  • the rest of the catalysts CAT2 and CAT5 ⁇ 10 were prepared similarly to CAT3 and CAT4.
  • the relationship between the specific preparation conditions of the catalyst and the numbering is shown in Table 1.
  • the catalyst composition determined by XR (X-ray fluorescence spectroscopy, PANalytical, The Netherlands) is shown in Table 2.
  • the reaction volume space velocity in the present invention is defined as the volumetric flow rate of the reaction feedstock (in standard conditions) entering the reaction system per hour divided by the mass of the catalyst. Expressed in GHSV, the unit is mlg - 10 g of 20-40 mesh of the above catalyst is charged into the fixed bed reactor thermostat. Before the reaction, the catalyst was subjected to on-line reduction, the reduction temperature was 260 ° C, the pressure was 0.1 MPa, the reducing gas was 5% H 2 + 95% N 2 , and the reduction time was 24 h.
  • FID column HP-PLOT-Q 19091P-Q04, 30m x 0.32mm (inside diameter), 20 ⁇ film thickness
  • Carrier gas helium, 2 ml/min
  • Oven temperature 50°C-240°C, 10°C/min
  • TCD column carbon molecular sieve column, TDX-01 2m X 2mm (inside diameter)
  • Carrier gas helium, 35ml/min
  • Oven temperature 50°C-240°C, 10°C/min
  • Catalyst CAT4 is co-fed with butyl acetate (C 6 H 12 0 2 ) and syngas (volume composition 87.72% 3 ⁇ 4/11.70% CO/0.58% C 6 H 12 O 2 ) at different temperatures.
  • the reaction performance of C2 ⁇ C4 lower alcohols produced in parallel is shown in Table 4.
  • Catalyst CAT7 was prepared by co-feeding propyl butyrate (C 7 H 14 0 2 ) gas (volume composition 86.20% CO/12.93% CO/0.87% C 7 H 14 O 2 ) under different pressures.
  • the reaction performance of the parallel production of lower alcohols is shown in Table 5.
  • the invention has the advantages that, by using the copper-based catalyst of the invention, the synthesis of methanol and the co-production of C2-C4 lower alcohol are achieved by adding a small amount of a lower ester (the total carbon number of the lower carbon ester is not higher than 8) in the synthesis gas, and The addition of the lower carbon ester promotes the catalytic activity (increased single pass conversion of carbon monoxide) without affecting the catalyst life (the catalyst life is similar to that of the single synthesis gas hydrogenation to methanol).
  • the product composition can be easily regulated by changing the syngas/lower ester feed ratio for flexible operation and greater economics.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

La présente invention concerne un procédé de production de méthanol et de coproduction d'alcools en C2-C4 avec un ester inférieur et un gaz de synthèse co-alimentés en tant que matières premières. Un gaz matière première contenant un ester inférieur et un gaz de synthèse traverse un réacteur équipé d'un catalyseur et des alcools de multiples classes sont produits dans des conditions de température de réaction de 150-350 °C, de pression de réaction de 0,1-20 MPa, de vitesse spatiale du volume réactionnel de 100-40000 mlg-1h-1, et de vitesse spatiale de la masse à faible teneur en carbone de 0,01-3,0 h-1, les composants actifs du catalyseur étant le cuivre et éventuellement le zinc et/ou l'aluminium. Le procédé de la présente invention synthétise du méthanol sur un catalyseur d'un réacteur, et, en même temps, coproduit un certain volume d'alcools en C2-C4 dans des conditions utilisant l'ester inférieur et le gaz de synthèse co-alimentés, le rapport entre les alcools produits étant ajustable.
PCT/CN2013/089536 2013-12-16 2013-12-16 Procédé destiné à être utilisé dans la production de méthanol et la coproduction d'alcools en c2-c4 WO2015089703A1 (fr)

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