CN117623852A - 一种由环戊酮和甲醇一步合成甲基环戊二烯的方法 - Google Patents
一种由环戊酮和甲醇一步合成甲基环戊二烯的方法 Download PDFInfo
- Publication number
- CN117623852A CN117623852A CN202210956520.4A CN202210956520A CN117623852A CN 117623852 A CN117623852 A CN 117623852A CN 202210956520 A CN202210956520 A CN 202210956520A CN 117623852 A CN117623852 A CN 117623852A
- Authority
- CN
- China
- Prior art keywords
- cyclopentanone
- metal
- deionized water
- metal oxide
- 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
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 title claims abstract description 150
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 43
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 9
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 60
- 229910052739 hydrogen Inorganic materials 0.000 claims description 53
- 239000001257 hydrogen Substances 0.000 claims description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 52
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010668 complexation reaction Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000000643 oven drying Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 7
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 16
- 230000001276 controlling effect Effects 0.000 description 13
- 239000011701 zinc Substances 0.000 description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 10
- 239000006004 Quartz sand Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- QKZBDPCURVINQZ-UHFFFAOYSA-N cyclopenta-1,3-diene;potassium Chemical class [K].C1C=CC=C1 QKZBDPCURVINQZ-UHFFFAOYSA-N 0.000 description 2
- NUUNDIOOYFEMQN-UHFFFAOYSA-N cyclopenta-1,3-diene;sodium Chemical compound [Na].C1C=CC=C1 NUUNDIOOYFEMQN-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- -1 potassium metals Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- OONRXMHENUMURA-UHFFFAOYSA-N manganese;1-methylcyclopenta-1,3-diene Chemical compound [Mn].CC1=CC=CC1 OONRXMHENUMURA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/88—Molybdenum
-
- 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
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
-
- 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
- B01J23/888—Tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/08—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring
- C07C13/15—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring with a cyclopentadiene ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种由环戊酮和甲醇一步合成甲基环戊二烯的方法,以环戊酮和甲醇为原料,通过在AxByOz型复合金属氧化物催化剂上的级联脱氢/羟醛缩合/选择性加氢脱氧反应,于固定床连续式反应器中合成目标产物甲基环戊二烯。本发明工艺路线简易,催化剂制备方便,对环境友好,实现了环戊酮和甲醇到高附加值甲基环戊二烯的直接转化。
Description
技术领域
本发明涉及一种由环戊酮和甲醇一步合成甲基环戊二烯的方法。
背景技术
甲基环戊二烯是生产汽油添加剂甲基环戊二烯三羰基锰的重要原料,同时可应用于合成高级树脂、表面涂层、高档染料、增塑剂、固化剂和高能火箭燃料RJ-4等。目前,工业上制备甲基环戊二烯的方法主要有两种:一种是以环戊二烯为原料,甲烷作为烷基化剂,通过烷基化反应合成甲基环戊二烯;另一种是从裂解乙烯的副产物C9馏分中分离得到甲基环戊二烯。CN101205168A公开了一种制备甲基环戊二烯的方法,环戊二烯与金属钠、钾等反应生成环戊二烯钠、钾盐,再通入液态一氯甲烷中进行液相甲基化反应制取甲基环戊二烯。易燃的金属钠等的使用且产生易燃易爆的氢气,使得该路线安全性差,污染大,反应条件也极其严苛,成本较高。另外,CN105111036A公开了从乙烯副产C9中分离甲基环戊二烯的新方法,采用一个高温裂解反应器和三个精馏塔串联,将乙烯副产C9及其夹带剂一起通入高温裂解反应器;高温裂解后的混和汽体通入第一精馏塔,通过精馏在塔顶分离出含有环戊二烯和甲基环戊二烯混和的馏分;进而通入第二精馏塔,塔顶采出环戊二烯,塔底采出甲基环戊二烯。虽然该路线安全可行,但是以储量有限且短时间无法再生的化石能源为原料,同时涉及反复解聚精馏过程,工艺设备复杂,能耗高。因此,开发绿色可持续合成甲基环戊二烯的新路线已经刻不容缓。
随着社会对可持续发展和环境问题的日益关注,探索利用可再生、丰富和二二氧化碳中性的生物质资源生产高性能燃料和高附加值化学品的新技术受到了广泛关注。例如,CN113968776A公开了一种生物质原料制备环戊酮的方法,该体系在一定的反应条件下可以将原生物质中的半纤维素、木聚糖、木糖、阿拉伯糖一步制备出高收率的环戊酮。但是,截止到目前,还没有文献报道过以生物质环戊酮为原料合成甲基环戊二烯。
发明内容
本发明的目的在于提供一种由环戊酮和甲醇一步合成甲基环戊二烯的方法,具体地涉及以环戊酮和甲醇为原料,在固定床连续式反应器中,在AxByOz型复合金属氧化物催化剂的作用下,通过级联脱氢/羟醛缩合/选择性加氢脱氧反应,直接合成甲基环戊二烯目标产物,为环戊酮和甲醇合成高附加值甲基环戊二烯化学品提供一种新型、简易、高效的方法。
本发明是通过以下技术方案实现的:
一种由环戊酮和甲醇一步合成甲基环戊二烯的方法,以环戊酮和甲醇为原料,通过在AxByOz型复合金属氧化物催化剂上的级联脱氢/羟醛缩合/选择性加氢脱氧反应,反应温度300-500℃(优选350-480℃,更优选400-470℃),氢气压力0.0001-1MPa(优选0.0001-0.9MPa,更优选0.0001-0.8MPa),氢气与环戊酮的摩尔比为20-400:1(30-350:1,更优选50-300:1),甲醇与环戊酮的摩尔比为0.1-10:1(优选1-10:1,更优选2-10:1),环戊酮的时空速为0.01-10h-1(优选0.05-9h-1,更优选0.1-8h-1)下,在固定床连续式反应器中一步转化得到目标产物甲基环戊二烯。
上述的原料环戊酮、甲醇及目标产物甲基环戊二烯的化学结构式见表1。
表1化合物的结构式
基于上述方案,优选地,所述AxByOz型复合金属氧化物催化剂包括:CuxMoyOz、ZnxMoyOz、NixMoyOz、CoxMoyOz、MnxMoyOz、FexMoyOz、CrxMoyOz、CuxWyOz、NixWyOz、CoxWyOz、FexWyOz、ZnxWyOz、ZnxVyOz中的一种或多种;其中,x为0.5-8,优选0.8-7,更优选1-6;y为0.5-8,优选0.8-7,更优选1-6;z为1-16,优选1-14,更优选1-12。
基于上述方案,优选地,所述AxByOz型复合金属氧化物催化剂采用水热法、沉积沉淀法或柠檬酸络合法制备,且使用前在氢气中进行还原处理,其中,还原条件为:氢气压力0.001-2.0MPa(优选0.005-1.5MPa,更优选0.01-1MPa),氢气流速2-300mL/min(优选5-250mL/min,更优选10-200mL/min),还原温度400-600℃(优选450-580℃,更优选480-570℃),还原时间0.5-12h(优选0.7-10h,更优选1-8h)。
基于上述方案,优选地,所述AxByOz型复合金属氧化物催化剂采用水热法制备,具体制备过程为:将一定量A的金属盐与B的金属盐混合溶解在去离子水中,室温下超声得到悬浮液;将混合溶液转移至带聚四氟乙烯内衬的水热釜中,在80-220℃(优选90-200℃,更优选100-180℃)下反应5-48h(优选6-42h,更优选8-36h)后过滤洗涤,得到的粉末在80℃下干燥1-8h(优选2-6h,更优选3-5h)后于300-800℃(优选350-750℃,更优选400-700℃)下焙烧0.5-6h(优选1-5h,更优选1-4h),即可得到AxByOz型复合金属氧化物催化剂。
基于上述方案,优选地,所述AxByOz型复合金属氧化物催化剂也可以采用沉积沉淀法制备,具体制备过程为:将一定量的B的金属盐溶于去离子水中,使用浓度为0.5-14mol/L(优选1-8mol/L,更优选1.5-6mol/L)氨水溶液作为沉淀剂调节该溶液的PH值调节为8-12后,滴加A的金属酸盐水溶液,搅拌0.5-4h(优选1-3.5h,更优选1-3h)后,将得到的沉淀过滤出来,经去离子水和乙醇洗涤后,于在50-120℃烘箱内烘干4-48h,再在300-800℃(优选350-750℃,更优选400-700℃)下焙烧0.5-10h(优选1-8h,更优选1-6h),即可得到AxByOz型复合金属氧化物催化剂。
基于上述方案,优选地,所述AxByOz型复合金属氧化物催化剂还可以使用柠檬酸络合法制备,具体制备过程是:按摩尔比M:柠檬酸=1:1-1:3(优选1:1.05-1:2,更优选1:1.1-1:1.5)称取B的金属酸盐、A的金属酸盐、柠檬酸,M为处于阴离子中的金属B和阳离子金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在300-800℃(优选350-750℃,更优选400-700℃)下焙烧0.5-10h(优选1-8h,更优选1-6h)后,即可得到AxByOz型复合金属氧化物催化剂。
本发明所述的方法可实现环戊酮和甲醇直接合成高附加值的甲基环戊二烯。
本发明的有益效果是:本发明首次以环戊酮和甲醇为原料,于固定床连续式反应器中,在AxByOz型复合金属氧化物催化剂的作用下,通过级联脱氢/羟醛缩合/选择性加氢脱氧反应,一步直接合成具有高附加值的甲基环戊二烯;同时催化剂制备简单、可大量合成,反应条件温和,环戊酮转化率在95%以上,甲基环戊二烯选择性在75%以上,催化性能良好,且稳定性和再生性能好。本发明工艺路线简单,操作方便,能耗低、对环境友好,是一条绿色高效的新催化方法,可用于实际的工业化生产。截止到目前,还没有以环戊酮和甲醇为原料,通过级联脱氢/羟醛缩合/选择性加氢脱氧反应来一步合成甲基环戊二烯的相关报道。
附图说明
图1为实施例6中环戊酮和甲醇合成甲基环戊二烯的产物的气相色谱图。
图2为目标产物甲基环戊二烯的质谱对照图。
具体实施方式
以下结合具体实施例进一步详细描述本发明的技术方案,但本发明的保护范围不局限于这些实施例。
实施例1
(1)AxByOz型复合金属氧化物催化剂MnMoO4的制备:按摩尔比M:柠檬酸=1:1.2称取钼酸铵1.24g、50wt%的硝酸锰水溶液2.51g、柠檬酸3.53g,M为处于阴离子中的金属B和阳离子金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在600℃下焙烧5h后,即得MnMoO4复合金属氧化物催化剂。
(2)将上述MnMoO4催化剂0.2g与2g石英砂(40-70目)均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.01MPa、氢气流量150mL/min、还原温度400℃下还原2h,然后控制反应温度400℃,氢气压力0.01MPa,氢气与环戊酮的摩尔比为100:1,甲醇与环戊酮的摩尔比为3:1,环戊酮的时空速为1.26h-1,其环戊酮的转化率为100%,甲基环戊二烯的选择性为79%。
实施例2
(1)AxByOz型复合金属氧化物催化剂CoMoO4的制备:称取2.47g钼酸铵,溶于200mL去离子水中。使用浓度为2mol/L的氨水溶液作为沉淀剂将该溶液的PH值调节为9.5,滴加硝酸钴(4.07g溶于100mL去离子水中)水溶液,搅拌2h后,将得到的沉淀过滤出来,经去离子水和乙醇洗涤后,于在50℃烘箱内烘干4h,再在500℃下焙烧2h,即得CoMoO4复合金属氧化物催化剂。
(2)将上述CoMoO4催化剂0.4g与2g石英砂(40-70目)均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.05MPa、氢气流量90mL/min、还原温度450℃下还原0.5h,然后控制反应温度450℃,氢气压力0.005MPa,氢气与环戊酮的摩尔比为50:1,甲醇与环戊酮的摩尔比为1:1,环戊酮的时空速为0.63h-1,其环戊酮的转化率为96%,环戊二烯的选择性为83%。
实施例3
(1)AxByOz型复合金属氧化物催化剂Cr2(MoO4)3的制备:按摩尔比M:柠檬酸=1:1.2称取钼酸铵1.24g、九水合硝酸铬1.87g、柠檬酸2.94g,M为处于阴离子中的金属B和阳离子金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在650℃下焙烧3h后,即得Cr2(MoO4)3复合金属氧化物催化剂。
(2)将上述Cr2(MoO4)3催化剂0.1g与实施例2中合成的CoMoO4催化剂0.1g机械混合后,再与2g石英砂(40-70目)均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.001MPa、氢气流量120mL/min、还原温度425℃下还原1h,然后控制反应温度425℃,氢气压力0.001MPa,氢气与环戊酮的摩尔比为100:1,甲醇与环戊酮的摩尔比为3:1,环戊酮的时空速为2.52h-1,其环戊酮的转化率为97%,甲基环戊二烯的选择性为85%。
实施例4
(1)AxByOz型复合金属氧化物催化剂ZnWO4的制备:将0.55g醋酸锌与0.99g二水合钨酸钠溶解在60mL去离子水中,室温下超声得到悬浮液;将混合溶液转移至带聚四氟乙烯内衬的水热釜中,在120℃下反应12h后过滤洗涤,得到的粉末于80℃烘干3h后于600℃下焙烧2h,即可得到ZnWO4复合金属氧化物催化剂。
(2)将上述ZnWO4催化剂0.2g与2g石英砂(40-70目)均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.01MPa、氢气流量150mL/min、还原温度400℃下还原2h,然后控制反应温度450℃,氢气压力0.01MPa,氢气与环戊酮的摩尔比为75:1,甲醇与环戊酮的摩尔比为2:1,环戊酮的时空速为1.26h-1,其环戊酮的转化率为97%,甲基环戊二烯的选择性为82%。
实施例5
(1)AxByOz型复合金属氧化物催化剂CuMoO4的制备:按摩尔比M:柠檬酸=1:1.2称取钼酸铵1.24g、硝酸铜1.69g、柠檬酸3.53g,M为处于阴离子中的金属B和阳离子金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在600℃下焙烧5h后,即得CuMoO4催化剂。
(2)将上述CuMoO4催化剂0.2g与2g石英砂(40-70目)均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.05MPa、氢气流量100mL/min、还原温度400℃下还原2h,然后控制反应温度400℃,反应压力0.05MPa,氢气与环戊酮的摩尔比为70:1,甲醇与环戊酮的摩尔比为1:1,环戊酮的时空速为2.52h-1,其环戊酮的转化率为95%,甲基环戊二烯的选择性为81%。
实施例6
(1)AxByOz型复合金属氧化物催化剂ZnMoO4的制备:称取2.47g钼酸铵,溶于200mL去离子水中。使用浓度为2mol/L的氨水溶液作为沉淀剂调节该溶液的PH值调节为8.9后,滴加硝酸锌(4.16g溶于100mL去离子水中)水溶液,搅拌2h后,将得到的沉淀过滤出来,经去离子水和乙醇洗涤后,于在100℃烘箱内烘干5h,再在450℃下焙烧2h,即得ZnMoO4复合金属氧化物催化剂。
(2)将上述ZnMoO4催化剂0.2g与实施例4中合成的ZnWO4催化剂0.2g机械混合,然后再与2g石英砂(40-70目)均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.01MPa、氢气流量120mL/min、还原温度450℃下还原0.5h,然后控制反应温度470℃,氢气压力0.01MPa,氢气与环戊酮的摩尔比为50:1,甲醇与环戊酮的摩尔比为1:1,环戊酮的时空速为0.67h-1,其环戊酮的转化率为99%,甲基环戊二烯的选择性为86%。
上述的实施例1-6的实验结果见表2。
表2由环戊酮和甲醇通过级联脱氢/羟醛缩合/选择性加氢脱氧反应合成甲基环戊二烯
以实施例6中的ZnMoO4作为催化剂,将ZnMoO4催化剂0.2g与2g石英砂(40-70目)均匀混合,填装于固定床连续式反应器中,以环戊酮和甲醇为原料,然后在氢气压力0.01MPa,还原温度450℃下还原0.5h,然后在一定的反应温度、氢气压力、氢气与环戊酮的摩尔比、甲醇与环戊酮的摩尔比以及环戊酮的时空速下进行反应。
表3ZnMoO4催化环戊酮和甲醇经级联脱氢/羟醛缩合/选择性加氢脱氧反应合成甲基环戊二烯
实施例23
(1)AxByOz型复合金属氧化物催化剂Zn3Mo2O9的制备:称取2.47g钼酸铵,溶于200mL去离子水中。使用浓度为4mol/L的氨水溶液作为沉淀剂调节该溶液的PH值调节为9.2后,滴加硝酸锌(4.16g溶于100mL去离子水中)水溶液,搅拌2h后,将得到的沉淀过滤出来,经去离子水和乙醇洗涤后,于在50℃烘箱内烘干6h,再在400℃下焙烧2h,即得Zn3Mo2O9复合金属氧化物催化剂。
(2)将上述Zn3Mo2O9催化剂0.2g与2g石英砂(40-70目)均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.01MPa、氢气流量150mL/min、还原温度450℃下还原0.5h,然后控制反应温度450℃,氢气压力0.01MPa,氢气与环戊酮的摩尔比为100:1,甲醇与环戊酮的摩尔比为3:1,环戊酮的时空速为1.26h-1,其环戊酮的转化率为98%,甲基环戊二烯的选择性为86%。
在实施例23中的Zn3Mo2O9催化剂的制备过程中,其他条件不变,通过改变所加入钼酸铵的质量来得到不同Zn/Mo比的ZnxMoyOz复合金属氧化物催化剂,即为实施例24-28。将所得ZnxMoyOz催化剂0.2g与2g石英砂(40-70目)均匀混合,填装于固定床连续式反应器中,在氢气压力0.01MPa、氢气流量150mL/min、还原温度450℃下还原0.5h,然后在反应温度450℃,氢气压力0.01MPa,氢气与环戊酮的摩尔比为100:1,甲醇与环戊酮的摩尔比为3:1,环戊酮的时空速为1.26h-1的条件下进行反应。
表4不同Zn/Mo比的ZnxMoyOz催化环戊酮和甲醇通过级联脱氢/羟醛缩合/选择性加氢脱氧反应合成甲基环戊二烯
Claims (10)
1.一种由环戊酮和甲醇一步合成甲基环戊二烯的方法,其特征在于,所述方法如下:以环戊酮和甲醇为原料,通过在AxByOz型复合金属氧化物催化剂上的级联脱氢/羟醛缩合/选择性加氢脱氧反应,反应温度300-500℃,氢气压力0.0001-1MPa,氢气与环戊酮的摩尔比为20-400:1,甲醇与环戊酮/的摩尔比为0.1-10:1,环戊酮的时空速为0.01-10h-1,在固定床连续式反应器中一步转化直接得到甲基环戊二烯。
2.按照权利要求1所述的方法,其特征在于:反应温度350-480℃,氢气压力0.0001-0.9MPa,氢气与环戊酮的摩尔比为30-350:1,甲醇与环戊酮/的摩尔比为1-10:1,环戊酮的时空速为0.05-9h-1。
3.按照权利要求2所述的方法,其特征在于:反应温度400-470℃,氢气压力0.0001-0.8MPa,氢气与环戊酮的摩尔比为50-300:1,甲醇与环戊酮/的摩尔比为2-10:1,环戊酮的时空速为0.1-8h-1。
4.按照权利要求1所述的方法,其特征在于:所述AxByOz型复合金属氧化物催化剂包括:CuxMoyOz、ZnxMoyOz、NixMoyOz、CoxMoyOz、MnxMoyOz、FexMoyOz、CrxMoyOz、CuxWyOz、NixWyOz、CoxWyOz、FexWyOz、ZnxWyOz、ZnxVyOz中的一种或多种;其中,x为0.5-8,优选0.8-7,更优选1-6;y为0.5-8,优选0.8-7,更优选1-6;z为1-16,优选1-14,更优选1-12。
5.按照权利要求1或4所述的方法,其特征在于:所述AxByOz型复合金属氧化物催化剂采用水热法、沉积沉淀法或柠檬酸络合法制备,且使用前在氢气中进行还原处理;其中,还原处理的条件为:氢气压力0.001-2.0MPa,氢气流速2-300mL/min,温度400-600℃,时间0.5-12h。
6.按照权利要求5所述的方法,其特征在于,所述还原处理的条件为:氢气压力0.005-1.5MPa,氢气流速5-250mL/min,温度450-580℃,时间0.7-10h。
7.按照权利要求6所述的方法,其特征在于,所述还原处理的条件为:氢气压力0.01-1MPa,氢气流速10-200mL/min,温度480-570℃,时间1-8h。
8.按照权利要求5所述的方法,其特征在于,所述水热法包括以下步骤:将A的金属盐与B的金属盐混合溶解在去离子水中,室温下超声得到悬浮液;将所述悬浮液转移至水热釜中,在80-220℃下反应5-48h,然后过滤、洗涤,80℃下干燥1-8h,然后于300-800℃下焙烧0.5-6h,得到所述AxByOz型复合金属氧化物催化剂;
所述沉积沉淀法包括以下步骤:将B的金属盐溶于去离子水中,使用浓度为0.5-14mol/L氨水溶液作为沉淀剂将PH值调节为8-12,滴加A的金属酸盐水溶液,搅拌0.5-4h(优选1-3.5h,更优选1-3h)后,将得到的沉淀过滤出来,经去离子水和乙醇洗涤后,在50-120℃烘干4-48h,再在300-800℃下焙烧0.5-10h,得到所述AxByOz型复合金属氧化物催化剂;
所述柠檬酸络合法包括以下步骤:按摩尔比M:柠檬酸=1:1~1:3称取B的金属酸盐、A的金属酸盐、柠檬酸,M为金属B和金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在300-800℃下焙烧0.5-10h后,得到所述AxByOz型复合金属氧化物催化剂。
9.按照权利要求8所述的方法,其特征在于,所述水热法包括以下步骤:将A的金属盐与B的金属盐混合溶解在去离子水中,室温下超声得到悬浮液;将所述悬浮液转移至水热釜中,在90-200℃下反应6-42h,然后过滤、洗涤,80℃下干燥2-6h,然后于350-750℃下焙烧1-5h,得到所述AxByOz型复合金属氧化物催化剂;
所述沉积沉淀法包括以下步骤:将B的金属盐溶于去离子水中,使用浓度为0.5-14mol/L1-8 mol/L氨水溶液作为沉淀剂将PH值调节为8-12,滴加A的金属酸盐水溶液,搅拌1-3.5h后,将得到的沉淀过滤出来,经去离子水和乙醇洗涤后,在50-120℃烘干4-48h,再在350-750℃下焙烧1-8h,得到所述AxByOz型复合金属氧化物催化剂;
所述柠檬酸络合法包括以下步骤:按摩尔比M:柠檬酸=1:1.05~1:2称取B的金属酸盐、A的金属酸盐、柠檬酸,M为金属B和金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在350-750℃下焙烧1-8h后,得到所述AxByOz型复合金属氧化物催化剂。
10.按照权利要求9所述的方法,其特征在于,所述水热法包括以下步骤:将A的金属盐与B的金属盐混合溶解在去离子水中,室温下超声得到悬浮液;将所述悬浮液转移至水热釜中,在100-180℃下反应8-36h,然后过滤、洗涤,80℃下干燥3-5h,然后于400-700℃下焙烧1-4h,得到所述AxByOz型复合金属氧化物催化剂;
所述沉积沉淀法包括以下步骤:将B的金属盐溶于去离子水中,使用浓度为1.5-6mol/L氨水溶液作为沉淀剂将PH值调节为8-12,滴加A的金属酸盐水溶液,搅拌1-3h后,将得到的沉淀过滤出来,经去离子水和乙醇洗涤后,在50-120℃烘干4-48h,再在400-700℃下焙烧1-6h,得到所述AxByOz型复合金属氧化物催化剂;
所述柠檬酸络合法包括以下步骤:按摩尔比M:柠檬酸=1:1~1:31:1.1~1:1.5称取B的金属酸盐、A的金属酸盐、柠檬酸,M为金属B和金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在400-700℃下焙烧1-6h后,得到所述AxByOz型复合金属氧化物催化剂。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210956520.4A CN117623852A (zh) | 2022-08-10 | 2022-08-10 | 一种由环戊酮和甲醇一步合成甲基环戊二烯的方法 |
PCT/CN2022/135841 WO2024031876A1 (zh) | 2022-08-10 | 2022-12-01 | 一种由环戊酮和甲醇一步合成甲基环戊二烯的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210956520.4A CN117623852A (zh) | 2022-08-10 | 2022-08-10 | 一种由环戊酮和甲醇一步合成甲基环戊二烯的方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117623852A true CN117623852A (zh) | 2024-03-01 |
Family
ID=89850486
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210956520.4A Pending CN117623852A (zh) | 2022-08-10 | 2022-08-10 | 一种由环戊酮和甲醇一步合成甲基环戊二烯的方法 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN117623852A (zh) |
WO (1) | WO2024031876A1 (zh) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1020173A (en) * | 1972-11-24 | 1977-11-01 | Hoechst Aktiengesellschaft | Process for alkylating ketones |
US4567308A (en) * | 1984-03-26 | 1986-01-28 | Asahi Chemical Co., Ltd. | Process for preparing alkylcyclopentadiene derivatives |
CN113860987B (zh) * | 2020-06-30 | 2023-11-17 | 中国科学院大连化学物理研究所 | 一种甲醇和共进料物种共进料制备环戊二烯类化合物的方法 |
CN114315504B (zh) * | 2020-09-29 | 2023-02-28 | 中国科学院大连化学物理研究所 | AxByOz型复合金属氧化物催化制备甲基环戊二烯的方法 |
-
2022
- 2022-08-10 CN CN202210956520.4A patent/CN117623852A/zh active Pending
- 2022-12-01 WO PCT/CN2022/135841 patent/WO2024031876A1/zh unknown
Also Published As
Publication number | Publication date |
---|---|
WO2024031876A1 (zh) | 2024-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106031871B (zh) | 一种co2加氢制取低碳烯烃的铁基催化剂及其制备和应用 | |
CN114315504B (zh) | AxByOz型复合金属氧化物催化制备甲基环戊二烯的方法 | |
KR20180113448A (ko) | 금속이 첨가된, 실리카-담지 나트륨 텅스테이트 촉매, 이의 제조방법 및 이를 이용한 메탄의 산화이량화 반응방법 | |
JPH0336571B2 (zh) | ||
CN112871200B (zh) | 一种从合成气制备轻质芳烃的催化剂体系及其应用 | |
CN103130604A (zh) | 一种改性分子筛催化剂用于异丁烷催化裂解的方法 | |
CN111036278B (zh) | 由合成气制备低碳烯烃的方法 | |
CN102553624A (zh) | 一种用于合成甲基丙烯酸的催化剂的制备方法 | |
CN112973773A (zh) | 一种二氧化碳加氢制液态燃料复合催化剂制备及应用 | |
CN103933989A (zh) | 用于合成低碳烯烃的催化剂及其制备方法 | |
CN109569623B (zh) | 合成气直接制烯烃的催化剂、制备方法及使用方法 | |
CN104707646B (zh) | 一种二甲醚氧化脱氢制备甲苯的催化剂及其制备方法和应用 | |
CN112403475B (zh) | 一种用于二氧化碳重整制合成气的催化剂的制备方法 | |
CN113385171A (zh) | 一种寡层碳保护的金属基催化剂及其在环氧乙烷羰基化中的应用 | |
WO2016180000A1 (zh) | 一种纤维素两步法制备乙二醇和1,2-丙二醇的方法 | |
CN104230641B (zh) | 生产异丙苯的方法 | |
CN1044339C (zh) | 用于甲醇氧化制甲醛的催化剂的制法 | |
CN102249890B (zh) | 一种以甘油为原料制备丙烯酸的方法 | |
CN117623852A (zh) | 一种由环戊酮和甲醇一步合成甲基环戊二烯的方法 | |
CN111036284B (zh) | 催化剂及其制备方法以及由合成气制备低碳烯烃的方法 | |
CN112844390B (zh) | 制备低碳烯烃的铁镍双金属费托催化剂及制备方法与应用 | |
CN112619662B (zh) | 一种生产低碳烯烃的催化剂及其制备方法和应用 | |
WO2024031877A1 (zh) | 环戊酮合成环戊二烯的方法 | |
CN106607049B (zh) | 合成气制低碳烯烃的催化剂及其制备方法 | |
CN114436859B (zh) | 一种通过醚后c4制备仲丁胺的方法 |
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 |