CN116474779A - 用于二氧化碳加氢合成甲醇的催化剂及其制备方法和用途、二氧化碳加氢合成甲醇的方法 - Google Patents
用于二氧化碳加氢合成甲醇的催化剂及其制备方法和用途、二氧化碳加氢合成甲醇的方法 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 4
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 4
- 239000011029 spinel Substances 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 241000282326 Felis catus Species 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 7
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229960004543 anhydrous citric acid Drugs 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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Abstract
本发明提供一种用于二氧化碳加氢合成甲醇的催化剂及其制备方法和用途、二氧化碳加氢合成甲醇的方法。该催化剂的通式为xM‑ZnFe2O4,M元素选自In、Pd、Pt、Cu、Cr、Ga、Zr中的至少一种,M元素的含量x=0~5wt%,具有尖晶石结构。该制备方法:将包括锌盐、铁盐、可选M元素的盐、有机溶剂和水的混合溶液进行干燥和焙烧。该催化剂用于二氧化碳加氢合成甲醇。该二氧化碳加氢合成甲醇的方法:包含CO2和H2的原料气在该催化剂条件下反应。本发明催化剂在280℃以上高温条件下稳定运行,并具有较高的甲醇选择性,通过M元素掺杂促进CO2和H2的吸附活化,进一步提高CO2转化率以及甲醇时空收率。
Description
技术领域
本发明属于催化剂技术领域,具体涉及一种用于二氧化碳加氢合成甲醇的催化剂及其制备方法和用途、二氧化碳加氢合成甲醇的方法。
背景技术
将CO2转化为高附加值的化学品和燃料,不仅能解决过多CO2排放导致的全球变暖等环境问题,而且能有效缓解对化石燃料的过渡依赖问题。其中,甲醇作为理想的低碳清洁燃料,可替代油气,有助于解决交通碳排放问题;作为中间体广泛应用于化学工业、材料合成等基础工业,可推动绿色制造;作为性能优异的储氢材料,可缓解氢能储运安全、成本等难题。因此,借助可再生能源制得的绿色氢气将CO2转化为高附加值的甲醇,不仅可以解决能源的储运问题,还可中和CO2,实现碳的循环利用。
其中Cu基催化剂应用最为广泛,这归因于Cu基催化剂具有较高的反应活性和甲醇时空收率。然而,传统Cu基催化剂耐水性差导致活性位易烧结,严重影响了其催化活性稳定性,而催化剂作为CO2加氢反应体系中的核心部分,当前还存在一些问题,例如催化剂本身对于CO2的催化转化效率较低,且难以在高温高压的反应条件下维持长久稳定性;现有的一些催化剂原材料昂贵,且制备流程繁琐,时间成本较高等,因此,开发一种稳定性强,甲醇选择性好、制备过程简单,成本低的用于二氧化碳加氢制甲醇的催化剂具有重要意义。
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加氢合成甲醇的催化剂及其制备方法和用途、二氧化碳加氢合成甲醇的方法。
为实现上述目的及其他相关目的,本发明第一方面提供一种用于二氧化碳加氢合成甲醇的催化剂,所述催化剂的通式为xM-ZnFe2O4,M元素选自In、Pd、Pt、Cu、Cr、Ga、Zr中的至少一种,M元素的含量x=0~5wt%,如0~1wt%、1~2wt%、2~3wt%、3~4wt%或4~5wt%,所述催化剂具有尖晶石结构。
x为M元素的质量占M元素和ZnFe2O4总质量的百分比。M元素以氧化物形态存在于催化剂中。
优选地,所述催化剂为纳米颗粒,平均颗粒尺寸为10~15nm。
本发明第二方面提供上述催化剂的制备方法,将包括锌盐、铁盐、可选M元素的盐、有机溶剂和水的混合溶液进行干燥和焙烧,得到所述催化剂。
优选地,所述锌盐选自硝酸锌、乙酸锌和氯化锌中的至少一种;
和/或,所述铁盐选自硝酸铁、氯化铁和柠檬酸铁中的至少一种;
和/或,所述M元素的盐选自M元素的硝酸盐和M元素的氯化盐中的至少一种;
和/或,所述有机溶剂选自尿素、柠檬酸、草酸和蔗糖中的至少一种。
优选地,所述锌盐、所述铁盐和所述有机溶剂的摩尔比为1:2:3~6,如所述锌盐与所述有机溶剂的摩尔比为1:3~4.5或1:4.5~6;
和/或,所述M元素的含量为0~5wt%,如0~1wt%、1~2wt%、2~3wt%、3~4wt%或4~5wt%;
和/或,干燥的温度为80~120℃,如80~90℃、90~100℃、100~110℃或110~120℃;
和/或,干燥的时间为2~4小时;
和/或,焙烧的温度为350~430℃,如350~400℃或400~430℃;
和/或,焙烧的时间为4~8小时,如4~6小时或6~8小时。
本发明第三方面提供上述催化剂的用途,用于二氧化碳加氢合成甲醇。
优选地,包含CO2和H2的原料气在所述催化剂条件下反应,得到甲醇。
更优选地,H2与CO2的摩尔比为2~4,如2~3或3~4;
和/或,反应的质量空速为2000~20000mL/gcat/h,如2000~9000mL/gcat/h、9000~15000mL/gcat/h、15000~18000mL/gcat/h或18000~20000mL/gcat/h;
和/或,反应的压力为3~5Mpa,如3~4Mpa或4~5Mpa;
和/或,反应的温度为280~340℃,如280~290℃、290~300℃、300~310℃、310~320℃、320~330℃或330~340℃;
和/或,所述反应在固定床反应器中进行。
本发明第四方面提供一种二氧化碳加氢合成甲醇的方法,包含CO2和H2的原料气在上述催化剂条件下反应,得到甲醇。
优选地,H2与CO2的摩尔比为2~4,如2~3或3~4;
和/或,反应的质量空速为2000~20000mL/gcat/h,如2000~9000mL/gcat/h、9000~15000mL/gcat/h、15000~18000mL/gcat/h或18000~20000mL/gcat/h;
和/或,反应的压力为3~5MPa,如3~4Mpa或4~5Mpa;
和/或,反应的温度为280~340℃,如280~290℃、290~300℃、300~310℃、310~320℃、320~330℃或330~340℃。
和/或,所述反应在固定床反应器中进行。
如上所述,本发明具有以下有益效果中的至少一项:
1)本发明催化剂为具有尖晶石结构的纳米颗粒,其平均颗粒尺寸为10~15nm。
2)本发明催化剂的制备方法采用有机燃烧法,制备流程简短,极大地节约制备催化剂的时间成本和经济成本,有利于工业化放大生产。
3)本发明催化剂能够在高温条件下稳定运行,并具有较高的甲醇选择性,通过M金属元素掺杂得到的xM-ZnFe2O4,能够促进CO2和H2的吸附活化,进一步提升CO2转化率和甲醇时空收率。
4)本发明催化剂在280℃以上高温条件下稳定运行,并具有较高的甲醇选择性(高达87.6%),通过M金属元素掺杂可进一步提高CO2转化率和甲醇收率。
附图说明
图1为实施例1产品的XRD谱图。
图2为实施例1产品的TEM图。
具体实施方式
下面结合实施例进一步阐述本发明。应理解,这些实施例仅用于说明本发明,而非限制本发明的范围。下列实施例中未注明具体条件的实验方法及未说明配方的试剂均为按照常规条件或者制造商建议的条件进行或配置。
实施例1
催化剂的制备:将5.95g Zn(NO3)2·6H2O、16.16g Fe(NO3)3·9H2O以及23.05g无水柠檬酸溶解于20mL去离子水中搅拌均匀,待完全溶解后升高温度至90℃干燥4h,然后将上述所得产物转移至马弗炉中在400℃焙烧6h,将其过筛至40~60目,得到的催化剂命名为ZnFe2O4,XRD谱图见图1,TEM图见图2。
取上述催化剂1.00g装填于固定床反应器中,反应条件为:H2与CO2的摩尔比为3,反应的温度为300℃,反应的压力为5MPa,反应的质量空速为18000mL/gcat/h。反应结果见表1。
实施例2
催化剂的制备:将5.95g Zn(NO3)2·6H2O、16.16g Fe(NO3)3·9H2O以及17.29g无水柠檬酸溶解于20mL去离子水中搅拌均匀,按照In的最终负载量为2wt%,再向其中加入0.26gIn(NO3)3,待完全溶解后升高温度至100℃干燥4h,然后将上述所得产物转移至马弗炉中在400℃焙烧4h,将其过筛至40~60目,得到的催化剂命名为In-ZnFe2O4。
取上述催化剂1.00g装填于固定床反应器中,反应条件为:H2与CO2的摩尔比为3,反应的温度为330℃,反应的压力为5MPa,反应的质量空速为20000mL/gcat/h。反应结果见表1。
实施例3
催化剂的制备:将4.39g C4H6O4Zn·2H2O、9.80g C6H5FeO7以及5.41g尿素溶解于20mL去离子水中搅拌均匀,按照Pd的最终负载量为1wt%,再向其中加入0.97g硝酸钯溶液(Pd,5wt%),待完全溶解后升高温度至110℃干燥4h,然后将上述所得产物转移至马弗炉中在350℃焙烧6h,将其过筛至40~60目,得到的催化剂命名为Pd-ZnFe2O4。
取上述催化剂1.00g装填于固定床反应器中,反应条件为:H2与CO2的摩尔比为3,反应的温度为280℃,反应的压力为3MPa,反应的质量空速为15000mL/gcat/h。反应结果见表1。
实施例4
催化剂的制备:将2.73g ZnCl2、10.81g FeCl3·6H2O以及8.10g草酸溶解于20mL去离子水中搅拌均匀,按照Pt的最终负载量为1wt%,再向其中加入0.97g硝酸铂溶液(Pt,5wt%),待完全溶解后升高温度至120℃干燥2h,然后将上述所得产物转移至马弗炉中在350℃焙烧8h,将其过筛至40~60目,得到的催化剂命名为Pt-ZnFe2O4。
取上述催化剂1.00g装填于固定床反应器中,反应条件为:H2与CO2的摩尔比为2,反应的温度为290℃,反应的压力为4MPa,反应的质量空速为2000mL/gcat/h。反应结果见表1。
实施例5
催化剂的制备:将5.95g Zn(NO3)2·6H2O、16.16g Fe(NO3)3·9H2O以及30.81g蔗糖溶解于20mL去离子水中搅拌均匀,按照Cu的最终负载量为5wt%,再向其中加入0.96gCu(NO3)2·3H2O,待完全溶解后升高温度至100℃干燥4h,然后将上述所得产物转移至马弗炉中在400℃焙烧6h,将其过筛至40~60目,得到的催化剂命名为Cu-ZnFe2O4。
取上述催化剂1.00g装填于固定床反应器中,反应条件为:H2与CO2的摩尔比为4,反应的温度为300℃,反应的压力为5MPa,反应的质量空速为15000mL/gcat/h。反应结果见表1。
实施例6
催化剂的制备:将5.95g Zn(NO3)2·6H2O、16.16g Fe(NO3)3·9H2O以及8.10g草酸溶解于20mL去离子水中搅拌均匀,按照Cr的最终负载量为2wt%,再向其中加入0.76gCr(NO3)3·9H2O,待完全溶解后升高温度至100℃干燥4h,然后将上述所得产物转移至马弗炉中在430℃焙烧6h,将其过筛至40~60目,得到的催化剂命名为Cr-ZnFe2O4。
取上述催化剂1.00g装填于固定床反应器中,反应条件为:H2与CO2的摩尔比为3,反应的温度为340℃,反应的压力为5MPa,反应的质量空速为20000mL/gcat/h。反应结果见表1。
实施例7
催化剂的制备:将5.95g Zn(NO3)2·6H2O、16.16g Fe(NO3)3·9H2O以及30.81g蔗糖溶解于20mL去离子水中搅拌均匀,按照Ga的最终负载量为3wt%,再向其中加入0.55gGa(NO3)3·xH2O,待完全溶解后升高温度至100℃干燥4h,然后将上述所得产物转移至马弗炉中在400℃焙烧6h,将其过筛至40~60目,得到的催化剂命名为Ga-ZnFe2O4。
取上述催化剂1.00g装填于固定床反应器中,反应条件为:H2与CO2的摩尔比为3,反应的温度为310℃,反应的压力为5MPa,反应的质量空速为9000mL/gcat/h。反应结果见表1。
实施例8
催化剂的制备:将5.95g Zn(NO3)2·6H2O、16.16g Fe(NO3)3·9H2O以及11.53g无水柠檬酸溶解于20mL去离子水中搅拌均匀,按照Zr的最终负载量为4wt%,再向其中加入0.51gZrO(NO3)2·xH2O,待完全溶解后升高温度至100℃干燥4h,然后将上述所得产物转移至马弗炉中在400℃焙烧6h,将其过筛至40~60目,得到的催化剂命名为Zr-ZnFe2O4。
取上述催化剂1.00g装填于固定床反应器中,反应条件为:H2与CO2的摩尔比为3,反应的温度为320℃,反应的压力为5MPa,反应的质量空速为9000mL/gcat/h。反应结果见表1。
表1
以上的实施例是为了说明本发明公开的实施方案,并不能理解为对本发明的限制。此外,本文所列出的各种修改以及发明中方法、组合物的变化,在不脱离本发明的范围和精神的前提下对本领域内的技术人员来说是显而易见的。虽然已结合本发明的多种具体优选实施例对本发明进行了具体的描述,但应当理解,本发明不应仅限于这些具体实施例。事实上,各种如上所述的对本领域内的技术人员来说显而易见的修改来获取发明都应包括在本发明的范围内。
Claims (10)
1.一种用于二氧化碳加氢合成甲醇的催化剂,其特征在于,所述催化剂的通式为xM-ZnFe2O4,M元素选自In、Pd、Pt、Cu、Cr、Ga、Zr中的至少一种,M元素的含量x=0~5wt%,所述催化剂具有尖晶石结构。
2.如权利要求1所述的催化剂,其特征在于,所述催化剂为纳米颗粒,平均颗粒尺寸为10~15nm。
3.如权利要求1或2所述的催化剂的制备方法,其特征在于,将包括锌盐、铁盐、可选M元素的盐、有机溶剂和水的混合溶液进行干燥和焙烧,得到所述催化剂。
4.如权利要求3所述的催化剂的制备方法,其特征在于,所述锌盐选自硝酸锌、乙酸锌和氯化锌中的至少一种;
和/或,所述铁盐选自硝酸铁、氯化铁和柠檬酸铁中的至少一种;
和/或,所述M元素的盐选自M元素的硝酸盐和M元素的氯化盐中的至少一种;
和/或,所述有机溶剂选自尿素、柠檬酸、草酸和蔗糖中的至少一种。
5.如权利要求3所述的催化剂的制备方法,其特征在于,所述锌盐、所述铁盐和所述有机溶剂的摩尔比为1:2:3~6;
和/或,所述M元素的含量为0~5wt%;
和/或,干燥的温度为80~120℃;
和/或,干燥的时间为2~4小时;
和/或,焙烧的温度为350~430℃;
和/或,焙烧的时间为4~8小时。
6.如权利要求1或2所述的催化剂用于二氧化碳加氢合成甲醇。
7.如权利要求6所述的催化剂的用途,其特征在于,包含CO2和H2的原料气在所述催化剂条件下反应,得到甲醇。
8.如权利要求7所述的催化剂的用途,其特征在于,H2与CO2的摩尔比为2~4;
和/或,反应的质量空速为2000~20000mL/gcat/h;
和/或,反应的压力为3~5MPa;
和/或,反应的温度为280~340℃;
和/或,所述反应在固定床反应器中进行。
9.一种二氧化碳加氢合成甲醇的方法,其特征在于,包含CO2和H2的原料气在如权利要求1或2所述的催化剂条件下反应,得到甲醇。
10.如权利要求9所述的二氧化碳加氢合成甲醇的方法,其特征在于,H2与CO2的摩尔比为2~4;
和/或,反应的质量空速为2000~20000mL/gcat/h;
和/或,反应的压力为3~5MPa;
和/或,反应的温度为280~340℃;
和/或,所述反应在固定床反应器中进行。
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