WO2018120576A1 - 一种用于二氧化碳一步加氢制备烃类的催化剂及其制备方法 - Google Patents

一种用于二氧化碳一步加氢制备烃类的催化剂及其制备方法 Download PDF

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Publication number
WO2018120576A1
WO2018120576A1 PCT/CN2017/083680 CN2017083680W WO2018120576A1 WO 2018120576 A1 WO2018120576 A1 WO 2018120576A1 CN 2017083680 W CN2017083680 W CN 2017083680W WO 2018120576 A1 WO2018120576 A1 WO 2018120576A1
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Prior art keywords
catalyst
metal oxide
molecular sieve
solution
carbon dioxide
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English (en)
French (fr)
Inventor
孙予罕
党闪闪
高鹏
卜宪昵
刘子玉
王慧
钟良枢
邱明煌
石志彪
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Shanghai Advanced Research Institute of CAS
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Shanghai Advanced Research Institute of CAS
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Priority to EP17888274.2A priority Critical patent/EP3593901A4/en
Priority to US16/475,122 priority patent/US11583839B2/en
Publication of WO2018120576A1 publication Critical patent/WO2018120576A1/zh
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    • B01J37/08—Heat treatment

Definitions

  • the invention relates to the technical field of catalysts, in particular to a catalyst for preparing hydrocarbons by one-step hydrogenation of carbon dioxide and a preparation method thereof.
  • the hydrogenation of CO 2 by hydrogen produced by new energy can convert CO 2 into chemicals (methanol, formic acid and dimethyl ether, etc.), synthesis gas, materials and liquid fuels.
  • the research on the hydrogenation of CO 2 to form hydrocarbons is mainly divided into two types: one is a reaction similar to methanol-like Fischer-Tropsch synthesis (FTS); the other is a reaction through an intermediate species of methanol.
  • FTS methanol-like Fischer-Tropsch synthesis
  • most of the research work uses an FTS-like reaction path that does not pass through methanol.
  • CO 2 first reacts with reverse water gas shift (RWGS) to form CO, and then CO hydrogenates and then undergoes FTS reaction.
  • RWGS reverse water gas shift
  • the catalytic component of CO 2 -based FTS is generally similar to that of conventional FTS.
  • the industrial FTS synthesis catalyst mainly has two types of cobalt-based and iron-based catalysts.
  • the cobalt-based catalyst is generally used as a methanation catalyst instead of an FTS catalyst in a CO 2 hydrogenation atmosphere.
  • Cobalt-based catalysts have no activity on RWGS reaction.
  • Iron-based catalysts are active in both WGS and RWGS. Therefore, the study of CO 2 -based FTS focuses on the modification of iron-based catalysts, especially for the synthesis of olefins. Activity.
  • the iron-based catalyst has a complicated phase structure, poor chain growth ability, short life, and low Fischer-Tropsch activity, resulting in high selectivity of by-product CO. These factors make iron-based catalysts have no advantage in synthesizing long-chain hydrocarbons. Advantages.
  • an object of the present invention is to provide a catalyst for preparing a hydrocarbon by one-step hydrogenation of carbon dioxide and a preparation method thereof, which have excellent catalytic performance, good reaction stability, and selection of target products. High sex.
  • the present invention provides a catalyst for the one-step hydrogenation of carbon dioxide to produce a hydrocarbon, comprising a nano metal oxide and a multi-stage pore zeolite molecular sieve, the nano metal oxide accounting for the mass of the catalyst
  • the fraction is from 10% to 90%
  • the multistage pore zeolite molecular sieve accounts for 10% to 90% of the mass fraction of the catalyst.
  • the nano metal oxide is selected from the group consisting of MgO, ZnO, Al 2 O 3 , Cr 2 O 3 , Y 2 O 3 , La 2 O 3 , Ga 2 O 3 , In 2 O 3 , Fe 3 O 4 , MnO. 2 , any one or more of TiO 2 , ZrO 2 , SnO 2 and CeO 2 .
  • the nano metal oxide particles have a small size, a particle diameter of 10 to 30 nm, a large specific surface area, a specific surface area of 70 to 150 m 2 /g, and a higher reactivity.
  • the multistage pore zeolite molecular sieve is a double pore structure zeolite molecular sieve having micropores and mesopores obtained by alkali treatment of a microporous zeolite molecular sieve.
  • the introduction of mesopores by alkali treatment can greatly shorten the diffusion distance of molecules in the micropores of zeolites, which is beneficial to the transfer of substances, thereby enhancing the apparent catalytic activity and improving the stability of the catalyst.
  • Micropores are used as a microreactor. A reactive center or adsorption site is provided, which is also selective for the shape and size of the molecule.
  • microporous zeolite molecule is screened with any one or more of Y, ZSM-5, ZSM-22, Beta, MCM-22 and SAPO-34 type zeolite molecular sieves.
  • the alkali treatment can be carried out using a process in the prior art.
  • a process in the prior art For example: (1) 0.15 ⁇ 0.25mol / L NaOH as the alkali source, the treatment temperature is 60 ⁇ 75 ° C, the treatment time is 25 ⁇ 35min.
  • the multistage pore zeolite molecular sieve has a specific surface area of from 100 to 1000 m 2 /g.
  • the multistage pore zeolite molecular sieve comprises micropores and mesopores, wherein the mesopores have a pore diameter of 2 to 40 nm and a mesoporous pore volume of 0.1 to 0.9 cm 3 /g.
  • the present invention also discloses a method of preparing a catalyst as described above, comprising the steps of:
  • the metal oxide obtained in the step 4) is mixed with the multi-stage pore molecular sieve according to the catalyst composition ratio to prepare a composite catalyst.
  • the metal salt is selected from any one or more of a hydrochloride, a nitrate, a bromide, an acetate, an oxalate and an ammonium salt.
  • the solution is selected from one or both of water and alcohol.
  • the solution is a combination of both alcohol and water, and the volume ratio of the alcohol to the water is (1 to 3): (1 to 4).
  • the alcohol is selected from methanol, ethanol or propanol.
  • the concentration of the metal salt solution is from 0.1 to 1 mol/L.
  • the precipitating agent is selected from any one or more of ammonia water, ammonium carbonate, sodium carbonate, sodium hydroxide and sodium acetate.
  • the solution is selected from one or both of water and alcohol.
  • the solution is selected from a combination of both alcohol and water, and the volume ratio of the alcohol to the water is (1 to 3): (1 to 4). Further preferably, the alcohol is selected from methanol, ethanol or propanol.
  • the concentration of the precipitant solution is from 0.1 to 2 mol/L.
  • the reaction temperature is 10 to 40 ° C; after the reaction is completed, the pH of the precipitation mother liquid is 7 to 11.
  • the precipitated mother liquor is aged at a certain temperature such that the precipitated particles are further enlarged.
  • the aging conditions are: the aging temperature is 60 to 100 ° C, and the aging time is 0.1 to 10 h.
  • the drying temperature is 60 to 120 ° C, and the drying time is 6 to 24 hours.
  • the calcination temperature is from 250 to 600 ° C, and the calcination time is from 1 to 8 h.
  • the mixing method is any one of mechanical mixing, grinding mixing or ball milling mixing.
  • the mechanical mixing comprises the steps of: compressing and sieving the metal oxide and the multi-stage pore molecular sieve to obtain nano-particles of 20-80 mesh, loading into a glass container, and uniformly mixing by vibration. .
  • the grinding and mixing comprises the steps of: grinding the metal oxide and the multi-stage pore molecular sieve in an agate mortar for 0.1 to 4 hours, then pressing and sieving to obtain nano-particles of 20-80 mesh.
  • the ball milling mixing comprises the steps of: ball-milling the metal oxide and the multi-stage pore molecular sieve in a ball mill for 0.1 to 24 h, then pressing and sieving to obtain nano-particles of 20-80 mesh.
  • the invention also discloses the use of a catalyst as described above for the preparation of a hydrocarbon reaction by the catalyst for the one-step hydrogenation of carbon dioxide.
  • the catalyst is activated prior to use of the catalyst for the one-step hydrogenation of carbon dioxide to produce hydrocarbons in an inert gas atmosphere of Ar, N 2 or He or a reducing gas H 2 atmosphere.
  • the gradient is raised to 250-600 ° C, and the activation time is 1-10 h.
  • the one-step hydrogenation of the carbon dioxide to produce a hydrocarbon reaction is carried out on a fixed bed.
  • the catalyst for the preparation of hydrocarbons by one-step hydrogenation of carbon dioxide provided by the present invention and the preparation method thereof have the following beneficial effects:
  • the invention fully mixes the reactant metal salt and the precipitant in proportion to form a solid phase precursor which is easily decomposed, and obtains a nano metal oxide by washing, calcining and grinding a plurality of times, and recovers the nano metal oxide and the multi-stage zeolite molecular sieve.
  • the preparation of the composite catalyst, the nano metal oxide catalyst particle size is small, the CO 2 activation ability is high, and the hydrogenation ability is moderate;
  • the multi-stage pore zeolite molecular sieve catalyst has a mesopores which is beneficial to the mass transfer and diffusion of the intermediate species during the reaction, It helps to pull the reaction equilibrium and obtain higher target product selectivity. It also helps to reduce carbon deposit and improve catalyst stability.
  • the preparation process of the catalyst in the invention is simple and controllable, the production efficiency is improved, and the production cost is greatly reduced.
  • a 0.1 mol/L precipitant solution is prepared in a mixed solution of absolute ethanol, and the precipitant solution is added dropwise to the metal salt solution at a temperature of 20 ° C, and the dropping process is sufficiently stirred, and the final pH is maintained at 9, After the completion of the precipitation reaction, the obtained product was aged under stirring at 70 ° C for 4 h, and then the resulting precipitate was washed several times with deionized water, then dried at 80 ° C for 12 h, and then calcined at 350 ° C for 4 h to obtain a metal oxide, which was characterized. It was found that the particle diameter was 20 nm and the specific surface area was 75 m 2 /g.
  • a multistage pore zeolite molecular sieve h-ZSM-5 having a specific surface area of 500 m 2 /g, a mesoporous pore diameter of 4.1 nm, and a mesoporous pore volume of 0.41 cm 3 /g was used.
  • the content of the metal oxide is 10%, and the content of the multi-stage pore zeolite molecular sieve is 90%.
  • the metal oxide is ground in the agate mortar together with the multi-stage pore molecular sieve for 2 hours, and then tableted, After sieving, a 40 to 60 mesh composite catalyst was obtained.
  • the obtained product is aged at 60 ° C for 6 hours, and then the resulting precipitate is washed several times with deionized water and then dried at 60 ° C for 18 hours.
  • a metal oxide was obtained, and the particle size was 10 nm, the specific surface area was 136 m 2 /g, and the tablet was sieved to 20 to 40 mesh.
  • the content of the metal oxide is 50%
  • the content of the multi-stage pore zeolite molecular sieve is 50%
  • the particles of the metal oxide and the molecular sieve are charged into the glass container according to the ratio, and the composite catalyst is obtained by uniform mixing by vibration. .
  • the final pH was maintained at 11, and the obtained product was aged at 100 ° C for 1.5 h after the completion of the precipitation reaction, and then the resulting precipitate was washed several times with deionized water, then dried at 60 ° C for 24 h, and then calcined at 300 ° C for 7 h.
  • a metal oxide was obtained, which was characterized by a particle size of 23 nm and a specific surface area of 112 m 2 /g.
  • the molecular sieve used a multistage zeolite molecular sieve h-ZSM-22 having a specific surface area of 445 m 2 /g, a mesoporous pore diameter of 4.39 nm and a mesoporous pore volume of 0.49 cm 3 /g. Based on the total mass of the catalyst, the content of the metal oxide is 33.3%, and the content of the multi-stage pore zeolite molecular sieve is 66.7%.
  • the metal oxide is ball-milled together with the multi-stage pore molecular sieve in the ball mill for 24 hours, and then pressed and sieved. A composite catalyst of 60 to 80 mesh was obtained.
  • the hydrogenation of carbon dioxide to synthesize hydrocarbons is carried out in a stainless steel reactor of 8 mm internal diameter.
  • the evaluation results are shown in Table 1.
  • the final pH was kept at 10, and the obtained product was aged at 80 ° C for 5 h after the completion of the precipitation reaction, and then the resulting precipitate was washed several times with deionized water, then dried at 65 ° C for 16 h, and then passed through 500 ° C.
  • the metal oxide was obtained by calcination for 5 hours, and it was characterized that the particle diameter was 16 nm and the specific surface area was 98 m 2 /g.
  • the molecular sieve used a multistage pore zeolite molecular sieve h-Beta having a specific surface area of 650 m 2 /g, a mesoporous pore diameter of 13.5 nm, and a mesoporous pore volume of 0.55 cm 3 /g. Based on the total mass of the catalyst, the content of metal oxide is 25%, and the content of multi-stage pore zeolite molecular sieve is 75%.
  • the metal oxide is ball milled together with the multi-stage pore molecular sieve in the ball mill for 11 hours, then pressed and sieved. A composite catalyst of 20 to 40 mesh was obtained.
  • the obtained product is aged under stirring at 100 ° C for 2 h, and then the resulting precipitate is washed several times with deionized water. Then, it was dried at 100 ° C for 10 h and then calcined at 500 ° C for 2.5 h to obtain a metal oxide.
  • the particle size was 27 nm, the specific surface area was 70 m 2 /g, and the tablet was sieved to 40 to 60 mesh.
  • a multistage pore zeolite molecular sieve hY pellet having a specific surface area of 580 m 2 /g, a mesoporous pore diameter of 7 nm and a mesoporous pore volume of 0.85 cm 3 /g was sieved to 40 to 60 mesh.
  • the content of metal oxide is 20%
  • the content of multi-stage pore zeolite molecular sieve is 80%
  • the 40-60 mesh particles obtained by tableting and sieving the metal oxide and molecular sieve are filled into the glass container according to the ratio of the total mass of the catalyst.
  • the composite catalyst is obtained by uniform mixing by shaking.
  • the hydrogenation of carbon dioxide to synthesize hydrocarbons is carried out in a stainless steel reactor of 8 mm internal diameter.
  • the obtained product was aged under stirring at 80 ° C for 2 h, and then the resulting precipitate was washed several times with deionized water, then dried at 100 ° C for 7 h, and calcined at 350 ° C for 5 h to obtain a metal oxide, which was characterized. It was found that the particle diameter was 15 nm, the specific surface area was 131 m 2 /g, and the tablet was sieved to 40 to 60 mesh.
  • a multistage pore zeolite molecular sieve having a specific surface area of 600 m 2 /g, a mesoporous pore size of 15.3 nm and a mesoporous pore volume of 0.46 cm 3 /g
  • the h-ZSM-5 tablet was sieved to 40 to 60 mesh.
  • the content of the metal oxide is 80%, and the content of the multi-stage pore zeolite molecular sieve is 20%, and the metal oxide and the molecular sieve are tableted and sieved to obtain 40-60 mesh particles in the glass container.
  • the composite catalyst is obtained by uniform mixing by shaking.
  • the obtained product is aged at 80 ° C for 2.5 h, and then the resulting precipitate is washed several times with deionized water, then dried at 90 ° C for 13 h, and then passed. After calcination at 400 ° C for 3 h, a metal oxide was obtained, which was characterized by a particle size of 16 nm and a specific surface area of 131 m 2 /g.
  • the molecular sieve used a multistage pore zeolite molecular sieve h-ZSM-5 having a specific surface area of 700 m 2 /g, a mesoporous pore diameter of 5.6 nm, and a mesoporous pore volume of 0.57 cm 3 /g. Based on the total mass of the catalyst, the content of the metal oxide is 50%, and the content of the multi-stage pore zeolite molecular sieve is 50%. The metal oxide is ground together with the multi-stage pore molecular sieve in the agate mortar for 0.2 h, and then tableted. And sieving to obtain a composite catalyst of 20 to 40 mesh.
  • the metal oxide was obtained by calcination for 8 hours, and it was characterized that the particle diameter was 13 nm and the specific surface area was 150 m 2 /g.
  • the molecular sieve used a multistage pore zeolite molecular sieve h-SAPO-34 having a specific surface area of 340 m 2 /g, a mesoporous pore diameter of 28 nm, and a mesoporous pore volume of 0.18 cm 3 /g.
  • the content of the metal oxide is 75%, and the content of the multi-stage pore zeolite molecular sieve is 25%.
  • the metal oxide is ball milled together with the multi-stage pore molecular sieve in the ball mill for 0.2 h, and then pressed and passed. Sieve to obtain a composite catalyst of 60 to 80 mesh.
  • the dropping process Stir well, the final pH is maintained at 9, after the end of the precipitation reaction, the product is aged at 70 ° C for 10 h, then the resulting precipitate is washed several times with deionized water, then dried at 80 ° C for 12 h, then 400
  • the metal oxide was obtained by calcination at ° C for 5 hours, and it was characterized that the particle diameter was 13 nm and the specific surface area was 119 m 2 /g.
  • the catalyst used was a multistage pore zeolite molecular sieve h-Beta having a specific surface area of 650 m 2 /g, a mesoporous pore diameter of 13.5 nm, and a mesoporous pore volume of 0.55 cm 3 /g.
  • the content of the metal oxide is 10%, and the content of the multi-stage pore zeolite molecular sieve is 90%.
  • the metal oxide is ground in the agate mortar together with the multi-stage pore molecular sieve for 4 hours, and then tableted, After sieving, a 40 to 60 mesh composite catalyst was obtained.
  • the use of the catalyst described in this patent for the one-step hydrogenation of carbon dioxide can improve the selectivity of the target product and reduce the selectivity of methane under appropriate conditions.

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Abstract

一种用于二氧化碳一步加氢制备烃类的催化剂及其制备方法。催化剂包括纳米金属氧化物和多级孔沸石分子筛，纳米金属氧化物占催化剂的质量分数为10%-90%，多级孔沸石分子筛占催化剂质量分数为10%-90%。催化剂具有优良的催化性能，反应稳定性好，目标产物选择性高，烃类产物中的C 2 =—C 4 =最高达80%、C 5+最高达85%、芳烃最高达65%。

Description

一种用于二氧化碳一步加氢制备烃类的催化剂及其制备方法 技术领域
本发明涉及催化剂技术领域，特别是涉及一种用于二氧化碳一步加氢制备烃类的催化剂及其制备方法。
背景技术
二氧化碳(CO2)作为一种自然界大量存在的“碳源”化合物，将其转化为有价值的化学品或燃料，不仅能解决过多CO2排放导致的环境问题，还能够缓解化石燃料过度依赖的问题。采用新能源制得的氢气对CO2进行加氢转化，可以将CO2转化为化学品(甲醇、甲酸和二甲醚等)、合成气、材料和液体燃料等产物。在众多产物中，由于经济价值和应用广泛性等原因，烃类化合物被认为是更具潜力的目标产物，如低碳烯烃(C2 ＝～C4 ＝)、高碳烃类(C5+)或芳烃等。由于CO2的化学惰性，CO2加氢转化为甲烷、甲醇和一氧化碳等碳一分子相对容易，但是很难转化为含有两个以上碳原子的化合物。
CO2加氢生成烃类方面的研究主要分为两类：一种是不经过甲醇类似费托合成(FTS)的反应；另一种是经过甲醇中间物种的反应。目前，大部分的研究工作采用不经过甲醇的类FTS反应路径，CO2先通过反水煤气变换(RWGS)反应生成CO，然后CO加氢再发生FTS反应。CO2基FTS的催化组分通常与传统FTS类似，工业FTS合成催化剂主要有钴基和铁基催化剂两类，钴基催化剂在CO2加氢气氛下一般作为甲烷化催化剂而不是FTS催化剂，且钴基催化剂对RWGS反应没有活性，铁基催化剂对WGS和RWGS变化反应均具有活性，因此，CO2基FTS的研究集中在对铁基催化剂的改性，尤其是对合成烯烃类产物具有很高的活性。然而，铁基催化剂物相结构复杂、链增长能力较差、寿命短，且费托活性较低导致副产物CO的选择性较高，这些因素使得铁基催化剂在合成长链烃类方面不具有优势，另外，尽管铁基催化剂对CO2甲烷化的活性比钴基催化剂低很多，但是仍有不少副产物甲烷生成，甲烷选择性通常高于20％。对于经甲醇或相应中间物种一步转化生成烃类的过程，CO2与H2在铜锌基等金属催化剂上先生成甲醇或相应中间物种，继而再转化为其他烃类化合物。生成烃类化合物的反应是吸热反应，温度越高越有利，然而，生成甲醇或相应中间物种的反应是放热反应，温度越高越不利于甲醇的生成，因而如何突破热力学平衡，在保证较低甲烷选择性的前提下，高选择性的得到目标烃类化合物是关键。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种用于二氧化碳一步加氢制备烃类的催化剂及其制备方法，该催化剂具有优良的催化性能，反应稳定性好，目标产物选择性高。
为实现上述目的及其他相关目的，本发明提供一种用于二氧化碳一步加氢制备烃类的催化剂，包括纳米金属氧化物和多级孔沸石分子筛，所述纳米金属氧化物占所述催化剂的质量分数为10％～90％，所述多级孔沸石分子筛占所述催化剂的质量分数为10％～90％。
优选地，所述纳米金属氧化物选用MgO、ZnO、Al2O3、Cr2O3、Y2O3、La2O3、Ga2O3、In2O3、Fe3O4、MnO2、TiO2、ZrO2、SnO2和CeO2中的任意一种或多种。与常规的金属氧化物相比，纳米金属氧化物颗粒尺寸小，粒径为10～30nm，比表面积大，比表面积为70～150m2/g，反应活性更高。
优选地，多级孔沸石分子筛是由微孔沸石分子筛进行碱处理后获得的具有微孔和介孔的双重孔结构沸石分子筛。通过碱处理引入介孔可极大地缩短分子在沸石微孔道中的扩散距离，有利于物质的传递，从而增强表观催化反应活性及提高催化剂的稳定性，微孔作为一种微反应器，不仅提供了反应活性中心或吸附位，还对分子的形状和大小具有选择性。
更优选地，所述微孔沸石分子筛选用Y、ZSM-5、ZSM-22、Beta、MCM-22和SAPO-34型沸石分子筛中的任意一种或多种。
更优选地，所述碱处理可采用现有技术中工艺进行。比如：(1)以0.15～0.25mol/L的NaOH为碱源，处理温度为60～75℃，处理时间为25～35min。(2)以0.15～0.30mol/L有机碱(四丙基氢氧化铵、四丁基氢氧化铵和四甲基氢氧化铵)作为碱源，处理温度为60～75℃，处理时间为25～50min。
优选地，所述多级孔沸石分子筛比表面积为100～1000m2/g。
优选地，所述多级孔沸石分子筛包括微孔和介孔，其中，介孔孔径为2～40nm，介孔孔容为0.1～0.9cm3/g。
本发明还公开一种制备如上述所述的催化剂的方法，包括以下步骤：
1)将金属盐溶解在溶液中配制成金属盐溶液；
2)将沉淀剂溶解在溶液中配制成沉淀剂溶液；
3)将步骤2)得到的所述沉淀剂溶液逐滴加到步骤1)得到的所述金属盐溶液中，经反应生成沉淀母液；
4)将所述沉淀母液老化、洗涤，然后干燥、焙烧，得到金属氧化物；
5)按照催化剂组成配比，将步骤4)得到的所述金属氧化物与所述多级孔分子筛混合，制备获得复合催化剂。
优选地，在步骤1)中，所述金属盐选用盐酸盐、硝酸盐、溴化盐、乙酸盐、草酸盐和铵盐中的任意一种或多种。
优选地，在步骤1)中，所述溶液选用水和醇中的一种或两种。
更优选地，在步骤1)中，所述溶液选用醇和水两者的组合，所述醇与所述水的体积比为(1～3):(1～4)。进一步优选地，所述醇选用甲醇、乙醇或丙醇。
优选地，在步骤1)中，所述金属盐溶液的浓度为0.1～1mol/L。
优选地，在步骤2)中，所述沉淀剂选用氨水、碳酸铵、碳酸钠、氢氧化钠和乙酸钠的任意一种或多种。
优选地，在步骤2)中，所述溶液选用水和醇中的一种或两种。
更优选地，在步骤2)中，所述溶液选用醇和水两者的组合，所述醇与所述水的体积比为(1～3):(1～4)。进一步优选地，所述醇选用甲醇、乙醇或丙醇。
优选地，在步骤2)中，所述沉淀剂溶液的浓度为0.1～2mol/L。
优选地，在步骤3)中，反应温度为10～40℃；在反应完成后，所述沉淀母液的pH为7～11。
优选地，在步骤4)中，沉淀母液在一定温度下老化，使得沉淀颗粒进一步变大。老化的条件为：老化温度为60～100℃，老化时间为0.1～10h。
优选地，在步骤4)中，干燥温度为60～120℃，干燥时间6～24h。
优选地，在步骤4)中，焙烧温度为250～600℃，焙烧时间1～8h。
优选地，在步骤5)中，混合的方式选用机械混合、研磨混合或球磨混合中的任意一种。
优选地，所述机械混合包括以下步骤：将所述金属氧化物与所述多级孔分子筛进行压片、过筛的得到20～80目的纳米颗粒，装入玻璃容器中，通过震动实现均匀混合。
优选地，所述研磨混合包括以下步骤：将所述金属氧化物与所述多级孔分子筛置于玛瑙研钵中研磨0.1～4h，然后压片、过筛，得到20～80目的纳米颗粒。
优选地，所述球磨混合包括以下步骤：将所述金属氧化物与所述多级孔分子筛置于球磨机中球磨0.1～24h，然后压片、过筛，得到20～80目的纳米颗粒。
本发明还公开一种如上述所述催化剂的用途，为使所述催化剂用于进行二氧化碳一步加氢制备烃类反应。
优选地，在将所述催化剂用于进行二氧化碳一步加氢制备烃类前先将所述催化剂进行 活化，活化条件为：在惰性气体Ar、N2或He氛围中，或者还原气H2氛围中，梯度升温至250～600℃，活化时间为1～10h。
优选地，所述二氧化碳一步加氢制备烃类反应的条件为：反应压力为0.3～5.0MPa，反应温度为300～450℃，体积空速为1000～12000h-1，H2/CO2摩尔比＝1～5。
优选地，所述二氧化碳一步加氢制备烃类反应在固定床上进行。
如上所述，本发明提供的用于二氧化碳一步加氢制备烃类的催化剂及其制备方法，具有以下有益效果：
本发明将反应物金属盐和沉淀剂按比例充分混合，生成易分解的固相前驱物，经多次洗涤、煅烧、研磨得到纳米金属氧化物，将纳米金属氧化物与多级沸石分子筛进行复配制备成复合催化剂，纳米金属氧化物催化剂颗粒尺寸小、CO2活化能力高，且加氢能力适中；多级孔沸石分子筛催化剂具有的介孔有利于反应过程中中间物种的传质扩散，有助于反应平衡的拉动、获得较高的目标产物选择性，还有助于减少积碳，提升催化剂稳定性。
本发明获得的催化剂具有优良的催化性能，反应稳定性好，目标产物选择性高，烃类产物中的C2 ＝～C4 ＝最高达80％、C5+最高达85％、芳烃最高达65％；副产物甲烷选择性低，CH4选择性低于5％。
本发明中催化剂的制备过程简单可控，提高生产效率，大大降低生产成本。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
实施例1
将40.4g Fe(NO3)3·9H2O加入到1L去离子水中，配制成金属离子浓度为0.1mol/L混合金属盐溶液，将5.30g碳酸钠加入到0.25L去离子水与0.25L无水乙醇的混合溶液中配成0.1mol/L的沉淀剂溶液，在20℃温度下将沉淀剂溶液逐滴加入到金属盐溶液中，滴加过程需充分搅拌，最终pH值保持在9，沉淀反应结束后将所得产物在70℃搅拌条件下老化4h，随后将所得沉淀用去离子水洗涤数次，然后在80℃下干燥12h，再经350℃焙烧4h，得到金属氧化物，经表征得知其粒径为20nm、比表面积为75m2/g。将比表面积为500m2/g、介孔孔径为4.1nm、介孔孔容为0.41cm3/g的多级孔沸石分子筛h-ZSM-5。以催化剂总质 量计，金属氧化物的含量为10％，多级孔沸石分子筛含量为90％，按该比例将金属氧化物与多级孔分子筛一起在玛瑙研钵中研磨2h，然后压片、过筛，得到40～60目的复合催化剂。
二氧化碳加氢合成烃类反应在8mm内径的不锈钢反应器中进行。反应前先将催化剂在惰性气体Ar氛围中梯度升温至350℃，活化4h，然后通入H2/CO2摩尔比＝3:1的混合气进行反应，反应条件为：P＝5.0MPa，T＝300℃，GHSV＝4000h-1，以冰水浴收集液相产物，气相色谱分析产物组成，评价结果见表1。
实施例2
分别将13.32g Cr(NO3)2·9H2O与28.62g Zr(NO3)4·5H2O加入到0.1L水与0.025L无水乙醇的混合溶液中，配制成金属离子浓度为0.8mol/L混合金属盐溶液，将3.3mL氨水加入到0.05L无水乙醇的混合溶液中配成1mol/L的沉淀剂溶液，在25℃温度下将沉淀剂溶液逐滴加入到金属盐溶液中，滴加过程需充分搅拌，最终pH值保持在10，沉淀反应结束后将所得产物在60℃搅拌条件下老化6h，随后将所得沉淀用去离子水洗涤数次，然后在60℃下干燥18h，再经300℃焙烧3h，得到金属氧化物，经表征得知其粒径为10nm、比表面积为136m2/g，压片过筛成20～40目。将比表面积为340m2/g、介孔孔径为28nm、介孔孔容为0.19cm3/g的多级孔沸石分子筛h-SAPO-34压片成40～60目。以催化剂总质量计，金属氧化物的含量为50％，多级孔沸石分子筛含量为50％，按该比例将金属氧化物与分子筛的颗粒装入玻璃容器中，通过震动实现均匀混合获得复合催化剂。
二氧化碳加氢合成烃类反应在8mm内径的不锈钢反应器中进行，反应前先将催化剂在惰性气体Ar氛围中梯度升温至400℃，活化2h，然后通入H2/CO2摩尔比＝2:1的混合气进行反应，反应条件为：P＝3.0MPa，T＝400℃，GHSV＝9000h-1，以冰水浴收集液相产物，气相色谱分析产物组成，评价结果见表1。
实施例3
将41.79g Ga(NO3)3·xH2O加入到0.12L水与0.08L无水乙醇的混合溶液中，配制成金属离子浓度为0.5mol/L混合金属盐溶液，将3.3mL氨水加入到0.01L去离子水与0.02L无水乙醇的混合溶液中配成1.67mol/L的沉淀剂溶液，在15℃下将沉淀剂溶液逐滴加入到金属盐溶液中，滴加过程需充分搅拌，最终pH值保持在11，沉淀反应结束后将所得产物在100℃搅拌条件下老化1.5h，随后将所得沉淀用去离子水洗涤数次，然后在60℃下干燥24h，再经300℃焙烧7h，得到金属氧化物，经表征得知其粒径为23nm、比表面积为112m2/g。分子筛使用比表面积为445m2/g、介孔孔径为4.39nm、介孔孔容为0.49cm3/g多级孔沸石 分子筛h-ZSM-22。以催化剂总质量计，金属氧化物的含量为33.3％，多级孔沸石分子筛含量为66.7％，按该比例将金属氧化物与多级孔分子筛一起在球磨机中球磨24h，然后压片、过筛，得到60～80目的复合催化剂。
二氧化碳加氢合成烃类反应在8mm内径的不锈钢反应器中进行，反应前先将催化剂在惰性气体N2氛围中梯度升温至350℃，活化5h，然后通入H2/CO2摩尔比＝4:1的混合气进行反应，反应条件如下：P＝0.5MPa，T＝350℃，GHSV＝2000h-1，以冰水浴收集液相产物，气相色谱分析产物组成，评价结果见表1。
实施例4
将38.3g Y(NO3)4·6H2O加入到0.125L去离子水和0.125L无水乙醇的混合溶液中，配制成金属离子浓度为0.4mol/L混合金属盐溶液，将7.86g碳酸铵加入到0.067L去离子水与0.033L无水乙醇的混合溶液中配成0.5mol/L的沉淀剂溶液，在30℃下将沉淀剂溶液逐滴加入到金属盐溶液中，滴加过程需充分搅拌，最终pH值保持在10，沉淀反应结束后将所得产物在80℃搅拌条件下老化5h，随后将所得沉淀用去离子水洗涤数次，然后在65℃下干燥16h，再经500℃焙烧5h得到金属氧化物，经表征得知其粒径为16nm、比表面积为98m2/g。分子筛使用比表面积为650m2/g、介孔孔径为13.5nm、介孔孔容为0.55cm3/g的多级孔沸石分子筛h-Beta。以催化剂总质量计，金属氧化物的含量为25％，多级孔沸石分子筛含量为75％，按该比例将金属氧化物与多级孔分子筛一起在球磨机中球磨11h，然后压片、过筛，得到20～40目的复合催化剂。
二氧化碳加氢合成烃类反应在8mm内径的不锈钢反应器中进行，反应前先将催化剂在惰性气体N2氛围中梯度升温至600℃，活化3h，然后通入H2/CO2摩尔比＝5:1的混合气进行反应，反应条件如下：P＝2MPa，T＝450℃，GHSV＝12000h-1，以冰水浴收集液相产物，气相色谱分析产物组成，评价结果见表1。
实施例5
分别将9.91g Zn(NO3)2·6H2O与28.64g Zr(NO3)4·5H2O加入到0.025L去离子水与0.1L无水乙醇的混合溶液中，配制成金属离子浓度为0.8mol/L混合金属盐溶液，将5.30g碳酸钠加入到0.015L去离子水与0.01L无水乙醇的混合溶液中配成2mol/L的沉淀剂溶液，在40℃下将沉淀剂溶液逐滴加入到金属盐溶液中，滴加过程需充分搅拌，最终pH值保持在8，沉淀反应结束后将所得产物在100℃搅拌条件下老化2h，随后将所得沉淀用去离子水洗涤数次，然后在100℃下干燥10h，再经500℃焙烧2.5h得到金属氧化物，经表征得知其粒径为27nm、比表面积为70m2/g，压片过筛成40～60目。将比表面积为580m2/g、介孔孔 径为7nm、介孔孔容为0.85cm3/g的多级孔沸石分子筛h-Y压片过筛成40～60目。以催化剂总质量计，金属氧化物的含量为20％，多级孔沸石分子筛含量为80％，按该比例将金属氧化物与分子筛压片、过筛得到的40～60目颗粒装入玻璃容器中，通过震动实现均匀混合获得复合催化剂。
二氧化碳加氢合成烃类反应在8mm内径的不锈钢反应器中进行，反应前先将催化剂在惰性气体N2氛围中梯度升温至600℃，活化1.5h，然后通入H2/CO2摩尔比＝3:1的混合气进行反应，反应条件为：P＝3MPa，T＝450℃，GHSV＝7000h-1，以冰水浴收集液相产物，气相色谱分析产物组成，评价结果见表1。
实施例6
分别将9.91g Zn(NO3)2·6H2O与28.64g Zr(NO3)4·5H2O加入到0.1L去离子水中，配制成金属离子浓度为1mol/L混合金属盐溶液，将5.30g碳酸钠加入到0.05L去离子水中配成1mol/L的沉淀剂溶液，在40℃下将沉淀剂溶液逐滴加入到金属盐溶液中，滴加过程需充分搅拌，最终pH值保持在7，沉淀反应结束后将所得产物在80℃搅拌条件下老化2h，随后将所得沉淀用去离子水洗涤数次，然后在100℃下干燥7h，再经350℃焙烧5h，得到金属氧化物，经表征得知其粒径为15nm、比表面积为131m2/g，压片过筛成40～60目。将比表面积为600m2/g、介孔孔径为15.3nm、介孔孔容为0.46cm3/g的多级孔沸石分子筛
h-ZSM-5压片过筛成40～60目。以催化剂总质量计，金属氧化物的含量为80％，多级孔沸石分子筛含量为20％，按该比例将金属氧化物与分子筛压片、过筛的得到40～60目颗粒装入玻璃容器中，通过震动实现均匀混合获得复合催化剂。
二氧化碳加氢合成烃类反应在8mm内径的不锈钢反应器中进行，反应前先将催化剂在惰性气体N2氛围中梯度升温至500℃，活化1.5h，然后通入H2/CO2摩尔比＝2:1的混合气进行反应，反应条件如下：P＝3.0MPa，T＝450℃，GHSV＝9000h-1，以冰水浴收集液相产物，气相色谱分析产物组成，评价结果见表1。
实施例7
将38.18g In(NO3)3·4.5H2O加入到0.4L去离子水与1.6L无水乙醇的混合溶液中，配制成金属离子浓度为0.05mol/L混合金属盐溶液，将7.86g碳酸铵加入到0.1L去离子水与0.15L无水乙醇的混合溶液中配成0.2mol/L的沉淀剂溶液，在20℃下将沉淀剂溶液逐滴加入到金属盐溶液中，滴加过程需充分搅拌，最终pH值保持在8.5，沉淀反应结束后将所得产物在80℃搅拌条件下老化2.5h，随后将所得沉淀用去离子水洗涤数次，然后在90℃下干燥13h，再经400℃焙烧3h，得到金属氧化物，经表征得知其粒径为16nm、比表面积为131 m2/g。分子筛使用比表面积为700m2/g、介孔孔径为5.6nm、介孔孔容为0.57cm3/g的多级孔沸石分子筛h-ZSM-5。以催化剂总质量计，金属氧化物的含量为50％，多级孔沸石分子筛含量为50％，按该比例将金属氧化物与多级孔分子筛一起在玛瑙研钵中研磨0.2h，然后压片、过筛，得到20～40目的复合催化剂。
二氧化碳加氢合成烃类反应在8mm内径的不锈钢反应器中进行，反应前先将催化剂在惰性气体H2氛围中梯度升温至450℃，活化2h，然后通入H2/CO2摩尔比＝3:1的混合气进行反应，反应条件如下：P＝4MPa，T＝340℃，GHSV＝3000h-1，以冰水浴收集液相产物，气相色谱分析产物组成，评价结果见表1。
实施例8
将38.18g In(NO3)3·4.5H2O加入到0.05L去离子水与0.05L无水乙醇的混合溶液中，配制成金属离子浓度为1mol/L混合金属盐溶液，将3.3mL氨水加入到0.025L去离子水与0.025L无水乙醇的混合溶液中配成1mol/L的沉淀剂溶液，在25℃温度下将沉淀剂溶液逐滴加入到金属盐溶液中，滴加过程需充分搅拌，最终pH值保持在11，沉淀反应结束后将所得产物在75℃搅拌条件下老化0.5h，随后将所得沉淀用去离子水洗涤数次，然后在100℃下干燥15h，再经250℃焙烧8h得到金属氧化物，经表征得知其粒径为13nm、比表面积为150m2/g。分子筛使用比表面积为340m2/g、介孔孔径为28nm、介孔孔容为0.18cm3/g的多级孔沸石分子筛h-SAPO-34。以催化剂总质量计，金属氧化物的含量为75％，多级孔沸石分子筛含量为25％，按该比例将金属氧化物与多级孔分子筛一起在球磨机中球磨0.2h，然后压片、过筛，得到60～80目的复合催化剂。
二氧化碳加氢合成烃类反应在8mm内径的不锈钢反应器中进行，反应前先将催化剂在惰性气体Ar氛围中梯度升温至300℃，活化10h，然后通入H2/CO2摩尔比＝1:1的混合气进行反应，反应条件如下：P＝3MPa，T＝380℃，GHSV＝6000h-1，以冰水浴收集液相产物，气相色谱分析产物组成，评价结果见表1。
实施例9
将40.4g Fe(NO3)3·9H2O加入到0.14L去离子水与0.06L无水乙醇的混合溶液中，配制成金属离子浓度为0.5mol/L混合金属盐溶液，将5.30g碳酸钠加入到0.036L去离子水与0.009L无水乙醇的混合溶液中配成1.1mol/L的沉淀剂溶液，在18℃温度下将金属盐溶液逐滴加入到沉淀剂溶液中，滴加过程需充分搅拌，最终pH值保持在9，沉淀反应结束后将所得产物在70℃搅拌条件下老化10h，随后将所得沉淀用去离子水洗涤数次，然后在80℃下干燥12h，再经400℃焙烧5h得到金属氧化物，经表征得知其粒径为13nm、比表面积 为119m2/g。催化剂使用比表面积为650m2/g、介孔孔径为13.5nm、介孔孔容为0.55cm3/g的多级孔沸石分子筛h-Beta。以催化剂总质量计，金属氧化物的含量为10％，多级孔沸石分子筛含量为90％，按该比例将金属氧化物与多级孔分子筛一起在玛瑙研钵中研磨4h，然后压片、过筛，得到40～60目的复合催化剂。
二氧化碳加氢合成烃类反应在8mm内径的不锈钢反应器中进行，反应前先将催化剂在惰性气体H2氛围中梯度升温至500℃，活化3h，然后通入H2/CO2摩尔比＝3:1的混合气进行反应，反应条件如下：P＝4MPa，T＝370℃，GHSV＝10000h-1，以冰水浴收集液相产物，气相色谱分析产物组成，评价结果见表1。
表1实施例1至9获得的催化剂的反应结果
Figure PCTCN2017083680-appb-000001
由表1可以看出，采用本专利所述催化剂用于二氧化碳一步加氢反应中在适当的条件下可提高目标产物选择性，降低甲烷的选择性。具体地：实施例1至9获得的催化剂在P＝0.3～5.0MPa、T＝300～450℃、GHSV＝1000～12000h-1和n(H2)/n(CO2)＝1～5的条件下，目标产物选择性高，烃类产物中的C2 ＝～C4 ＝最高达80.2％、C5+最高达84.7％、芳烃最高达64.7％；主要副产物甲烷选择性低，CH4选择性低于5％；催化剂的失活速率低，不高于2.2％。因此，实施例1至9获得催化剂反应活性高，主要副产物CH4选择性低，目标产物低碳烯烃、高碳烃类或芳烃化合物选择性高，失活速率低。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (11)

  1. 一种用于二氧化碳一步加氢制备烃类的催化剂，其特征在于，包括纳米金属氧化物和多级孔沸石分子筛，所述纳米金属氧化物占所述催化剂的质量分数为10％～90％，所述多级孔沸石分子筛占所述催化剂的质量分数为10％～90％。
  2. 如权利要求1所述的用于二氧化碳一步加氢制备烃类的催化剂，其特征在于，所述纳米金属氧化物选用MgO、ZnO、Al2O3、Cr2O3、Y2O3、La2O3、Ga2O3、In2O3、Fe3O4、MnO2、TiO2、ZrO2、SnO2和CeO2中的任意一种或多种；所述多级孔沸石分子筛选用Y、ZSM-5、ZSM-22、Beta、MCM-22和SAPO-34型分子筛中的任意一种或多种。
  3. 一种制备如权利要求1或2所述的催化剂的方法，其特征在于，包括以下步骤：
    1)将金属盐溶解在溶液中配制成金属盐溶液；
    2)将沉淀剂溶解在溶液中配制成沉淀剂溶液；
    3)将步骤2)得到的所述沉淀剂溶液逐滴加到步骤1)得到的所述金属盐溶液中，经反应生成沉淀母液；
    4)将所述沉淀母液老化、洗涤，然后干燥、焙烧，得到金属氧化物；
    5)按照催化剂组成配比，将步骤4)得到的所述金属氧化物与所述多级孔分子筛混合，制备获得复合催化剂。
  4. 如权利要求3所述的方法，其特征在于，还包括以下特征中任一项或多项：
    1)在步骤1)中，所述金属盐选用盐酸盐、硝酸盐、溴化盐、乙酸盐、草酸盐和铵盐中的任意一种或多种；
    2)在步骤1)中，所述溶液选用水和醇中的一种或两种；
    3)在步骤1)中，所述金属盐溶液的浓度为0.1～1mol/L；
    4)在步骤2)中，所述沉淀剂选用氨水、碳酸铵、碳酸钠、氢氧化钠和乙酸钠的任意一种或多种；
    5)在步骤2)中，所述溶液选用水和醇中的一种或两种；
    6)在步骤2)中，所述沉淀剂溶液的浓度为0.1～2mol/L；
    7)在步骤3)中，反应温度为10～40℃；在反应完成后，所述沉淀母液的pH为7～11；
    8)在步骤4)中，老化的条件为：老化温度为60～100℃，老化时间为0.1～10h；
    9)在步骤4)中，干燥温度为60～120℃，干燥时间6～24h；
    10)在步骤4)中，焙烧温度为250～600℃，焙烧时间1～8h。
  5. 如权利要求4所述的方法，其特征在于，在步骤5)中，混合的方式选用机械混合、研 磨混合或球磨混合中的任意一种。
  6. 如权利要求5所述的方法，其特征在于，所述机械混合包括以下步骤：将所述金属氧化物与所述多级孔分子筛进行压片、过筛的得到20～80目的纳米颗粒，装入玻璃容器中，通过震动实现均匀混合。
  7. 如权利要求5所述的方法，其特征在于，所述研磨混合包括以下步骤：将所述金属氧化物与所述多级孔分子筛置于玛瑙研钵中研磨0.1～4h，然后压片、过筛，得到20～80目的纳米颗粒。
  8. 如权利要求5所述的方法，其特征在于，所述球磨混合包括以下步骤：将所述金属氧化物与所述多级孔分子筛置于球磨机中球磨0.1～24h，然后压片、过筛，得到20～80目的纳米颗粒。
  9. 一种如权利要求1至2任一所述催化剂的用途，为使所述催化剂用于进行二氧化碳一步加氢制备烃类反应。
  10. 如权利要求9所述的用途，其特征在于，在将所述催化剂用于进行二氧化碳一步加氢制备烃类前先将所述催化剂进行活化，活化条件为：在惰性气体Ar、N2或He氛围中，或者还原气H2氛围中，梯度升温至250～600℃，活化时间为1～10h。
  11. 如权利要求9所述的用途，其特征在于，所述二氧化碳一步加氢制备烃类反应的条件为：反应压力为0.3～5.0MPa，反应温度为300～450℃，体积空速为1000～12000h-1，H2/CO2摩尔比＝1～5。
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