CN113976126A - 一种用于二氧化碳加氢制甲醇的催化剂及制备方法和应用 - Google Patents
一种用于二氧化碳加氢制甲醇的催化剂及制备方法和应用 Download PDFInfo
- Publication number
- CN113976126A CN113976126A CN202111261269.1A CN202111261269A CN113976126A CN 113976126 A CN113976126 A CN 113976126A CN 202111261269 A CN202111261269 A CN 202111261269A CN 113976126 A CN113976126 A CN 113976126A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carbon dioxide
- preparing
- supported
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 98
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 43
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 41
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 46
- 239000011029 spinel Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000010949 copper Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 150000002940 palladium Chemical class 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 1
- 229910052763 palladium Inorganic materials 0.000 abstract 1
- 229910001676 gahnite Inorganic materials 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910018576 CuAl2O4 Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 241001629697 Panicum turgidum Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007486 ZnGa2O4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01J23/005—Spinels
-
- 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
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
-
- 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
- B01J23/825—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 gallium, indium or thallium
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种用于二氧化碳加氢制甲醇的催化剂及制备方法和应用，所述催化剂为非负载型或负载型的尖晶石相催化剂，组成可记为AB2O4、Cu/AB2O4或Pd/AB2O4，其中A为Zn/Mg/Co，B为Al/Ga/Cr/Fe/In，Cu/AB2O4中Cu的负载量为0.001％～0.5％，Pd/AB2O4中Pd的负载量为0.1％～1％。利用共沉淀法制备非负载型的尖晶石相催化剂，尖晶石相催化剂作为载体分别通过离子交换法增加铜组分，通过浸渍法负载金属钯制备负载型尖晶石催化剂。制备方法简单，成本低廉。具有二氧化碳转化率及甲醇选择性高，稳定性好等优点。
Description
技术领域
本发明涉及催化技术领域，尤其涉及一种用于二氧化碳加氢制甲醇的催化剂及制备方法和应用。
背景技术
化石燃料的开发利用加快了人类走入工业社会的步伐，使人类社会得到前所未有的繁荣发展；但是也带来诸多环境问题，例如二氧化碳大量排放造成了严重的温室效应，引发全球气候变化，对人类生产生活造成严重的影响。现在化石燃料能源也面临枯竭的危险，急需寻找可替代的清洁能源。其中一个策略就是开发新型催化剂将二氧化碳转化成甲醇，甲醇作为分子转化平台可以进一步转化成液体燃料和一些具有高附加价值的化学品，最终实现变废为宝。因此二氧化碳加氢合成甲醇的反应得到人们的广泛关注。
工业上使用CuOZnOAl2O3作为甲醇合成催化剂，但是CuOZnOAl2O3甲醇选择性较低，这是由于铜基催化剂本身就是水气变换反应的活性中心。由于Cu塔曼温度较低，Al2O3对H2O又具有很好的亲和性，导致该催化剂在反应条件下很容易失活，催化剂稳定性差。
发明内容
本发明的目的在于解决现有技术中的上述问题，提供一种用于二氧化碳加氢制甲醇的催化剂及制备方法和应用，该催化剂为尖晶石相，具有很好的稳定性，该催化剂表现出优异的甲醇合成性能。
为达到上述目的，本发明采用如下技术方案：
一种用于二氧化碳加氢制甲醇的催化剂，所述催化剂为非负载型或负载型的尖晶石相催化剂，组成可记为AB2O4、Cu/AB2O4或Pd/AB2O4，其中A为Zn/Mg/Co，B为Al/Ga/Cr/Fe/In，Cu/AB2O4中Cu的负载量为0.001％～0.5％，Pd/AB2O4中Pd的负载量为0.1％～1％。
所述非负载型的尖晶石相催化剂的制备方法如下：将金属盐溶液与沉淀剂加热搅拌的条件下进行共沉淀，然后过滤、洗涤、干燥，最后焙烧得到非负载型的尖晶石相催化剂。
所用金属盐为硝酸盐/醋酸盐/卤化物/硫酸盐中的一种或几种；所用的沉淀剂为氨水/碳酸铵/氢氧化钠/碳酸钠/碳酸氢钠中的一种或几种。
所述加热的温度为60～80℃，控制的pH值为6.5～8.0。
所述负载型的尖晶石相催化剂Cu/AB2O4的制备方法如下：将非负载型的尖晶石相催化剂分散于铜盐溶液中，采用离子交换的方法使铜负载于尖晶石催化剂表面，离心、洗涤、干燥、焙烧，即得到负载型的尖晶石相催化剂Cu/AB2O4。
所述铜盐为硝酸盐/醋酸盐/卤化物/硫酸盐中的一种或几种。
所述负载型的尖晶石相催化剂Pd/AB2O4的制备方法如下：将非负载型的尖晶石相催化剂分散于去离子水中，加入钯盐溶液，加热搅拌，将溶剂蒸干，焙烧即得到负载型的尖晶石相催化剂Pd/AB2O4。
所述钯盐为硝酸盐/醋酸盐/卤化物/硫酸盐中的一种或几种。
所述催化剂用于二氧化碳加氢制甲醇。反应前用还原性气体或保护性气体对催化剂进行预处理活化，然后通入原料气，在一定的压力和温度下进行二氧化碳加氢合成甲醇；所述还原性气体为纯氢或含10％氢气的氢氩混合气，所述保护性气体为氮气或氩气；预处理温度为200～400℃，处理时间为1～2h，反应温度为220～400℃，反应压力为3～6MPa，空速为3000～30000mL h-1g-1，n(氢气):n(二氧化碳)＝1～6。
相对于现有技术，本发明技术方案取得的有益效果是：
本发明制备方法简单，通过制备尖晶石相催化剂，用于二氧化碳加氢制甲醇，可以显著提高二氧化碳的转化效率，甲醇的选择性可以达到90％。
本发明尖晶石相催化剂经过100h的测试，具有很好的稳定性，说明本发明制备的催化剂寿命长，稳定性能好，不易失活。
本发明制备的负载型尖晶石相催化剂，金属Pd以原子级状态分散在均匀分散在ZnAl2O4尖晶石表面，原子级Pd组分的添加，提高催化剂的加氢性能，显著地提高二氧化碳加氢制甲醇的性能。
本发明制备的催化剂有较高的比表面积，具有大量的二氧化碳分子吸附活化的反应位点，且具有优异的二氧化碳吸附、活化能力。
附图说明
图1为Pd/ZnAl2O4负载型尖晶石相催化剂的稳定性测试图；
图2为Pd/ZnAl2O4负载型尖晶石相催化剂的XRD表征图；
图3为Pd/ZnAl2O4负载型尖晶石相催化剂的N2-物理吸附表征图；
图4为Pd/ZnAl2O4负载型尖晶石相催化剂催化二氧化碳加氢的原位红外表征。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚、明白，以下结合附图和实施例，对本发明做进一步详细说明。
本发明一种用于二氧化碳加氢制甲醇的催化剂，所述催化剂为非负载型或负载型的尖晶石相催化剂，组成可记为AB2O4、Cu/AB2O4或Pd/AB2O4，其中A为Zn/Mg/Co，B为Al/Ga/Cr/Fe/In，Cu/AB2O4中Cu的负载量为0.001％～0.5％，Pd/AB2O4中Pd的负载量为0.1％～1％。
所述催化剂的制备方法，包括如下步骤：
(1)配制摩尔比为1:2的A和B的金属盐溶液，浓度为0.1～1mol/L；配制沉淀剂溶液，浓度与金属盐溶液浓度相同。两个溶液在60～80℃的水中进行共沉淀，控制pH为6.5～8.0。相同温度下水浴搅拌1h后室温静置。
(2)过滤得到沉淀，用去离子水和乙醇洗涤3～5次。将所得沉淀于60～80℃烘箱中干燥8～20h。在空气中400～600℃焙烧5～12h，得到尖晶石相催化剂。
(3)将一定量的尖晶石催化剂分散于1mol/L的Cu(NO3)2·3H2O水溶液中室温下搅拌2h，转速8000rmb离心，并用去离子水和乙醇洗涤。将所得催化剂于60～80℃烘箱中干燥8～20h。在空气中400～600℃焙烧5～12h，得到Cu负载型尖晶石相催化剂。
(4)将一定量的尖晶石催化剂分散于去离子水中，于60～80℃水浴加热搅拌。配置一定浓度的Pd金属盐溶液，浓度为0.001～0.02mol/L。将Pd盐溶液逐滴加入尖晶石催化剂悬浊液中，继续加热搅拌，直至溶剂蒸干。将所得催化剂于60～80℃烘箱中干燥8～20h。在空气中400～600℃焙烧5～12h，得到Pd负载型尖晶石相催化剂。
催化剂催化二氧化碳加氢合成甲醇反应的反应性能评价在高温高压固定床连续流动反应器上进行，利用气相色谱在线分析检测反应尾气。反应前用氩气稀释的氢气/纯氢/氮气/氩气中的一种或几种对催化剂在200～400℃温度下进行预处理活化。预处理后冷却至室温，进行二氧化碳加氢合成甲醇的反应评价，反应温度为220～400℃，反应压力为3～6MPa，空速为3000～30000mL h-1g-1，n(氢气):n(二氧化碳)＝1～6。反应产物利用气相色谱进行在线分析，使用TCD和FID检测器进行产物的定量分析。
实施例1
称取35mmol Zn(NO3)2·6H2O和70mmol Al(NO3)2·9H2O配制成70mL水溶液。将该溶液与0.5mol/L的(NH4)2CO3溶液共同滴加入盛有少量去离子水的烧杯中，滴加过程中混合溶液pH值需控制在7.0，70℃下搅拌1h。室温冷却，过滤，用去离子水和乙醇洗涤3～4次。80℃下烘干，空气中500℃下焙烧5h得到ZnAl2O4催化剂。将ZnAl2O4催化剂在10MPa下压片，成型，选取粒度大小为30～60目的ZnAl2O4催化剂用于性能测试。
称取0.3g成型好的ZnAl2O4催化剂装入石英反应管中，在常压和纯氢气氛下进行催化剂的预处理。以10℃/min的升温速度程序升温升至300℃，恒温1h，自然冷却至室温。之后进行反应评价，充入原料气n(氢气):n(二氧化碳)＝3，使反应器中的原料气压力达到3MPa，反应空速GHSV＝6000mL h-1g-1，以5℃/min的升温速度升温至280℃开始ZnAl2O4催化剂催化二氧化碳加氢合成甲醇反应催化性能的评价。催化剂评价结果见表1。
实施例2
称取35mmol Zn(NO3)2·6H2O和70mmol Ga(NO3)2·xH2O配置成70mL水溶液。其他制备及反应性能评价步骤与实施例1相同，催化剂评价结果见表1。
实施例3
称取35mmol Zn(NO3)2·6H2O和70mmol Fe(NO3)2·9H2O配置成70mL水溶液。其他制备及反应性能评价步骤与实施例1相同，催化剂评价结果见表1。
实施例4
称取35mmol Zn(NO3)2·6H2O和70mmol In(NO3)3·xH2O配置成70mL水溶液。其他制备及反应性能评价步骤与实施例1相同，催化剂评价结果见表1。
实施例5
称取1g ZnAl2O4催化剂分散于20ml的1mol/L Cu(NO3)2·3H2O水溶液中室温下搅拌2h，使用离心机以8000rmb离心，并用去离子水和乙醇洗涤3～4次。将所得催化剂于80℃烘箱中干燥12h。500℃焙烧5h，得到Cu/ZnAl2O4负载型尖晶石相催化剂。反应性能评价步骤与实施例1相同，催化剂评价结果见表1。
实施例6
称取1g ZnGa2O4催化剂分散于20ml的1mol/L Cu(NO3)2·3H2O水溶液中。其他制备及反应性能评价步骤与实施例6相同，催化剂评价结果见表1。
实施例7
称取1g ZnGr2O4催化剂分散于20ml的1mol/L Cu(NO3)2·3H2O水溶液中。其他制备及反应性能评价步骤与实施例6相同，催化剂评价结果见表1。
实施例8
称取1g ZnAl2O4催化剂分散于20ml去离子水中，60℃下水浴搅拌。将10ml的9mmol/L的Pd(NO)3溶液逐滴加入上述溶液中。继续加热搅拌，直至溶剂蒸干。将所得催化剂于80℃烘箱中干燥12h。500℃焙烧5h，得到Pd/ZnAl2O4负载型尖晶石相催化剂。
将实施例8制备的Pd/ZnAl2O4负载型尖晶石相催化剂进行稳定性测试如下：
称取0.3g成型好的Pd/ZnAl2O4负载型催化剂装入石英反应管中，在常压和纯氢气氛下进行催化剂的预处理。以10℃/min的升温速度程序升温升至300℃，恒温1h，自然冷却至室温。之后进行反应评价，充入原料气n(氢气):n(二氧化碳)＝3，使反应器中的原料气压力达到3MPa，反应空速GHSV＝6000mL h-1g-1，以5℃/min的升温速度升温至280℃，开始Pd/ZnAl2O4催化二氧化碳加氢合成甲醇反应催化稳定性能的评价。从图1可以看出，制备的Pd/ZnAl2O4负载型催化剂经过100h的测试，具有很好的稳定性。说明本发明制备的催化剂催化寿命长，稳定性能好，不易失活。
如图2所示为实施例8制备的Pd/ZnAl2O4负载型尖晶石相催化剂的XRD图，X射线粉末衍射(XRD)用于表征Pd/ZnAl2O4负载型催化剂的晶形结构，在Rigaku Ultima IV型X射线粉末衍射仪上进行实验。测试条件为Cu(Kα)(λ＝0.15418nm),管电压设定为35kV，管电流设定为15mA。从图2表征中可以看出，Pd/ZnAl2O4晶形结构为尖晶石结构，该结构稳定性能优异，保证催化剂的稳定性，使催化剂在反应条件下也能保持结型结构不变；图2没有观察到Pd的衍射峰，说明Pd以原子级状态分散在均匀分散在ZnAl2O4尖晶石表面，原子级Pd组分的添加，提高催化剂的加氢性能，显著的提高二氧化碳加氢制甲醇的性能。
图3为实施例8制备的Pd/ZnAl2O4负载型尖晶石相催化剂的N2-物理吸附，N2-物理吸脱附用于表征Pd/ZnAl2O4负载型催化剂的比表面积，在Micromeritics Tri-StarⅡ型物理吸附仪上进行实验。进行N2物理吸脱附实验之前，样品先经过200℃下真空处理2h。图3中样品Pd/ZnAl2O4比表面积通过BET方法计算为151cm-1g-1，证明该催化剂具有较高的比表面积，具有大量的二氧化碳分子吸附活化的反应位点。
图4为实施例8制备的Pd/ZnAl2O4负载型尖晶石相催化剂催化二氧化碳加氢的原位红外，Pd/ZnAl2O4负载型催化剂催化二氧化碳加氢的原位红外用于表征反应的产生路径，在傅里叶红外光谱仪Nicolet 6700上测试。波数在2979，2876，2737cm-1位置的峰是甲酸盐物的C-H键收缩振动，波数在1359，1380，1363cm-1位置的峰是分别是甲酸盐物的C-O键不对称振动，C-H键弯曲振动，C-O键对称振动；波数在2930，2823cm-1位置的峰是甲氧基物的C-H键收缩振动，波数在1142，1049cm-1位置的峰是甲氧基物的C-H键收缩振动。从图4可以看到，随着CO2混合气的通入，Pd/ZnAl2O4表面检测到大量的甲酸盐物种，表明CO2在Pd/ZnAl2O4表面很容易被活化加氢转化为甲酸盐，随着反应时间的进行出现了甲氧基的红外吸收峰。以上结果说明Pd/ZnAl2O4负载型尖晶石能够吸附大量的二氧化碳，在氢气气氛下吸附的二氧化碳快速加氢生成甲酸盐中间体，甲酸盐中间体在Pd/ZnAl2O4负载作用下进一步加氢生成甲氧基中间体。最后由甲氧基加氢生成甲醇。原位红外结果表明Pd/ZnAl2O4负载型催化剂具有优异的二氧化碳吸附、活化能力。
对比例1
称取35mmol Cu(NO3)2·3H2O，70mmol Al(NO3)2·9H2O和120mmol一水合柠檬酸配制成70mL水溶液。70℃下水浴搅拌得到溶胶凝胶。80摄氏度下发泡，空气中500℃下焙烧得到CuAl2O4催化剂。其他制备及反应性能评价步骤与实施例1相同，催化剂评价结果见表1。
表1
本发明制备方法简单，通过制备尖晶石相催化剂，用于二氧化碳加氢制甲醇，可以显著提高二氧化碳的转化效率，甲醇的选择性可以达到90％。
Claims (10)
1.一种用于二氧化碳加氢制甲醇的催化剂，其特征在于：所述催化剂为非负载型或负载型的尖晶石相催化剂，组成可记为AB2O4、Cu/AB2O4或Pd/AB2O4，其中A为Zn/Mg/Co，B为Al/Ga/Cr/Fe/In，Cu/AB2O4中Cu的负载量为0.001％～0.5％，Pd/AB2O4中Pd的负载量为0.1％～1％。
2.权利要求1所述的一种用于二氧化碳加氢制甲醇的催化剂的制备方法，其特征在于所述非负载型的尖晶石相催化剂的制备方法如下：将金属盐溶液与沉淀剂加热搅拌的条件下进行共沉淀，然后过滤、洗涤、干燥，最后焙烧得到非负载型的尖晶石相催化剂。
3.权利要求2所述的一种用于二氧化碳加氢制甲醇的催化剂的制备方法，其特征在于：所用金属盐为硝酸盐/醋酸盐/卤化物/硫酸盐中的一种或几种；所用的沉淀剂为氨水/碳酸铵/氢氧化钠/碳酸钠/碳酸氢钠中的一种或几种。
4.权利要求2所述的一种用于二氧化碳加氢制甲醇的催化剂的制备方法，其特征在于：所述加热的温度为60～80℃，控制的pH值为6.5～8.0。
5.权利要求1所述的一种用于二氧化碳加氢制甲醇的催化剂的制备方法，其特征在于所述负载型的尖晶石相催化剂Cu/AB2O4的制备方法如下：将非负载型的尖晶石相催化剂分散于铜盐溶液中，采用离子交换的方法使铜负载于尖晶石催化剂表面，离心、洗涤、干燥、焙烧，即得到负载型的尖晶石相催化剂Cu/AB2O4。
6.权利要求5所述的一种用于二氧化碳加氢制甲醇的催化剂的制备方法，其特征在于：所述铜盐为硝酸盐/醋酸盐/卤化物/硫酸盐中的一种或几种。
7.权利要求1所述的一种用于二氧化碳加氢制甲醇的催化剂的制备方法，其特征在于所述负载型的尖晶石相催化剂Pd/AB2O4的制备方法如下：将非负载型的尖晶石相催化剂分散于去离子水中，加入钯盐溶液，加热搅拌，将溶剂蒸干，焙烧即得到负载型的尖晶石相催化剂Pd/AB2O4。
8.权利要求7所述的一种用于二氧化碳加氢制甲醇的催化剂的制备方法，其特征在于：所述钯盐为硝酸盐/醋酸盐/卤化物/硫酸盐中的一种或几种。
9.权利要求1所述的催化剂以及权利要求2～8制备方法所制备的催化剂的应用，其特征在于：所述催化剂用于二氧化碳加氢制甲醇。
10.如权利要求9所述的应用，其特征在于：反应前用还原性气体或保护性气体对催化剂进行预处理活化，然后通入原料气，在一定的压力和温度下进行二氧化碳加氢合成甲醇；所述还原性气体为纯氢或含10％氢气的氢氩混合气，所述保护性气体为氮气或氩气；预处理温度为200～400℃，处理时间为1～2h，反应温度为220～400℃，反应压力为3～6MPa，空速为3000～30000mL h-1g-1，n(氢气):n(二氧化碳)＝1～6。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111261269.1A CN113976126A (zh) | 2021-10-28 | 2021-10-28 | 一种用于二氧化碳加氢制甲醇的催化剂及制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111261269.1A CN113976126A (zh) | 2021-10-28 | 2021-10-28 | 一种用于二氧化碳加氢制甲醇的催化剂及制备方法和应用 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113976126A true CN113976126A (zh) | 2022-01-28 |
Family
ID=79743207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111261269.1A Pending CN113976126A (zh) | 2021-10-28 | 2021-10-28 | 一种用于二氧化碳加氢制甲醇的催化剂及制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113976126A (zh) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010011101A2 (ko) * | 2008-07-24 | 2010-01-28 | 현대중공업 주식회사 | 합성가스로부터 메탄올 합성용 촉매 및 이의 제조방법 |
| CN102145281A (zh) * | 2010-02-10 | 2011-08-10 | 中国科学院大连化学物理研究所 | 一种甲醇水蒸汽重整制氢的催化剂及制备和应用 |
| CN103599785A (zh) * | 2013-11-27 | 2014-02-26 | 上海大学 | 用于焦炉煤气干重整的尖晶石负载型催化剂及其制备方法 |
| WO2018049735A1 (en) * | 2016-09-14 | 2018-03-22 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A metal oxide catalyst for methanol synthesis from co2 hydrogenation and preparation method of the catalyst |
| CN107952437A (zh) * | 2017-11-09 | 2018-04-24 | 华南理工大学 | 用于二氧化碳加氢合成甲醇的Cu/二氧化钛纳米片催化剂及其制备方法 |
| CN108250010A (zh) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | 一种甲醇制烯烃产物的选择加氢方法 |
| CN108855065A (zh) * | 2018-05-24 | 2018-11-23 | 厦门大学 | 一种将Pd/ZnAl2O4催化剂用于甲醇蒸汽重整制氢的方法 |
| CN112973773A (zh) * | 2021-03-02 | 2021-06-18 | 临涣焦化股份有限公司 | 一种二氧化碳加氢制液态燃料复合催化剂制备及应用 |
-
2021
- 2021-10-28 CN CN202111261269.1A patent/CN113976126A/zh active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010011101A2 (ko) * | 2008-07-24 | 2010-01-28 | 현대중공업 주식회사 | 합성가스로부터 메탄올 합성용 촉매 및 이의 제조방법 |
| CN102145281A (zh) * | 2010-02-10 | 2011-08-10 | 中国科学院大连化学物理研究所 | 一种甲醇水蒸汽重整制氢的催化剂及制备和应用 |
| CN103599785A (zh) * | 2013-11-27 | 2014-02-26 | 上海大学 | 用于焦炉煤气干重整的尖晶石负载型催化剂及其制备方法 |
| WO2018049735A1 (en) * | 2016-09-14 | 2018-03-22 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A metal oxide catalyst for methanol synthesis from co2 hydrogenation and preparation method of the catalyst |
| CN108250010A (zh) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | 一种甲醇制烯烃产物的选择加氢方法 |
| CN107952437A (zh) * | 2017-11-09 | 2018-04-24 | 华南理工大学 | 用于二氧化碳加氢合成甲醇的Cu/二氧化钛纳米片催化剂及其制备方法 |
| CN108855065A (zh) * | 2018-05-24 | 2018-11-23 | 厦门大学 | 一种将Pd/ZnAl2O4催化剂用于甲醇蒸汽重整制氢的方法 |
| CN112973773A (zh) * | 2021-03-02 | 2021-06-18 | 临涣焦化股份有限公司 | 一种二氧化碳加氢制液态燃料复合催化剂制备及应用 |
Non-Patent Citations (6)
| Title |
|---|
| JIA YANG ET AL.: ""The Improvement of Coralline-Like ZnGa2O4 by Cocatalysts for the Photocatalytic Degradation of Rhodamine B"", 《CATALYSTS》 * |
| JIMIN SONG ET AL.: ""The role of Al doping in Pd/ZnO catalyst for CO2 hydrogenation to methanol"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| LIMIAO CHEN ET AL.: ""Porous ZnAl2O4 synthesized by a modified citrate technique"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| MOLLY MENG-JUNG LI ET AL.: ""Enhanced CO2 hydrogenation to methanol over CuZn nanoalloy in Ga modified Cu/ZnO catalysts"", 《JOURNAL OF CATALYSIS》 * |
| PAWEL MIERCZYNSKI ET AL.: ""Cu/ZnxAlyOz supported catalysts (ZnO: Al2O3 = 1, 2, 4) for methanol synthesis"", 《CATALYSIS TODAY》 * |
| XINBAO ZHANG ET AL.: ""Reaction-driven surface reconstruction of ZnAl2O4 boosts the methanol selectivity in CO2 catalytic hydrogenation"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110327933B (zh) | 二氧化碳加氢制备甲醇的催化剂及其制备方法和应用 | |
| CN113181957A (zh) | 一种低温起活高效氨分解催化剂 | |
| Tu et al. | Low temperature methanation of CO 2 over an amorphous cobalt-based catalyst | |
| CN110721678A (zh) | 一种光热耦合催化CO2甲烷化的Ru基催化剂 | |
| WO2022166084A1 (zh) | 一种溶剂配位金属催化剂的制备方法及应用 | |
| CN111229213A (zh) | 一种钌基催化剂的制备方法 | |
| CN108623436B (zh) | 一种一锅法转化纤维素为生物乙醇的方法 | |
| CN103191744B (zh) | 一种改性蛭石负载镍催化剂及其制备方法 | |
| WO2021042874A1 (zh) | 一种二氧化碳甲烷化镍基催化剂及其制备方法和应用 | |
| Du et al. | Nanosheets-assembled Ni (Co) doped CeO2 microspheres toward NO+ CO reaction | |
| CN114192152A (zh) | 抗碳沉积光热催化甲烷干重整催化剂及其制备方法与用途 | |
| CN110433811B (zh) | MgO改性的Ni/CaO双功能催化剂及制备方法和应用 | |
| CN106861689B (zh) | 一种Pd基催化剂及其制备和应用 | |
| CN108114724B (zh) | 一氧化碳水汽变换低温催化剂的制备方法 | |
| CN109908906B (zh) | 一种制合成气催化剂及其制备方法 | |
| CN102417437A (zh) | 一种合成气制低碳混合醇催化剂及其制法和应用 | |
| CN111135857B (zh) | 还原型催化剂的制备方法及其用途 | |
| Du et al. | Carbon dioxide reforming of methane over bimetallic catalysts of Pt-Ru/γ-Al 2 O 3 for thermochemical energy storage | |
| CN113976126A (zh) | 一种用于二氧化碳加氢制甲醇的催化剂及制备方法和应用 | |
| CN113649014B (zh) | 一种镍-锌基催化剂及其制备方法和应用 | |
| CN114768804B (zh) | 一种固溶体光热催化co2转化反应的应用 | |
| CN114602449A (zh) | 一种ZnZrO2表面固溶体催化剂及其制备方法和应用 | |
| CN114534754B (zh) | 一种α-MoC1-x负载Pt-Cu双金属水煤气变换催化剂制备方法及其应用 | |
| CN109908907B (zh) | 甲烷二氧化碳重整制合成气催化剂及其制法 | |
| CN103157473B (zh) | 一种甲醇裂解催化剂及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |