WO2019144954A1 - Alkali-modified composite catalyst and method for preparing ethylene by hydrogenation of carbon monoxide - Google Patents

Alkali-modified composite catalyst and method for preparing ethylene by hydrogenation of carbon monoxide Download PDF

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WO2019144954A1
WO2019144954A1 PCT/CN2019/073388 CN2019073388W WO2019144954A1 WO 2019144954 A1 WO2019144954 A1 WO 2019144954A1 CN 2019073388 W CN2019073388 W CN 2019073388W WO 2019144954 A1 WO2019144954 A1 WO 2019144954A1
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component
catalyst
selectivity
molecular sieve
specific surface
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Chinese (zh)
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潘秀莲
焦峰
包信和
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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
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    • B01J37/04—Mixing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
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    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
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    • 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 invention belongs to a low-carbon olefin high-value chemical for hydrogenation of carbon monoxide, and particularly relates to a base modified composite catalyst and a method for hydrogenating carbon monoxide to ethylene.
  • Ethylene is a very important basic chemical raw material and one of the largest chemical products in the world.
  • the ethylene industry is the core of the petrochemical industry and plays an important role in the national economy.
  • the lower olefin refers to an olefin having a carbon number of 4 or less.
  • Low-carbon olefins represented by ethylene and propylene are very important basic organic chemical raw materials.
  • China's ethylene industry has developed rapidly and has an important position in the world ethylene market.
  • the low-carbon olefins market has been in short supply for a long time.
  • the production of ethylene mainly uses naphtha, light diesel oil cracking petrochemical route or ethane cracking technology.
  • a high activity (CO conversion 90%) and selectivity (low carbon olefin selectivity 66%) can be obtained at a reaction pressure of 1.0 to 5.0 MPa in a synthesis gas to produce a low-carbon olefin, and a reaction temperature of 300 to 400 ° C. .
  • the Fe/activated carbon catalyst prepared by using the vacuum impregnation method to prepare manganese, copper, zinc silicon, potassium and the like as an auxiliary agent for the synthesis of low-carbon olefins in the synthesis gas, in the absence of raw material gas circulation Under the conditions, the CO conversion rate is 96%, and the selectivity of the low-carbon olefin in the hydrocarbon is 68%.
  • the catalyst reported above uses metal iron or iron carbide as the active component, and the reaction follows the chain growth reaction mechanism of the metal surface.
  • the selectivity of the product low olefin is low, especially the selectivity of a single product such as ethylene is less than 30%.
  • researcher Sun Yuhan and researcher Zhong Liangshu of Shanghai Institute of Advanced Studies reported a preferential exposure to [101] and [020] manganese-assisted cobalt-based catalysts, achieving a CO. conversion of 31.8% and a low carbon olefin of 60.8%.
  • Selective and 5% selectivity to methane is less than 20%.
  • a bifunctional catalyst containing oxygen vacancies combined with MOR molecular sieves is used for the synthesis of olefins in a synthesis gas to increase the selectivity of ethylene to 30-75%, but the number of carbon atoms in by-products exceeds 3 more hydrocarbons, affecting the application of this technology.
  • the invention further modulates the acidity of the MOR molecular sieve, so that the selectivity of the methane by-product is further lowered, and the selectivity of the hydrocarbon product above C4 is further reduced.
  • the present invention solves the problem: overcoming the deficiencies of the prior art, providing a base-modified catalyst and a method for hydrogenating carbon monoxide to ethylene, the catalyst of the invention catalyzing direct conversion of carbon monoxide to high selectivity to form low-carbon olefins, and
  • the selectivity of the C2-C3 olefin is as high as 83-90%, the selectivity of the single product ethylene can be as high as 75-85%, the methane selectivity is less than 5%, and the hydrocarbon selectivity of C4 and above is less than 7%.
  • the technical scheme of the present invention is: a catalyst comprising a component I and a component II, the component I and the component II being compounded together by mechanical mixing, and the active component of the component I is a metal oxide
  • Component II is a molecular sieve of MOR topology; the molecular sieve of the MOR topology is treated by an organic base modification; the modification treatment is to disperse the organic base into the 12-ring channel of the molecular sieve of the MOR topology.
  • a B acid site; the organic base is a heterocyclic compound; preferably a heteroaryl group; further preferably a heteroaryl group having 1 to 2 hetero atoms; more preferably a 5 or 6 membered heteroaryl group having 1 to 2 N atoms .
  • the MOR topology of the present invention is an orthorhombic system having a one-dimensional channel structure with elliptical through-channels parallel to each other, comprising an 8-ring pocket and a 12-ring one-dimensional channel.
  • the mechanical mixing according to the present invention may be compounded by one or more of mechanical stirring, ball milling, shaker mixing, and mechanical grinding.
  • the molecular sieve of the MOR topology is modified by a heterocyclic compound to prevent the organic base molecules from entering the 8-ring channel, but selectively occupying the 12-ring B acid sites.
  • the use of meta-position-substituted molecules can avoid the problem that the contact between the organic base and the B-acid is weak due to the steric hindrance effect, and the adsorption is not strong.
  • the heterocyclic compound may be furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, anthracene, quinoline, pteridine, acridine.
  • the heterocyclic compound may have one or two or more substituents of a methyl group, an ethyl group, an amino group, and a nitro group. Preference is given to meta and/or para substitution.
  • the metal oxide is MnO x , Mn a Cr (1-a) O x , Mn a Al (1-a) O x , Mn a Zr (1-a) O x , Mn a In (1-a ) O x , ZnO x , Zn a Cr (1-a) O x , Zn a Al (1-a) O x , Zn a Ga (1-a) O x , Zn a In (1-a) O x , CeO x , Co a Al (1-a) O x , Fe a Al (1-a) O x , GaO x , BiO x , InO x , In a Al b Mn (1-ab) O x , In a One or more of Ga b Mn (1-ab) O x ;
  • the specific surface area of the MnO x , ZnO x , CeO x , GaO x , BiO x , InO x is 1-100 m 2 /g; preferably the specific surface area is 50-100 m 2 /g;
  • the specific surface area of Fe a Al (1-a) O x , In a Al b Mn (1-ab) O x , and In a Ga b Mn (1-ab) O x is 5-150 m 2 /g.
  • the specific surface area is 50-150 m 2 /g;
  • the value of x ranges from 0.7 to 3.7, the range of a ranges from 0 to 1, and the range of a+b ranges from 0 to 1.
  • a, b, (1-a), (1-a-b), x represent only the relative proportions of the chemical compositions of the elements in the metal oxide, and all metal oxides having the same ratio are regarded as the same metal oxide.
  • the weight ratio of the active ingredient to the component II in the component I is from 0.1 to 20, preferably from 0.3 to 8, and the multi-component synergy is effective in allowing the reaction to proceed efficiently, and one of too much or too little is disadvantageous for the progress of the reaction.
  • a dispersant is further added to the component I, and the metal oxide is dispersed in a dispersant, and the dispersant is Al 2 O 3 , SiO 2 , Cr 2 O 3 , ZrO 2 , TiO 2 , Ga 2 O 3 , One or more of activated carbon, graphene, and carbon nanotubes.
  • the dispersant is contained in an amount of from 0.05 to 90% by weight, the balance being a metal oxide.
  • the skeleton element composition of the molecular sieve having the MOR topology may be Si-Al-O, Ga-Si-O, Ga-Si-Al-O, Ti-Si-O, Ti-Al-Si-O, Ca-.
  • the modification of the organic base in the present invention refers to the use of an organic base molecule to occupy the B acid site in the circular channel of the MOR molecular sieve 12, which may be completely occupied or partially occupied.
  • the B acid site in the occupied 12-ring channel is 50-100%
  • the method for dispersing an organic base into a B acid site in the annular channel of the MOR molecular sieve 12, and all known methods for achieving the object can meet the requirements.
  • the vacuum dehydration adsorption method of the present invention is taken as an example.
  • the invention relates to a method for directly converting ethylene into ethylene, which comprises syngas as a reaction raw material, and the syngas may further contain a certain amount of carbon dioxide, and the conversion reaction is carried out in a fixed bed or a moving bed, and ethylene can be formed with high selectivity.
  • the catalyst is the above catalyst.
  • the pressure of the synthesis gas is from 0.5 to 10 MPa, preferably from 1 to 8 MPa, more preferably from 2 to 8 MPa; the reaction temperature is from 300 to 600 ° C, preferably from 300 to 450 ° C; and the space velocity is from 300 to 10000 h -1 , preferably 500 - 9000h -1, more preferably 500-6000h -1, a higher space-time yield can be obtained.
  • the reaction synthesis gas H 2 /CO molar ratio is from 0.2 to 3.5, preferably from 0.3 to 2.5, to obtain higher space-time yield and selectivity.
  • the synthesis gas may also contain CO 2 wherein the volume concentration of CO 2 in the synthesis gas is from 0.1 to 50%.
  • the above catalyst of the invention is used for one-step direct conversion of synthesis gas to ethylene or C2-C3 olefin, wherein the selectivity of C2-C3 olefin is as high as 83-90%, the selectivity of ethylene reaches 75-85%, and the by-product methane is also The selectivity is extremely low ( ⁇ 5%) and the selectivity for hydrocarbons above C4 and above is less than 7%.
  • the present invention is different from the conventional methanol-made low-carbon olefin technology (abbreviated as MTO), and realizes a direct conversion of synthesis gas to ethylene.
  • MTO methanol-made low-carbon olefin technology
  • the ethylene single product in the product of the invention has high selectivity, can reach 75-85%, and has high space-time yield (the olefin yield is as high as 1.42 mmol/h ⁇ g), and the product is easy to be separated, and has a good application prospect. .
  • the metal oxide in the catalyst has a high specific surface area, so that the metal oxide has more active sites on the surface, which is more favorable for the catalytic reaction.
  • component II in the catalyst The role of component II in the catalyst is to convert the active gas phase intermediate produced by component I to a lower olefin by coupling with component I, and the effect of component II on the equilibrium pull of the series reaction can be Promoting the activation and conversion of the synthesis gas by the component I to increase the conversion rate.
  • the special pore structure of the molecular sieve in the component II used in the invention has a unique shape selection effect, and can obtain more ethylene products with high selectivity. .
  • the function of the present invention can not be achieved at all by using the component I or the component II described in the present invention separately, for example, when the component I is used alone, the methane selectivity in the product is very high and the conversion rate is low, and When component II is used alone, the converted synthesis gas can hardly be activated, and only component I and component II can be synergistically catalyzed to achieve efficient synthesis gas conversion and excellent selectivity.
  • component I can activate the synthesis gas to form a specific active gas phase intermediate, and the intermediate diffuses into the pores of component II via the gas phase. Due to the molecular sieve of the MOR structure selected by the present invention, it has a special pore structure and acidity.
  • the active gas phase intermediate produced by component I is further activated to be converted to an olefin. Due to the special pore structure of the II component, the product has a special selectivity.
  • the component II of the catalyst of the invention is modified by using a heterocyclic organic base, and the selectivity of the catalytic synthesis gas conversion to obtain a single component ethylene is as high as 75-85%, and the methane selectivity is less than 5%, and the inhibition is greatly suppressed. Selectivity of hydrocarbons above C4.
  • the specific surface area of the sample can be tested by means of physical adsorption of nitrogen or argon.
  • the metal oxide of the present invention can be obtained by purchasing a commercially available high specific surface area metal oxide, or can be obtained by the following methods:
  • the atmosphere is an inert gas, a reducing gas or an oxidizing gas; the inert gas is one or more of N 2 , He and Ar; the reducing gas is one or two of H 2 and CO, and the reducing gas is also
  • the inert gas may be contained; the oxidizing gas may be one or more of O 2 , O 3 , and NO 2 , and the oxidizing gas may contain an inert gas.
  • the calcination temperature is 300-700 ° C and the time is 0.5 h-12 h.
  • the purpose of the calcination is to decompose the precipitated metal oxide precursor into high specific surface area oxide nanoparticles at a high temperature, and the oxide surface adsorbed species formed by decomposition can be cleaned by high temperature treatment of baking.
  • ZnO#4 in the table is a commercially available ZnO single crystal having a low specific surface area.
  • the preparation process is the same as the above ZnO#2, except that the precursor of Zn is replaced by the corresponding precursor of Mn, which may be one of manganese nitrate, manganese chloride and manganese acetate, here is manganese nitrate, corresponding
  • MnO the specific surface area was: 23 m 2 /g.
  • the preparation process is the same as the above ZnO#2, except that the precursor of Zn is replaced by the corresponding precursor of Ce, which may be one of cerium nitrate, cerium chloride and cerium acetate, which is cerium nitrate, corresponding thereto.
  • the product was defined as CeO 2 ; the specific surface area was: 92 m 2 /g.
  • the preparation process is the same as the above ZnO#2, except that the precursor of Zn is replaced by the corresponding precursor of Ga, which may be one of gallium nitrate, gallium chloride or gallium acetate, here is gallium nitrate, corresponding
  • the product was defined as Ga 2 O 3 ; the specific surface area was: 55 m 2 /g.
  • the preparation process is the same as that of the above ZnO #2, except that the precursor of Zn is replaced by the corresponding precursor of Bi, which may be one of cerium nitrate, cerium chloride or cerium acetate, here cerium nitrate.
  • the corresponding product was defined as Bi 2 O 3 ; the specific surface area was: 87 m 2 /g.
  • the preparation process is the same as the above ZnO#2, except that the precursor of Zn is replaced by the corresponding precursor of In, which may be one of indium nitrate, indium chloride and indium acetate, here is indium nitrate, corresponding
  • the product is defined as In 2 O 3 ; the specific surface area is: 52 m 2 /g
  • ammonium carbonate Using zinc nitrate, aluminum nitrate, chromium nitrate, manganese nitrate, zirconium nitrate, indium nitrate, cobalt nitrate, ferric nitrate as precursors, and ammonium carbonate, mixed with water at room temperature (in which ammonium carbonate is used as a precipitant, the ratio of feed is The ammonium carbonate is excessive or preferably the ratio of ammonium ion to metal ion is 1:1); the above mixture is aged, then taken out, washed, filtered and dried, and the obtained solid is calcined in an air atmosphere to obtain a metal oxide having a high specific surface area.
  • Table 2 The specific samples and their preparation conditions are shown in Table 2 below.
  • a Cr 2 O 3 , Al 2 O 3 or ZrO 2 dispersed metal oxide is prepared by a precipitation deposition method using a dispersant Cr 2 O 3 , Al 2 O 3 or ZrO 2 as a carrier.
  • a dispersant Cr 2 O 3 , Al 2 O 3 or ZrO 2 as a carrier.
  • commercial Cr 2 O 3 specifically surface area is about 5 m 2 /g
  • Al 2 O 3 specifically surface area of about 20 m 2 /g
  • ZrO 2 specific surface area of about 10 m 2 / g
  • sodium hydroxide precipitating agent are mixed at room temperature and the precipitate, the molar concentration of 0.067M Zn 2+, Zn 2+ and the mole fraction ratio of precipitant 1:8; then aged at 160 ° C for 24 hours to obtain Cr 2 O 3 , Al 2 O 3 or ZrO 2 as a carrier-dispersed ZnO (the content of the dispersant in the component I is 0.1 w
  • SiO 2 specific surface area of about 2 m 2 /g
  • Ga 2 O 3 specific surface area of about 10 m 2 /g
  • TiO 2 specific surface area of about 15 m 2 /g
  • the MnO oxide the content of the dispersant in the component I is 5 wt%, 30 wt%, 60 wt%, respectively
  • the product is defined as the dispersed oxide 4-6. It was a specific surface area: 97m 2 / g, 64m 2 / g, 56m 2 / g.
  • activated carbon having a specific surface area of about 1000 m 2 /g
  • graphene having a specific surface area of about 500 m 2 /g
  • carbon nanotubes having a specific surface area of about 300 m 2 /g
  • the oxide the content of the dispersant in the component I was 5% by weight, 30% by weight, 60% by weight in this order
  • the product was defined as the dispersed oxide 7-9. It was a specific surface area: 177m 2 / g, 245m 2 / g, 307m 2 / g.
  • the MOR topology is an orthorhombic system having a one-dimensional channel structure with elliptical through-channels parallel to each other, including 8-ring and 12-ring parallel one-dimensional through-channels, and 12-ring main channel sides 8 Ring pockets are connected.
  • the MOR molecular sieve of the present invention may be a commercially available molecular sieve directly purchased, or may be a self-synthesized molecular sieve.
  • the MOR molecular sieve produced by Nankai University Catalyst Factory was used as MOR1; at the same time, seven molecular sieves with MOR structure were prepared by hydrothermal synthesis.
  • Na-MOR was taken, mixed with a 1 mol/L ammonium chloride solution, stirred at 90 ° C for 3 hours, washed, dried, continuously carried out 4 times, and calcined at 450 degrees for 6 hours to obtain a hydrogen-type mordenite.
  • the skeleton element composition of the molecular sieve having the MOR topology prepared according to the above process may be Si-Al-O, Ga-Si-O, Ga-Si-Al-O, Ti-Si-O, Ti-Al-Si-O.
  • the prepared molecular sieve is subjected to dehydration and degassing treatment under vacuum, the temperature is 400 ° C, the pressure is 10 -4 Pa, and after 10 h, it is lowered to 300 ° C, and then 200 Pa of organic alkali gas is introduced into the vacuum chamber, and after 10 hours of equilibration. Desorbed at the same temperature for 1 h.
  • MOR1 was used in sequence: furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, pteridine, acridine to obtain MOR9-21.
  • MOR2 is obtained by 1-methylfuran to obtain MOR22; MOR3 is treated with 1-methylpyrrole to obtain MOR23; MOR4 is treated with 3,5-lutidine to obtain MOR24; MOR5 was treated with 4-ethylpyridine to obtain MOR25; MOR6 was treated with 3-methylquinoline to obtain MOR26; MOR7 was treated with 4-methylindole to obtain MOR27; MOR8 was treated with 5-methylacridine to obtain MOR28.
  • a mixing temperature of 20-100 ° C can be set, which can be carried out in an atmosphere or directly in the air, and the atmosphere is selected from any of the following gases:
  • the mechanical mixing may be compounded by one or more of mechanical stirring, ball milling, shaker mixing, and mechanical grinding, as follows:
  • Ball Milling Using the abrasive and the catalyst to tumbling at high speed in the grinding tank, the catalyst is strongly impacted and crushed to achieve the function of dispersing and mixing the component I and the component II.
  • the abrasive material can be stainless steel, agate, quartz. Size range: 5mm-15mm). Ratio to catalyst (mass ratio range: 20-100:1).
  • Shaker mixing method premixing component I and component II into a container; mixing of component I and component II by controlling reciprocating oscillation or circumferential oscillation of the shaker; adjusting the oscillation speed (range) : 1-70 rpm) and time (range: 5 min - 120 min) for uniform mixing.
  • a fixed bed reaction is exemplified, but the catalyst is also suitable for use in a moving bed reactor.
  • the device is equipped with a gas mass flow meter and an online product analysis chromatograph (the exhaust gas of the reactor is directly connected to the chromatographic quantitative valve for periodic real-time sampling analysis).
  • the selectivity of ethylene propylene in the product is as high as 83-90%, and the conversion of raw materials is 10-60%. Due to the effective synergy between molecular sieve and oxide, the mass production of methane is avoided, and the selectivity of methane is less than 5%. The selectivity is 75-85%.
  • the component I of the catalyst used in Comparative Example 2 was a metal ZnCo, and the ZnCo molar ratio was 1:1, and the remaining parameters and the mixing process were the same as the catalyst C.
  • the component I of the catalyst used in Comparative Example 3 was TiO 2 , and the remaining parameters and the mixing process were the same as the catalyst C.
  • the catalyst used in Comparative Example 12 was only the component I, which was ZnO #1, and did not contain the MOR molecular sieve.
  • the reaction conversion rate was very low, and the product was mainly composed of dimethyl ether, methane and other by-products, and almost no ethylene was formed. .
  • the catalyst used in Comparative Example 13 was a sample having only component II, being a MOR9 molecular sieve, and containing no component I, and the catalytic reaction was almost inactive.
  • Comparative Examples 12 and 13 show that only the component I or the component II has an extremely poor reaction effect and does not have the excellent reaction properties as described in the present invention.

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Abstract

Disclosed are an alkali-modified composite catalyst and a method for preparing ethylene by the hydrogenation of carbon monoxide. A conversion reaction is carried out on a fixed bed or a moving bed using a mixed gas of carbon monoxide and hydrogen as a reaction raw material, wherein the catalyst used is a composite catalyst compounded from a component I and a component II by means of mechanical mixing. The active component of the component I is a metallic oxide, and the component II is a molecular sieve of an organic alkali-modified MOR structure, wherein the organic alkali is a heterocyclic compound, and the modification treatment is to disperse the organic alkali into a B acid site within a 12-membered ring pore channel of the molecular sieve; and the weight ratio of the active component of the component I and the component II is 0.1:20. The reaction has a very high product yield and selectivity, wherein the selectivity of a side product of methane is very low and the selectivity and the space-time yield of ethylene are significantly improved, and the reaction has very bright application prospects.

Description

一种碱修饰的复合催化剂及一氧化碳加氢反应制乙烯的方法Alkali modified composite catalyst and method for hydrogenating carbon monoxide to ethylene 技术领域Technical field
本发明属于一氧化碳加氢制低碳烯烃高值化学品，具体涉及一种碱修饰的复合催化剂及一氧化碳加氢反应制乙烯的方法。The invention belongs to a low-carbon olefin high-value chemical for hydrogenation of carbon monoxide, and particularly relates to a base modified composite catalyst and a method for hydrogenating carbon monoxide to ethylene.
背景技术Background technique
乙烯是非常重要的基本化工原料，是世界上产量最大的化学产品之一，乙烯工业是石油化工产业的核心，在国民经济中占有重要的地位。低碳烯烃是指碳原子数小于或等于4的烯烃。以乙烯、丙烯为代表的低碳烯烃是非常重要的基本有机化工原料，随着我国经济的快速增长，我国乙烯行业发展迅猛，在世界乙烯市场占有重要的地位。长期以来，低碳烯烃市场供不应求。目前，乙烯的生产主要采用石脑油、轻柴油裂解的石油化工路线或者乙烷裂解的技术，由于我国石油长期依赖进口，我国的能源安全存在较大风险，急需开发出不依赖石油的乙烯生产技术。将煤炭、天然气、生物质和其他可再生材料等转化为一氧化碳和氢气的混合气即合成气，合成气中一氧化碳和氢气的比例随原材料不同而不同；再以这些合成气为原料，通过调节一氧化碳和氢气的比例到合适的值之后，使一氧化碳和氢在合适的催化剂作用下，通过费托合成反应直接制得碳原子数小于或等于4的低碳烯烃的过程，这样可以一步生产烯烃，该路线为石脑油裂解技术生产乙烯提供了一条替代方案。该工艺无需像间接法工艺那样从合成气经甲醇或二甲醚，进一步制备烯烃，简化工艺流程，大大减少投资。Ethylene is a very important basic chemical raw material and one of the largest chemical products in the world. The ethylene industry is the core of the petrochemical industry and plays an important role in the national economy. The lower olefin refers to an olefin having a carbon number of 4 or less. Low-carbon olefins represented by ethylene and propylene are very important basic organic chemical raw materials. With the rapid growth of China's economy, China's ethylene industry has developed rapidly and has an important position in the world ethylene market. The low-carbon olefins market has been in short supply for a long time. At present, the production of ethylene mainly uses naphtha, light diesel oil cracking petrochemical route or ethane cracking technology. Due to the long-term dependence of China's oil on imports, China's energy security has great risks, and it is urgent to develop petroleum-free ethylene production. technology. Converting coal, natural gas, biomass and other renewable materials into a mixture of carbon monoxide and hydrogen, ie, synthesis gas. The ratio of carbon monoxide to hydrogen in the synthesis gas varies with the raw materials; and these synthesis gases are used as raw materials to regulate carbon monoxide. After the ratio of hydrogen to hydrogen is adjusted to a suitable value, carbon monoxide and hydrogen are directly subjected to a Fischer-Tropsch synthesis reaction to produce a low-carbon olefin having a carbon number of 4 or less under a suitable catalyst, so that the olefin can be produced in one step. The route provides an alternative to the production of ethylene from naphtha cracking technology. The process does not require further production of olefins from syngas via methanol or dimethyl ether as in the indirect process, simplifying the process and greatly reducing investment.
通过费托合成直接制取低碳烯烃，一直是合成气直接生产烯烃的研究热点之一。中科院大连化学物理研究所公开的专利CN1083415A中，用MgO等IIA族碱金属氧化物或高硅沸石分子筛(或磷铝沸石)担载的铁–锰催化剂体系，以强碱K或Cs离子作助剂，在合成气制低碳烯烃反应压力为1.0～5.0Mpa，反应温度300～400℃下，可获得较高的活性(CO转化率90％)和选择性(低碳烯烃选择性66％)。北京化工大学所申报的专利ZL03109585.2中，采用真空浸渍法制备锰、铜、锌硅、钾等为助剂的Fe/活性炭催化剂用于合成气制低碳烯烃反应，在无原料气循环的条件下，CO转化率96％，低碳烯烃在碳氢化合物中的选择性68％。上述报道的催化剂是采用金属铁或者碳化铁为活性组分，反应遵循金属表面的链增长反应机理，产物低碳烯烃的选择性较低，尤其单种产物如乙烯的选择性低于30％。2016年，上海高等研究院孙予罕研究员及钟良枢研究员报道了一种择优暴露[101]及[020]锰助碳化钴基催化剂，实现了31.8％的CO转化率下，60.8％的低碳烯烃选择性，且甲烷选择性5％。但是乙烯单一选择性却低于20％。中国科 学院大连化学物理研究所包信和和潘秀莲团队报道了氧化铝负载的ZnCr 2O 4氧化物与多级孔SAPO-34分子筛复合双功能催化剂(Jiao et al.,Science 351(2016)1065-1068)，实现了CO转化率17％时,低碳烯烃80％的选择性，但乙烯的选择性低于30％。在他们申请的专利201610600945.6中，使用含有氧空穴与MOR分子筛复合的双功能催化剂用于合成气一步制烯烃反应，将乙烯的选择性提高至30-75％，但副产物中碳原子数超过3的烃类较多，影响了该技术的应用。而本发明进一步通过调变MOR分子筛的酸性特点，使甲烷副产物的选择性低进一步，且C4以上的烃类产物的选择性也进一步降低。 The direct preparation of low-carbon olefins by Fischer-Tropsch synthesis has been one of the research hotspots for the direct production of olefins from syngas. In the patent CN1083415A published by the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, an iron-manganese catalyst system supported by a Group IIA alkali metal oxide such as MgO or a high silica zeolite molecular sieve (or aluminophosphate) is assisted by a strong base K or Cs ion. A high activity (CO conversion 90%) and selectivity (low carbon olefin selectivity 66%) can be obtained at a reaction pressure of 1.0 to 5.0 MPa in a synthesis gas to produce a low-carbon olefin, and a reaction temperature of 300 to 400 ° C. . In the patent ZL03109585.2 declared by Beijing University of Chemical Technology, the Fe/activated carbon catalyst prepared by using the vacuum impregnation method to prepare manganese, copper, zinc silicon, potassium and the like as an auxiliary agent for the synthesis of low-carbon olefins in the synthesis gas, in the absence of raw material gas circulation Under the conditions, the CO conversion rate is 96%, and the selectivity of the low-carbon olefin in the hydrocarbon is 68%. The catalyst reported above uses metal iron or iron carbide as the active component, and the reaction follows the chain growth reaction mechanism of the metal surface. The selectivity of the product low olefin is low, especially the selectivity of a single product such as ethylene is less than 30%. In 2016, researcher Sun Yuhan and researcher Zhong Liangshu of Shanghai Institute of Advanced Studies reported a preferential exposure to [101] and [020] manganese-assisted cobalt-based catalysts, achieving a CO. conversion of 31.8% and a low carbon olefin of 60.8%. Selective and 5% selectivity to methane. However, the single selectivity of ethylene is less than 20%. The Institute of Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Bao Xinhe and Pan Xiulian team reported on alumina-supported ZnCr 2 O 4 oxide and multi-stage pore SAPO-34 molecular sieve composite bifunctional catalyst (Jiao et al., Science 351 (2016) 1065-1068 ), when the CO conversion rate is 17%, the selectivity of the low carbon olefin is 80%, but the selectivity of ethylene is less than 30%. In their patent application 201610600945.6, a bifunctional catalyst containing oxygen vacancies combined with MOR molecular sieves is used for the synthesis of olefins in a synthesis gas to increase the selectivity of ethylene to 30-75%, but the number of carbon atoms in by-products exceeds 3 more hydrocarbons, affecting the application of this technology. The invention further modulates the acidity of the MOR molecular sieve, so that the selectivity of the methane by-product is further lowered, and the selectivity of the hydrocarbon product above C4 is further reduced.
发明内容Summary of the invention
本发明技术解决问题：克服现有技术的不足，提供一种碱修饰的催化剂及一氧化碳加氢反应制乙烯的方法，所发明的催化剂可催化一氧化碳加氢直接转化高选择性生成低碳烯烃，并且C2-C3烯烃的选择性高达83-90％，单种产物乙烯的选择性可高达75-85％，甲烷选择性低于5％，C4及以上烃类选择性低于7％。The present invention solves the problem: overcoming the deficiencies of the prior art, providing a base-modified catalyst and a method for hydrogenating carbon monoxide to ethylene, the catalyst of the invention catalyzing direct conversion of carbon monoxide to high selectivity to form low-carbon olefins, and The selectivity of the C2-C3 olefin is as high as 83-90%, the selectivity of the single product ethylene can be as high as 75-85%, the methane selectivity is less than 5%, and the hydrocarbon selectivity of C4 and above is less than 7%.
本发明的技术方案为：一种催化剂，所述催化剂包括组分Ⅰ和组分Ⅱ，所述组分Ⅰ和组分Ⅱ以机械混合方式复合在一起，组分Ⅰ的活性成份为金属氧化物，组分Ⅱ为MOR拓扑结构的分子筛；所述MOR拓扑结构的分子筛经有机碱改性处理；所述改性处理是将有机碱分散到所述MOR拓扑结构的分子筛的12圆环孔道内的B酸位点；所述有机碱是杂环化合物；优选杂芳基；进一步优选含1-2个杂原子的杂芳基；更优选含1-2个N原子的5或6元杂芳基。The technical scheme of the present invention is: a catalyst comprising a component I and a component II, the component I and the component II being compounded together by mechanical mixing, and the active component of the component I is a metal oxide Component II is a molecular sieve of MOR topology; the molecular sieve of the MOR topology is treated by an organic base modification; the modification treatment is to disperse the organic base into the 12-ring channel of the molecular sieve of the MOR topology. a B acid site; the organic base is a heterocyclic compound; preferably a heteroaryl group; further preferably a heteroaryl group having 1 to 2 hetero atoms; more preferably a 5 or 6 membered heteroaryl group having 1 to 2 N atoms .
本发明所述MOR拓扑结构是一种正交晶系，具有相互平行的椭圆形直通孔道的一维孔道结构，含有8圆环口袋与12圆环一维孔道。The MOR topology of the present invention is an orthorhombic system having a one-dimensional channel structure with elliptical through-channels parallel to each other, comprising an 8-ring pocket and a 12-ring one-dimensional channel.
本发明所述机械混合可采用机械搅拌、球磨、摇床混合、机械研磨中的一种或二种以上进行复合。The mechanical mixing according to the present invention may be compounded by one or more of mechanical stirring, ball milling, shaker mixing, and mechanical grinding.
所述MOR拓扑结构的分子筛经杂环化合物改性处理，可以避免有机碱分子进入8圆环孔道，而是选择性的占据12圆环的B酸位点。而使用间位对位取代的分子可以避免空间位阻效应导致的有机碱与B酸接触较弱，吸附不牢的问题。The molecular sieve of the MOR topology is modified by a heterocyclic compound to prevent the organic base molecules from entering the 8-ring channel, but selectively occupying the 12-ring B acid sites. The use of meta-position-substituted molecules can avoid the problem that the contact between the organic base and the B-acid is weak due to the steric hindrance effect, and the adsorption is not strong.
所述杂环化合物可以是呋喃、噻吩、吡咯、噻唑、咪唑、吡啶、吡嗪、嘧啶、哒嗪、吲哚、喹啉、蝶啶、吖啶。所述杂环化合物可以带有甲基，乙基，氨基，硝基中的一种或两种以上的取代基。优选间位和/或对位取代。The heterocyclic compound may be furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, anthracene, quinoline, pteridine, acridine. The heterocyclic compound may have one or two or more substituents of a methyl group, an ethyl group, an amino group, and a nitro group. Preference is given to meta and/or para substitution.
所述的金属氧化物为MnO x、Mn aCr (1-a)O x、Mn aAl (1-a)O x、Mn aZr (1-a)O x、Mn aIn (1-a)O x、ZnO x、Zn aCr (1-a)O x、Zn aAl (1-a)O x、Zn aGa (1-a)O x、Zn aIn (1-a)O x、CeO x、Co aAl (1-a)O x、Fe aAl (1-a)O x、GaO x、BiO x、InO x、In aAl bMn (1-a-b)O x、In aGa bMn (1-a-b)O x中的一种或二种以上； The metal oxide is MnO x , Mn a Cr (1-a) O x , Mn a Al (1-a) O x , Mn a Zr (1-a) O x , Mn a In (1-a ) O x , ZnO x , Zn a Cr (1-a) O x , Zn a Al (1-a) O x , Zn a Ga (1-a) O x , Zn a In (1-a) O x , CeO x , Co a Al (1-a) O x , Fe a Al (1-a) O x , GaO x , BiO x , InO x , In a Al b Mn (1-ab) O x , In a One or more of Ga b Mn (1-ab) O x ;
所述MnO x、ZnO x、CeO x、GaO x、BiO x、InO x的比表面积是1-100m 2/g；优选比表面积是50-100m 2/g； The specific surface area of the MnO x , ZnO x , CeO x , GaO x , BiO x , InO x is 1-100 m 2 /g; preferably the specific surface area is 50-100 m 2 /g;
所述Mn aCr (1-a)O x、Mn aAl (1-a)O x、Mn aZr (1-a)O x、Mn aIn (1-a)O x、Zn aCr (1-a)O x、Zn aAl (1-a)O x、Zn aGa (1-a)O x、Zn aIn (1-a)O x、Co aAl (1-a)O x、Fe aAl (1-a)O x、In aAl bMn (1-a-b)O x、In aGa bMn (1-a-b)O x的比表面积是5-150m 2/g。优选比表面积是50-150m 2/g； The Mn a Cr (1-a) O x , Mn a Al (1-a) O x , Mn a Zr (1-a) O x , Mn a In (1-a) O x , Zn a Cr ( 1-a) O x , Zn a Al (1-a) O x , Zn a Ga (1-a) O x , Zn a In (1-a) O x , Co a Al (1-a) O x The specific surface area of Fe a Al (1-a) O x , In a Al b Mn (1-ab) O x , and In a Ga b Mn (1-ab) O x is 5-150 m 2 /g. Preferably the specific surface area is 50-150 m 2 /g;
所述x的取值范围是0.7～3.7，a的取值范围是0～1；a+b的取值范围是0～1；The value of x ranges from 0.7 to 3.7, the range of a ranges from 0 to 1, and the range of a+b ranges from 0 to 1.
本发明所述的a,b,(1-a),(1-a-b),x仅代表金属氧化物中元素化学组成的相对比例，凡是比例相同的金属氧化物视为同一种金属氧化物。In the present invention, a, b, (1-a), (1-a-b), x represent only the relative proportions of the chemical compositions of the elements in the metal oxide, and all metal oxides having the same ratio are regarded as the same metal oxide.
组分Ⅰ中的活性成份与组分Ⅱ的重量比为0.1-20，优选为0.3-8，多组分协同才能使得反应有效进行，其中一种过多或过少都会不利于反应的进行。The weight ratio of the active ingredient to the component II in the component I is from 0.1 to 20, preferably from 0.3 to 8, and the multi-component synergy is effective in allowing the reaction to proceed efficiently, and one of too much or too little is disadvantageous for the progress of the reaction.
所述组分Ⅰ中还添加有分散剂，所述金属氧化物分散于分散剂中，分散剂为Al 2O 3、SiO 2、Cr 2O 3、ZrO 2、TiO 2、Ga 2O 3、活性炭、石墨烯、碳纳米管中的一种或二种以上。所述组分Ⅰ中，分散剂的含量在0.05-90wt％，其余为金属氧化物。 A dispersant is further added to the component I, and the metal oxide is dispersed in a dispersant, and the dispersant is Al 2 O 3 , SiO 2 , Cr 2 O 3 , ZrO 2 , TiO 2 , Ga 2 O 3 , One or more of activated carbon, graphene, and carbon nanotubes. In the component I, the dispersant is contained in an amount of from 0.05 to 90% by weight, the balance being a metal oxide.
所述具有MOR拓扑结构的分子筛的骨架元素组成可以是Si-Al-O、Ga-Si-O、Ga-Si-Al-O、Ti-Si-O、Ti-Al-Si-O、Ca-Al-O、Ca-Si-Al-O中的一种或二种以上。The skeleton element composition of the molecular sieve having the MOR topology may be Si-Al-O, Ga-Si-O, Ga-Si-Al-O, Ti-Si-O, Ti-Al-Si-O, Ca-. One or more of Al-O and Ca-Si-Al-O.
本发明所述有机碱改性是指利用有机碱分子，占据MOR分子筛12圆环孔道内的B酸位点，可以是完全占据也可以是部分占据。被占据的12圆环孔道中的B酸位点是50-100％The modification of the organic base in the present invention refers to the use of an organic base molecule to occupy the B acid site in the circular channel of the MOR molecular sieve 12, which may be completely occupied or partially occupied. The B acid site in the occupied 12-ring channel is 50-100%
所述将有机碱分散到所述MOR分子筛12圆环孔道内的B酸位点的方法，所有公知的可以实现该目的的方法均可以满足要求，本发明以真空脱水吸附法为例，先在真空线上控制温度对分子筛样品进行脱水脱气处理温度350-500℃，压力1Pa-10 -5Pa，时间4h-24h，进一步对脱气的分子筛暴露在10Pa-100kPa的有机碱的气氛中或惰性气体稀释的有机碱的气氛中，控制吸附温度是室温至300℃，并用无机气体在200-330℃进行吹扫30min-12h后得到有机碱改性的分子筛。 The method for dispersing an organic base into a B acid site in the annular channel of the MOR molecular sieve 12, and all known methods for achieving the object can meet the requirements. The vacuum dehydration adsorption method of the present invention is taken as an example. Control the temperature on the vacuum line to dehydrate the degassing sample at a temperature of 350-500 ° C, pressure 1Pa-10 -5 Pa, time 4h-24h, further expose the degassed molecular sieve to an atmosphere of 10Pa-100kPa organic base or In an atmosphere of an organic base diluted with an inert gas, the adsorption temperature is controlled from room temperature to 300 ° C, and an organic gas-modified molecular sieve is obtained by purging with an inorganic gas at 200-330 ° C for 30 min to 12 h.
一种合成气直接转化制乙烯的方法，涉及以合成气为反应原料，合成气中还可以含有一定量的二氧化碳，在固定床或移动床上进行转化反应，可以高选择性地生成乙烯，所采用的催化剂为上述的催化剂。The invention relates to a method for directly converting ethylene into ethylene, which comprises syngas as a reaction raw material, and the syngas may further contain a certain amount of carbon dioxide, and the conversion reaction is carried out in a fixed bed or a moving bed, and ethylene can be formed with high selectivity. The catalyst is the above catalyst.
合成气的压力为0.5-10MPa，优选为1-8MPa，更优选为2-8MPa；反应温度为300-600℃，优选为300-450℃；空速为300-10000h -1，优选为500-9000h -1，更优选为500-6000h -1，可以获得更高的时空收率。 The pressure of the synthesis gas is from 0.5 to 10 MPa, preferably from 1 to 8 MPa, more preferably from 2 to 8 MPa; the reaction temperature is from 300 to 600 ° C, preferably from 300 to 450 ° C; and the space velocity is from 300 to 10000 h -1 , preferably 500 - 9000h -1, more preferably 500-6000h -1, a higher space-time yield can be obtained.
所述反应用合成气H 2/CO摩尔比为0.2-3.5，优选为0.3-2.5，可以获得更高的时空收率和选择性。合成气中还可以含有CO 2，其中CO 2在合成气中的体积浓度为0.1-50％。 The reaction synthesis gas H 2 /CO molar ratio is from 0.2 to 3.5, preferably from 0.3 to 2.5, to obtain higher space-time yield and selectivity. The synthesis gas may also contain CO 2 wherein the volume concentration of CO 2 in the synthesis gas is from 0.1 to 50%.
本发明上述催化剂用于合成气一步法直接转化制乙烯或者C2-C3的烯烃，其中C2-C3烯烃的选择性高达83-90％，乙烯选择性达到75-85％，同还时副产物甲烷选择性极低(<5％)，C4及以上烃类选择性低于7％。The above catalyst of the invention is used for one-step direct conversion of synthesis gas to ethylene or C2-C3 olefin, wherein the selectivity of C2-C3 olefin is as high as 83-90%, the selectivity of ethylene reaches 75-85%, and the by-product methane is also The selectivity is extremely low (<5%) and the selectivity for hydrocarbons above C4 and above is less than 7%.
本发明具有如下优点：The invention has the following advantages:
(1)本发明与传统的甲醇制低碳烯烃技术(简称为MTO)不同，实现了一步直接将合成气转化制乙烯。(1) The present invention is different from the conventional methanol-made low-carbon olefin technology (abbreviated as MTO), and realizes a direct conversion of synthesis gas to ethylene.
(2)本发明产物中乙烯单一产物选择性高，可达到75-85％，且时空收率高(烯烃收率高至1.42mmol/h·g)，产物易于分离，具有很好的应用前景。(2) The ethylene single product in the product of the invention has high selectivity, can reach 75-85%, and has high space-time yield (the olefin yield is as high as 1.42 mmol/h·g), and the product is easy to be separated, and has a good application prospect. .
(3)催化剂中金属氧化物具有较高的比表面积，因此金属氧化物表面上具有更多的活性位点，更有利于催化反应的进行。(3) The metal oxide in the catalyst has a high specific surface area, so that the metal oxide has more active sites on the surface, which is more favorable for the catalytic reaction.
(4)催化剂中组分Ⅱ的作用一方面是通过与组分I进行耦合，将组分I产生的活泼气相中间体进一步转化获得低碳烯烃，由于组分II对串联反应平衡拉动的作用可以促进组分I对合成气的活化转化进而提高转化率，另一方面本发明使用的组分II中分子筛特殊的孔道结构，具有独特的择型效应，可以高选择性的获得更多的乙烯产物。(4) The role of component II in the catalyst is to convert the active gas phase intermediate produced by component I to a lower olefin by coupling with component I, and the effect of component II on the equilibrium pull of the series reaction can be Promoting the activation and conversion of the synthesis gas by the component I to increase the conversion rate. On the other hand, the special pore structure of the molecular sieve in the component II used in the invention has a unique shape selection effect, and can obtain more ethylene products with high selectivity. .
(5)单独分别使用本发明中所述的组分I或组分II完全不能实现本发明的功能，例如单独使用组分I时，产物中甲烷选择性非常高，且转化率很低，而单独使用组分II时，几乎不能活化转化合成气，只有组分I与组分II协同催化才能实现高效的合成气转化，并获得优异的选择性。这是由于组分I可以活化合成气生成特定的活泼气相中间体，中间体经由气相扩散到组分II的孔道内，由于本发明选择的MOR结构的分子筛，具有特殊的孔道结构和酸性可以有效的将组分I产生的活泼气相中间体进一步活化转化为烯烃。由于II组分的特殊孔道结构使得产物具有特殊的选择性。(5) The function of the present invention can not be achieved at all by using the component I or the component II described in the present invention separately, for example, when the component I is used alone, the methane selectivity in the product is very high and the conversion rate is low, and When component II is used alone, the converted synthesis gas can hardly be activated, and only component I and component II can be synergistically catalyzed to achieve efficient synthesis gas conversion and excellent selectivity. This is because component I can activate the synthesis gas to form a specific active gas phase intermediate, and the intermediate diffuses into the pores of component II via the gas phase. Due to the molecular sieve of the MOR structure selected by the present invention, it has a special pore structure and acidity. The active gas phase intermediate produced by component I is further activated to be converted to an olefin. Due to the special pore structure of the II component, the product has a special selectivity.
(6)本发明催化剂中组分II使用杂环有机碱进行改性，催化合成气转化得到单一组份乙烯的选择性高达75-85％，且甲烷选择性低于5％，并且大大抑制了C4以上的烃类的选择性。(6) The component II of the catalyst of the invention is modified by using a heterocyclic organic base, and the selectivity of the catalytic synthesis gas conversion to obtain a single component ethylene is as high as 75-85%, and the methane selectivity is less than 5%, and the inhibition is greatly suppressed. Selectivity of hydrocarbons above C4.
具体实施方式Detailed ways
下面通过实施例对本发明做进一步阐述，但是本发明的权利要求范围不受这些实施例的限制。同时，实施例只是给出了实现此目的的部分条件，但并不意味着必须满足这些条件才可以达到此目的。The invention is further illustrated by the following examples, but the scope of the claims of the invention is not limited by the examples. At the same time, the examples only give some of the conditions for achieving this purpose, but it does not mean that these conditions must be met to achieve this.
实施例1Example 1
一、I组分的制备I. Preparation of I component
下面通过实施例对本发明做进一步阐述，但是本发明的权利要求范围不受这些实施 例的限制。同时，实施例只是给出了实现此目的的部分条件，但并不意味着必须满足这些条件才可以达到此目的。The invention is further illustrated by the following examples, but the scope of the claims of the invention is not limited by the examples. At the same time, the examples only give some of the conditions for achieving this purpose, but it does not mean that these conditions must be met to achieve this.
样品的比表面积可以通过氮气或氩气物理吸附的方法进行测试。The specific surface area of the sample can be tested by means of physical adsorption of nitrogen or argon.
本发明所述的金属氧化物可以通过购买市购的高比表面积的金属氧化物获得，也可以通过下述几种方法获得：The metal oxide of the present invention can be obtained by purchasing a commercially available high specific surface area metal oxide, or can be obtained by the following methods:
一、催化剂组分Ⅰ的制备I. Preparation of catalyst component I
(一)、沉淀法合成具有高比表面的ZnO材料：(1) Synthesis of ZnO materials with high specific surface by precipitation method:
(1)分别称取3份、每份0.446g(1.5mmol)Zn(NO 3) 2·6H 2O于3个容器中，再分别称取0.300g(7.5mmol)、0.480g(12mmol)、0.720g(18mmol)NaOH依次加入上述3个容器中，再各量取30ml去离子水加入到3个容器中，70℃搅拌0.5h以上使溶液混合均匀，自然冷却至室温。反应液离心分离收集离心分离后的沉淀物，用去离子水洗涤2次获得ZnO金属氧化物前驱体； (1) Weigh 3 parts, 0.446 g (1.5 mmol) of Zn(NO 3 ) 2 ·6H 2 O in 3 containers, and weigh 0.300 g (7.5 mmol) and 0.480 g (12 mmol), respectively. 0.720 g (18 mmol) of NaOH was sequentially added to the above three containers, and 30 ml of deionized water was added to each of the three containers, and the mixture was stirred at 70 ° C for 0.5 h or more to uniformly mix the solution, and naturally cooled to room temperature. The reaction solution was centrifuged to collect the precipitate after centrifugation, and washed twice with deionized water to obtain a ZnO metal oxide precursor;
(2)焙烧：上述获得的产物在空气中烘干以后，在气氛中进行焙烧处理，即得到高比表面的ZnO材料。气氛为惰性气体、还原性气体或者氧化性气体；惰性气体为N 2、He和Ar中的一种或二种以上；还原性气体为H 2、CO的一种或二种，还原气中也可以含有惰性气体；氧化性气体是O 2、O 3、NO 2中的一种或两种以上，氧化气体中也可以含有惰性气体。焙烧温度为300-700℃，时间为0.5h-12h。 (2) Calcination: After the above-obtained product is dried in the air, it is calcined in an atmosphere to obtain a ZnO material having a high specific surface. The atmosphere is an inert gas, a reducing gas or an oxidizing gas; the inert gas is one or more of N 2 , He and Ar; the reducing gas is one or two of H 2 and CO, and the reducing gas is also The inert gas may be contained; the oxidizing gas may be one or more of O 2 , O 3 , and NO 2 , and the oxidizing gas may contain an inert gas. The calcination temperature is 300-700 ° C and the time is 0.5 h-12 h.
焙烧的目的是为了将沉淀后的金属氧化物前驱体在高温下分解为高比表面积的氧化物纳米粒子，并且通过焙烧的高温处理可以将分解生成的氧化物表面吸附物种处理干净。The purpose of the calcination is to decompose the precipitated metal oxide precursor into high specific surface area oxide nanoparticles at a high temperature, and the oxide surface adsorbed species formed by decomposition can be cleaned by high temperature treatment of baking.
具体样品及其制备条件如下表1，作为对比例，表中ZnO#4是市售低比表面积的ZnO单晶。The specific samples and their preparation conditions are shown in Table 1 below. As a comparative example, ZnO#4 in the table is a commercially available ZnO single crystal having a low specific surface area.
表1 ZnO材料的制备及其参数性能Table 1 Preparation of ZnO materials and their parameter properties
Figure PCTCN2019073388-appb-000001
Figure PCTCN2019073388-appb-000001
(二)共沉淀法合成具有高比表面积的MnO材料：(2) Synthesis of MnO materials with high specific surface area by coprecipitation method:
制备过程同上述ZnO#2，不同之处在于将Zn的前驱体换成了Mn的对应的前驱体，可为硝酸锰、氯化锰、醋酸锰中的一种，在此为硝酸锰，对应产物定义为MnO；比表面 积是：23m 2/g。 The preparation process is the same as the above ZnO#2, except that the precursor of Zn is replaced by the corresponding precursor of Mn, which may be one of manganese nitrate, manganese chloride and manganese acetate, here is manganese nitrate, corresponding The product was defined as MnO; the specific surface area was: 23 m 2 /g.
(三)共沉淀法合成具有高比表面积的CeO 2材料： (3) Synthesis of CeO 2 materials with high specific surface area by coprecipitation:
制备过程同上述ZnO#2，不同之处在于将Zn的前驱体换成了Ce的对应的前驱体，可为硝酸铈、氯化铈、醋酸铈中的一种，在此为硝酸铈,对应产物定义为CeO 2；比表面积是：92m 2/g。 The preparation process is the same as the above ZnO#2, except that the precursor of Zn is replaced by the corresponding precursor of Ce, which may be one of cerium nitrate, cerium chloride and cerium acetate, which is cerium nitrate, corresponding thereto. The product was defined as CeO 2 ; the specific surface area was: 92 m 2 /g.
(四)共沉淀法合成具有高比表面积的Ga 2O 3材料： (4) Synthesis of Ga 2 O 3 materials with high specific surface area by coprecipitation method:
制备过程同上述ZnO#2，不同之处在于将Zn的前驱体换成了Ga的对应的前驱体，可为硝酸镓、氯化镓、醋酸镓中的一种，在此为硝酸镓，对应产物定义为Ga 2O 3；比表面积是：55m 2/g。 The preparation process is the same as the above ZnO#2, except that the precursor of Zn is replaced by the corresponding precursor of Ga, which may be one of gallium nitrate, gallium chloride or gallium acetate, here is gallium nitrate, corresponding The product was defined as Ga 2 O 3 ; the specific surface area was: 55 m 2 /g.
(五)共沉淀法合成具有高比表面积的Bi 2O 3材料： (5) Synthesis of Bi 2 O 3 material with high specific surface area by coprecipitation method:
制备过程同上述ZnO#2，不同之处在于将Zn的前驱体换成了Bi的对应的前驱体，可为硝酸铋、氯化铋、醋酸铋中的一种，在此为硝酸铋。对应产物定义为Bi 2O 3；比表面积分别是：87m 2/g。 The preparation process is the same as that of the above ZnO #2, except that the precursor of Zn is replaced by the corresponding precursor of Bi, which may be one of cerium nitrate, cerium chloride or cerium acetate, here cerium nitrate. The corresponding product was defined as Bi 2 O 3 ; the specific surface area was: 87 m 2 /g.
(六)共沉淀法合成具有高比表面积的In 2O 3材料： (6) Synthesis of In 2 O 3 materials with high specific surface area by coprecipitation method:
制备过程同上述ZnO#2，不同之处在于将Zn的前驱体换成了In的对应的前驱体，可为硝酸铟、氯化铟、醋酸铟中的一种，在此为硝酸铟，对应产物定义为In 2O 3；比表面积是：52m 2/g The preparation process is the same as the above ZnO#2, except that the precursor of Zn is replaced by the corresponding precursor of In, which may be one of indium nitrate, indium chloride and indium acetate, here is indium nitrate, corresponding The product is defined as In 2 O 3 ; the specific surface area is: 52 m 2 /g
(七)沉淀法合成具有高比表面积的Mn aCr (1-a)O x、Mn aAl (1-a)O x、Mn aZr (1-a)O x、Mn aIn (1-a)O x、Zn aCr (1-a)O x、Zn aAl (1-a)O x、Zn aGa (1-a)O x、Zn aIn (1-a)O x、Co aAl (1-a)O x、Fe aAl (1-a)O x、In aAl bMn (1-a-b)O x、In aGa bMn (1-a-b)O x： (7) Synthesis of Mn a Cr (1-a) O x , Mn a Al (1-a) O x , Mn a Zr (1-a) O x , Mn a In (1 ) with high specific surface area by precipitation method a) O x , Zn a Cr (1-a) O x , Zn a Al (1-a) O x , Zn a Ga (1-a) O x , Zn a In (1-a) O x , Co a Al (1-a) O x , Fe a Al (1-a) O x , In a Al b Mn (1-ab) O x , In a Ga b Mn (1-ab) O x :
采用硝酸锌、硝酸铝、硝酸铬、硝酸锰、硝酸锆、硝酸铟、硝酸钴、硝酸铁为前驱体，与碳酸铵，在室温下于水中相互混合(其中碳酸铵作为沉淀剂，投料比例为碳酸铵过量或者优选铵离子与金属离子的比例为1:1)；将上述混合液陈化，然后取出洗涤、过滤和干燥，所得的固体在空气气氛下焙烧，获得高比表面的金属氧化物，具体样品及其制备条件如下表2。Using zinc nitrate, aluminum nitrate, chromium nitrate, manganese nitrate, zirconium nitrate, indium nitrate, cobalt nitrate, ferric nitrate as precursors, and ammonium carbonate, mixed with water at room temperature (in which ammonium carbonate is used as a precipitant, the ratio of feed is The ammonium carbonate is excessive or preferably the ratio of ammonium ion to metal ion is 1:1); the above mixture is aged, then taken out, washed, filtered and dried, and the obtained solid is calcined in an air atmosphere to obtain a metal oxide having a high specific surface area. The specific samples and their preparation conditions are shown in Table 2 below.
表2高比表面积金属氧化物的制备及其性能参数Table 2 Preparation of high specific surface area metal oxides and their performance parameters
Figure PCTCN2019073388-appb-000002
Figure PCTCN2019073388-appb-000002
Figure PCTCN2019073388-appb-000003
Figure PCTCN2019073388-appb-000003
(八)、分散剂Cr 2O 3、Al 2O 3或ZrO 2分散的金属氧化物 (8) Dispersing agent Cr 2 O 3 , Al 2 O 3 or ZrO 2 dispersed metal oxide
以分散剂Cr 2O 3、Al 2O 3或ZrO 2为载体，沉淀沉积法制备Cr 2O 3、Al 2O 3或ZrO 2分散的金属氧化物。以分散ZnO的制备为例，将商业Cr 2O 3(比表面积约为5m 2/g)、Al 2O 3(比表面积约为20m 2/g)或ZrO 2(比表面积约为10m 2/g)作为载体预先分散于水中，然后采用硝酸锌为原料，与氢氧化钠沉淀剂在室温下混合沉淀，Zn 2+的摩尔浓度为0.067M，Zn 2+与沉淀剂的摩尔份数比为1：8；然后在160℃下陈化24小时，获得Cr 2O 3、Al 2O 3或ZrO 2为载体分散的ZnO(分散剂于组分Ⅰ中的含量依次为0.1wt％、20wt％、85wt％)。得到的样品在空气下500℃焙烧1h，产物依次定义为分散氧化物1-3，其比表面积依次为：148m 2/g，115m 2/g，127m 2/g。 A Cr 2 O 3 , Al 2 O 3 or ZrO 2 dispersed metal oxide is prepared by a precipitation deposition method using a dispersant Cr 2 O 3 , Al 2 O 3 or ZrO 2 as a carrier. Taking the preparation of dispersed ZnO as an example, commercial Cr 2 O 3 (specific surface area is about 5 m 2 /g), Al 2 O 3 (specific surface area of about 20 m 2 /g) or ZrO 2 (specific surface area of about 10 m 2 / g) previously dispersed in water as a carrier, and zinc nitrate as raw materials, and sodium hydroxide precipitating agent are mixed at room temperature and the precipitate, the molar concentration of 0.067M Zn 2+, Zn 2+ and the mole fraction ratio of precipitant 1:8; then aged at 160 ° C for 24 hours to obtain Cr 2 O 3 , Al 2 O 3 or ZrO 2 as a carrier-dispersed ZnO (the content of the dispersant in the component I is 0.1 wt%, 20 wt%, respectively) , 85wt%). The obtained sample was calcined at 500 ℃ IH, successively product defined in an air dispersed oxide 1-3, which were specific surface area: 148m 2 / g, 115m 2 / g, 127m 2 / g.
以同样的方法，可以获得SiO 2(比表面积约为2m 2/g)、Ga 2O 3(比表面积约为10m 2/g)或TiO 2(比表面积约为15m 2/g)为载体分散的MnO氧化物(分散剂于组分Ⅰ中的含量依次为5wt％、30wt％、60wt％)，产物依次定义为分散氧化物4-6。其比表面积依次为：97m 2/g，64m 2/g，56m 2/g。 In the same manner, SiO 2 (specific surface area of about 2 m 2 /g), Ga 2 O 3 (specific surface area of about 10 m 2 /g) or TiO 2 (specific surface area of about 15 m 2 /g) can be obtained as a carrier dispersion. The MnO oxide (the content of the dispersant in the component I is 5 wt%, 30 wt%, 60 wt%, respectively), and the product is defined as the dispersed oxide 4-6. It was a specific surface area: 97m 2 / g, 64m 2 / g, 56m 2 / g.
以同样的方法，可以获得活性炭(比表面积约为1000m 2/g)、石墨烯(比表面积约为500m 2/g)或碳纳米管(比表面积约为300m 2/g)为载体分散的ZnO氧化物(分散剂 于组分Ⅰ中的含量依次为5wt％、30wt％、60wt％)，产物依次定义为分散氧化物7-9。其比表面积依次为：177m 2/g，245m 2/g，307m 2/g。 In the same manner, activated carbon (having a specific surface area of about 1000 m 2 /g), graphene (having a specific surface area of about 500 m 2 /g) or carbon nanotubes (having a specific surface area of about 300 m 2 /g) can be obtained as a carrier-dispersed ZnO. The oxide (the content of the dispersant in the component I was 5% by weight, 30% by weight, 60% by weight in this order), and the product was defined as the dispersed oxide 7-9. It was a specific surface area: 177m 2 / g, 245m 2 / g, 307m 2 / g.
二、II组分(MOR拓扑结构的分子筛)的制备Preparation of II component (molecular sieve of MOR topology)
所述MOR拓扑结构是一种正交晶系，具有相互平行的椭圆形直通孔道的一维孔道结构，含有8圆环与12圆环平行一维直通孔道，12圆环主孔道侧边存在8圆环口袋连通。The MOR topology is an orthorhombic system having a one-dimensional channel structure with elliptical through-channels parallel to each other, including 8-ring and 12-ring parallel one-dimensional through-channels, and 12-ring main channel sides 8 Ring pockets are connected.
本发明所述的MOR分子筛可以是直接购买的商品分子筛，也可以是自行合成的分子筛。这里使用南开大学催化剂厂生产的MOR分子筛作为MOR1；同时也自行通过水热合成法为例制备了7个具有MOR结构的分子筛；The MOR molecular sieve of the present invention may be a commercially available molecular sieve directly purchased, or may be a self-synthesized molecular sieve. Here, the MOR molecular sieve produced by Nankai University Catalyst Factory was used as MOR1; at the same time, seven molecular sieves with MOR structure were prepared by hydrothermal synthesis.
具体制备过程为：The specific preparation process is:
按照n(SiO 2)/n(Al 2O 3)＝15,n(Na 2O)/n(SiO 2)＝0.2,n(H 2O)/n(SiO 2)＝26. According to n(SiO 2 )/n(Al 2 O 3 )=15, n(Na 2 O)/n(SiO 2 )=0.2, n(H 2 O)/n(SiO 2 )=26.
将硫酸铝与氢氧化钠溶液混合，然后加入硅溶胶，搅拌1h得到均一相的初始凝胶，然后将其转移到高压合成釜中，180℃静态晶化24h后骤冷、洗涤、干燥，即得到丝光沸石样品，标记为Na-MOR。Mixing aluminum sulfate with sodium hydroxide solution, then adding silica sol, stirring for 1h to obtain a uniform gel of the same phase, then transferring it to a high pressure synthesis kettle, static crystallization at 180 ° C for 24 h, quenching, washing, drying, ie A mordenite sample was obtained, labeled as Na-MOR.
取Na-MOR，将其与1mol/L的氯化铵溶液混合，在90℃下搅拌3h，洗涤，烘干，连续进行4次，450度焙烧6h，得到氢型丝光沸石。Na-MOR was taken, mixed with a 1 mol/L ammonium chloride solution, stirred at 90 ° C for 3 hours, washed, dried, continuously carried out 4 times, and calcined at 450 degrees for 6 hours to obtain a hydrogen-type mordenite.
按上述过程制备的具有MOR拓扑结构的分子筛的骨架元素组成可以是Si-Al-O、Ga-Si-O、Ga-Si-Al-O、Ti-Si-O、Ti-Al-Si-O、Ca-Al-O、Ca-Si-Al-O中的一种；The skeleton element composition of the molecular sieve having the MOR topology prepared according to the above process may be Si-Al-O, Ga-Si-O, Ga-Si-Al-O, Ti-Si-O, Ti-Al-Si-O. One of Ca-Al-O and Ca-Si-Al-O;
部分骨架的O元素上连接H，对应产物依次定义为MOR1-8；The O element of some skeletons is connected to H, and the corresponding products are sequentially defined as MOR1-8;
表3具有MOR拓扑结构的分子筛的制备及其性能参数Table 3 Preparation of molecular sieves with MOR topology and their performance parameters
Figure PCTCN2019073388-appb-000004
Figure PCTCN2019073388-appb-000004
Figure PCTCN2019073388-appb-000005
Figure PCTCN2019073388-appb-000005
将制备好的分子筛，取适量于真空下进行脱水脱气处理，温度400℃，压力10 -4Pa，10h之后降至300℃后，向真空腔体内通入200Pa的有机碱气体，平衡10h后在相同温度下脱附1h。 The prepared molecular sieve is subjected to dehydration and degassing treatment under vacuum, the temperature is 400 ° C, the pressure is 10 -4 Pa, and after 10 h, it is lowered to 300 ° C, and then 200 Pa of organic alkali gas is introduced into the vacuum chamber, and after 10 hours of equilibration. Desorbed at the same temperature for 1 h.
将MOR1依次使用：呋喃、噻吩、吡咯、噻唑、咪唑、吡啶、吡嗪、嘧啶、哒嗪、吲哚、喹啉、蝶啶、吖啶处理得到MOR9-21。MOR1 was used in sequence: furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, pteridine, acridine to obtain MOR9-21.
为了举例说明含取代基的杂环化合物的修饰作用，将MOR2经1-甲基呋喃得MOR22；MOR3经1-甲基吡咯处理得MOR23；MOR4经3，5-二甲基吡啶处理得到MOR24；MOR5经4-乙基吡啶处理得到MOR25；MOR6经3-甲基喹啉处理得到MOR26；MOR7经过4-甲基吲哚处理得到MOR27；MOR8经过5-甲基吖啶处理得到MOR28。In order to illustrate the modification of the substituent-containing heterocyclic compound, MOR2 is obtained by 1-methylfuran to obtain MOR22; MOR3 is treated with 1-methylpyrrole to obtain MOR23; MOR4 is treated with 3,5-lutidine to obtain MOR24; MOR5 was treated with 4-ethylpyridine to obtain MOR25; MOR6 was treated with 3-methylquinoline to obtain MOR26; MOR7 was treated with 4-methylindole to obtain MOR27; MOR8 was treated with 5-methylacridine to obtain MOR28.
三、催化剂的制备Third, the preparation of the catalyst
将所需比例的组分Ⅰ和组分Ⅱ加入容器中，利用这些物料和/或容器的高速运动产生的挤压力、撞击力、裁剪力、摩擦力等中的一种或两种以上作用实现分离、破碎、混匀等目的，通过调变温度与载气气氛实现机械能、热能与化学能的转换，进一步调节不同组分间的相互作用。Adding the required proportion of component I and component II to the container, and utilizing one or more of pressing force, impact force, cutting force, friction force, etc. generated by high-speed movement of these materials and/or containers The purpose of separation, crushing, mixing, etc., to achieve the conversion of mechanical energy, thermal energy and chemical energy through the modulation temperature and the carrier gas atmosphere, further adjust the interaction between different components.
机械混合过程中，可以设置混合温度20-100℃，可以在气氛中或者直接在空气中进行，气氛选自以下任意的气体：During the mechanical mixing process, a mixing temperature of 20-100 ° C can be set, which can be carried out in an atmosphere or directly in the air, and the atmosphere is selected from any of the following gases:
a)氮气和/或惰性气体；a) nitrogen and / or inert gas;
b)氢气与氮气和/或惰性气体的混合气，其中氢气于混合气中的体积为5～50％；b) a mixture of hydrogen and nitrogen and / or an inert gas, wherein the volume of hydrogen in the mixture is 5 to 50%;
c)CO与氮气和/或惰性气体的混合气，其中CO于混合气中的体积为5～20％；c) a mixture of CO and nitrogen and / or an inert gas, wherein the volume of CO in the mixed gas is 5 to 20%;
d)O 2与氮气和/或惰性气体的混合气，其中O 2于混合气中的体积为5-20％，所述惰性气体为氦气、氩气、氖气中的一种或两种以上。 d) a mixture of O 2 and nitrogen and/or an inert gas, wherein the volume of O 2 in the mixed gas is 5-20%, and the inert gas is one or both of helium, argon and helium. the above.
机械混合可采用机械搅拌、球磨、摇床混合、机械研磨中的一种或二种以上进行复合，具体如下：The mechanical mixing may be compounded by one or more of mechanical stirring, ball milling, shaker mixing, and mechanical grinding, as follows:
机械搅拌：在搅拌槽中，采用搅拌棒将组分Ⅰ和组分Ⅱ进行混合，通过控制搅拌时间(5min-120min)和速率(30-300转/min)，可以调节组分Ⅰ和组分Ⅱ的混合程度。Mechanical agitation: Mixing component I and component II with a stir bar in a stirred tank, adjusting component I and components by controlling the stirring time (5 min-120 min) and rate (30-300 rpm) The degree of mixing of II.
球磨：利用磨料与催化剂在研磨罐内高速翻滚，对催化剂产生强烈冲击、碾压，达到分散、混合组分Ⅰ和组分Ⅱ的作用。通过控制磨料(材质可以是不锈钢、玛瑙、石英。尺寸范围：5mm-15mm)。与催化剂的比例(质量比范围：20-100:1)。Ball Milling: Using the abrasive and the catalyst to tumbling at high speed in the grinding tank, the catalyst is strongly impacted and crushed to achieve the function of dispersing and mixing the component I and the component II. By controlling the abrasive (material can be stainless steel, agate, quartz. Size range: 5mm-15mm). Ratio to catalyst (mass ratio range: 20-100:1).
摇床混合法：将组分Ⅰ和组分Ⅱ预混合，并装入容器中；通过控制摇床的往复振荡或圆周振荡，实现组分Ⅰ和组分Ⅱ的混合；通过调节振荡速度(范围：1-70转/分)和时间(范围：5min-120min)，实现均匀混合。Shaker mixing method: premixing component I and component II into a container; mixing of component I and component II by controlling reciprocating oscillation or circumferential oscillation of the shaker; adjusting the oscillation speed (range) : 1-70 rpm) and time (range: 5 min - 120 min) for uniform mixing.
机械研磨法：将组分Ⅰ和组分Ⅱ预混合，并装入容器中；在一定的压力(范围:5公斤-20公斤)下,通过研具与混合的催化剂进行相对运动(速率范围：30-300转/min)，实现均匀混合的作用。Mechanical grinding method: Premixing component I and component II into a container; under a certain pressure (range: 5 kg-20 kg), the relative motion is carried out by the lap and the mixed catalyst (rate range: 30-300 rev / min), to achieve a uniform mixing effect.
具体的催化剂制备及其参数特征如表4所示。The specific catalyst preparation and its parameter characteristics are shown in Table 4.
表4催化剂的制备及其参数特征Table 4 Preparation of catalysts and their parameter characteristics
Figure PCTCN2019073388-appb-000006
Figure PCTCN2019073388-appb-000006
Figure PCTCN2019073388-appb-000007
Figure PCTCN2019073388-appb-000007
Figure PCTCN2019073388-appb-000008
Figure PCTCN2019073388-appb-000008
Figure PCTCN2019073388-appb-000009
Figure PCTCN2019073388-appb-000009
催化反应实例Catalytic reaction example
以固定床反应为例，但是催化剂也适用于移动床反应器。该装置配备气体质量流量计、在线产物分析色谱(反应器的尾气直接与色谱的定量阀连接，进行周期实时采样分析)。A fixed bed reaction is exemplified, but the catalyst is also suitable for use in a moving bed reactor. The device is equipped with a gas mass flow meter and an online product analysis chromatograph (the exhaust gas of the reactor is directly connected to the chromatographic quantitative valve for periodic real-time sampling analysis).
将上述本发明的催化剂2g，置于固定床反应器中，使用Ar置换反应器中的空气，然后再在H 2气氛中升温至300℃，切换合成气(H 2/CO摩尔比＝0.2-3.5)，合成气的压力为0.5-10MPa，升温至反应温度300-600℃，调节反应原料气的空速至500-8000ml/g/h。产物由在线色谱检测分析。 2 g of the above catalyst of the present invention was placed in a fixed bed reactor, the air in the reactor was replaced with Ar, and then the temperature was raised to 300 ° C in a H 2 atmosphere to switch the synthesis gas (H 2 /CO molar ratio = 0.2-). 3.5), the pressure of the synthesis gas is 0.5-10 MPa, the temperature is raised to a reaction temperature of 300-600 ° C, and the space velocity of the reaction raw material gas is adjusted to 500-8000 ml/g/h. The product was analyzed by on-line chromatography.
改变温度、压力和空速，可以改变反应性能。乙烯丙烯在产物中的选择性高达83-90％，原料转化率10-60％；由于分子筛与氧化物有效的协同作用，避免了甲烷的大量生成，甲烷选择性低于5％，其中乙烯的选择性达到75-85％。Changing the temperature, pressure and airspeed can change the reaction performance. The selectivity of ethylene propylene in the product is as high as 83-90%, and the conversion of raw materials is 10-60%. Due to the effective synergy between molecular sieve and oxide, the mass production of methane is avoided, and the selectivity of methane is less than 5%. The selectivity is 75-85%.
表5催化剂的应用及其效果Table 5 catalyst application and its effect
Figure PCTCN2019073388-appb-000010
Figure PCTCN2019073388-appb-000010
Figure PCTCN2019073388-appb-000011
Figure PCTCN2019073388-appb-000011
对比例2采用的催化剂的组分I为金属ZnCo，ZnCo摩尔比1：1，其余参数及混合过程等均同催化剂C。The component I of the catalyst used in Comparative Example 2 was a metal ZnCo, and the ZnCo molar ratio was 1:1, and the remaining parameters and the mixing process were the same as the catalyst C.
对比例3采用的催化剂的组分I为TiO 2，其余参数及混合过程等均同催化剂C。 The component I of the catalyst used in Comparative Example 3 was TiO 2 , and the remaining parameters and the mixing process were the same as the catalyst C.
对比例4-11的反应结果表明，MOR使用有机碱进行改性处理对催化性能调控作用明显，相比不使用有机碱进行调控的催化剂，调控后的催化剂明显降低了甲烷及C4以上烃类的选择性，同时提高了低碳烯烃和乙烯选择性。The results of the reaction of Comparative Example 4-11 show that the modification of MOR with organic base has a significant effect on the catalytic performance. Compared with the catalyst without the use of organic base, the controlled catalyst significantly reduces the hydrocarbons of methane and above. Selectivity while increasing the selectivity of low carbon olefins and ethylene.
对比例12采用的催化剂是仅有组分I，为ZnO#1，不含有MOR分子筛的样品，反应转化率很低，且产物主要以二甲醚，甲烷等副产物为主，几乎没有乙烯生成。The catalyst used in Comparative Example 12 was only the component I, which was ZnO #1, and did not contain the MOR molecular sieve. The reaction conversion rate was very low, and the product was mainly composed of dimethyl ether, methane and other by-products, and almost no ethylene was formed. .
对比例13采用的催化剂是仅有组分II，为MOR9分子筛，不含有组分I的样品，催化反应几乎没有活性。The catalyst used in Comparative Example 13 was a sample having only component II, being a MOR9 molecular sieve, and containing no component I, and the catalytic reaction was almost inactive.
对比例12,13表明只有组分I或组分II时反应效果极其差，完全不具备本发明所述的优异反应性能。Comparative Examples 12 and 13 show that only the component I or the component II has an extremely poor reaction effect and does not have the excellent reaction properties as described in the present invention.
提供以上实施例仅仅是为了描述本发明的目的，而并非要限制本发明的范围。本发明的范围由所附权利要求限定。不脱离本发明的精神和原理而做出的各种等同替换和修改，均应涵盖在本发明的范围之内。The above examples are provided solely for the purpose of describing the invention and are not intended to limit the scope of the invention. The scope of the invention is defined by the appended claims. Various equivalents and modifications may be made without departing from the spirit and scope of the invention.

Claims (10)

  1. 一种催化剂，其特征在于：所述催化剂包括组分Ⅰ和组分Ⅱ，所述组分Ⅰ和组分Ⅱ以机械混合方式复合在一起，组分Ⅰ的活性成份为金属氧化物，组分Ⅱ为MOR拓扑结构的分子筛；所述MOR拓扑结构的分子筛经有机碱改性处理；所述改性处理是将有机碱分散到所述MOR拓扑结构的分子筛的12圆环孔道内的B酸位点；所述有机碱是杂环化合物；优选杂芳基；进一步优选含1-2个杂原子的杂芳基；更优选含1-2个N原子的5或6元杂芳基。A catalyst characterized in that the catalyst comprises a component I and a component II, the component I and the component II are compounded together by mechanical mixing, and the active component of the component I is a metal oxide, a component II is a molecular sieve of MOR topology; the molecular sieve of the MOR topology is treated by an organic base; the modification treatment is to disperse the organic base to the B acid site in the 12-ring channel of the molecular sieve of the MOR topology. The organic base is a heterocyclic compound; preferably a heteroaryl group; further preferably a heteroaryl group having 1 to 2 hetero atoms; more preferably a 5- or 6-membered heteroaryl group having 1 to 2 N atoms.
  2. 根据权利要求1所述的催化剂，其特征在于：所述杂环化合物是呋喃、噻吩、吡咯、噻唑、咪唑、吡啶、吡嗪、嘧啶、哒嗪、吲哚、喹啉、蝶啶或吖啶；优选所述杂环化合物带有甲基，乙基，氨基，硝基中的一种或两种以上的取代基，进一步优选间位和/或对位取代。The catalyst according to claim 1, wherein the heterocyclic compound is furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, anthracene, quinoline, pteridine or acridine Preferably, the heterocyclic compound has one or two or more substituents of a methyl group, an ethyl group, an amino group, and a nitro group, and further preferably a meta and/or para substitution.
  3. 根据权利要求1所述的催化剂，其特征在于：所述的金属氧化物为MnO x、Mn aCr (1-a)O x、Mn aAl (1-a)O x、Mn aZr (1-a)O x、Mn aIn (1-a)O x、ZnO x、Zn aCr (1-a)O x、Zn aAl (1-a)O x、Zn aGa (1-a)O x、Zn aIn (1-a)O x、CeO x、Co aAl (1-a)O x、Fe aAl (1-a)O x、GaO x、BiO x、InO x、In aAl bMn (1-a-b)O x、In aGa bMn (1-a-b)O x中的一种或二种以上； The catalyst according to claim 1, wherein said metal oxide is MnO x , Mn a Cr (1-a) O x , Mn a Al (1-a) O x , Mn a Zr (1) -a) O x , Mn a In (1-a) O x , ZnO x , Zn a Cr (1-a) O x , Zn a Al (1-a) O x , Zn a Ga (1-a) O x , Zn a In (1-a) O x , CeO x , Co a Al (1-a) O x , Fe a Al (1-a) O x , GaO x , BiO x , InO x , In a One or more of Al b Mn (1-ab) O x and In a Ga b Mn (1-ab) O x ;
    所述MnO x、ZnO x、CeO x、GaO x、BiO x、InO x的比表面积是1-100m 2/g；优选比表面积是50-100m 2/g； The specific surface area of the MnO x , ZnO x , CeO x , GaO x , BiO x , InO x is 1-100 m 2 /g; preferably the specific surface area is 50-100 m 2 /g;
    所述Mn aCr (1-a)O x、Mn aAl (1-a)O x、Mn aZr (1-a)O x、Mn aIn (1-a)O x、Zn aCr (1-a)O x、Zn aAl (1-a)O x、Zn aGa (1-a)O x、Zn aIn (1-a)O x、Co aAl (1-a)O x、Fe aAl (1-a)O x、In aAl bMn (1-a-b)O x、In aGa bMn (1-a-b)O x的比表面积是5-150m 2/g。优选比表面积是50-150m 2/g； The Mn a Cr (1-a) O x , Mn a Al (1-a) O x , Mn a Zr (1-a) O x , Mn a In (1-a) O x , Zn a Cr ( 1-a) O x , Zn a Al (1-a) O x , Zn a Ga (1-a) O x , Zn a In (1-a) O x , Co a Al (1-a) O x The specific surface area of Fe a Al (1-a) O x , In a Al b Mn (1-ab) O x , and In a Ga b Mn (1-ab) O x is 5-150 m 2 /g. Preferably the specific surface area is 50-150 m 2 /g;
    所述x的取值范围是0.7～3.7，a的取值范围是0～1；a+b的取值范围是0～1；The value of x ranges from 0.7 to 3.7, the range of a ranges from 0 to 1, and the range of a+b ranges from 0 to 1.
  4. 按照权利要求1所述的催化剂，其特征在于：组分Ⅰ中的活性成份与组分Ⅱ的重量比为0.1-20，优选为0.3-8。Catalyst according to claim 1, characterized in that the weight ratio of active ingredient to component II in component I is from 0.1 to 20, preferably from 0.3 to 8.
  5. 按照权利要求1所述的催化剂，其特征在于：所述组分I中还添加有分散剂，所述金属氧化物分散于分散剂中，分散剂为Al 2O 3、SiO 2、Cr 2O 3、ZrO 2、TiO 2、Ga 2O 3、活性炭、石墨烯、碳纳米管中的一种或二种以上。 The catalyst according to claim 1, wherein said component I further contains a dispersing agent, said metal oxide being dispersed in a dispersing agent, said dispersing agent being Al 2 O 3 , SiO 2 , Cr 2 O 3 , one or more of ZrO 2 , TiO 2 , Ga 2 O 3 , activated carbon, graphene, and carbon nanotubes.
  6. 按照权利要求1所述的催化剂，其特征在于：所述组分Ⅰ中，分散剂的含量在0.05-90wt％，其余为金属氧化物。The catalyst according to claim 1, wherein in the component I, the dispersant is contained in an amount of from 0.05 to 90% by weight, the balance being a metal oxide.
  7. 按照权利要求1-6任一项所述的催化剂，其特征在于：所述MOR拓扑结构分子筛的骨架元素组成是Si-Al-O、Ga-Si-O、Ga-Si-Al-O、Ti-Si-O、Ti-Al-Si-O、Ca-Al-O、Ca-Si-Al-O中的一种或二种以上。The catalyst according to any one of claims 1 to 6, wherein the skeleton element composition of the MOR topology molecular sieve is Si-Al-O, Ga-Si-O, Ga-Si-Al-O, Ti. One or more of -Si-O, Ti-Al-Si-O, Ca-Al-O, and Ca-Si-Al-O.
  8. 一种合成气反应高选择性制乙烯的方法，其特征在于：以合成气混合气为反应原料，在固定床或移动床上进行转化反应，得到乙烯为主的低碳烯烃产物，所采用的催化剂为权利要求1-7任一所述的催化剂。The invention relates to a method for synthesizing high selectivity ethylene to syngas, characterized in that: a synthesis gas mixture gas is used as a reaction raw material, and a conversion reaction is carried out on a fixed bed or a moving bed to obtain an ethylene-based low-carbon olefin product, and the catalyst used A catalyst according to any one of claims 1-7.
  9. 根据权利要求8所述的方法，其特征在于：所述合成气的压力为0.5-10MPa，优选为1-8MPa，更优选为2-8MPa；反应温度为300-600℃，优选为350-450℃；空速为 300-10000h -1，优选为500-9000h -1，更优选为500-6000h -1。所述合成气为含有H 2/CO混合气，H 2/CO摩尔比为0.2-3.5，优选为0.3-2.5；所述合成气中还可以含有CO 2，其中CO 2在合成气中的体积浓度为0.1-50％。 The method according to claim 8, characterized in that the pressure of the synthesis gas is from 0.5 to 10 MPa, preferably from 1 to 8 MPa, more preferably from 2 to 8 MPa; and the reaction temperature is from 300 to 600 ° C, preferably from 350 to 450. ℃; space velocity 300-10000h -1, preferably 500-9000h -1, more preferably 500-6000h -1. The synthesis gas is a H 2 /CO mixed gas having a H 2 /CO molar ratio of 0.2-3.5, preferably 0.3-2.5; the synthesis gas may further contain CO 2 , wherein the volume of CO 2 in the synthesis gas The concentration is 0.1-50%.
  10. 按照权利要求8所述的方法，其特征在于：所述方法以合成气一步法直接转化制C 2-4烯烃，乙烯选择性为75-85％，副产物甲烷选择性<5％。 Process according to claim 8, characterized in that the process is directly converted to a C 2-4 olefin by a one-step synthesis gas with an ethylene selectivity of 75-85% and a by-product methane selectivity of <5%.
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