WO2019144953A1 - 一种有机碱修饰的复合催化剂及一氧化碳加氢制乙烯的方法 - Google Patents
一种有机碱修饰的复合催化剂及一氧化碳加氢制乙烯的方法 Download PDFInfo
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- WO2019144953A1 WO2019144953A1 PCT/CN2019/073387 CN2019073387W WO2019144953A1 WO 2019144953 A1 WO2019144953 A1 WO 2019144953A1 CN 2019073387 W CN2019073387 W CN 2019073387W WO 2019144953 A1 WO2019144953 A1 WO 2019144953A1
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Definitions
- the invention belongs to high-value chemicals such as hydrogenation of carbon monoxide to low-carbon olefins, and particularly relates to an organic 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 and a reaction temperature of 300 to 400 ° C in a synthesis gas.
- 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 holes and MOR molecular sieves is used for the one-step olefin reaction of syngas to increase the selectivity of ethylene to 75-80%, 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 to further reduce the selectivity of the methane by-product to below 9%, and further reduces the selectivity of the hydrocarbon above C4.
- 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 the reaction of carbon monoxide and hydrogen to directly form a low-carbon olefin, and a C2-C3 olefin
- the selectivity is as high as 78-87%
- the selectivity of the single product ethylene can be as high as 75-82%
- the methane selectivity is lower than 9%
- the hydrocarbon selectivity of C4 and above is less than 10%.
- the technical scheme of the present invention is: a catalyst comprising component I and components, component I and component II are compounded together by mechanical mixing, the active component of component I is metal oxide, and component II is MOR.
- the molecular sieve of the topology, in the component II, the molecular sieve of the MOR topology is treated by a fatty amine modification, and the modification treatment is to disperse the fatty amine into the 12-ring channel of the molecular sieve of the MOR topology. Acid site.
- the fatty amine is dimethylamine, trimethylamine, diethylamine, triethylamine, ethylenediamine, monopropylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, 1,2-dimethylpropylamine, 1 , 2-propanediamine, 2-propenylamine, cyclopropylamine, n-butylamine, di-n-butylamine, isobutylamine, sec-butylamine, 1,4-butanediamine, tert-butylamine, diisobutylamine hexylamine, 2 One or two or more of ethylhexylamine, hexamethylenediamine, and trioctylamine.
- 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 treated by fatty amine modification, which can prevent the organic base molecules from entering the 8-ring channel, but selectively occupy the 12-ring B acid sites.
- 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 aperture.
- the fatty amine modification of the present invention refers to the use of a fatty amine molecule to occupy the B acid site in the 12-ring channel of the MOR molecular sieve, 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 a fatty amine into the B acid site in the annular channel of the MOR molecular sieve 12 all known methods for achieving the purpose can meet the requirements, here the vacuum dehydration adsorption method is taken as an example, first in the vacuum The temperature of the molecular sieve is dehydrated and degassed at a temperature of 350-500 ° C, the pressure is 1 Pa-10 -5 Pa, and the time is 4 h-24 h, and the degassed molecular sieve is further exposed to an atmosphere of 10 Pa-100 kPa of a fatty amine or inert.
- the adsorption temperature is controlled to be room temperature -300 ° C, and the inorganic amine-modified molecular sieve is obtained by purging with an inorganic gas at 200-330 ° C for 30 min to 12 h.
- 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 in component I to component II is 0.1-20 times, preferably 0.3-8; multi-component synergy can make the reaction work efficiently, and one of them is too much or too little to be detrimental to the reaction. .
- a dispersing agent is further added to the component I, and the dispersing agent is one of Al 2 O 3 , SiO 2 , Cr 2 O 3 , ZrO 2 , TiO 2 , Ga 2 O 3 , activated carbon, graphene, and carbon nanotubes.
- the metal oxide is dispersed in the dispersing agent in an amount of from 0.05 to 90% by weight, preferably from 0.05 to 25% by weight, based on the active 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 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 0.2-3.5, preferably 0.3-2.5, and a higher space-time yield can be obtained and the selective synthesis gas can also contain CO 2 , wherein the CO 2 is in the synthesis gas.
- the volume concentration is 0.1-50%.
- 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 78-87%, the selectivity of ethylene reaches 75-82%, and the by-product methane is also The selectivity is extremely low ( ⁇ 9%) and the selectivity for hydrocarbons above C4 and above is less than 10%.
- 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 75-82%, and has high space-time yield (the olefin yield is as high as 1.33 mmol/hg), 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, the product of the component I alone has a very high selectivity for methane and a low conversion rate, and is used alone.
- Component II can hardly activate the conversion synthesis gas, and only component I and component II can be catalyzed to achieve efficient synthesis gas conversion and obtain 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 component II, the product has a special selectivity.
- component II is modified with a fatty amine, and the selectivity of catalytic synthesis gas conversion to single component ethylene is as high as 75-82%, and methane is less than 9%, and hydrocarbons above C4 are greatly inhibited.
- the selectivity of the class is less than 10%.
- 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, MOR2, MOR3, MOR4, MOR5, MOR6, MOR7, MOR 8 are used sequentially: dimethylamine, trimethylamine, diethylamine, triethylamine, ethylenediamine, monopropylamine, dipropylamine, tripropylamine, isopropylamine , diisopropylamine, 1,2-dimethylpropylamine, 1,2-propylenediamine, 2-propenylamine, cyclopropylamine, n-butylamine, di-n-butylamine, isobutylamine, sec-butylamine, 1,4 After treatment with butyl diamine, tert-butylamine, diisobutylamine hexylamine, 2-ethylhexylamine, hexamethylenediamine and trioctylamine, MOR9, MOR10, MOR11, MOR12, MOR13, MOR14, MOR15, MOR16, MOR17 were obtained
- 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 synthesis gas may also contain CO 2 , wherein the volume concentration of CO 2 in the synthesis gas is 0.1-50%.
- 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 300-10000 ml/g/h.
- the product was analyzed by on-line chromatography.
- Changing the temperature, pressure and airspeed can change the reaction performance.
- the selectivity of ethylene propylene in the product is as high as 78-87%, and the conversion of raw materials is 10-60%. Due to the effective synergy between the molecular sieve and the oxide, the mass production of methane and C 4+ hydrocarbons is avoided.
- the component I of the catalyst used in Comparative Example 10 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 11 was TiO 2 , and the remaining parameters and the mixing process were the same as Catalyst C.
- the catalyst used in Comparative Example 12 was a sample in which only component I was ZnO #1 and did not contain MOR molecular sieve, and 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 component II-only MOR9 molecular sieve, and did not contain the metal oxide of the component I as an active component, 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.
Abstract
Description
Claims (9)
- 一种催化剂,其特征在于:包括组分I和组分II,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,II组分中,所述MOR拓扑结构的分子筛经脂肪胺改性处理;所述改性处理是将脂肪胺分散到所述MOR拓扑结构的分子筛的12圆环孔道内的B酸位点。
- 根据权利要求1所述的催化剂,其特征在于:所述脂肪胺是二甲胺、三甲胺、二乙胺、三乙胺、乙二胺、一丙胺、二丙胺、三丙胺、异丙胺、二异丙胺、1,2-二甲基丙胺、1,2-丙二胺、2-丙烯胺、环丙胺、正丁胺、二正丁胺、异丁胺、仲丁胺、1,4-丁二胺、叔丁胺、二异丁胺己胺、2-乙基己胺、己二胺、三辛胺中的一种或两种以上。
- 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;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;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;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;
- 根据权利要求1所述的催化剂,其特征在于:所述组分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。
- 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,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,金属氧化物分散于分散剂中,分散剂于I组分中的含量在0.05-90wt%,优选0.05-25wt%,其余为活性金属氧化物。
- 按照权利要求1-5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。
- 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1-6任一所述的催化剂。
- 根据权利要求7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300-450℃;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%。
- 按照权利要求7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75-82%,副产物甲烷选择性<9%,4个C原子以上的烃类产物选择性低于10%。
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EP3744424A1 (en) | 2020-12-02 |
CN109939722A (zh) | 2019-06-28 |
US20200346992A1 (en) | 2020-11-05 |
JP7007763B2 (ja) | 2022-02-10 |
CA3087611C (en) | 2023-06-13 |
RU2749513C1 (ru) | 2021-06-11 |
SA520412485B1 (ar) | 2023-02-05 |
AU2019210781A1 (en) | 2020-08-06 |
ZA202101245B (en) | 2022-07-27 |
US11365165B2 (en) | 2022-06-21 |
EP3744424A4 (en) | 2021-11-03 |
CN109939722B (zh) | 2021-05-25 |
AU2019210781B2 (en) | 2021-08-12 |
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