WO2023274289A1 - Method for co-production of methanol and ethanol from synthesis gas - Google Patents

Method for co-production of methanol and ethanol from synthesis gas Download PDF

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WO2023274289A1
WO2023274289A1 PCT/CN2022/102266 CN2022102266W WO2023274289A1 WO 2023274289 A1 WO2023274289 A1 WO 2023274289A1 CN 2022102266 W CN2022102266 W CN 2022102266W WO 2023274289 A1 WO2023274289 A1 WO 2023274289A1
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reactor
synthesis gas
methanol
reaction
ethanol
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PCT/CN2022/102266
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French (fr)
Chinese (zh)
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袁兴东
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高化学株式会社
袁兴东
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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
    • B01J23/76—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
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/04—Methanol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/08—Ethanol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
    • 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

Definitions

  • the invention relates to a method for co-producing methanol and ethanol from synthesis gas.
  • Methanol and ethanol are important basic chemical raw materials.
  • methanol is mainly produced from coal-to-synthesis gas.
  • the processes include high-pressure, medium-pressure and low-pressure synthesis methods.
  • medium and low pressure processes are used, and copper-based metal catalysts are mainly used, which have high activity and good selectivity.
  • Ethanol can be used to manufacture acetaldehyde, ethylene, ethylamine, ethyl chloride, etc. It is the basic raw material for medicines, dyes, paints, synthetic rubber, detergents, etc.
  • High potential, good anti-violence performance, etc. can be directly used as liquid fuel or mixed with gasoline to reduce emissions of carbon monoxide, hydrocarbons, particulate matter, nitrogen oxides and benzene-based harmful substances in automobile exhaust, and effectively improve environmental quality. It is of great significance to solve the problem of air pollution and realize sustainable development.
  • the existing ethanol production processes mainly include sugar or cellulose fermentation based on biomass route and ethylene hydration method based on petroleum route.
  • China's fuel ethanol production and sales have grown rapidly, and China has become the world's third largest fuel ethanol producer after the United States and Brazil.
  • the development of new processes for synthesizing ethanol from coal or biomass-based syngas has become an important development direction of the fuel energy industry.
  • CN 109574798 A provides a method for directly producing ethanol from synthesis gas.
  • the method takes syngas as raw material, integrates the processes of methanol synthesis, methanol to dimethyl ether (abbreviated as DME), dimethyl ether carbonylation to methyl acetate (abbreviated as MA) and methyl acetate hydrogenation to ethanol, realizing the synthesis gas to produce ethanol directly.
  • DME dimethyl ether
  • MA dimethyl ether carbonylation to methyl acetate
  • methyl acetate hydrogenation to ethanol directly.
  • the invention reduces the methanol synthesis unit and the corresponding separation unit, and also reduces the separation unit for the carbonylation of dimethyl ether to produce methyl acetate.
  • CN 103012062 B discloses a method for indirectly preparing ethanol from synthesis gas.
  • methanol is first synthesized from synthetic gas formed by mixing hydrogen and carbon monoxide, and methanol is dehydrated to prepare dimethyl ether, and then dimethyl ether is mixed with carbon monoxide and hydrogen for carbonylation reaction to produce methyl acetate.
  • Hydrogen the hydrogenation product is purified to obtain ethanol.
  • the hydrogenation part of the process uses pure hydrogen, which needs to be separated from the synthesis gas first, and also requires a synthesis gas methanol plant, which is economically insufficient.
  • the present invention combines the above two methods and proposes a new method for producing ethanol from synthesis gas, that is, firstly in the first reactor, the synthesis gas is used to react with dimethyl ether to generate methyl acetate and trace acetic acid; By-products of usability and hydrogenation catalyst stability, optionally removal of unconverted DME, purified MA, unreacted synthesis gas from the first reactor enters the second reactor; in order to maintain a high hydrogen-to-ester ratio, the second reactor The effluent from the outlet of the second reactor is circulated into the second reactor after the separated gas, and MA and synthesis gas are reacted in the second reactor to generate methanol and ethanol at the same time; hydrogenation catalysts with different compositions can be selected according to the requirements of the subsequent process.
  • the purpose of the present invention is to overcome some problems in the prior art and provide a method for converting synthesis gas, which can realize the co-production of methanol and ethanol from the synthesis gas.
  • a method for the coproduction of methanol and ethanol by synthesis gas comprising:
  • step d) Optionally, passing methanol from step c) to a third reactor for dehydration to dimethyl ether, and passing the resulting dimethyl ether together with unconverted synthesis gas to said first reactor to circular reaction.
  • volume content of synthesis gas in the raw material is 10-100%
  • the volume content of dimethyl ether is 0-90%
  • the volume of carbon monoxide and hydrogen in the synthesis gas The ratio is 0.1-10; preferably, the volume content of carbon monoxide and hydrogen in the raw material is 50-100%; the volume content of any one or several gases in nitrogen, helium, argon and carbon dioxide in the synthesis gas raw material 0-50%.
  • reaction temperature of the first reactor is 100-300°C, preferably 120-250°C, and the reaction pressure is 0.5-20MPa, preferably 1-15MPa
  • the reaction temperature of the second reactor is 100-300°C, preferably 150-175°C, the reaction pressure is 0.5-20MPa, preferably 1.0-15.0Mpa, the hydrogen-ester ratio is 30-300, preferably 50-150;
  • the third reactor The reaction temperature is 180-420°C, preferably 200-400°C, and the reaction pressure is 0.1-4MPa, preferably 0.2-3MPa.
  • the solid acid catalyst in the first reactor comprises at least one molecular sieve of the following: FER zeolite molecular sieve, MFI zeolite molecular sieve, MOR zeolite Molecular sieves, ETL zeolite molecular sieves, MFS zeolite molecular sieves and their molecular sieve products modified by elements other than framework elements or pyridine, preferably pyridine-modified MOR zeolite molecular sieves.
  • the solid acid catalyst is the hydrogen-form product of the zeolite molecular sieve, or consists of 10-95% by weight of the hydrogen-form product and the balance
  • the matrix constitutes, or is a molecular sieve product obtained by modifying the hydrogen-form product with pyridine, wherein the matrix is at least one selected from alumina, silica, kaolin and magnesia.
  • the copper-based catalyst comprises 15-90% by weight of SiO2 as a support, 5-50% by weight of Cu and 0-50% by weight of transition metals, alkaline earth metals and At least one of the zinc group elements
  • the transition metal is preferably at least one of Fe, Co, W, Mo, Ti, V, Ni, Zr, Pt, Pd and Au
  • the alkaline earth metal is preferably Ca
  • the zinc group element is preferably Zn.
  • the catalyst in the third reactor is a methanol-to-dimethyl ether solid acid catalyst, preferably a molecular sieve-based and oxide-based catalyst, more preferably HZSM- 5.
  • a molecular sieve-based and oxide-based catalyst more preferably HZSM- 5.
  • first reactor and/or the second reactor and/or the third reactor are fixed bed or fluidized bed reactions device, preferably a fixed bed tube reactor.
  • a copper-based catalyst comprising 15-90% by weight of SiO 2 as a carrier, 5-50% by weight of Cu and 0-50% by weight of at least one of transition metals, alkaline earth metals and zinc group elements
  • the transition metal is preferably at least one of Fe, Co, W, Mo, Ti, V, Ni, Zr, Pt, Pd and Au
  • the alkaline earth metal is preferably at least one of Ca, Mg and Ba
  • the zinc group element is preferably Zn.
  • syngas is always used as raw material, which reduces the process of syngas separation and improves economy.
  • the method of the present invention comprises the following steps: dimethyl ether and synthesis gas are contacted and reacted with a solid acid catalyst in a first reactor to obtain an oxygen-containing compound MA; then, after separation, liquid-phase by-products are removed, and unconverted DME.
  • Syngas and purified methyl acetate are contacted and reacted with a hydrogenation catalyst in a second reactor to produce methanol and ethanol; ethanol is then separated as a product and methanol is either separated as a product or in
  • dimethyl ether is generated through dehydration, and the obtained dimethyl ether is circulated into the reaction system and synthetic gas is used as a reaction raw material to enter the first reactor for carbonylation.
  • the method can realize the co-production of methanol and ethanol from synthesis gas, and the ratio of methanol to ethanol can be controlled by selecting hydrogenation catalysts with different compositions.
  • This invention reduces the number of separate methanol synthesis units and uses synthesis gas in the entire process, reducing the Equipment investment and energy consumption, the whole process is simple.
  • the purification of the MA produced in the first reactor improves the corrosion resistance of the second reactor and the stability of the catalyst.
  • a high hydrogen-to-ester ratio is used to improve the stability of the catalyst. This process has a good application prospect.
  • the reaction is completed in the first reactor, the second reactor and optionally the third reactor, the method comprising:
  • the molar ratio of methanol to ethanol is 1.1-5.0, such as 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, more Preferably 1.5-3.0;
  • step d) Optionally, passing methanol from step c) to a third reactor for dehydration to dimethyl ether, and passing the resulting dimethyl ether together with unconverted synthesis gas to said first reactor to circular reaction.
  • the volume content of the synthesis gas in the raw material is 10-100%, such as 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%.
  • the volume content of dimethyl ether in the raw material is 0-90%, such as 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70% , 80%.
  • the volume ratio of carbon monoxide and hydrogen in the synthesis gas in the raw material is 0.1-10, such as 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5 , 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5; the molar ratio of synthesis gas to DME is 10-100, such as 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95.
  • the synthesis gas in addition to carbon monoxide and hydrogen, may also contain any one or several inert gases in nitrogen, helium, argon and carbon dioxide.
  • the volume content of carbon monoxide and hydrogen is 50-100%, such as 60%, 70%, 80%, 90%; any one or several gases in nitrogen, helium, argon and carbon dioxide in the synthesis gas
  • the volume content is 0-50%, such as 10%, 20%, 30%, 40%.
  • the reaction temperature of the first reactor is 100-300°C, such as 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C
  • the reaction pressure is 0.5-20MPa, such as 1MPa, 2MPa, 3MPa, 4MPa, 5MPa , 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, 15MPa, 16MPa, 17MPa, 18MPa, 19MPa
  • CO/DME ratio is 1-20, such as 1, 2, 3, 4, 5, 6 , 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19.
  • the reaction temperature of the second reactor is 100-300°C, such as 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C
  • the reaction pressure is 0.5-20MPa, such as 1MPa, 2MPa, 3MPa, 4MPa, 5MPa , 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, 15MPa, 16MPa, 17MPa, 18MPa, 19MPa
  • hydrogen ester ratio is 30-300, such as 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220,
  • the reaction temperature of the third reactor is 180-420°C, such as 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C
  • the reaction pressure is 0.1- 4MPa, such as 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa.
  • the solid acid catalyst in the first reactor comprises at least one molecular sieve in the following items: FER zeolite molecular sieve, MFI zeolite molecular sieve, MOR zeolite molecular sieve, ETL zeolite molecular sieve, MFS zeolite Molecular sieves and their molecular sieve products modified by elements other than skeleton constituent elements or pyridine, preferably pyridine-modified MOR zeolite molecular sieves.
  • the solid acid catalyst in the first reactor is a pyridine-modified MOR zeolite molecular sieve.
  • a pyridine-modified MOR zeolite molecular sieve Preferably, from 5-95% by weight, such as 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 50% by weight, 55% by weight, 60% by weight , 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight of pyridine modified MOR zeolite molecular sieve obtained.
  • the solid acid catalyst is the hydrogen form of the zeolite molecular sieve, or consists of 10-95% by weight, such as 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight , 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight of the hydrogen-form product and the remainder Matrix composition, or a molecular sieve product obtained by modifying the hydrogen-form product with pyridine.
  • the matrix is at least one selected from alumina, silica, kaolin and magnesia.
  • the catalyst in the second reactor is a hydrogenation catalyst with methanol synthesis and ester hydrogenation properties.
  • the hydrogenation catalyst in the second reactor is a copper-based catalyst.
  • the support of the copper-based catalyst is SiO 2
  • the copper-based catalyst contains 15-90% by weight, such as 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight %, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight of SiO 2 , 5-50% by weight, such as 10% by weight, 15% by weight %, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% Cu and 0-50 wt%, such as 5 wt%, 10 wt%, 15 wt%, 20 wt% , 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight of at least one of transition metals, alkaline earth metals and zinc group elements, the transition metals are preferably Fe, Co, W, Mo, At least one of Ti,
  • step b) of the process according to the invention the effluent from said first reactor is subjected to separation to remove by-products affecting the stability of the hydrogenation catalyst, optionally to remove unconverted DME.
  • the catalyst in the third reactor is a methanol-to-dimethyl ether solid acid catalyst, preferably a molecular sieve-based and oxide-based catalyst, more preferably HZSM-5, ⁇ molecular sieve, silicoaluminophosphoric acid Salt molecular sieves and active Al2O3 and mixtures thereof.
  • the first reactor and/or the second reactor and/or the third reactor is a fixed bed or fluidized bed reactor, preferably a fixed bed tube reaction device.
  • the reaction conditions of the first reactor the reaction temperature is 120-250°C, the reaction pressure is 1-15MPa; the reaction conditions of the second reactor: the reaction temperature is 120-175°C, the reaction The pressure is 1-15MPa; the ratio of hydrogen to ester is 50-150; the reaction conditions of the third reactor: the reaction temperature is 200-400°C, and the reaction pressure is 0.2-3MPa.
  • Inner diameter 14.00mm, 10g Py-MOR catalyst is loaded in the first reactor of the stainless steel column of length 60cm, pass into and contain CO and H Syngas (composition is 32%CO/64%H 2 / 4 %Ar) , the flow rate is 400mL/min.
  • the dimethyl ether was liquefied under pressure, it was pumped into the first reactor at a rate of 0.038 g/min with a micropump.
  • the reaction temperature was 160° C.
  • the reaction pressure was 4.5 MPa
  • the reaction time was 4 hours.
  • On-line sampling of the side line of the reaction effluent for full component analysis was carried out by Shimadzu 2014 gas chromatography, and the detector was FID.
  • the flow rate of MA is 0.04 g/min
  • the gas is synthesis gas (composition is 32% CO/64% H 2 / 4% Ar)
  • the flow rate is 1525mL/min
  • the reaction temperature is 170°C
  • the reaction pressure is 3.0MPa
  • the hydrogen-to-ester ratio is 80
  • the reaction time is 4 hours.
  • the gas phase part is analyzed by TCD.
  • the analysis conditions are that the analytical column is a 4m-long activated carbon stainless steel column, the column temperature is 80 ° C, and the detector temperature is 120 ° C.
  • the conversion rate of CO is calculated; the liquid phase part adopts the same analysis as the first reactor. method.
  • the third reactor uses 5.0 g of dehydration catalyst, and injects methanol separated from the second reactor with a high-pressure liquid pump at a flow rate of 3.5 g/h, a reaction temperature of 270° C., and a pressure of normal pressure. After the reaction, the amount of DME produced was 2.3 g/h.
  • Example 2 The difference from Example 1 is that 10.0 g of catalyst B-2 is loaded into the second reactor. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 2 The difference from Example 1 is that the second reactor is loaded with 10.0 g of catalyst B-3. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 2 The difference from Example 1 is that the second reactor is loaded with 10.0 g of catalyst B-4. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 2 The difference from Example 1 is that the second reactor is loaded with 10.0 g of catalyst B-5. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 2 The difference from Example 1 is that the second reactor is loaded with 10.0 g of catalyst B-6. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 2 The difference from Example 1 is that the second reactor is loaded with 10.0 g of catalyst B-7. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 2 The difference from Example 1 is that the second reactor is loaded with 4.0 g of Catalyst B-6. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 2 The difference from Example 1 was that the second reactor was charged with 7.0 g of Catalyst B-6. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 2 The difference from Example 1 is that the second reactor is loaded with 13.0 g of catalyst B-6. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • the difference with embodiment 6 is that in the first reactor, the upper section is loaded with 10.0g Py-MOR catalyst, and the lower section is loaded with 10.0g B-6 catalyst, and the second reactor is removed. Sampling and analysis after 4 hours of reaction, the reaction results at the outlet of the first reactor are as follows: the conversion rate of DME is 70.5%, the conversion rate of CO is 24.60%, and the product composition is 1.23% of MA, 60.00% of methanol, and 34.97% of ethanol and 3.80% other.
  • Example 6 The difference from Example 6 is that the gas raw material of the second reactor is pure hydrogen. After reacting for 4 hours, samples were taken and analyzed, and the results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that the effluent from the outlet of the first reactor directly enters the second reactor without further separation after being separated to remove unconverted DME. After reacting for 4 hours, samples were taken and analyzed, and the results at the outlet of the second reactor are shown in Table 2.
  • the difference with embodiment 1 is that the second reactor is loaded with 10.0g catalyst B-1'. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that the reaction temperature of the second reactor is 160°C. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that the reaction temperature of the second reactor is 165°C. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that the reaction temperature of the second reactor is 175°C. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that the flow rate of the synthesis gas in the second reactor is 762.5 mL/min, and the ratio of hydrogen to ester is 40. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that the flow rate of the synthesis gas in the second reactor is 1144mL/min, and the ratio of hydrogen to ester is 60. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that the flow rate of the synthesis gas in the second reactor is 1906 mL/min, and the ratio of hydrogen to ester is 100. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that the flow rate of the synthesis gas in the second reactor is 2288mL/min, and the ratio of hydrogen to ester is 120. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that the sample was analyzed after 100 hours of reaction, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that after 500 hours of reaction, samples were taken for analysis, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that after 1000 hours of reaction, samples were taken for analysis, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that after 1500 hours of reaction, sampling and analysis are performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
  • Example 6 The difference from Example 6 is that after 2000 hours of reaction, sampling and analysis, the reaction results at the outlet of the second reactor are shown in Table 2.

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  • Organic Chemistry (AREA)
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Abstract

The present invention relates to a method for co-production of methanol and ethanol from a synthesis gas, the reaction process being completed in three reactors. The method comprises: a) causing raw material synthesis gas and dimethyl ether to enter a first reactor to contact a solid acid catalyst in the first reactor to react, obtaining an effluent containing methyl acetate and/or acetic acid; b) causing the effluent from the first reactor to undergo separation and purification, and causing purified MA and synthesis gas to enter a second reactor to contact a hydrogenation catalyst in the second reactor and undergo a reaction, obtaining an effluent containing methanol and ethanol; c) separating the effluent from the second reactor, obtaining product methanol and ethanol; and d) optionally, causing methanol from step c) to enter a third reactor so as to perform a dehydration reaction, obtaining dimethyl ether, and causing the obtained dimethyl ether and unconverted synthesis gas to enter the first reactor for cyclic reaction. The present process has the flexibility to generate methanol and ethanol from a synthesis gas, and at the same time solves the problem of stability of the MA hydrogenation catalyst. Compared with indirect methods, it does not have the step of producing methanol from a synthesis gas, nor does it require separation of carbon monoxide and hydrogen from the synthesis gas, and co-production of methanol and ethanol from the synthesis gas can be achieved.

Description

一种由合成气联产甲醇与乙醇的方法A method for the co-production of methanol and ethanol from synthesis gas 技术领域technical field
本发明涉及一种由合成气联产甲醇与乙醇的方法。The invention relates to a method for co-producing methanol and ethanol from synthesis gas.
背景技术Background technique
甲醇与乙醇是重要的基本化工原料。目前甲醇主要从煤制合成气制备，工艺有高压、中压和低压合成法，一般采用中低压工艺，主要采用铜基金属催化剂，活性高、选择性好。乙醇可以用于制造乙醛、乙烯、乙胺、氯乙烷等，是医药、染料、涂料、合成橡胶、洗涤剂等产品的基础原料，同时在燃料能源产业应用中具有热值低、气化潜能高、抗暴性能好等特点，可直接用作液体燃料或同汽油混合使用，以降低汽车尾气中一氧化碳、碳氢化合物、颗粒物、氮氧化合物及苯系有害物的排放，有效改善环境质量，对解决大气污染问题，实现可持续发展具有重要意义。现有的乙醇生产工艺主要有基于生物质路线的糖类或纤维素发酵法和基于石油路线的乙烯水合法。近年来，中国燃料乙醇产销量迅速增长，已经成为继美国、巴西之后的世界第三大燃料乙醇生产国。基于中国煤资源相对丰富的能源结构现状，发展以煤或生物质基合成气合成乙醇的新工艺，已经成为燃料能源工业的重要发展方向。Methanol and ethanol are important basic chemical raw materials. At present, methanol is mainly produced from coal-to-synthesis gas. The processes include high-pressure, medium-pressure and low-pressure synthesis methods. Generally, medium and low pressure processes are used, and copper-based metal catalysts are mainly used, which have high activity and good selectivity. Ethanol can be used to manufacture acetaldehyde, ethylene, ethylamine, ethyl chloride, etc. It is the basic raw material for medicines, dyes, paints, synthetic rubber, detergents, etc. High potential, good anti-violence performance, etc., can be directly used as liquid fuel or mixed with gasoline to reduce emissions of carbon monoxide, hydrocarbons, particulate matter, nitrogen oxides and benzene-based harmful substances in automobile exhaust, and effectively improve environmental quality. It is of great significance to solve the problem of air pollution and realize sustainable development. The existing ethanol production processes mainly include sugar or cellulose fermentation based on biomass route and ethylene hydration method based on petroleum route. In recent years, China's fuel ethanol production and sales have grown rapidly, and China has become the world's third largest fuel ethanol producer after the United States and Brazil. Based on the status quo of China's energy structure with relatively abundant coal resources, the development of new processes for synthesizing ethanol from coal or biomass-based syngas has become an important development direction of the fuel energy industry.
CN 109574798 A提供了一种合成气直接生产乙醇的方法。该方法以合成气为原料，整合了甲醇合成、甲醇制二甲醚(简称DME)、二甲醚羰基化制乙酸甲酯(简称MA)以及乙酸甲酯加氢制乙醇的过程，实现了合成气直接生产乙醇。该发明减少了甲醇合成单元以及相应的分离单元，还减少了二甲醚羰基化制乙酸甲酯的分离单元。但是二甲醚羰基化过程中会生成乙酸等副产物，乙酸具有较强的腐蚀性，尤其是对后段加氢反应器具有腐蚀性，对加氢催化剂的稳定性 也有影响；同时，第二反应器中氢气/乙酸甲酯的比值(氢酯比)低，影响加氢催化剂的稳定性。该发明没有提到工艺的稳定性问题。CN 109574798 A provides a method for directly producing ethanol from synthesis gas. The method takes syngas as raw material, integrates the processes of methanol synthesis, methanol to dimethyl ether (abbreviated as DME), dimethyl ether carbonylation to methyl acetate (abbreviated as MA) and methyl acetate hydrogenation to ethanol, realizing the synthesis gas to produce ethanol directly. The invention reduces the methanol synthesis unit and the corresponding separation unit, and also reduces the separation unit for the carbonylation of dimethyl ether to produce methyl acetate. However, by-products such as acetic acid will be generated during the carbonylation of dimethyl ether, and acetic acid is highly corrosive, especially to the subsequent hydrogenation reactor, and also has an impact on the stability of the hydrogenation catalyst; meanwhile, the second The hydrogen/methyl acetate ratio (hydrogen ester ratio) in the reactor is low, which affects the stability of the hydrogenation catalyst. This invention does not mention the stability problem of process.
CN 103012062 B公开了一种合成气间接制备乙醇的方法。该方法先以氢气和一氧化碳混合形成的合成气为原料合成甲醇，甲醇再脱水制备二甲醚，然后二甲醚与一氧化碳和氢气混合进行羰基化反应制乙酸甲酯，乙酸甲酯经纯化进行加氢，加氢产物经纯化得到乙醇。该工艺加氢部分使用纯氢，需要首先从合成气进行分离得到，另外还需要一个合成气制甲醇装置，经济上具有不足。CN 103012062 B discloses a method for indirectly preparing ethanol from synthesis gas. In this method, methanol is first synthesized from synthetic gas formed by mixing hydrogen and carbon monoxide, and methanol is dehydrated to prepare dimethyl ether, and then dimethyl ether is mixed with carbon monoxide and hydrogen for carbonylation reaction to produce methyl acetate. Hydrogen, the hydrogenation product is purified to obtain ethanol. The hydrogenation part of the process uses pure hydrogen, which needs to be separated from the synthesis gas first, and also requires a synthesis gas methanol plant, which is economically insufficient.
发明内容Contents of the invention
本发明人经过研究，认为直接法虽然工艺简单、流程短，但是具有腐蚀性和影响加氢催化剂稳定性的问题；而间接法具有工艺流程长、经济上不合理的问题。本发明结合上述两方法，对合成气制乙醇提出了一种新方法，即首先在第一反应器中，采用合成气与二甲醚反应，生成乙酸甲酯和微量乙酸；经过分离去除影响装置使用性和加氢催化剂稳定性的副产物，任选地去除未转化的DME，经纯化的MA、第一反应器未反应的合成气进入第二反应器；为了保持高的氢酯比，第二反应器出口流出物经分离后的气体循环打入第二反应器，MA与合成气在第二反应器中进行反应，同时生成甲醇和乙醇；选择不同组成的加氢催化剂可以按后续工艺的需要生成不同比例的甲醇与乙醇混合物，尤其是甲醇与乙醇的摩尔比为1.1-5.0的混合物，经过分离，分别得到纯的甲醇与乙醇。甲醇与乙醇可以直接作为产品得到，甲醇也可以再进入一个脱水反应器生成第一个羰基化反应器所需要的DME。该工艺具有从合成气生成甲醇与乙醇的灵活性，同时在第二反应器可以采用高的氢酯比，解决了MA加氢催化剂稳定性问题，与间接法相比，没有合成气制甲醇步骤，也不需要从合成气分离一氧化碳和氢气，从而可以实现由合成气联产甲醇与乙醇。After research, the inventors believe that although the direct method has a simple process and a short process, it has the problems of corrosion and affecting the stability of the hydrogenation catalyst; while the indirect method has the problems of long process and unreasonable economy. The present invention combines the above two methods and proposes a new method for producing ethanol from synthesis gas, that is, firstly in the first reactor, the synthesis gas is used to react with dimethyl ether to generate methyl acetate and trace acetic acid; By-products of usability and hydrogenation catalyst stability, optionally removal of unconverted DME, purified MA, unreacted synthesis gas from the first reactor enters the second reactor; in order to maintain a high hydrogen-to-ester ratio, the second reactor The effluent from the outlet of the second reactor is circulated into the second reactor after the separated gas, and MA and synthesis gas are reacted in the second reactor to generate methanol and ethanol at the same time; hydrogenation catalysts with different compositions can be selected according to the requirements of the subsequent process. It is necessary to generate mixtures of methanol and ethanol in different proportions, especially mixtures with a molar ratio of methanol to ethanol of 1.1-5.0, which are separated to obtain pure methanol and ethanol respectively. Methanol and ethanol can be directly obtained as products, and methanol can also enter a dehydration reactor to generate DME required by the first carbonylation reactor. This process has the flexibility to generate methanol and ethanol from synthesis gas, and at the same time, a high hydrogen-to-ester ratio can be used in the second reactor, which solves the stability problem of MA hydrogenation catalyst. Compared with the indirect method, there is no synthesis gas to methanol step, There is also no need to separate carbon monoxide and hydrogen from the synthesis gas, so that the co-production of methanol and ethanol from the synthesis gas can be achieved.
本发明的目的是克服现有技术中的一些问题，提供一种合成气转化的方法，利用该方法可以实现由合成气联产甲醇和乙醇。The purpose of the present invention is to overcome some problems in the prior art and provide a method for converting synthesis gas, which can realize the co-production of methanol and ethanol from the synthesis gas.
实现本发明的上述目的的实施方案可概括如下：The embodiment that realizes above-mentioned object of the present invention can be summarized as follows:
1.一种由合成气联产甲醇与乙醇的方法，包括：1. A method for the coproduction of methanol and ethanol by synthesis gas, comprising:
a)使作为原料的合成气和二甲醚进入第一反应器，以与所述第一反应器中的固体酸催化剂接触并发生反应，得到含有乙酸甲酯和/或乙酸的流出物；a) making synthesis gas and dimethyl ether as raw materials enter a first reactor to contact and react with the solid acid catalyst in the first reactor to obtain an effluent containing methyl acetate and/or acetic acid;
b)使来自所述第一反应器的流出物经过分离而纯化，经纯化的MA与合成气进入第二反应器，以与所述第二反应器中的加氢催化剂接触并发生反应，得到含有甲醇和乙醇的流出物；b) separating and purifying the effluent from said first reactor, the purified MA and synthesis gas entering a second reactor to contact and react with a hydrogenation catalyst in said second reactor to obtain Effluents containing methanol and ethanol;
c)对来自所述第二反应器的流出物进行分离，得到产物甲醇和乙醇，优选甲醇与乙醇的摩尔比为1.1-5.0，更优选1.5-3.0；c) separating the effluent from the second reactor to obtain the products methanol and ethanol, preferably with a molar ratio of methanol to ethanol of 1.1-5.0, more preferably 1.5-3.0;
d)任选地，使来自步骤c)的甲醇进入第三反应器以进行脱水反应，得到二甲醚，并使所得到的二甲醚以及未转化的合成气进入所述第一反应器以循环反应。d) Optionally, passing methanol from step c) to a third reactor for dehydration to dimethyl ether, and passing the resulting dimethyl ether together with unconverted synthesis gas to said first reactor to circular reaction.
2.根据实施方案1所述的方法，其中所述原料中合成气的体积含量为10-100％，二甲醚的体积含量为0-90％，并且所述合成气中一氧化碳与氢气的体积比为0.1-10；优选地，所述原料中一氧化碳和氢气的体积含量为50-100％；氮气、氦气、氩气和二氧化碳中的任意一种或几种气体在合成气原料的体积含量为0-50％。2. The method according to embodiment 1, wherein the volume content of synthesis gas in the raw material is 10-100%, the volume content of dimethyl ether is 0-90%, and the volume of carbon monoxide and hydrogen in the synthesis gas The ratio is 0.1-10; preferably, the volume content of carbon monoxide and hydrogen in the raw material is 50-100%; the volume content of any one or several gases in nitrogen, helium, argon and carbon dioxide in the synthesis gas raw material 0-50%.
3.根据实施方案1或2所述的方法，其中所述第一反应器的反应温度为100-300℃，优选120-250℃，反应压力为0.5-20MPa，优选1-15MPa；所述第二反应器的反应温度为100-300℃，优选150-175℃，反应压力为0.5-20MPa，优选1.0-15.0Mpa，氢酯比为30-300，优选50-150；所述第三反应器的反应温度为180-420℃，优选200-400℃，反应压力为0.1-4MPa，优选0.2-3MPa。3. The method according to embodiment 1 or 2, wherein the reaction temperature of the first reactor is 100-300°C, preferably 120-250°C, and the reaction pressure is 0.5-20MPa, preferably 1-15MPa; The reaction temperature of the second reactor is 100-300°C, preferably 150-175°C, the reaction pressure is 0.5-20MPa, preferably 1.0-15.0Mpa, the hydrogen-ester ratio is 30-300, preferably 50-150; the third reactor The reaction temperature is 180-420°C, preferably 200-400°C, and the reaction pressure is 0.1-4MPa, preferably 0.2-3MPa.
4.根据实施方案1-3中任一项所述的方法，其中所述第一反应器中的固体酸催化剂包含以下各项中的至少一种分子筛：FER沸石分子筛、MFI沸石分子筛、MOR沸石分子筛、ETL沸石分子筛、MFS沸石分子筛以及它们经骨架组成元素以外的元素或吡啶改性得到的分子筛产物，优选吡啶改性的MOR沸石分子筛。4. The method of any one of embodiments 1-3, wherein the solid acid catalyst in the first reactor comprises at least one molecular sieve of the following: FER zeolite molecular sieve, MFI zeolite molecular sieve, MOR zeolite Molecular sieves, ETL zeolite molecular sieves, MFS zeolite molecular sieves and their molecular sieve products modified by elements other than framework elements or pyridine, preferably pyridine-modified MOR zeolite molecular sieves.
5.根据实施方案1-4中任一项所述的方法，其中所述固体酸催化剂是所述沸石分子筛的氢型产物，或者由10-95重量％的所述氢型产物和余量的基质构成，或者是所述氢型产物经吡啶改性得到的分子筛产物，其中所述基质为选自氧化铝、氧化硅、高岭土和氧化镁中的至少一种。5. The method according to any one of embodiments 1-4, wherein the solid acid catalyst is the hydrogen-form product of the zeolite molecular sieve, or consists of 10-95% by weight of the hydrogen-form product and the balance The matrix constitutes, or is a molecular sieve product obtained by modifying the hydrogen-form product with pyridine, wherein the matrix is at least one selected from alumina, silica, kaolin and magnesia.
6.根据实施方案1-5中任一项所述的方法，其中所述第二反应器中的加氢催化剂为铜基催化剂。6. The method of any one of embodiments 1-5, wherein the hydrogenation catalyst in the second reactor is a copper-based catalyst.
7.根据实施方案6所述的方法，其中所述铜基催化剂包含15-90重量％的作为载体的SiO 2，5-50重量％的Cu和0-50重量％的过渡金属、碱土金属和锌族元素中的至少一种，所述过渡金属优选为Fe、Co、W、Mo、Ti、V、Ni、Zr、Pt、Pd和Au中的至少一种，所述碱土金属优选为Ca、Mg和Ba中的至少一种，所述锌族元素优选为Zn。 7. The method according to embodiment 6, wherein the copper-based catalyst comprises 15-90% by weight of SiO2 as a support, 5-50% by weight of Cu and 0-50% by weight of transition metals, alkaline earth metals and At least one of the zinc group elements, the transition metal is preferably at least one of Fe, Co, W, Mo, Ti, V, Ni, Zr, Pt, Pd and Au, and the alkaline earth metal is preferably Ca, At least one of Mg and Ba, the zinc group element is preferably Zn.
8.根据实施方案1-7中任一项所述的方法，其中所述第三反应器中的催化剂为甲醇制二甲醚固体酸催化剂，优选分子筛基和氧化物基催化剂，更优选HZSM-5、β分子筛、硅铝磷酸盐分子筛和活性Al 2O 3及其混合物。 8. The method according to any one of embodiments 1-7, wherein the catalyst in the third reactor is a methanol-to-dimethyl ether solid acid catalyst, preferably a molecular sieve-based and oxide-based catalyst, more preferably HZSM- 5. β molecular sieve, silicoaluminophosphate molecular sieve and active Al 2 O 3 and their mixtures.
9.根据实施方案1-8中任一项所述的方法，其中所述第一反应器和/或所述第二反应器和/或所述第三反应器为固定床或流化床反应器，优选固定床列管反应器。9. The process according to any one of embodiments 1-8, wherein the first reactor and/or the second reactor and/or the third reactor are fixed bed or fluidized bed reactions device, preferably a fixed bed tube reactor.
10.一种铜基催化剂，包含15-90重量％的作为载体的SiO 2，5-50重量％的Cu和0-50重量％的过渡金属、碱土金属和锌族元素中的至少一种，所述过渡金属优选为Fe、Co、W、Mo、Ti、V、Ni、Zr、Pt、Pd和Au中的至少一种，所述碱土金属优选为Ca、Mg和Ba中的至少一种，所述锌族元素优选为Zn。 10. A copper-based catalyst comprising 15-90% by weight of SiO 2 as a carrier, 5-50% by weight of Cu and 0-50% by weight of at least one of transition metals, alkaline earth metals and zinc group elements, The transition metal is preferably at least one of Fe, Co, W, Mo, Ti, V, Ni, Zr, Pt, Pd and Au, and the alkaline earth metal is preferably at least one of Ca, Mg and Ba, The zinc group element is preferably Zn.
本发明包括但不限于以下有益效果：The present invention includes but not limited to the following beneficial effects:
1、提供一种由合成气联产甲醇和乙醇的方法，该方法简化了合成气制甲醇装置，采用合成气作为气源在加氢反应器上实现了联产甲醇与乙醇，甲醇与乙醇的摩尔比可以在1.1-5.0之间灵活调整。由于对第一反应器的流出物进行了纯化处理，同时在第二反应器中采用了高的氢酯比，保障了第二反应器的催化剂使用寿命。1. Provide a method for the co-production of methanol and ethanol from synthesis gas. This method simplifies the synthesis gas-to-methanol plant, and uses synthesis gas as the gas source to realize the co-production of methanol and ethanol and the combination of methanol and ethanol on the hydrogenation reactor. The molar ratio can be flexibly adjusted between 1.1-5.0. Since the effluent of the first reactor is purified and a high hydrogen-ester ratio is adopted in the second reactor, the service life of the catalyst in the second reactor is ensured.
2、本发明的工艺流程中一直采用合成气作为原料，减少了合成气分离的过程，提高了经济性。2. In the technological process of the present invention, syngas is always used as raw material, which reduces the process of syngas separation and improves economy.
具体实施方式detailed description
本发明的方法包括以下步骤：二甲醚和合成气与固体酸催化剂在第一反应器接触发生反应，得到含氧化合物MA；然后，经过分离，去除液相副产物，任选地去除未转化的DME。The method of the present invention comprises the following steps: dimethyl ether and synthesis gas are contacted and reacted with a solid acid catalyst in a first reactor to obtain an oxygen-containing compound MA; then, after separation, liquid-phase by-products are removed, and unconverted DME.
合成气和经纯化的乙酸甲酯与加氢催化剂在第二反应器中接触并发生反应，生成甲醇和乙醇；随后，乙醇作为产物被分离出去，甲醇既可以作为产物被分离出去，也可以在第三反应器中经脱水生成二甲醚，将所得的二甲醚循环进入反应系统与合成气作为反应原料进入第一反应器羰基化。该方法可以实现由合成气联产甲醇与乙醇，甲醇与乙醇比可以通过选择不同组成的加氢催化剂来控制，该发明减少了单独的甲醇合成单元、在整个工艺流程中采用合成气，降低了设备投资及能耗，整个工艺过程简单。另外，对第一反应器中生成的MA进行纯化，提高了第二反应器的抗腐蚀性与催化剂的稳定性，同时，采用高的氢酯比，提高催化剂稳定性，该工艺应用前景好。Syngas and purified methyl acetate are contacted and reacted with a hydrogenation catalyst in a second reactor to produce methanol and ethanol; ethanol is then separated as a product and methanol is either separated as a product or in In the third reactor, dimethyl ether is generated through dehydration, and the obtained dimethyl ether is circulated into the reaction system and synthetic gas is used as a reaction raw material to enter the first reactor for carbonylation. The method can realize the co-production of methanol and ethanol from synthesis gas, and the ratio of methanol to ethanol can be controlled by selecting hydrogenation catalysts with different compositions. This invention reduces the number of separate methanol synthesis units and uses synthesis gas in the entire process, reducing the Equipment investment and energy consumption, the whole process is simple. In addition, the purification of the MA produced in the first reactor improves the corrosion resistance of the second reactor and the stability of the catalyst. At the same time, a high hydrogen-to-ester ratio is used to improve the stability of the catalyst. This process has a good application prospect.
更具体地，在本发明的由合成气联产甲醇与乙醇的方法中，反应在第一反应器、第二反应器和任选地第三反应器中完成，所述方法包括：More specifically, in the method for the co-production of methanol and ethanol from synthesis gas of the present invention, the reaction is completed in the first reactor, the second reactor and optionally the third reactor, the method comprising:
a)使作为原料的合成气和二甲醚进入第一反应器，以与所述第一反应器中的固体酸催化剂接触并发生反应，得到含有乙酸甲酯和/或乙酸的流出物；a) making synthesis gas and dimethyl ether as raw materials enter a first reactor to contact and react with the solid acid catalyst in the first reactor to obtain an effluent containing methyl acetate and/or acetic acid;
b)使来自所述第一反应器的流出物经过分离而纯化，经纯化的MA与合成气进入第二反应器，以与所述第二反应器中的加氢催化剂接触并发生反应，得到含有甲醇和乙醇的流出物；b) separating and purifying the effluent from said first reactor, the purified MA and synthesis gas entering a second reactor to contact and react with a hydrogenation catalyst in said second reactor to obtain Effluents containing methanol and ethanol;
c)对来自所述第二反应器的流出物进行分离，得到产物甲醇和乙醇，优选甲醇与乙醇的摩尔比为1.1-5.0，例如1.5，2.0，2.5，3.0，3.5，4.0，4.5，更优选1.5-3.0；c) separating the effluent from the second reactor to obtain the products methanol and ethanol, preferably the molar ratio of methanol to ethanol is 1.1-5.0, such as 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, more Preferably 1.5-3.0;
d)任选地，使来自步骤c)的甲醇进入第三反应器以进行脱水反应，得到二甲醚，并使所得到的二甲醚以及未转化的合成气进入所述第一反应器以循环反应。d) Optionally, passing methanol from step c) to a third reactor for dehydration to dimethyl ether, and passing the resulting dimethyl ether together with unconverted synthesis gas to said first reactor to circular reaction.
在本发明方法的一个实施方案中，所述原料中合成气的体积含量为10-100％，例如20％，30％，40％，50％，60％，70％，80％，90％。In one embodiment of the method of the present invention, the volume content of the synthesis gas in the raw material is 10-100%, such as 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%.
在本发明方法的一个实施方案中，所述原料中二甲醚的体积含量为0-90％，例如5％，10％，20％，30％，40％，50％，60％，70％，80％。In one embodiment of the method of the present invention, the volume content of dimethyl ether in the raw material is 0-90%, such as 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70% , 80%.
在本发明方法的一个实施方案中，所述原料中合成气中一氧化碳与氢气的体积比为0.1-10，例如0.5，1.0，1.5，2.0，2.5，3.0，3.5，4.0，4.5，5.0，5.5，6.0，6.5，7.0，7.5，8.0，8.5，9.0，9.5；合成气与DME的摩尔比为10-100，例如15，20，25，30，35，40，45，50，55，60，65，70，75，80，85，90，95。In one embodiment of the method of the present invention, the volume ratio of carbon monoxide and hydrogen in the synthesis gas in the raw material is 0.1-10, such as 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5 , 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5; the molar ratio of synthesis gas to DME is 10-100, such as 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95.
在本发明方法的一个实施方案中，除了一氧化碳和氢气之外，合成气也可含有氮气、氦气、氩气和二氧化碳中的任意一种或几种惰性气体。优选地，一氧化碳和氢气的体积含量为50-100％，例如60％，70％，80％，90％；氮气、氦气、氩气和二氧化碳中的任意一种或几种气体在合成气中的体积含量为0-50％，例如10％，20％，30％，40％。In one embodiment of the method of the present invention, in addition to carbon monoxide and hydrogen, the synthesis gas may also contain any one or several inert gases in nitrogen, helium, argon and carbon dioxide. Preferably, the volume content of carbon monoxide and hydrogen is 50-100%, such as 60%, 70%, 80%, 90%; any one or several gases in nitrogen, helium, argon and carbon dioxide in the synthesis gas The volume content is 0-50%, such as 10%, 20%, 30%, 40%.
在本发明方法的一个实施方案中，所述第一反应器的反应温度为100-300℃，例如110℃，120℃，130℃，140℃，150℃，160℃，170℃，180℃，190℃，200℃，210℃，220℃，230℃，240℃，250℃，260℃，270℃，280℃，290℃，反应压力为0.5-20MPa，例如1MPa，2MPa，3MPa，4MPa，5MPa，6MPa，7MPa，8MPa，9MPa，10MPa，11MPa，12MPa，13MPa，14MPa，15MPa，16MPa，17MPa，18MPa，19MPa；CO/DME比为1-20，例如1，2，3，4，5，6，7，8，9，10，11，12，13，14，15，16，17，18，19。In one embodiment of the method of the present invention, the reaction temperature of the first reactor is 100-300°C, such as 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, the reaction pressure is 0.5-20MPa, such as 1MPa, 2MPa, 3MPa, 4MPa, 5MPa , 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, 15MPa, 16MPa, 17MPa, 18MPa, 19MPa; CO/DME ratio is 1-20, such as 1, 2, 3, 4, 5, 6 , 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19.
在本发明方法的一个实施方案中，所述第二反应器的反应温度为100-300℃，例如110℃，120℃，130℃，140℃，150℃，160℃，170℃，180℃，190℃，200℃，210℃，220℃，230℃，240℃，250℃，260℃，270℃，280℃，290℃， 反应压力为0.5-20MPa，例如1MPa，2MPa，3MPa，4MPa，5MPa，6MPa，7MPa，8MPa，9MPa，10MPa，11MPa，12MPa，13MPa，14MPa，15MPa，16MPa，17MPa，18MPa，19MPa；氢酯比为30-300，例如40，50，60，70，80，90，100，110，120，130，140，150，160，170，180，190，200，210，220，230，240，250，260，270，280，290。In one embodiment of the method of the present invention, the reaction temperature of the second reactor is 100-300°C, such as 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, the reaction pressure is 0.5-20MPa, such as 1MPa, 2MPa, 3MPa, 4MPa, 5MPa , 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, 15MPa, 16MPa, 17MPa, 18MPa, 19MPa; hydrogen ester ratio is 30-300, such as 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290.
在本发明方法的一个实施方案中，所述第三反应器的反应温度为180-420℃，例如190℃，200℃，210℃，220℃，230℃，240℃，250℃，260℃，270℃，280℃，290℃，300℃，310℃，320℃，330℃，340℃，350℃，360℃，370℃，380℃，390℃，400℃，410℃，反应压力为0.1-4MPa，例如0.5MPa，1MPa，1.5MPa，2MPa，2.5MPa，3MPa，3.5MPa。In one embodiment of the method of the present invention, the reaction temperature of the third reactor is 180-420°C, such as 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, the reaction pressure is 0.1- 4MPa, such as 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa.
在本发明方法的一个实施方案中，所述第一反应器中的固体酸催化剂包含以下各项中的至少一种分子筛：FER沸石分子筛、MFI沸石分子筛、MOR沸石分子筛、ETL沸石分子筛、MFS沸石分子筛以及它们经骨架组成元素以外的元素或吡啶改性得到的分子筛产物，优选吡啶改性的MOR沸石分子筛。In one embodiment of the method of the present invention, the solid acid catalyst in the first reactor comprises at least one molecular sieve in the following items: FER zeolite molecular sieve, MFI zeolite molecular sieve, MOR zeolite molecular sieve, ETL zeolite molecular sieve, MFS zeolite Molecular sieves and their molecular sieve products modified by elements other than skeleton constituent elements or pyridine, preferably pyridine-modified MOR zeolite molecular sieves.
优选地，第一反应器中的固体酸催化剂为吡啶改性的MOR沸石分子筛。优选地，由5-95重量％，例如10重量％，15重量％，20重量％，25重量％，30重量％，35重量％，40重量％，50重量％，55重量％，60重量％，65重量％，70重量％，75重量％，80重量％，85重量％，90重量％的吡啶改性得到的MOR沸石分子筛。Preferably, the solid acid catalyst in the first reactor is a pyridine-modified MOR zeolite molecular sieve. Preferably, from 5-95% by weight, such as 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 50% by weight, 55% by weight, 60% by weight , 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight of pyridine modified MOR zeolite molecular sieve obtained.
优选地，所述固体酸催化剂是所述沸石分子筛的氢型产物，或者由10-95重量％，例如15重量％，20重量％，25重量％，30重量％，35重量％，40重量％，45重量％，50重量％，55重量％，60重量％，65重量％，70重量％，75重量％，80重量％，85重量％，90重量％的所述氢型产物和余量的基质构成，或者是所述氢型产物经吡啶改性得到的分子筛产物。Preferably, the solid acid catalyst is the hydrogen form of the zeolite molecular sieve, or consists of 10-95% by weight, such as 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight , 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight of the hydrogen-form product and the remainder Matrix composition, or a molecular sieve product obtained by modifying the hydrogen-form product with pyridine.
优选地，所述基质为选自氧化铝、氧化硅、高岭土和氧化镁中的至少一种。Preferably, the matrix is at least one selected from alumina, silica, kaolin and magnesia.
在本发明方法的一个实施方案中，所述第二反应器中的催化剂为具有甲醇 合成以及酯加氢性能的加氢催化剂。In one embodiment of the inventive method, the catalyst in the second reactor is a hydrogenation catalyst with methanol synthesis and ester hydrogenation properties.
优选地，所述第二反应器中的加氢催化剂为铜基催化剂。Preferably, the hydrogenation catalyst in the second reactor is a copper-based catalyst.
更优选地，所述铜基催化剂的载体为SiO 2，所述铜基催化剂包含15-90重量％，例如20重量％，25重量％，30重量％，35重量％，40重量％，45重量％，50重量％，55重量％，60重量％，65重量％，70重量％，75重量％，80重量％，85重量％的SiO 2，5-50重量％，例如10重量％，15重量％，20重量％，25重量％，30重量％，35重量％，40重量％，45重量％的Cu和0-50重量％，例如5重量％，10重量％，15重量％，20重量％，25重量％，30重量％，35重量％，40重量％，45重量％的过渡金属、碱土金属和锌族元素中的至少一种，所述过渡金属优选为Fe、Co、W、Mo、Ti、V、Ni、Zr、Pt、Pd和Au中的至少一种，所述碱土金属优选为Ca、Mg和Ba中的至少一种，所述锌族元素优选为Zn。 More preferably, the support of the copper-based catalyst is SiO 2 , and the copper-based catalyst contains 15-90% by weight, such as 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight %, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight of SiO 2 , 5-50% by weight, such as 10% by weight, 15% by weight %, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% Cu and 0-50 wt%, such as 5 wt%, 10 wt%, 15 wt%, 20 wt% , 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight of at least one of transition metals, alkaline earth metals and zinc group elements, the transition metals are preferably Fe, Co, W, Mo, At least one of Ti, V, Ni, Zr, Pt, Pd and Au, the alkaline earth metal is preferably at least one of Ca, Mg and Ba, and the zinc group element is preferably Zn.
在本发明方法的步骤b)的一个实施方案中，使来自所述第一反应器的流出物经过分离去除影响加氢催化剂稳定性的副产物，任选地去除未转化的DME。In one embodiment of step b) of the process according to the invention, the effluent from said first reactor is subjected to separation to remove by-products affecting the stability of the hydrogenation catalyst, optionally to remove unconverted DME.
在本发明方法的一个实施方案中，所述第三反应器中的催化剂为甲醇制二甲醚固体酸催化剂，优选分子筛基和氧化物基催化剂，更优选HZSM-5、β分子筛、硅铝磷酸盐分子筛和活性Al 2O 3及其混合物。 In one embodiment of the method of the present invention, the catalyst in the third reactor is a methanol-to-dimethyl ether solid acid catalyst, preferably a molecular sieve-based and oxide-based catalyst, more preferably HZSM-5, β molecular sieve, silicoaluminophosphoric acid Salt molecular sieves and active Al2O3 and mixtures thereof.
在本发明方法的一个实施方案中，所述第一反应器和/或所述第二反应器和/或所述第三反应器为固定床或流化床反应器，优选固定床列管反应器。In one embodiment of the method of the present invention, the first reactor and/or the second reactor and/or the third reactor is a fixed bed or fluidized bed reactor, preferably a fixed bed tube reaction device.
在进一步优选的实施方案中，所述第一反应器的反应条件：反应温度为120-250℃，反应压力为1-15MPa；第二反应器的反应条件：反应温度为120-175℃，反应压力为1-15MPa；氢酯比为50-150；第三反应器的反应条件：反应温度为200-400℃，反应压力为0.2-3MPa。In a further preferred embodiment, the reaction conditions of the first reactor: the reaction temperature is 120-250°C, the reaction pressure is 1-15MPa; the reaction conditions of the second reactor: the reaction temperature is 120-175°C, the reaction The pressure is 1-15MPa; the ratio of hydrogen to ester is 50-150; the reaction conditions of the third reactor: the reaction temperature is 200-400°C, and the reaction pressure is 0.2-3MPa.
通过以下实施例对本发明进行具体举例说明，但本发明并不局限于这些实施例。The present invention is specifically illustrated by the following examples, but the present invention is not limited to these examples.
实施例Example
固体酸催化剂—吡啶改性的氢型样品的制备Solid Acid Catalyst—Preparation of Pyridine-Modified Hydrogen Form
将10g氢型MOR(SiO 2/Al 2O 3＝25，东曹公司提供)样品装入反应管中，在100mL/min氮气气氛下逐步升温至350℃，保持4小时；然后用氮气携带吡啶，在常温下处理8小时；然后用纯N 2气体，在300℃下处理8小时，制得吡啶含量为7重量％的吡啶改性样品，用Py-MOR标记。 Put 10 g of hydrogen-form MOR (SiO 2 /Al 2 O 3 =25, provided by Tosoh Corporation) into a reaction tube, gradually raise the temperature to 350° C. under a nitrogen atmosphere of 100 mL/min, and keep it for 4 hours; then use nitrogen to carry pyridine , treated at room temperature for 8 hours; then treated with pure N 2 gas at 300°C for 8 hours to prepare a pyridine-modified sample with a pyridine content of 7 wt%, which was labeled with Py-MOR.
MA加氢催化剂—铜基催化剂的制备Preparation of MA hydrogenation catalyst—copper-based catalyst
在烧杯中，将如表1所示量的Cu(NO 3) 2·3H 2O和Zn(NO 3) 2·6H 2O溶于300g去离子水中，得到混合金属硝酸盐水溶液。在另一个烧杯中，用100g去离子水稀释91.7g浓氨水(28％)，加入如表1所示量的SiO 2(A380，德国EVONIK提供)粉末，并在室温下剧烈搅拌氨水溶液，然后将所得的混合金属硝酸盐水溶液缓慢加入该氨水溶液中，加入时间为30min左右，蒸发去除氨和水。然后，将沉淀用去离子水洗涤至中性，离心分离。将所得沉淀在120℃烘箱中干燥24小时，干燥后样品经研磨，压片，破碎和筛分，然后置于马弗炉中，以1℃/min的升温速率升温到450℃，焙烧5小时，得到焙烧后的样品。各样品的组成见表1。 In a beaker, Cu(NO 3 ) 2 ·3H 2 O and Zn(NO 3 ) 2 ·6H 2 O in the amounts shown in Table 1 were dissolved in 300 g of deionized water to obtain a mixed metal nitrate aqueous solution. In another beaker, dilute 91.7g of concentrated ammonia water (28%) with 100g of deionized water, add the amount of SiO shown in Table 1 2 (A380, Germany EVONIK provides) powder, and vigorously stir the ammonia solution at room temperature, then Slowly add the obtained mixed metal nitrate aqueous solution into the ammonia solution for about 30 minutes, and evaporate to remove ammonia and water. Then, the precipitate was washed with deionized water until neutral, and centrifuged. The resulting precipitate was dried in an oven at 120°C for 24 hours. After drying, the sample was ground, pressed into tablets, crushed and sieved, then placed in a muffle furnace, heated to 450°C at a rate of 1°C/min, and roasted for 5 hours. , to obtain the calcined sample. The composition of each sample is shown in Table 1.
表1Table 1
Figure PCTCN2022102266-appb-000001
Figure PCTCN2022102266-appb-000001
甲醇制二甲醚催化剂的制备Preparation of Methanol to Dimethyl Ether Catalyst
甲醇制二甲醚催化剂为氢型ZSM-5(SiO 2/Al 2O 3＝50，东曹提供)分子筛和 γ-氧化铝按50∶50捏合而成，标记为脱水催化剂。 The methanol-to-dimethyl ether catalyst is made by kneading hydrogen-type ZSM-5 (SiO 2 /Al 2 O 3 =50, provided by Tosoh) molecular sieve and γ-alumina at a ratio of 50:50, and is marked as a dehydration catalyst.
实施例1Example 1
在内径14.00mm，长60cm的不锈钢柱的第一反应器中装入10g Py-MOR催化剂，通入含有CO和H 2的合成气(组成为32％CO/64％H 2/4％Ar)，流速为400mL/min。二甲醚经加压液化后，以0.038g/min的速度用微量泵打入第一反应器中，反应温度为160℃，反应压力为4.5MPa，反应时间为4小时。反应流出物侧线在线采样全组分分析，采用岛津2014气相色谱分析，检测器为FID。分析条件：柱长30m毛细管色谱柱，柱温采用程序升温，初始温度为30℃，保持3min，然后以4℃/min，升到120℃，检测器温度为220℃。根据色谱定量结果，计算DME转化率和产物分布。DME的转化率为72.40％，MA选择性为95.28％，乙酸选择性为0.22％，其它为4.50％。反应流出物经过气液分离后，气相部分进入第二反应器；液相部分DME经循环进入第一反应器，MA作为第二反应器的原料。 Inner diameter 14.00mm, 10g Py-MOR catalyst is loaded in the first reactor of the stainless steel column of length 60cm, pass into and contain CO and H Syngas (composition is 32%CO/64%H 2 / 4 %Ar) , the flow rate is 400mL/min. After the dimethyl ether was liquefied under pressure, it was pumped into the first reactor at a rate of 0.038 g/min with a micropump. The reaction temperature was 160° C., the reaction pressure was 4.5 MPa, and the reaction time was 4 hours. On-line sampling of the side line of the reaction effluent for full component analysis was carried out by Shimadzu 2014 gas chromatography, and the detector was FID. Analysis conditions: column length 30m capillary chromatographic column, column temperature adopts temperature program, the initial temperature is 30°C, keep for 3min, then rise to 120°C at 4°C/min, detector temperature is 220°C. According to the chromatographic quantitative results, the DME conversion and product distribution were calculated. The conversion rate of DME is 72.40%, the MA selectivity is 95.28%, the acetic acid selectivity is 0.22%, and the others are 4.50%. After the gas-liquid separation of the reaction effluent, the gas phase part enters the second reactor; the liquid phase part DME enters the first reactor through circulation, and MA is used as the raw material of the second reactor.
在尺寸与第一反应器相同的第二反应器中装入10.0g加氢催化剂B-1；MA的流速为0.04g/min，气体为合成气(组成为32％CO/64％H 2/4％Ar)，流速为1525mL/min，反应温度为170℃，反应压力为3.0MPa，氢酯比为80，反应时间为4小时。经过分离，气相部分采用TCD分析，分析条件为分析柱为4m长活性炭不锈钢柱，柱温80℃，检测器温度120℃，计算CO的转化率；液相部分采用与第一反应器相同的分析方法。计算MA的转化率以及产物组成。经计算可以得到1.48g乙醇和1.37g甲醇，甲醇与乙醇的摩尔比为1.32。第二反应器出口的反应结果见表2。 Charge 10.0 g of hydrogenation catalyst B-1 in a second reactor with the same size as the first reactor; the flow rate of MA is 0.04 g/min, and the gas is synthesis gas (composition is 32% CO/64% H 2 / 4% Ar), the flow rate is 1525mL/min, the reaction temperature is 170°C, the reaction pressure is 3.0MPa, the hydrogen-to-ester ratio is 80, and the reaction time is 4 hours. After separation, the gas phase part is analyzed by TCD. The analysis conditions are that the analytical column is a 4m-long activated carbon stainless steel column, the column temperature is 80 ° C, and the detector temperature is 120 ° C. The conversion rate of CO is calculated; the liquid phase part adopts the same analysis as the first reactor. method. The conversion of MA and the product composition were calculated. After calculation, 1.48g of ethanol and 1.37g of methanol can be obtained, and the molar ratio of methanol to ethanol is 1.32. The reaction results at the outlet of the second reactor are shown in Table 2.
第三反应器采用脱水催化剂5.0g，用高压液体泵打入从第二反应器分离后的甲醇，流速为3.5g/h，反应温度为270℃，压力为常压。反应后生成DME量为2.3g/h。The third reactor uses 5.0 g of dehydration catalyst, and injects methanol separated from the second reactor with a high-pressure liquid pump at a flow rate of 3.5 g/h, a reaction temperature of 270° C., and a pressure of normal pressure. After the reaction, the amount of DME produced was 2.3 g/h.
实施例2Example 2
与实施例1的不同在于，第二反应器中装入10.0g催化剂B-2。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 1 is that 10.0 g of catalyst B-2 is loaded into the second reactor. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例3Example 3
与实施例1的不同在于，第二反应器装入10.0g催化剂B-3。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 1 is that the second reactor is loaded with 10.0 g of catalyst B-3. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例4Example 4
与实施例1的不同在于，第二反应器装入10.0g催化剂B-4。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 1 is that the second reactor is loaded with 10.0 g of catalyst B-4. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例5Example 5
与实施例1的不同在于，第二反应器装入10.0g催化剂B-5。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 1 is that the second reactor is loaded with 10.0 g of catalyst B-5. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例6Example 6
与实施例1的不同在于，第二反应器装入10.0g催化剂B-6。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 1 is that the second reactor is loaded with 10.0 g of catalyst B-6. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例7Example 7
与实施例1的不同在于，第二反应器装入10.0g催化剂B-7。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 1 is that the second reactor is loaded with 10.0 g of catalyst B-7. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例8Example 8
与实施例1的不同在于，第二反应器装入4.0g催化剂B-6。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 1 is that the second reactor is loaded with 4.0 g of Catalyst B-6. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例9Example 9
与实施例1的不同在于，第二反应器装入7.0g催化剂B-6。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 1 was that the second reactor was charged with 7.0 g of Catalyst B-6. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例10Example 10
与实施例1的不同在于，第二反应器装入13.0g催化剂B-6。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 1 is that the second reactor is loaded with 13.0 g of catalyst B-6. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
对比实施例1Comparative Example 1
与实施例6的不同在于，在第一反应器中上段装入10.0g Py-MOR催化剂，下段装入10.0g B-6催化剂，去掉第二反应器。反应4小时后取样分析，第一反应器出口的反应结果如下：DME的转化率为70.5％，CO的转化率为24.60％，产物组成为1.23％的MA、60.00％的甲醇、34.97％的乙醇和3.80％的其它。The difference with embodiment 6 is that in the first reactor, the upper section is loaded with 10.0g Py-MOR catalyst, and the lower section is loaded with 10.0g B-6 catalyst, and the second reactor is removed. Sampling and analysis after 4 hours of reaction, the reaction results at the outlet of the first reactor are as follows: the conversion rate of DME is 70.5%, the conversion rate of CO is 24.60%, and the product composition is 1.23% of MA, 60.00% of methanol, and 34.97% of ethanol and 3.80% other.
对比实施例2Comparative Example 2
与实施例6的不同在于，第二反应器的气体原料为纯氢气。反应4小时后取样分析，第二反应器出口的结果见表2。The difference from Example 6 is that the gas raw material of the second reactor is pure hydrogen. After reacting for 4 hours, samples were taken and analyzed, and the results at the outlet of the second reactor are shown in Table 2.
对比实施例3Comparative Example 3
与实施例6的不同在于，第一反应器出口的流出物经过分离去掉未转化的DME后，不进一步分离，直接进入第二反应器。反应4小时后取样分析，第二反应器出口的结果见表2。The difference from Example 6 is that the effluent from the outlet of the first reactor directly enters the second reactor without further separation after being separated to remove unconverted DME. After reacting for 4 hours, samples were taken and analyzed, and the results at the outlet of the second reactor are shown in Table 2.
对比实施例4Comparative Example 4
与实施例1的不同在于，第二反应器装入10.0g催化剂B-1’。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference with embodiment 1 is that the second reactor is loaded with 10.0g catalyst B-1'. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例11Example 11
与实施例6的不同在于，第二反应器的反应温度为160℃。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 6 is that the reaction temperature of the second reactor is 160°C. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例12Example 12
与实施例6的不同在于，第二反应器的反应温度为165℃。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 6 is that the reaction temperature of the second reactor is 165°C. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例13Example 13
与实施例6的不同在于，第二反应器的反应温度为175℃。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 6 is that the reaction temperature of the second reactor is 175°C. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例14Example 14
与实施例6的不同在于，第二反应器的合成气的流速为762.5mL/min，氢酯比为40。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 6 is that the flow rate of the synthesis gas in the second reactor is 762.5 mL/min, and the ratio of hydrogen to ester is 40. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例15Example 15
与实施例6的不同在于，第二反应器的合成气的流速为1144mL/min，氢酯比为60。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 6 is that the flow rate of the synthesis gas in the second reactor is 1144mL/min, and the ratio of hydrogen to ester is 60. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例16Example 16
与实施例6的不同在于，第二反应器的合成气的流速为1906mL/min，氢酯比为100。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 6 is that the flow rate of the synthesis gas in the second reactor is 1906 mL/min, and the ratio of hydrogen to ester is 100. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例17Example 17
与实施例6的不同在于，第二反应器的合成气的流速为2288mL/min，氢酯 比为120。反应4小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 6 is that the flow rate of the synthesis gas in the second reactor is 2288mL/min, and the ratio of hydrogen to ester is 120. After 4 hours of reaction, sampling and analysis were performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例18Example 18
与实施例6的不同在于，反应100小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 6 is that the sample was analyzed after 100 hours of reaction, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例19Example 19
与实施例6的不同在于，反应500小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 6 is that after 500 hours of reaction, samples were taken for analysis, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例20Example 20
与实施例6的不同在于，反应1000小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 6 is that after 1000 hours of reaction, samples were taken for analysis, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例21Example 21
与实施例6的不同在于，反应1500小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 6 is that after 1500 hours of reaction, sampling and analysis are performed, and the reaction results at the outlet of the second reactor are shown in Table 2.
实施例22Example 22
与实施例6的不同在于，反应2000小时后取样分析，第二反应器出口的反应结果见表2。The difference from Example 6 is that after 2000 hours of reaction, sampling and analysis, the reaction results at the outlet of the second reactor are shown in Table 2.
表2：第二反应器出口的反应结果Table 2: Reaction results at the outlet of the second reactor
Figure PCTCN2022102266-appb-000002
Figure PCTCN2022102266-appb-000002
Figure PCTCN2022102266-appb-000003
Figure PCTCN2022102266-appb-000003

Claims (10)

  1. 一种由合成气联产甲醇与乙醇的方法，包括：A method for the co-production of methanol and ethanol from synthesis gas, comprising:
    a)使作为原料的合成气和二甲醚进入第一反应器，以与所述第一反应器中的固体酸催化剂接触并发生反应，得到含有乙酸甲酯和/或乙酸的流出物；a) making synthesis gas and dimethyl ether as raw materials enter a first reactor to contact and react with the solid acid catalyst in the first reactor to obtain an effluent containing methyl acetate and/or acetic acid;
    b)使来自所述第一反应器的流出物经过分离而纯化，经纯化的MA与合成气进入第二反应器，以与所述第二反应器中的加氢催化剂接触并发生反应，得到含有甲醇和乙醇的流出物；b) separating and purifying the effluent from said first reactor, the purified MA and synthesis gas entering a second reactor to contact and react with a hydrogenation catalyst in said second reactor to obtain Effluents containing methanol and ethanol;
    c)对来自所述第二反应器的流出物进行分离，得到产物甲醇和乙醇，优选甲醇与乙醇的摩尔比为1.1-5.0，更优选1.5-3.0；c) separating the effluent from the second reactor to obtain the products methanol and ethanol, preferably with a molar ratio of methanol to ethanol of 1.1-5.0, more preferably 1.5-3.0;
    d)任选地，使来自步骤c)的甲醇进入第三反应器以进行脱水反应，得到二甲醚，并使所得到的二甲醚以及未转化的合成气进入所述第一反应器以循环反应。d) Optionally, passing methanol from step c) to a third reactor for dehydration to dimethyl ether, and passing the resulting dimethyl ether together with unconverted synthesis gas to said first reactor to circular reaction.
  2. 根据权利要求1所述的方法，其中所述原料中合成气的体积含量为10-100％，二甲醚的体积含量为0-90％，并且所述合成气中一氧化碳与氢气的体积比为0.1-10；优选地，所述原料中一氧化碳和氢气的体积含量为50-100％；氮气、氦气、氩气和二氧化碳中的任意一种或几种气体在合成气原料的体积含量为0-50％。The method according to claim 1, wherein the volume content of synthesis gas in the raw material is 10-100%, the volume content of dimethyl ether is 0-90%, and the volume ratio of carbon monoxide and hydrogen in the synthesis gas is 0.1-10; Preferably, the volume content of carbon monoxide and hydrogen in the raw material is 50-100%; the volume content of any one or several gases in the synthesis gas raw material in nitrogen, helium, argon and carbon dioxide is 0 -50%.
  3. 根据权利要求1或2所述的方法，其中所述第一反应器的反应温度为100-300℃，优选120-250℃，反应压力为0.5-20MPa，优选1-15MPa；所述第二反应器的反应温度为100-300℃，优选150-175℃，反应压力为0.5-20MPa，优选1.0-15.0Mpa，氢酯比为30-300，优选50-150；所述第三反应器的反应温度为180-420℃，优选200-400℃，反应压力为0.1-4MPa，优选0.2-3MPa。The method according to claim 1 or 2, wherein the reaction temperature of the first reactor is 100-300°C, preferably 120-250°C, and the reaction pressure is 0.5-20MPa, preferably 1-15MPa; the second reaction The reaction temperature of the reactor is 100-300°C, preferably 150-175°C, the reaction pressure is 0.5-20MPa, preferably 1.0-15.0Mpa, the hydrogen-ester ratio is 30-300, preferably 50-150; the reaction of the third reactor The temperature is 180-420°C, preferably 200-400°C, and the reaction pressure is 0.1-4MPa, preferably 0.2-3MPa.
  4. 根据权利要求1-3中任一项所述的方法，其中所述第一反应器中的固体酸催化剂包含以下各项中的至少一种分子筛：FER沸石分子筛、MFI沸石分子筛、MOR沸石分子筛、ETL沸石分子筛、MFS沸石分子筛以及它们经骨架组成 元素以外的元素或吡啶改性得到的分子筛产物，优选吡啶改性的MOR沸石分子筛。The method according to any one of claims 1-3, wherein the solid acid catalyst in the first reactor comprises at least one molecular sieve in the following: FER zeolite molecular sieve, MFI zeolite molecular sieve, MOR zeolite molecular sieve, ETL zeolite molecular sieves, MFS zeolite molecular sieves and their molecular sieve products modified by elements other than the framework elements or pyridine, preferably pyridine-modified MOR zeolite molecular sieves.
  5. 根据权利要求1-4中任一项所述的方法，其中所述固体酸催化剂是所述沸石分子筛的氢型产物，或者由10-95重量％的所述氢型产物和余量的基质构成，或者是所述氢型产物经吡啶改性得到的分子筛产物，其中所述基质为选自氧化铝、氧化硅、高岭土和氧化镁中的至少一种。The method according to any one of claims 1-4, wherein the solid acid catalyst is the hydrogen-form product of the zeolite molecular sieve, or consists of 10-95% by weight of the hydrogen-form product and the rest of the matrix , or a molecular sieve product obtained by modifying the hydrogen-form product with pyridine, wherein the matrix is at least one selected from alumina, silica, kaolin and magnesia.
  6. 根据权利要求1-5中任一项所述的方法，其中所述第二反应器中的加氢催化剂为铜基催化剂。The method according to any one of claims 1-5, wherein the hydrogenation catalyst in the second reactor is a copper-based catalyst.
  7. 根据权利要求6所述的方法，其中所述铜基催化剂包含15-90重量％的作为载体的SiO 2，5-50重量％的Cu和0-50重量％的过渡金属、碱土金属和锌族元素中的至少一种，所述过渡金属优选为Fe、Co、W、Mo、Ti、V、Ni、Zr、Pt、Pd和Au中的至少一种，所述碱土金属优选为Ca、Mg和Ba中的至少一种，所述锌族元素优选为Zn。 The method according to claim 6, wherein the copper-based catalyst comprises 15-90% by weight of SiO 2 as a support, 5-50% by weight of Cu and 0-50% by weight of transition metals, alkaline earth metals and zinc groups At least one of the elements, the transition metal is preferably at least one of Fe, Co, W, Mo, Ti, V, Ni, Zr, Pt, Pd and Au, and the alkaline earth metal is preferably Ca, Mg and At least one of Ba, the zinc group element is preferably Zn.
  8. 根据权利要求1-7中任一项所述的方法，其中所述第三反应器中的催化剂为甲醇制二甲醚固体酸催化剂，优选分子筛基和氧化物基催化剂，更优选HZSM-5、β分子筛、硅铝磷酸盐分子筛和活性Al 2O 3及其混合物。 The method according to any one of claims 1-7, wherein the catalyst in the third reactor is a methanol dimethyl ether solid acid catalyst, preferably molecular sieve base and oxide base catalyst, more preferably HZSM-5, Beta molecular sieves, silicoaluminophosphate molecular sieves and active Al 2 O 3 and mixtures thereof.
  9. 根据权利要求1-8中任一项所述的方法，其中所述第一反应器和/或所述第二反应器和/或所述第三反应器为固定床或流化床反应器，优选固定床列管反应器。The method according to any one of claims 1-8, wherein the first reactor and/or the second reactor and/or the third reactor are fixed bed or fluidized bed reactors, A fixed bed tube reactor is preferred.
  10. 一种铜基催化剂，包含15-90重量％的作为载体的SiO 2，5-50重量％的Cu和0-50重量％的过渡金属、碱土金属和锌族元素中的至少一种，所述过渡金属优选为Fe、Co、W、Mo、Ti、V、Ni、Zr、Pt、Pd和Au中的至少一种，所述碱土金属优选为Ca、Mg和Ba中的至少一种，所述锌族元素优选为Zn。 A copper-based catalyst, comprising 15-90% by weight of SiO 2 as a carrier, 5-50% by weight of Cu and 0-50% by weight of at least one of transition metals, alkaline earth metals and zinc group elements, said The transition metal is preferably at least one of Fe, Co, W, Mo, Ti, V, Ni, Zr, Pt, Pd and Au, the alkaline earth metal is preferably at least one of Ca, Mg and Ba, the The zinc group element is preferably Zn.
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