CN102716766A - 液相co2甲烷化催化剂、制备方法及其应用 - Google Patents
液相co2甲烷化催化剂、制备方法及其应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 239000007791 liquid phase Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 239000002608 ionic liquid Substances 0.000 claims abstract description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000084 colloidal system Substances 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 239000011591 potassium Substances 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 239000010948 rhodium Substances 0.000 claims abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 239000000470 constituent Substances 0.000 claims description 38
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 13
- -1 tetrafluoroborate Chemical compound 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- RMLHVYNAGVXKKC-UHFFFAOYSA-N [SH2]=N.C(F)(F)F Chemical compound [SH2]=N.C(F)(F)F RMLHVYNAGVXKKC-UHFFFAOYSA-N 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridine hydrochloride Substances [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 37
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 16
- 239000000376 reactant Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- GENPYYYENQWHQS-UHFFFAOYSA-N 2-methyl-n,n-di(propan-2-yl)propan-2-amine Chemical compound CC(C)N(C(C)C)C(C)(C)C GENPYYYENQWHQS-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及液相CO2甲烷化催化剂、制备方法及其应用。它包括两亲性离子液体和分散在两亲性离子液体中的金属活性组分，所述金属活性组分在两亲性离子液体中以稳定胶体的状态存在，粒径0.5～20nm，形状为球形，其包括第一种金属活性组分和第二种金属活性组分，所述的第一金属活性组分为镍，所述的第二金属活性组分为镧、铈、钼、钌、镱、铑、钯、铂、钾、镁中的一种或一种以上的混合，所述第一金属活性组分和第二金属活性组分的摩尔比为10:0.1-2。该液相CO2甲烷化催化剂中金属活性组分粒径较小，分布较窄，易于分离，可实现循环利用，应用前景广；在100-200oC下低温液相可实现CO2的甲烷化，具有很好的低温催化活性、甲烷选择性和较好的热稳定性；制备方法简单易行，成本较低，易于推广。
Description
技术领域
本发明涉及催化合成及纳米材料领域，具体地指一种液相CO2甲烷化催化剂、制备方法及其应用。
背景技术
天然气是一种优质、清洁能源和高效碳氢资源。随着城市化进程的加快和人民生活水平的提高，人们对天然气的需求呈快速增长势头。天然气供需出现了较大缺口。合成天然气技术作为一种高碳能源向低碳、富氢能源转化的有效途径，具有良好的环境效益和经济效益。
同时，近年来，CO2排放增加导致全球气候变暖，将CO2甲烷化不仅可以解决CO2的排放问题，而且可以合成出优质、洁净的能源，因此CO2甲烷化反应引起了人们广泛的关注。过去几十年中，Ni基催化剂作为活性最高的甲烷化非贵金属类催化剂已经得到广泛的研究专利CN102091629 A、CN 101773833 A等公开了镍基CO2甲烷化催化剂，但这种方法不仅需要消耗较大的能量，而且在高温和较高水蒸气分压下催化剂的强度会下降，沉积在基体表面的催化剂层也将出现侵蚀和脱落，而限制CO2甲烷化催化剂的应用。
针对CO2甲烷化反应强放热、热力学上低温有利的特点，本发明结合纳米金属粒子催化剂独特的结构和限域效应，提供了一种在液相和低温条件下可实现CO2甲烷化的液相CO2甲烷化催化剂。
发明内容
本发明所要解决的技术问题在于针对现有CO2甲烷化技术中CO2甲烷化催化剂存在的不足，而提供一种在液相和低温条件下可实现CO2甲烷化的液相CO2甲烷化催化剂、制备方法及其应用。
为解决上述技术问题，本发明采用的技术方案为：
液相CO2甲烷化催化剂，其特征在于：它包括两亲性离子液体和分散在两亲性离子液体中的金属活性组分，所述金属活性组分在两亲性离子液体中以稳定胶体的状态存在，粒径0.5～20nm，形状为球形，其包括第一种金属活性组分和第二种金属活性组分，所述的第一金属活性组分为镍，所述的第二金属活性组分为镧、铈、钼、钌、镱、铑、钯、铂、钾、镁中的一种或一种以上的混合，所述第一金属活性组分和第二金属活性组分的摩尔比为10:0.1-2。
按上述方案，所述两亲性离子液体和第一金属活性组分的摩尔比为10:0.1-2。
按上述方案，所述两亲性离子液体为两亲性小分子离子液体或两亲性聚合物离子液体；
所述的两亲性小分子离子液体包括但不限于：N-烷基吡啶盐酸盐、N-烷基吡啶四氟硼酸盐、1，3-二烷基咪唑四氟硼酸盐、1，3-二烷基咪唑盐酸盐、1，3-二烷基咪唑六氟磷酸盐，其中所述烷基碳链长度在8-18之间；
所述的两亲性聚合物离子液体包括但不限于聚1-(4-苯乙烯基)-3-甲基咪唑六氟磷酸盐、聚1-(4-苯乙烯基)-3-甲基咪唑三氟甲磺酰亚胺盐、聚1-(4-苯乙烯基)-3-甲基咪唑四氟硼酸盐、聚1-(4-苯乙烯基)-3-丁基咪唑四氟硼酸盐、聚1-(4-苯乙烯基)-3-丁基咪唑-聚吡咯烷酮盐酸盐。
液相CO2甲烷化催化剂的制备方法，其特征在于：它包括以下步骤：在室温下将上述金属活性组分的可溶性盐与两亲性离子液体分散于液体介质中，其中所述第一金属活性组分的可溶性盐和第二金属活性组分的可溶性盐皆以金属离子计量，两者的摩尔比为10: 0.1-2，得到金属活性组分的可溶性盐、两亲性离子液体的混合体系溶液，然后调节体系pH到8-10，继续搅拌反应1-3h后，100-200oC、0.1-4.0Mpa以H2还原1-6h，最后离心后经过滤、洗涤、干燥即得。
按上述方案，所述的第一金属活性组分Ni的可溶性盐为硝酸盐、醋酸盐或氯化物；所述的第二金属活性组分的可溶性盐为硝酸盐。
按上述方案，将第一金属活性组分的可溶性盐以金属离子计量，所述的两亲性离子液体与和第一金属活性组分的可溶性盐的摩尔比为10:0.1-2；所述混合体系溶液中金属离子总浓度为0.0001-0.01mol/L。
按上述方案，所述的液体介质包括但不限于水、醇类、四氢呋喃、乙腈、1,4-二氧六环、正己烷、环己烷。
上述液相CO2甲烷化催化剂在CO2甲烷化中的应用方法：在反应釜中加入液相CO2甲烷化催化剂和溶剂，所述反应体系中液相CO2甲烷化催化剂的浓度控制在0.0001-0.01mol/L，然后通入CO2和H2加热到100-200oC、0.1-4.0Mpa 进行催化反应1-6小时。
按上述方案，所述溶剂包括但不限于水、醇类、四氢呋喃、乙腈、1,4-二氧六环、正己烷、环己烷。
按上述方案，所述催化反应中H2和CO2的摩尔比为0.5-5：1，优选为4.0；催化反应压力优选为3MPa。
本发明针对CO2甲烷化反应强放热、热力学上低温有利的特点，基于离子液体提出的液相CO2甲烷化催化剂可利用纳米金属粒子催化剂独特的结构和限域效应，实现对催化剂催化活性、甲烷选择性和稳定性的调控，在液相和低温条件下实现CO2的甲烷化。
本发明与现有技术相比所具有的优点和积极效果如下：
1. 本发明所述的液相CO2甲烷化催化剂中的金属活性组分粒径较小（0.5-20nm），分布较窄，由于两亲性离子液体的稳定和保护作用可以使其均匀分散在离子液体介质中，形成稳定的胶体，并在反应前后不会发生聚沉；反应后的催化剂易与产物甲烷和反应介质分离，实现催化剂的回收和循环利用，应用前景广；
2．本发明所述的液相CO2甲烷化催化剂中使用的两亲性离子液体保护剂不仅可以防止金属活性组分纳米粒子的聚集，而且可以将CO2吸附到金属活性组分纳米粒子表面，提高液相中催化活性中心表面CO2的浓度，有利于CO2甲烷化的进行，在液相和100-200oC低温条件下可实现CO2的甲烷化，具有很好的低温催化活性、甲烷选择性和较好的热稳定性；适用于液相二氧化碳甲烷化反应，也避免了常规CO2固载催化剂的催化剂层高温易脱落、活性组分聚集长大而导致寿命缩短的问题，同时可大大节约工艺能耗，降低成本；
3．制备方法简单易行，成本较低，易于推广。
附图说明
图1为本发明实施例1制备的液相CO2甲烷化催化剂的电镜照片；
图2为本发明实施例8的液相CO2甲烷化催化剂经300h的甲烷化活性趋势图。
具体实施方式
为了更好地解释本发明，以下结合具体实施例进一步阐明本发明的主要内容，但本发明的内容不仅仅局限于以下实施例。
实施例1
在室温下将硝酸镍、硝酸镁与1-16烷基-3-甲基咪唑盐酸盐离子液体按摩尔比为1：0.2：20混合分散于液体介质水中，得到混合体系溶液，所述混合体系溶液中硝酸镍的物质的量浓度为2.79×10-4mol/L，然后加入氨水调节体系pH值到9.0，继续搅拌反应3h后，将反应液转移到反应釜中在150oC、3.0MPa下通入H2还原 2h，最后离心后经过滤、水洗、乙醇洗涤、干燥即得。经TEM测试，见图1。由图1可知：该液相CO2甲烷化催化剂中的金属活性组分纳米粒子平均粒径11.8nm，粒径分布较窄，分布均匀。
将上述催化剂用于CO2甲烷化反应，具体为：取适量的上述催化剂加入到反应釜中，然后加入适量溶剂水，控制反应体系中催化剂的浓度为0.005mol/L，根据nH2：nCO2=4通入CO2和H2，然后加热到150oC、3MPa反应2h，测定CO2的转化率和甲烷选择率，结果见表1。
实施例2
在室温下将醋酸镍、硝酸镧与1-18烷基-3-甲基咪唑六氟磷酸盐离子液体按摩尔比为1:0.15：20混合分散于液体介质乙醇中，得到混合体系溶液，所述醋酸镍的物质的量浓度为3.61×10-4mol/L，然后加入三乙胺调节体系pH值到8.0，继续搅拌反应2h后，将反应液转移到反应釜中在100oC、3.0MPa压力下通入H2还原1.5h，最后离心后经过滤、水洗、乙醇洗涤、干燥即得。
将上述催化剂用于CO2甲烷化反应，具体为：取适量的上述催化剂加入到反应釜中，然后加入适量的溶剂水，控制反应体系中催化剂的浓度为0.005mol/L，根据nH2：nCO2=4，通入CO2和H2，然后加热到150oC、3MPa反应2h，测定CO2的转化率和甲烷选择率，结果见表1。
实施例3
在室温下将硝酸镍、硝酸铈与两亲性离子液体N-十二烷基吡啶四氟硼酸盐（C12PyBF4）按摩尔比为1:0.15:18 混合分散于液体介质乙腈中，得到混合体系溶液，所述混合体系中硝酸镍的物质的量浓度为1.32×10-3 mol/L，然后加入二异丙基叔丁胺调节体系pH值到10.0，继续搅拌反应3h后，将反应液转移到反应釜中在150oC、3.0MPa压力下通入H2还原1.5h，最后离心后经过滤、洗涤、干燥即得。
将上述催化剂用于CO2甲烷化反应，具体为：取适量的上述催化剂加入到反应釜中，然后加入适量的溶剂乙腈，控制反应体系中催化剂的浓度为0.005mol/L，根据nH2：nCO2=4，通入CO2和H2，然后加热到120oC、1MPa反应3h，测定CO2的转化率和甲烷选择率，结果见表1。
实施例4
在室温下将硝酸镍、硝酸钼与两亲性离子液体聚1-(4-苯乙烯基)-3-甲基咪唑三氟甲磺酰亚胺盐按摩尔比为1:0.12:16混合分散于液体介质水中，得到混合体系溶液，所述混合体系中硝酸镍的物质的量浓度为6.35×10-4 mol/L，然后加入氨水调节体系pH值到10.0，继续搅拌反应2.5h后，将反应液转移到反应釜中在200oC、2.0MPa压力下通入H2还原2h，最后离心后经过滤、洗涤、干燥即得。
将上述催化剂用于CO2甲烷化反应，具体为：取适量的上述催化剂加入到反应釜中，然后加入适量的溶剂二氧六环，控制反应体系中催化剂的浓度为0.005mol/L，根据nH2：nCO2=4，通入CO2和H2，然后加热到150oC、3MPa反应1h，测定CO2的转化率和甲烷选择率，结果见表1。
实施例5
在室温下将硝酸镍、硝酸钌和硝酸钾与两亲性离子液体N-十六烷基吡啶四氟硼酸盐按摩尔比为1：0.1：0.1：20 混合分散于液体介质四氢呋喃中，得到混合体系溶液，所述混合体系中硝酸镍的物质的量浓度为8.1×10-4mol/L，然后加入氨水调节体系pH值到8.0，继续搅拌反应1h后，将反应液转移到反应釜中在150oC、1.0MPa压力下通入H2还原5h，最后离心后经过滤、洗涤、干燥即得。
将上述催化剂用于CO2甲烷化反应，具体为：取适量的上述催化剂加入到反应釜中，然后加入适量的溶剂四氢呋喃，控制反应体系中催化剂的浓度为0.005mol/L，根据nH2：nCO2=4，通入CO2和H2，然后加热到110oC、3MPa反应2.5h，测定CO2的转化率和甲烷选择率，结果见表1。
实施例6
在室温下将醋酸镍、硝酸镱与两亲性离子液体聚1-(4-苯乙烯基)-3-甲基咪唑四氟硼酸盐按摩尔比为1:0.15:15 混合分散于液体介质环己烷中，得到混合体系溶液，所述混合体系中硝酸镍的物质的量浓度为9.81×10-4mol/L，然后加入氨水调节体系pH值到8.0，继续搅拌反应2h后，将反应液转移到反应釜中在150oC、0.1MPa压力下通入H2还原3h，最后离心后经过滤、洗涤、干燥后得到所述液相CO2甲烷化催化剂。
将上述催化剂用于CO2甲烷化反应，具体为：取适量的上述催化剂加入到反应釜中，然后加入适量的溶剂环己烷，控制反应体系中催化剂的浓度为0.005mol/L，根据nH2：nCO2=0.5，通入CO2和H2，然后加热到190oC、4MPa反应1.5h，测定CO2的转化率和甲烷选择率，结果见表1。
实施例7
在室温下将硝酸镍、硝酸铑与两亲性离子液体聚1-(4-苯乙烯基)-3-丁基咪唑四氟硼酸盐按摩尔比为1:0.16:10混合分散于液体介质乙醇中，得到混合体系溶液，所述混合体系中硝酸镍的物质的量浓度为1.28×10-3mol/L，然后加入氨水调节体系pH值到8.0，继续搅拌反应3h后，将反应液转移到反应釜中在100oC、0.5MPa压力下通入H2还原2h，最后离心后经过滤、洗涤、干燥后得到所述液相CO2甲烷化催化剂。
将上述催化剂用于CO2甲烷化反应，具体为：取适量的上述催化剂加入到反应釜中，然后加入适量的溶剂乙醇，控制反应体系中催化剂的浓度为0.003mol/L，根据nH2：nCO2=4，通入CO2和H2，然后加热到110oC、3MPa反应2h，测定CO2的转化率和甲烷选择率，结果见表1。
实施例8
在室温下将硝酸镍、硝酸钯与两亲性离子液体N-辛烷基吡啶四氟硼酸盐按摩尔比为1: 0.01: 100 混合分散于液体介质二氧六环中，得到混合体系溶液，所述混合体系中硝酸镍的物质的量浓度为3.18×10-3mol/L，然后加入氨水调节体系pH值到8.0，继续搅拌反应3h后，将反应液转移到反应釜中在200oC、3.0MPa压力下通入H2还原2h，最后离心后经过滤、洗涤、干燥后得到所述液相CO2甲烷化催化剂。
将上述催化剂用于CO2甲烷化反应，具体为：取适量的上述催化剂加入到反应釜中，然后加入适量的溶剂二氧六环，控制反应体系中催化剂的浓度为0.0005mol/L，根据nH2：nCO2=3，通入CO2和H2，然后加热到120oC、3MPa反应2h，测定CO2的转化率和甲烷选择率，结果见表1。
并将催化反应自催化反应始持续进行300h，检测该催化过程中二氧化碳的转化率和甲烷选择率随反应时间的变化趋势图，见图2。由图2可知：该液相CO2甲烷化催化剂的稳定性好。
实施例9
在室温下将氯化镍、硝酸铂与两亲性离子液体聚1-(4-苯乙烯基)-3-丁基咪唑-聚吡咯烷酮盐酸盐、按摩尔比为1:0.05:5混合分散于液体介质 正己烷中，得到混合体系溶液，所述混合体系中硝酸镍的物质的量浓度为6.28×10-4mol/L，然后加入氨水调节体系pH值到8.0，继续搅拌反应3h后，将反应液转移到反应釜中在100oC、4MPa压力下通入H2还原2h，最后离心后经过滤、洗涤、干燥后得到所述液相CO2甲烷化催化剂。
将上述催化剂用于CO2甲烷化反应，具体为：取适量的上述催化剂加入到反应釜中，然后加入适量的溶剂水，控制反应体系中催化剂的浓度为0.00015mol/L，根据nH2：nCO2=5，通入CO2和H2，然后加热到200oC、2MPa反应2h，测定CO2的转化率和甲烷选择率，结果见表1。
实施例10
在室温下将硝酸镍、硝酸铈和硝酸镁与两亲性离子液体1，3-二辛基咪唑四氟硼酸盐按摩尔比为1:0.15:0.05:10混合分散于液体介质水中，得到混合体系溶液，所述混合体系中硝酸镍的物质的量浓度为3.18×10-3mol/L，然后加入三乙胺调节体系pH值到9.0，继续搅拌反应3h后，将反应液转移到反应釜中在150oC、3.0MPa压力下通入H2还原2h，最后离心后经过滤、洗涤、干燥后得到所述液相CO2甲烷化催化剂。
将上述催化剂用于CO2甲烷化反应，具体为：取适量的上述催化剂加入到反应釜中，然后加入适量的溶剂正己烷，控制反应体系中催化剂的浓度为0.01mol/L，根据nH2：nCO2=4，通入CO2和H2，然后加热到100oC、3MPa反应2h，测定CO2的转化率和甲烷选择率，结果见表1。
本发明实施例均采用以下公式计算二氧化碳的转化率、产物的选择性。
表1：液相CO2甲烷化催化剂的制备条件及催化性能
Claims (10)
1.液相CO2甲烷化催化剂，其特征在于：它包括两亲性离子液体和分散在两亲性离子液体中的金属活性组分，所述金属活性组分在两亲性离子液体中以稳定胶体的状态存在，粒径0.5～20nm，形状为球形，其包括第一种金属活性组分和第二种金属活性组分，所述的第一金属活性组分为镍，所述的第二金属活性组分为镧、铈、钼、钌、镱、铑、钯、铂、钾、镁中的一种或一种以上的混合，所述第一金属活性组分和第二金属活性组分的摩尔比为10:0.1-2。
2.根据权利要求1所述的液相CO2甲烷化催化剂，其特征在于：所述两亲性离子液体和第一金属活性组分的摩尔比为10:0.1-2。
3.根据权利要求1所述的液相CO2甲烷化催化剂，其特征在于：所述两亲性离子液体为两亲性小分子离子液体或两亲性聚合物离子液体；
所述的两亲性小分子离子液体包括但不限于：N-烷基吡啶盐酸盐、N-烷基吡啶四氟硼酸盐、1，3-二烷基咪唑四氟硼酸盐、1，3-二烷基咪唑盐酸盐、1，3-二烷基咪唑六氟磷酸盐，其中所述烷基碳链长度在8-18之间；
所述的两亲性聚合物离子液体包括但不限于聚1-(4-苯乙烯基)-3-甲基咪唑六氟磷酸盐、聚1-(4-苯乙烯基)-3-甲基咪唑三氟甲磺酰亚胺盐、聚1-(4-苯乙烯基)-3-甲基咪唑四氟硼酸盐、聚1-(4-苯乙烯基)-3-丁基咪唑四氟硼酸盐、聚1-(4-苯乙烯基)-3-丁基咪唑-聚吡咯烷酮盐酸盐。
4.液相CO2甲烷化催化剂的制备方法，其特征在于：它包括以下步骤：在室温下将上述金属活性组分的可溶性盐与两亲性离子液体分散于液体介质中，其中所述第一金属活性组分的可溶性盐和第二金属活性组分的可溶性盐皆以金属离子计量，两者的摩尔比为10: 0.1-2，得到金属活性组分的可溶性盐、两亲性离子液体的混合体系溶液，然后调节体系pH到8-10，继续搅拌反应1-3h后，100-200oC、0.1-4.0Mpa以H2还原1-6h，最后离心后经过滤、洗涤、干燥即得。
5.根据权利要求4所述的液相CO2甲烷化催化剂的制备方法，其特征在于：所述的第一金属活性组分Ni的可溶性盐为硝酸盐、醋酸盐或氯化物；所述的第二金属活性组分的可溶性盐为硝酸盐。
6.根据权利要求4所述的液相CO2甲烷化催化剂的制备方法，其特征在于：将第一金属活性组分的可溶性盐以金属离子计量，所述的两亲性离子液体与和第一金属活性组分的可溶性盐的摩尔比为10:0.1-2；所述混合体系溶液中金属离子总浓度为0.0001-0.01mol/L。
7.根据权利要求4所述的液相CO2甲烷化催化剂的制备方法，其特征在于：所述的液体介质包括但不限于水、醇类、四氢呋喃、乙腈、1,4-二氧六环、正己烷、环己烷。
8.根据权利要求1所述的液相CO2甲烷化催化剂在CO2甲烷化中的应用方法，其特征在于：它是在反应釜中加入液相CO2甲烷化催化剂和溶剂，所述反应体系中液相CO2甲烷化催化剂的浓度控制在0.0001-0.01mol/L，然后通入CO2和H2加热到100-200oC、0.1-4.0Mpa 进行催化反应1-6小时。
9.根据权利要求8所述的液相CO2甲烷化催化剂在CO2甲烷化中的应用方法，其特征在于：所述溶剂包括但不限于水、醇类、四氢呋喃、乙腈、1,4-二氧六环、正己烷、环己烷。
10.根据权利要求8所述的液相CO2甲烷化催化剂在CO2甲烷化中的应用方法，其特征在于：所述催化反应中H2和CO2的摩尔比为0.5-5：1。
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| PCT/CN2013/076858 WO2013185559A1 (zh) | 2012-06-15 | 2013-06-06 | 液相co2甲烷化催化剂、制备方法及其应用 |
| EP13803691.8A EP2862628A4 (en) | 2012-06-15 | 2013-06-06 | LIQUID PHASE CO2 METHANIZATION CATALYST, MANUFACTURING METHOD AND USE THEREOF |
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| WO2013185559A1 (zh) * | 2012-06-15 | 2013-12-19 | 武汉凯迪工程技术研究总院有限公司 | 液相co2甲烷化催化剂、制备方法及其应用 |
| CN111389459A (zh) * | 2020-02-20 | 2020-07-10 | 嘉兴学院 | 一种用于催化还原二氧化碳或碳水化合物的组合物、及方法 |
| CN113522331A (zh) * | 2020-04-21 | 2021-10-22 | 中国科学院理化技术研究所 | 一种碳基钴钯双金属纳米催化剂及其制备与应用 |
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| CN111701618A (zh) * | 2020-06-28 | 2020-09-25 | 江苏思派新能源科技有限公司 | 一种离子液体催化剂及其制备方法和用途 |
| SE544807C2 (en) * | 2020-12-09 | 2022-11-22 | Gerald Mcinerney | A colloidal particle dispersion for use in an antimicrobial and virucidal surface coating |
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| CN102716766B (zh) * | 2012-06-15 | 2015-06-17 | 武汉凯迪工程技术研究总院有限公司 | 液相co2甲烷化催化剂、制备方法及其应用 |
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| WO2013185559A1 (zh) * | 2012-06-15 | 2013-12-19 | 武汉凯迪工程技术研究总院有限公司 | 液相co2甲烷化催化剂、制备方法及其应用 |
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