CN112973714B - Catalyst for preparing cyclopentene, preparation method and application thereof - Google Patents
Catalyst for preparing cyclopentene, preparation method and application thereof Download PDFInfo
- Publication number
- CN112973714B CN112973714B CN202110312753.6A CN202110312753A CN112973714B CN 112973714 B CN112973714 B CN 112973714B CN 202110312753 A CN202110312753 A CN 202110312753A CN 112973714 B CN112973714 B CN 112973714B
- Authority
- CN
- China
- Prior art keywords
- metal
- catalyst
- cyclopentene
- salt
- carrier
- 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.)
- Active
Links
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 239000003054 catalyst Substances 0.000 title claims abstract description 148
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims description 225
- 239000002184 metal Substances 0.000 claims description 225
- 238000005470 impregnation Methods 0.000 claims description 67
- 150000003839 salts Chemical class 0.000 claims description 63
- 239000007788 liquid Substances 0.000 claims description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000012018 catalyst precursor Substances 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 238000007654 immersion Methods 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 238000011065 in-situ storage Methods 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- -1 2-methylfuran-n-heptane Chemical compound 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 76
- 239000000243 solution Substances 0.000 description 28
- 229910052750 molybdenum Inorganic materials 0.000 description 27
- 229910004298 SiO 2 Inorganic materials 0.000 description 26
- 238000001179 sorption measurement Methods 0.000 description 23
- 239000000956 alloy Substances 0.000 description 18
- 229910045601 alloy Inorganic materials 0.000 description 18
- 239000011148 porous material Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 12
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 11
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 3
- 239000012847 fine chemical Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000002429 nitrogen sorption measurement Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000002249 anxiolytic agent Substances 0.000 description 1
- 230000000949 anxiolytic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QWCRAEMEVRGPNT-UHFFFAOYSA-N buspirone Chemical compound C1C(=O)N(CCCCN2CCN(CC2)C=2N=CC=CN=2)C(=O)CC21CCCC2 QWCRAEMEVRGPNT-UHFFFAOYSA-N 0.000 description 1
- 229960002495 buspirone Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- INILCLIQNYSABH-UHFFFAOYSA-N cobalt;sulfanylidenemolybdenum Chemical compound [Mo].[Co]=S INILCLIQNYSABH-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001940 cyclopentanes Chemical class 0.000 description 1
- KQBURNAXWQWQLS-UHFFFAOYSA-N cyclopentene hydrogen peroxide Chemical compound OO.C1=CCCC1 KQBURNAXWQWQLS-UHFFFAOYSA-N 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000006276 transfer reaction Methods 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
- B01J23/70—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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/882—Molybdenum and cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
-
- 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
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing cyclopentene, which is a mixed metal oxide consisting of Co, mo and Al or a mixed metal oxide consisting of Co, mo, al and Si; the catalyst contains, in terms of mass of oxides, 1 to 5wt% of Co, 9 to 18wt% of Mo, 65 to 90wt% of Al and 0 to 15wt% of Si. The invention also discloses a preparation method of the catalyst and application of the catalyst in preparation of cyclopentene by hydrodeoxygenation of 2-methylfuran. The yield of the cyclopentene prepared by the method applied to the hydrodeoxygenation reaction of 2-methylfuran is more than or equal to 85 percent.
Description
Technical Field
The invention relates to the technical field of cyclopentene production, and particularly relates to a catalyst for preparing cyclopentene, and a preparation method and application thereof.
Background
Cyclopentene is an important intermediate of fine chemical products, and the copolymerization component of cyclopentene used for polymers can change the elasticity of the copolymer. The addition of cyclopentene and hydrogen halide to produce halogenated cyclopentane is a key intermediate of pesticide, and its polyhalide is also used in the production of pesticide and medicine. In recent years, medical disinfectant is gradually replaced by glutaraldehyde from phenols, and the most economical synthesis method of the glutaraldehyde is to prepare the glutaraldehyde by oxidizing cyclopentene hydrogen peroxide. In addition, the production of cyclopentanone from cyclopentene is the most important field of application of cyclopentene. Cyclopentanone can be used for producing fine chemicals such as novel spices of methyl dihydrojasmonate, albendanone, and anxiolytic buspirone, and can also be used for synthesizing pesticides such as insecticides and herbicides.
In the process of preparing ethylene by steam cracking naphtha, a considerable amount of carbon five fraction is by-produced. Depending on the process and composition, such carbon five cuts can be divided into two categories: one is a carbon five fraction obtained by directly separating cracked carbon five fraction, and the carbon five fraction contains about 40-60% of isopreneDiolefins such as diene, cyclopentadiene, piperylene and the like, which are active in chemical property and are important raw materials of a plurality of fine chemical products, can be separated and purified by adopting the traditional means of combining the processes such as rectification separation, extractive rectification separation and the like; the second type is that C5-C9 fraction obtained in the process of preparing ethylene by naphtha steam cracking is firstly Pd/Al 2 O 3 Selectively hydrogenating to convert diolefin and alkyne into mono-olefin, rectifying and separating to obtain carbon five fraction, which may be called hydrogenated carbon five fraction. At present, the hydrogenated carbon five fraction is mainly hydrogenated to form partial hydrogenated carbon five fraction, and cyclopentene can be obtained by separating the partial hydrogenated carbon five fraction.
U.S. Pat. No. 6,804,804 describes a process for producing cyclopentane or (and) cyclopentene from a portion of hydrocracked gasoline by fractionation. Firstly, collecting a carbon five fraction with a low boiling point from the top of a first rectifying tower, collecting a heavy component containing six carbons or more from the bottom of the first rectifying tower, collecting a fraction containing at least 40% of cyclopentane and cyclopentene from a side line, sending the fraction into a hydrogenation reactor to convert olefin into alkane, sending a hydrogenation product into a second rectifying tower, separating a mixture of n-pentane and isopentane from the top of the second rectifying tower, and sending the tower bottom liquid into a third rectifying tower to obtain cyclopentane. Or directly rectifying and separating the fraction containing at least 40% of cyclopentane and cyclopentene to obtain cyclopentene and cyclopentane.
U.S. Pat. No. 6,6264799 teaches a process for the production of cyclopentane or (and) cyclopentene. Rectifying the hydrogenated carbon five fraction in a first rectifying tower, separating the low boiling point carbon five fraction from the tower top, feeding the tower bottom fraction into a second rectifying tower, and separating cyclopentene from the tower top.
Chinese patent CN100393676C discloses a method for producing high-purity cyclopentene and cyclopentane from crude piperylene obtained by separating carbon from ethylene byproduct from petroleum cracking. The crude pentadiene raw material enters an extraction tower in the presence of a polymerization inhibitor, a cyclopentene and cyclopentane mixed material is obtained from the tower top, and an extracting agent and pentadiene are taken as a tower kettle; feeding the obtained tower top material into a first rectifying tower, removing light components at the tower top, and obtaining a cyclopentene and cyclopentane mixed material at the tower bottom; and (3) feeding the material at the bottom of the first rectifying tower into a second rectifying tower, and obtaining a cyclopentene product with the concentration of more than 99% at the tower top.
Chinese patent CN106673938B discloses a method for producing cyclopentene by selective hydrogenation of cyclopentadiene. Mixing a cyclopentadiene-containing raw material with a solvent to obtain a hydrogenation reaction raw material, mixing the hydrogenation reaction raw material with hydrogen, and continuously passing through a fixed bed reactor filled with a selective hydrogenation catalyst; separating hydrogen from the hydrogenation product, introducing the hydrogen into a first rectifying tower, extracting heavy component impurities from the tower bottom, and extracting a distillate at the tower top as a feed of a second rectifying tower; and (4) introducing the distillate at the tower top of the first rectifying tower into a second rectifying tower, and extracting a cyclopentene product at the tower bottom.
Chinese patent CN108069814B discloses a method for preparing cyclopentene from dicyclopentadiene. A catalytic distillation tower is adopted, and the distillation tower comprises a rectifying section, a reaction rectifying section and a stripping section; heating and partially decomposing a dicyclopentadiene raw material, and directly feeding the dicyclopentadiene raw material and hydrogen into a distillation tower; the decomposition product of dicyclopentadiene and hydrogen gas flow upwards and enter a reaction rectification section, and contact, mass transfer, heat transfer and hydrogenation reaction are carried out on the reflux distillate oil light component on a hydrogenation catalyst filled in the reaction rectification section; the product after reaction is discharged from the top of the tower after passing through a rectifying section; light components of distillate oil which does not participate in the reaction are extracted from the lateral line of the rectifying section, cooled and then refluxed to a distillation tower; the undecomposed dicyclopentadiene material flows downwards into the stripping section, contacts with the distillate oil gas phase component rising from the tower bottom, transfers heat, and generates decomposition reaction. The invention can realize higher selectivity and yield of the target product cyclopentene.
The cracked C5 fraction contains only about 4% cyclopentene, which is commercially obtained mainly from the cracking of dicyclopentadiene and the selective hydrogenation of cyclopentadiene. Cyclopentadiene is selectively hydrogenated by catalyst to prepare cyclopentene, the catalyst is common used has skeleton nickel, niO/Al 2 O 3 、NiO/MgO-Al 2 O 3 、Pd/C、Pb/Al 2 O 3 、Ni-B/Al 2 O 3 And so on. When cyclopentadiene is used for preparing cyclopentene by catalytic hydrogenation, cyclopentene can be further hydrogenated to generate cyclopentane, and cyclopentene is influencedThe yield of (2). Thus, a combination of selective hydrogenation and rectification is usually employed to obtain cyclopentene.
At present, the hydrodeoxygenation reaction is widely used for upgrading the biomass oil to prepare high-quality oil. The selective hydrodeoxygenation of phenolic compounds to aromatics has attracted extensive attentionAngew Chem. Int. Ed., 46 (2007) 7164-7183). Common hydrodeoxygenation catalysts are cobalt molybdenum sulfide, nickel molybdenum sulfide, phosphides (e.g. Ni) 2 P), nitrides (e.g. Mo) 2 N), metal oxides (e.g. MoO) 3 、WO 3 ) And metal catalysts such as platinum, palladium, ruthenium, nickel, etc. Early Massoth et al in literature: (Appl. Catal34 (1987) 215-224) reported on methyl furans in CoMo/Al 2 O 3 The products of hydrodeoxygenation on the catalyst are pentene, pentane and 1% pentadiene, etc., but no cyclic olefin compound has been found so far.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalyst for preparing cyclopentene.
The invention also aims to provide a preparation method of the catalyst for preparing cyclopentene.
The third technical problem to be solved by the invention is to provide the application of the catalyst for preparing cyclopentene.
In order to solve the above problems, the present invention provides a catalyst for preparing cyclopentene, which is characterized in that: the catalyst is mixed metal oxide consisting of Co, mo and Al or mixed metal oxide consisting of Co, mo, al and Si; the catalyst contains, in terms of mass of oxides, 1 to 5wt% of Co, 9 to 18wt% of Mo, 65 to 90wt% of Al and 0 to 15wt% of Si.
The molar ratio of the Co to the Mo is 0.2 to 0.5.
The preparation method of the catalyst for preparing cyclopentene comprises the following steps:
activating an alumina or silicon-containing alumina carrier at 200 to 450 ℃ for 2 to 5 hours to obtain an activated carrier;
placing the activated carrier into an impregnating solution containing metal Co and/or metal Mo by an isometric impregnation method or an excess impregnation method through a one-step loading method or a step-by-step loading method, and impregnating for 10 to 24 hours at 10 to 50 ℃ to obtain a catalyst precursor;
and thirdly, performing temperature programming on the catalyst precursor at a temperature rise rate of 2-5 ℃/min, and roasting at 350-550 ℃ for 1-4 hours to obtain the catalyst for preparing cyclopentene.
The one-step loading method in the second step is to immerse the activated carrier in an immersion liquid containing metal Co and metal Mo, and dry the carrier to a constant weight at 90 to 150 ℃ to obtain the catalyst precursor.
The step load method in the step consists of a first step load and a second step load; the first-step loading refers to immersing the activated carrier in an impregnation solution containing metal Mo or an impregnation solution containing metal Co to respectively obtain a carrier containing Mo and a carrier containing Co; then respectively drying the Mo-containing carrier and the Co-containing carrier at 90-150 ℃ to constant weight, and then roasting at 350-550 ℃ for 0-4 hours to respectively obtain a Mo-containing precursor and a Co-containing precursor; and the second step of loading refers to that the Co-containing precursor is soaked in a soaking solution containing metal Mo, or the Mo-containing precursor is soaked in the soaking solution containing metal Co, and then the precursor is dried to constant weight at 90 to 150 ℃ to obtain the catalyst precursor.
The step of the moderate volume impregnation method is characterized in that (1) selected metal Co salt and metal Mo salt are decomposed into oxides, and the oxides account for 1 to 5wt% of Co and 9 to 18wt% of Mo in the catalyst; (2) weighing alumina or a silicon-containing alumina carrier with required weight, and measuring the volume of the impregnation liquid required by equal-volume impregnation by using deionized water; (3) calculating the weight of the required metal Co salt and Mo salt according to the weight of the salt selected in the step (1) and the weight of the carrier in the step (2); dissolving a metal Co salt in the deionized water with the volume determined in the step (2) to obtain an impregnation liquid containing metal Co, dissolving a metal Mo salt in the deionized water with the volume determined in the step (2) to obtain an impregnation liquid containing metal Mo, and simultaneously dissolving the metal Co salt and the metal Mo salt in the deionized water with the volume determined in the step (2) to obtain an impregnation liquid containing metal Co and metal Mo; (4) and (3) putting the activated carrier into an impregnation liquid for impregnation.
The excess impregnation method in the step II is that i selected metal Co salt and metal Mo salt are decomposed into oxides, and the oxides account for 1 to 5wt% of Co and 9 to 18wt% of Mo in the catalyst; ii, weighing the alumina or the silicon-containing alumina carrier with the required weight, and measuring the volume of the impregnation liquid required by the equal-volume impregnation by using deionized water; iii, weighing 3-5 times of the weight of the salt selected according to the step i and the carrier in the step ii, and calculating the weight of the required metal Co salt and Mo salt; then dissolving metal Co salt in deionized water with the volume being 3-5 times that measured in the step ii to obtain an impregnating solution containing metal Co, dissolving metal Mo salt in deionized water with the volume being 3-5 times that measured in the step ii to obtain an impregnating solution containing metal Mo, and simultaneously dissolving metal Co salt and metal Mo salt in deionized water with the volume being 3-5 times that measured in the step ii to obtain an impregnating solution containing metal Co and metal Mo; iv, placing the activated carrier in an impregnation liquid for impregnation, and removing the redundant impregnation liquid after impregnation through suction filtration.
The metal Co salt is one of cobalt nitrate, cobalt acetate and cobalt chloride.
The metal Mo salt is ammonium molybdate.
The application of the catalyst for preparing cyclopentene in the hydrodeoxygenation of 2-methylfuran to prepare cyclopentene is characterized in that: firstly, sequentially grinding, kneading and molding a catalyst; then carrying out in-situ pre-reduction treatment on the catalyst by hydrogen at the temperature of 300-500 ℃ on a fixed bed reactor; or carrying out in-situ pre-reduction treatment on the catalyst by using a mixed gas of hydrogen and nitrogen, wherein the volume content of nitrogen in the mixed gas is 10 to 30 percent; and finally, adding an n-heptane solution of the material 2-methylfuran, introducing hydrogen, and reacting at the temperature of 300-380 ℃ under the hydrogen pressure of 0.1-1.5 MPa in a volume ratio of 50:1 to 400: 1. the volume airspeed of the material is 1.0 to 10.0 h -1 The hydrodeoxygenation reaction is carried out under the conditions to obtain the cyclopentene.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts non-noble metal Co and Mo as active components and alumina or silicon-containing alumina as a carrier, not only has low cost, but also has easy control of the synthesis process and environmental protection, and can realize industrial production.
2. The specific surface area of the catalyst obtained by the invention is 50-300 m 2 The pore volume is 0.2 to 0.7 mL/g, and the yield of the cyclopentene prepared by the hydrodeoxygenation reaction of 2-methylfuran is more than or equal to 85 percent.
3. The cyclopentene is prepared by taking the n-heptane solution of the 2-methylfuran as a reactant, so that the dependence on petrochemical resources can be effectively reduced.
4. The invention provides a brand new cyclopentene preparation method by hydrodeoxygenation of 2-methylfuran.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a chromatogram of the product of the hydrodeoxygenation of 2-methylfuran using Cat-A catalyst of example 18 in the present invention, wherein the retention time is cyclopentene at 5.190 min, cyclopentane at 5.286 min, and 2-methylfuran at 5.604 min.
Detailed Description
A catalyst for preparing cyclopentene, which is a mixed metal oxide consisting of Co, mo and Al or a mixed metal oxide consisting of Co, mo, al and Si; the catalyst contains, in terms of oxide mass (g), 1 to 5wt% of Co, 9 to 18wt% of Mo, 65 to 90wt% of Al and 0 to 15wt% of Si. The molar ratio of Co to Mo is 0.2 to 0.5.
The preparation method of the catalyst for preparing cyclopentene comprises the following steps:
the method comprises the steps of activating an alumina or silicon-containing alumina carrier at 200-450 ℃ for 2-5 hours to obtain the activated carrier.
And secondly, placing the activated carrier into an impregnating solution containing metal Co and/or metal Mo by an isometric impregnation method or an excess impregnation method through a one-step loading method or a step-by-step loading method, and impregnating for 10 to 24 hours at 10 to 50 ℃ to obtain the catalyst precursor.
Wherein:
the one-step loading method is to dip the activated carrier into an immersion liquid containing metal Co and metal Mo, and dry the carrier to constant weight at 90-150 ℃ to obtain the catalyst precursor.
The step load method is composed of a first step load and a second step load. The first step of loading refers to that the activated carrier is immersed in an immersion liquid containing metal Mo or an immersion liquid containing metal Co to respectively obtain a carrier containing Mo and a carrier containing Co; then respectively drying the Mo-containing carrier and the Co-containing carrier at 90-150 ℃ to constant weight, and then roasting at 350-550 ℃ for 0-4 hours to respectively obtain a Mo-containing precursor and a Co-containing precursor; and the second step of loading is to dip the Co-containing precursor into a dipping solution containing metal Mo, or dip the Mo-containing precursor into a dipping solution containing metal Co, and then dry the precursor to constant weight at 90 to 150 ℃ to obtain the catalyst precursor.
The isovolumetric impregnation method is that (1) selected metal Co salt and metal Mo salt are decomposed into oxides, and the oxides account for 1 to 5wt% of Co and 9 to 18wt% of Mo in the catalyst; (2) weighing alumina or a silicon-containing alumina carrier with required weight, and measuring the volume of the impregnation liquid required by equal-volume impregnation by using deionized water; (3) calculating the weight of the required metal Co salt and Mo salt according to the weight of the salt selected in the step (1) and the weight of the carrier in the step (2); dissolving metal Co salt in the deionized water with the volume determined in the step (2) to obtain an impregnation liquid containing metal Co, dissolving metal Mo salt in the deionized water with the volume determined in the step (2) to obtain an impregnation liquid containing metal Mo, and simultaneously dissolving the metal Co salt and the metal Mo salt in the deionized water with the volume determined in the step (2) to obtain an impregnation liquid containing metal Co and metal Mo; (4) and (3) putting the activated carrier into an impregnation liquid for impregnation.
The excess impregnation method is that i selected metal Co salt and metal Mo salt are decomposed into oxides, and the oxides account for 1 to 5wt% of Co and 9 to 18wt% of Mo in the catalyst; ii, weighing the alumina or the silicon-containing alumina carrier with the required weight, and measuring the volume of the impregnation liquid required by the equal-volume impregnation by using deionized water; iii, weighing 3 to 5 times of the weight of the salt selected according to the step i and the carrier in the step ii, and calculating the weight of the required metal Co salt and Mo salt; then dissolving metal Co salt in deionized water with the volume being 3-5 times that measured in the step ii to obtain an immersion liquid containing metal Co, dissolving metal Mo salt in deionized water with the volume being 3-5 times that measured in the step ii to obtain an immersion liquid containing metal Mo, and simultaneously dissolving metal Co salt and metal Mo salt in deionized water with the volume being 3-5 times that measured in the step ii to obtain an immersion liquid containing metal Co and metal Mo; iv, placing the activated carrier into an impregnation liquid for impregnation, and removing the redundant impregnation liquid after impregnation through suction filtration.
The metal Co salt is one of cobalt nitrate, cobalt acetate and cobalt chloride. The metal Mo salt is ammonium molybdate.
And performing programmed heating on the catalyst precursor at a heating rate of 2-5 ℃/min, and roasting at 350-550 ℃ for 1-4 hours to obtain the catalyst for preparing cyclopentene.
[ step-by-step Supported catalyst preparation ]
Example 1A catalyst for the preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 3.5wt% of metal Co, 10wt% of metal Mo, 84.5wt% of metal Al and 2wt% of metal Si. The nitrogen adsorption of the catalyst measured specific surface area was 184 m 2 The pore volume is 0.47 mL/g.
The preparation method of the catalyst comprises the following steps:
first, siO 2 -Al 2 O 3 Activating the carrier at 450 ℃ for 4 hours to obtain activated SiO 2 -Al 2 O 3 And (3) a carrier.
The method comprises the following steps of loading metal Co and Mo by adopting a step-by-step loading method, and impregnating by using an isometric impregnation method:
after selected cobalt nitrate and ammonium molybdate are decomposed into oxides, the oxides contain 3.5wt% of Co and 10wt% of Mo; weighing 10 g of SiO 2 -Al 2 O 3 The volume of a solution required for isovolumetric impregnation is measured by deionized water, and is 12 mL; dissolving 1.57g of cobalt nitrate in 12 mL of deionized water to obtain a dipping solution of metal Co; 1.42g of ammonium molybdate was dissolved in 12 mL of deionized water to obtain an impregnation solution of metallic Mo.
10 g of activated SiO 2 -Al 2 O 3 The carrier was immersed in 12 mL of an immersion solution (25 ℃ C.) of Mo metal, and after completion of the adsorption of the aqueous solution, the carrier was allowed to stand for 12 hours to obtain Mo-containing SiO 2 -Al 2 O 3 A carrier; siO containing Mo 2 -Al 2 O 3 Drying the carrier at 120 ℃ to constant weight; then drying all the dried SiO containing Mo 2 -Al 2 O 3 The carrier was immersed in 12 mL of an immersion solution (25 ℃ C.) of metallic Co, allowed to stand for 12 hours after the adsorption of the aqueous solution, and finally, siO containing Co and Mo 2 -Al 2 O 3 Drying at 120 ℃ to constant weight to obtain the catalyst precursor.
Thirdly, performing temperature programmed roasting on the catalyst precursor, wherein the temperature rise rate is 2 ℃/min, the roasting temperature is 450 ℃, and the roasting time is 4 hours, so that the catalyst for preparing cyclopentene is obtained, and is represented by the catalyst Cat-A.
Example 2A catalyst for the preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 2wt% of metal Co, 11.5wt% of metal Mo, 84.5wt% of metal Al and 2wt% of metal Si. The specific surface area of the catalyst is 172 m according to nitrogen adsorption measurement 2 The pore volume is 0.50 mL/g.
In addition to SiO 2 -Al 2 O 3 The catalyst was prepared in the same manner as in example 1 except that the contents of metal Co and metal Mo supported on the carrier were different from those in example 1, and the synthesized catalyst was represented by Cat-B.
Example 3 a catalyst for the preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 5wt% of metal Co, 10wt% of metal Mo, 73wt% of metal Al and 12wt% of metal Si. The specific surface area of the catalyst measured by nitrogen adsorption was 143 m 2 The pore volume is 0.55 mL/g.
Except for the SiO used 2 -Al 2 O 3 SiO in carrier 2 The content, the content of supported metal Co and the content of metal Mo are different from those of example 1The preparation of the catalyst was otherwise the same as in example 1, and the synthesized catalyst was represented by Cat-C.
Example 4A catalyst for the preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 4wt% of metal Co, 16wt% of metal Mo, 65wt% of metal Al and 15wt% of metal Si. The specific surface area of the catalyst is 128m according to nitrogen adsorption measurement 2 The pore volume was 0.51 mL/g.
Except for the SiO used 2 -Al 2 O 3 SiO in carrier 2 The content, the content of supported metal Co and the content of metal Mo are different from those of example 1, the preparation method of the catalyst is the same as that of example 1, and the synthesized catalyst is represented by Cat-D.
Example 5A catalyst for the preparation of cyclopentene from Al as a support 2 O 3 Supported on Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 3wt% of metal Co, 7wt% of metal Mo and 90wt% of metal Al. The nitrogen adsorption of the catalyst measured the specific surface area of 253m 2 The pore volume was 0.43mL/g.
In addition to the Al used 2 O 3 The contents of the carrier, the supported metal Co and the metal Mo are different from those of example 1, the preparation method of the catalyst is the same as that of example 1, and the synthesized catalyst is represented by Cat-E.
Example 6A catalyst for the preparation of cyclopentene from Al as a support 2 O 3 Supported on Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 3wt% of metal Co, 15wt% of metal Mo and 82wt% of metal Al. The nitrogen adsorption of the catalyst measured the specific surface area of 226m 2 The pore volume is 0.45 mL/g.
In addition to the Al used 2 O 3 The contents of the carrier, the supported metal Co and the metal Mo are different from those of the catalyst in example 1, the preparation method of the catalyst is the same as that of the catalyst in example 1, and the synthesized catalyst is represented by Cat-F.
Example 7A catalyst for the preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 3wt% of metal Co, 12wt% of metal Mo, 80wt% of metal Al and 5wt% of metal Si. The specific surface area of the catalyst measured by nitrogen adsorption was 173 m 2 The pore volume is 0.46 mL/g.
Except for the SiO used 2 -Al 2 O 3 SiO in carrier 2 Content, content of supported metal Co, and content of metal Mo are different from those in example 1, except that in the preparation method of the catalyst, the activation temperature of the carrier is 200 ℃ and the activation time is 5 hours, other steps are the same as those in example 1, and the synthesized catalyst is represented by Cat-G.
Example 8A catalyst for the preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 4wt% of metal Co, 11wt% of metal Mo, 80wt% of metal Al and 5wt% of metal Si. The specific surface area of the catalyst measured by nitrogen adsorption was 167 m 2 The pore volume is 0.48mL/g.
Except for the SiO used 2 -Al 2 O 3 SiO in carrier 2 The content and the content of the supported metal Co and the metal Mo are different from those in the embodiment 1, the preparation method of the catalyst comprises the steps of soaking the metal Co and the Mo in the soaking liquid for soaking in the soaking liquid at the temperature of 50 ℃ for 10 hours, the rest time is 10 hours, the other steps are the same as those in the embodiment 1, and the synthesized catalyst is represented by Cat-H.
Example 9 catalyst for preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 3.2wt% of metal Co, 11.8wt% of metal Mo, 80wt% of metal Al and 5wt% of metal Si. The specific surface area of the catalyst measured by nitrogen adsorption was 159 m 2 The pore volume is 0.48mL/g.
Except for the SiO used 2 -Al 2 O 3 SiO in carrier 2 Content, content of Co and Mo metals loaded differently from example 1, this catalysisThe preparation method of the catalyst comprises the steps of heating and roasting the catalyst precursor in a program manner, wherein the heating rate is 5 ℃/min, the roasting temperature is 350 ℃, the roasting time is 4 hours, other steps are the same as those in the example 1, and the synthesized catalyst is represented by Cat-I.
Example 10A catalyst for the preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 4.7wt% of metal Co, 10.3wt% of metal Mo, 80wt% of metal Al and 5wt% of metal Si. The nitrogen adsorption of the catalyst measured the specific surface area to be 168 m 2 The pore volume is 0.50 mL/g.
Except for the SiO used 2 -Al 2 O 3 SiO in carrier 2 The preparation method of the catalyst is the same as that of example 1 except that the content of the supported metal Co and the content of the supported metal Mo, and the soluble salt of the metal Co used in the preparation process of the catalyst are cobalt acetate, and the synthesized catalyst is represented by Cat-J.
EXAMPLE 11A catalyst for the preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 3.8wt% of metal Co, 11.2wt% of metal Mo, 80wt% of metal Al and 5wt% of metal Si. The nitrogen adsorption of the catalyst measured the specific surface area to be 154 m 2 The pore volume was 0.51 mL/g.
Except for the SiO used 2 -Al 2 O 3 SiO in carrier 2 The preparation method of the catalyst is the same as that of example 1 except that the content of the supported metal Co and the content of the supported metal Mo, and the soluble salt of the metal Co used in the preparation process of the catalyst are cobalt chloride, and the synthesized catalyst is represented by Cat-K.
Example 12A catalyst for the preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 3.2wt% of metal Co, 10.3wt% of metal Mo, 84.5wt% of metal Al and 2wt% of metal Si. The nitrogen adsorption of the catalyst determined the specific surface area182 m 2 The pore volume was 0.43mL/g.
Except that the content of the loaded metal Co and the content of the loaded metal Mo are different from those in embodiment 1, the preparation method of the catalyst has the steps of. First 10 g of activated SiO 2 -Al 2 O 3 The carrier was immersed in 12 mL of an immersion liquid (25 ℃ C.) of metallic Mo, and after completion of the adsorption of the aqueous solution, the carrier was allowed to stand for 12 hours to obtain SiO containing Mo 2 -Al 2 O 3 A carrier; siO containing Mo 2 -Al 2 O 3 Drying the carrier at 120 ℃ to constant weight, and roasting at 400 ℃ for 3 hours; then all the roasted SiO containing Mo 2 -Al 2 O 3 The carrier was immersed in 12 mL of an immersion solution (25 ℃ C.) of metallic Co, allowed to stand for 12 hours after the adsorption of the aqueous solution, and finally, siO containing Co and Mo 2 -Al 2 O 3 Drying at 120 ℃ to constant weight to obtain the catalyst precursor. The synthesized catalyst is represented by Cat-L.
Example 13 catalyst for preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 4.5wt% of metal Co, 9wt% of metal Mo, 84.5wt% of metal Al and 2wt% of metal Si. The nitrogen adsorption of the catalyst measured the specific surface area to be 164 m 2 The pore volume is 0.48mL/g.
Except that the contents of supported metal Co and metal Mo were different from those of example 1; the preparation method of the catalyst has the same steps as those of embodiment 1, and the second step of soaking the metal Mo soaking liquid after soaking the metal Co soaking liquid is specifically as follows: first 10 g of activated SiO 2 -Al 2 O 3 The carrier was immersed in 12 mL of an immersion solution (25 ℃ C.) containing Co, and after completion of the adsorption of the aqueous solution, the carrier was allowed to stand for 12 hours to obtain SiO containing Co 2 -Al 2 O 3 Carrier, siO containing Co 2 -Al 2 O 3 Drying the carrier at 120 ℃ to constant weight; then drying all the dried SiO containing Co 2 -Al 2 O 3 The carrier was immersed in 12 mL of an immersion liquid (25 ℃ C.) containing metallic Mo and dissolved in waterStanding for 12 hours after the liquid is absorbed, and finally, adding SiO containing Mo and Co 2 -Al 2 O 3 Drying at 120 ℃ to constant weight to obtain the catalyst precursor. The synthesized catalyst is represented by Cat-M.
Example 14A catalyst for the preparation of cyclopentene from Al as a support 2 O 3 Supported on Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 3wt% of metal Co, 9wt% of metal Mo and 88wt% of metal Al. The nitrogen adsorption of the catalyst measured the specific surface area to be 181 m 2 The pore volume was 0.42 mL/g.
Except for the use of Al 2 O 3 The contents of the carrier, the supported metal Co and the metal Mo are different from those of the embodiment 1; the preparation method of the catalyst has the advantages that the steps are the first step and the second step, the impregnation liquid containing the metal Mo is impregnated after the impregnation liquid containing the metal Co is impregnated, and the preparation method specifically comprises the following steps: first, 10 g of Al to be activated 2 O 3 The carrier was immersed in 12 mL of an immersion liquid (30 ℃ C.) containing Co, and after completion of the adsorption of the aqueous solution, the carrier was allowed to stand for 12 hours to obtain Co-containing Al 2 O 3 Carrier of Al containing Co 2 O 3 Drying the carrier at 120 ℃ to constant weight, roasting at 550 ℃ for 2 hours, and then completely roasting the Co-containing Al 2 O 3 The carrier was immersed in 12 mL of an immersion liquid (30 ℃ C.) containing Mo, allowed to stand for 12 hours after the aqueous solution was completely adsorbed, and finally Al containing Mo and Co 2 O 3 Drying at 120 ℃ to constant weight to obtain the catalyst precursor. The synthesized catalyst is represented by Cat-N.
Example 15A catalyst for the preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 3.5wt% of metal Co, 10wt% of metal Mo, 84.5wt% of metal Al and 2wt% of metal Si. The nitrogen adsorption of the catalyst measured specific surface area was 185 m 2 The pore volume is 0.48mL/g.
The preparation method of the catalyst has the same steps as those of embodiment 1, and the second step is impregnation by adopting an excessive impregnation method, namely, the impregnation liquid of the metal Mo is impregnated firstly and then is impregnatedThe specific method of the metal Co impregnation liquid is as follows: after selected cobalt nitrate and ammonium molybdate are decomposed into oxides, the oxides comprise 3.5wt% of metal Co and 10wt% of metal Mo; weighing 10 g of SiO 2 -Al 2 O 3 The volume of a solution required for isovolumetric impregnation of the carrier is measured by deionized water and is 12 mL; dissolving 4.71g of cobalt nitrate in 36 mL of deionized water to obtain a metal Co impregnation solution; 4.26g of ammonium molybdate was dissolved in 36 mL of deionized water to obtain a metallic Mo impregnation solution.
10 g of activated SiO 2 -Al 2 O 3 The carrier is immersed in 36 mL of immersion liquid (25 ℃) of metal Mo, stands for adsorption for 12 hours, and then is filtered to obtain SiO containing Mo 2 -Al 2 O 3 A carrier; siO containing Mo 2 -Al 2 O 3 Drying the carrier at 120 ℃ to constant weight; then all the dried SiO containing Mo 2 -Al 2 O 3 Soaking the carrier in 36 mL of cobalt nitrate aqueous solution (25 ℃), standing for adsorption for 12 hours, then carrying out suction filtration, and finally, carrying out suction filtration on SiO containing Co and Mo 2 -Al 2 O 3 Drying at 120 ℃ to constant weight to obtain the catalyst precursor. The synthesized catalyst is represented by Cat-O.
[ one-step Supported preparation of catalyst ]
Example 16A catalyst for the preparation of cyclopentene from SiO support 2 -Al 2 O 3 Supported on SiO 2 -Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 3.5wt% of metal Co, 10wt% of metal Mo, 84.5wt% of metal Al and 2wt% of metal Si. The nitrogen adsorption of the catalyst measured the specific surface area to be 147 m 2 The pore volume is 0.50 mL/g.
The preparation method of the catalyst comprises the following steps:
preparing SiO 2 -Al 2 O 3 Activating the carrier at 450 ℃ for 4 hours to obtain activated SiO 2 -Al 2 O 3 And (3) a carrier.
The method comprises the following steps of:
after selected cobalt nitrate and ammonium molybdate are decomposed into oxides, the oxide is removedCalculated by oxide, the alloy contains 3.5wt% of metal Co and 10wt% of metal Mo; weighing 10 g of SiO 2 -Al 2 O 3 The volume of a solution required for isovolumetric impregnation of the carrier is measured by deionized water and is 12 mL; 1.57g of cobalt nitrate and 1.42g of ammonium molybdate were dissolved in 12 mL of deionized water to obtain an impregnation solution containing metal Co and metal Mo.
10 g of activated support SiO 2 -Al 2 O 3 The catalyst precursor is immersed in 12 mL of immersion liquid (25 ℃) containing metal Co and Mo, stands for 12 hours, and is dried to constant weight at 120 ℃ to obtain the catalyst precursor.
And performing temperature programming roasting on the catalyst precursor, wherein the temperature raising rate is 2 ℃/min, the roasting temperature is 450 ℃, and the roasting time is 4 hours, so as to obtain the catalyst for preparing the cyclopentene, which is expressed by the catalyst Cat-P.
Example 17A catalyst for the preparation of cyclopentene from Al as a support 2 O 3 Supported on Al 2 O 3 Metal Co and Mo on the carrier; wherein: calculated by oxide, the alloy contains 3.5wt% of metal Co, 10wt% of metal Mo and 86.5wt% of metal Al. The specific surface area of the catalyst measured by nitrogen adsorption is 153 m 2 The pore volume is 0.50 mL/g.
Except using Al 2 O 3 The carrier is cobalt acetate, co salt is used as the cobalt acetate, and the content of Co and Mo is different from that in the embodiment 16; the preparation method of the catalyst was the same as that of example 16, and the synthesized catalyst was represented by Cat-Q.
The application of a catalyst for preparing cyclopentene in the preparation of cyclopentene by hydrodeoxygenation of 2-methylfuran:
firstly, sequentially grinding, kneading and molding a catalyst;
then carrying out in-situ pre-reduction treatment on the catalyst by hydrogen at the temperature of 300-500 ℃ on a fixed bed reactor; or carrying out in-situ pre-reduction treatment on the catalyst by using a mixed gas of hydrogen and nitrogen, wherein the volume content of nitrogen in the mixed gas is 10 to 30 percent;
and finally, adding an n-heptane solution of 2-methylfuran as a material, introducing hydrogen, and reacting at the reaction temperature of 300 to 380 ℃, the hydrogen pressure of 0.1 to 1.5 MPa, and the volume ratio (L/L) of the hydrogen to the material of 50:1 to 400: 1. the volume airspeed of the material is 1.0 to 10.0 h -1 The hydrodeoxygenation reaction is carried out under the conditions to obtain the cyclopentene.
EXAMPLE 18 preparation of cyclopentene
The catalysts Cat-A, cat-B, cat-C, cat-D, cat-E, cat-F, cat-G, cat-H, cat-I, cat-J, cat-K, cat-L, cat-M, cat-N, cat-O, cat-P, cat-Q prepared in examples 1 to 17 were used. The catalyst was sieved into 20 to 40 mesh particles, and 2.0g of the catalyst was charged in a fixed bed reactor having a diameter of 1.1 cm. Before carrying out the 2-methylfuran hydrodeoxygenation reaction, carrying out in-situ pre-reduction treatment on the catalyst, wherein the specific pre-reduction condition is N 2 H content of 15% 2 /N 2 In a mixed gas, the reduction is carried out for 3 hours at 400 ℃, wherein H 2 /N 2 The flow rate of the mixed gas was 60 mL/min. After the reduction is finished, the hydrodeoxygenation performance of the 2-methylfuran is examined by taking 5 vol.% 2-methylfuran n-heptane solution as a reaction solution, wherein the specific reaction conditions are that the reaction temperature is 350 ℃, the hydrogen partial pressure is 0.5 MPa, the hydrogen-oil volume ratio is 200 NL/L, and the volume space velocity is 3.0 h -1 . Sampling, and quantitatively analyzing the product by using a gas chromatography internal standard method, wherein the main product is cyclopentene can be visually illustrated by figure 1. The results of the cyclopentene yield are shown in table 1.
TABLE 1
As can be seen from Table 1, the catalyst prepared by the invention is used for hydrodeoxygenation of 2-methylfuran to prepare cyclopentene, the yield of cyclopentene is up to 85%, and the yield of cyclopentene of part of the catalyst is more than 90%. Wherein, the content of carrier silicon in the Cat-C and Cat-D catalysts is higher, and the yield of cyclopentene is lower. In addition, the experimental results in table 1 show that the yield of cyclopentene in the hydrodeoxygenation reaction of the catalyst is affected by the metal content and the specific preparation method of the catalyst.
EXAMPLE 19 preparation of cyclopentene
Using the catalyst Cat-A of example 1, the conditions of the in-situ pre-reduction before the hydrodeoxygenation of 2-methylfuran were pure H 2 Reduction in gas at 400 ℃ for 3 hours, wherein H 2 The flow rate of the gas was 60 mL/min, and the other reaction conditions were carried out under the same conditions as described in example 18, and the yield of cyclopentene in the product was 88.5%.
EXAMPLE 20 preparation of cyclopentene
Using the catalyst Cat-A of example 1, in-situ prereduction was carried out before hydrodeoxygenation of 2-methylfuran under N 2 H content of 15% 2 /N 2 Reduction is carried out in a mixed gas at 500 ℃ for 3 hours, wherein H 2 /N 2 The flow rate of the mixed gas was 60 mL/min. The other reaction conditions were carried out under the same conditions as described in example 18, and the yield of cyclopentene in the product was 89.8%.
EXAMPLE 21 preparation of cyclopentene
The conditions for carrying out the hydrodeoxygenation reaction of 2-methylfuran using the catalyst Cat-a of example 1 are: the reaction temperature is 380 ℃, the hydrogen partial pressure is 0.1 MPa, the hydrogen-oil volume ratio is 200 NL/L, and the volume space velocity is 3.0 h -1 (ii) a The other reaction conditions were carried out under the same conditions as described in example 18, and the yield of cyclopentene in the product was 86.0%.
EXAMPLE 22 preparation of cyclopentene
The conditions for carrying out the hydrodeoxygenation reaction of 2-methylfuran using the catalyst Cat-A of example 1 were: the reaction temperature is 300 ℃, the hydrogen partial pressure is 1.0 MPa, the hydrogen-oil volume ratio is 300 NL/L, and the volume space velocity is 1.0 h -1 (ii) a The other reaction conditions were carried out under the same conditions as described in example 18, and the yield of cyclopentene in the product was 85.2%.
Claims (9)
1. The application of the catalyst for preparing cyclopentene in the preparation of cyclopentene by hydrodeoxygenation of 2-methylfuran is characterized in that: the catalyst is mixed metal oxide consisting of Co, mo and Al or mixed metal oxide consisting of Co, mo, al and Si; the catalyst contains 1 to 5wt% of Co, 9 to 18wt% of Mo, 65 to 90wt% of Al and 0 to 15wt% of Si in terms of mass of oxides; the molar ratio of the Co to the Mo is 0.2 to 0.5; the catalyst is subjected to pre-reduction treatment before catalytic reaction.
2. The use of a catalyst for the preparation of cyclopentene according to claim 1 for the hydrodeoxygenation of 2-methylfuran to cyclopentene, wherein: firstly, sequentially grinding, kneading and molding a catalyst; then carrying out in-situ pre-reduction treatment on the catalyst by hydrogen at the temperature of 300-500 ℃ on a fixed bed reactor; or carrying out in-situ pre-reduction treatment on the catalyst by using a mixed gas of hydrogen and nitrogen, wherein the volume content of nitrogen in the mixed gas is 10 to 30 percent; and finally, adding a material 2-methylfuran-n-heptane solution, introducing hydrogen, and reacting at the reaction temperature of 300 to 380 ℃, the hydrogen pressure of 0.1 to 1.5 MPa, the volume ratio of the hydrogen to the material of 50:1 to 400: 1. the volume airspeed of the material is 1.0 to 10.0 h -1 The hydrodeoxygenation reaction is carried out under the conditions to obtain the cyclopentene.
3. The use of a catalyst for the preparation of cyclopentene according to claim 1 for the hydrodeoxygenation of 2-methylfuran to cyclopentene, wherein: the preparation method of the catalyst comprises the following steps:
activating an alumina or silicon-containing alumina carrier at 200 to 450 ℃ for 2 to 5 hours to obtain an activated carrier;
placing the activated carrier into an impregnating solution containing metal Co and/or metal Mo by an isometric impregnation method or an excess impregnation method through a one-step loading method or a step-by-step loading method, and impregnating for 10 to 24 hours at 10 to 50 ℃ to obtain a catalyst precursor;
and thirdly, performing temperature programming on the catalyst precursor at a temperature rise rate of 2-5 ℃/min, and roasting at 350-550 ℃ for 1-4 hours to obtain the catalyst for preparing cyclopentene.
4. The use of a catalyst according to claim 3 for the preparation of cyclopentene by hydrodeoxygenation of 2-methylfuran, wherein: the one-step loading method in the second step is to immerse the activated carrier in an immersion liquid containing metal Co and metal Mo, and dry the carrier to a constant weight at 90 to 150 ℃ to obtain the catalyst precursor.
5. The use of a catalyst for the preparation of cyclopentene according to claim 3 in the hydrodeoxygenation of 2-methylfuran to cyclopentene, wherein: the step load method in the step consists of a first step load and a second step load; the first-step loading refers to immersing the activated carrier in an impregnation solution containing metal Mo or an impregnation solution containing metal Co to respectively obtain a carrier containing Mo and a carrier containing Co; then respectively drying the Mo-containing carrier and the Co-containing carrier at 90-150 ℃ to constant weight, and then roasting at 350-550 ℃ for 0-4 hours to respectively obtain a Mo-containing precursor and a Co-containing precursor; and the second step of loading refers to dipping the Co-containing precursor into dipping liquid containing metal Mo, or dipping the Mo-containing precursor into dipping liquid containing metal Co, and then drying at 90-150 ℃ to constant weight to obtain the catalyst precursor.
6. The use of a catalyst for the preparation of cyclopentene according to claim 3 in the hydrodeoxygenation of 2-methylfuran to cyclopentene, wherein: the step of the moderate volume impregnation method is characterized in that (1) selected metal Co salt and metal Mo salt are decomposed into oxides, and the oxides account for 1 to 5wt% of Co and 9 to 18wt% of Mo in the catalyst; (2) weighing alumina or a silicon-containing alumina carrier with required weight, and measuring the volume of the impregnation liquid required by equal volume impregnation by using deionized water; (3) calculating the weight of the required metal Co salt and Mo salt according to the weight of the salt selected in the step (1) and the weight of the carrier in the step (2); dissolving a metal Co salt in the deionized water with the volume determined in the step (2) to obtain an impregnation liquid containing metal Co, dissolving a metal Mo salt in the deionized water with the volume determined in the step (2) to obtain an impregnation liquid containing metal Mo, and simultaneously dissolving the metal Co salt and the metal Mo salt in the deionized water with the volume determined in the step (2) to obtain an impregnation liquid containing metal Co and metal Mo; (4) and (3) soaking the activated carrier in a soaking solution.
7. The use of a catalyst for the preparation of cyclopentene according to claim 3 in the hydrodeoxygenation of 2-methylfuran to cyclopentene, wherein: the excess impregnation method in the step II is that i selected metal Co salt and metal Mo salt are decomposed into oxides, and the oxides account for 1 to 5wt% of Co and 9 to 18wt% of Mo in the catalyst; ii, weighing the alumina or the silicon-containing alumina carrier with the required weight, and measuring the volume of the impregnation liquid required by the equal-volume impregnation by using deionized water; iii, weighing 3-5 times of the weight of the salt selected according to the step i and the carrier in the step ii, and calculating the weight of the required metal Co salt and Mo salt; then dissolving metal Co salt in deionized water with the volume being 3-5 times of the volume measured in the step ii to obtain an impregnating solution containing metal Co, dissolving metal Mo salt in deionized water with the volume being 3-5 times of the volume measured in the step ii to obtain an impregnating solution containing metal Mo, and simultaneously dissolving the metal Co salt and the metal Mo salt in deionized water with the volume being 3-5 times of the volume measured in the step ii to obtain an impregnating solution containing metal Co and metal Mo; iv, placing the activated carrier into an impregnation liquid for impregnation, and removing the redundant impregnation liquid after impregnation through suction filtration.
8. The use of a catalyst according to claim 6 or 7 for the preparation of cyclopentene by hydrodeoxygenation of 2-methylfuran, wherein: the metal Co salt is one of cobalt nitrate, cobalt acetate and cobalt chloride.
9. The use of a catalyst for the preparation of cyclopentene according to claim 6 or 7 for the hydrodeoxygenation of 2-methylfuran to cyclopentene, wherein: the metal Mo salt refers to ammonium molybdate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110312753.6A CN112973714B (en) | 2021-03-24 | 2021-03-24 | Catalyst for preparing cyclopentene, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110312753.6A CN112973714B (en) | 2021-03-24 | 2021-03-24 | Catalyst for preparing cyclopentene, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112973714A CN112973714A (en) | 2021-06-18 |
| CN112973714B true CN112973714B (en) | 2023-04-07 |
Family
ID=76333285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110312753.6A Active CN112973714B (en) | 2021-03-24 | 2021-03-24 | Catalyst for preparing cyclopentene, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112973714B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3853830A (en) * | 1973-03-02 | 1974-12-10 | Goodrich Co B F | Process for preparing polymers of cyclopentene |
| WO2010022001A1 (en) * | 2008-08-18 | 2010-02-25 | Im&T Research, Inc. | Methods for preparing fluoroalkyl arylsulfinyl compounds and fluorinated compounds thereto |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2853262B1 (en) * | 2003-04-07 | 2006-07-07 | Atofina | PROCESS FOR IMPREGNATING HYDROTREATMENT CATALYSTS WITH ORTHOPHTHALATE AND SULFURING METHOD EMPLOYING THE SAME |
| CN101462078B (en) * | 2007-12-18 | 2011-08-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst steeping fluid composition and preparation method of hydrogenation catalyst |
| CN101879447A (en) * | 2009-05-08 | 2010-11-10 | 中国科学院兰州化学物理研究所 | Catalyst for preparing glycol by hydrogenating oxalate, preparation method and application thereof |
| CN101927169B (en) * | 2009-06-26 | 2012-05-30 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal component concentration in gradient increasing distribution and preparation method thereof |
| CN102166520B (en) * | 2010-02-25 | 2013-03-27 | 中国石油天然气股份有限公司 | Hydrorefining catalyst |
| CN103304382A (en) * | 2012-03-13 | 2013-09-18 | 上海博润石化科技发展有限公司 | Combined process for comprehensively utilizing partial hydrogenation C5 fraction |
| WO2015041938A1 (en) * | 2013-09-18 | 2015-03-26 | Shell Oil Company | Methods and systems for supplying hydrogen to a hydrocatalytic reaction |
| JP6378902B2 (en) * | 2014-03-10 | 2018-08-22 | 日本ケッチェン株式会社 | Hydrotreating catalyst, method for producing the catalyst, and hydrotreating method for hydrocarbon oil using the catalyst |
| CN105585470B (en) * | 2014-11-07 | 2018-09-28 | 中国科学院大连化学物理研究所 | A method of 2- hydroxy-3-methyl -2- cyclopentene-1-ones are prepared by fructose |
| FR3073753B1 (en) * | 2017-11-22 | 2022-03-11 | Ifp Energies Now | CATALYST BASED ON A FURANIC COMPOUND AND ITS USE IN A HYDROTREATMENT AND/OR HYDROCRACKING PROCESS |
| CN110756196B (en) * | 2018-07-26 | 2022-10-04 | 中国石油天然气股份有限公司 | Preparation method of vegetable oil hydrodeoxygenation catalyst |
| CN111217657B (en) * | 2018-11-25 | 2021-04-30 | 中国科学院大连化学物理研究所 | Method for synthesizing methyl cyclopentadiene from 3-methyl-2-cyclopentene-1-ketone |
| CN109896988A (en) * | 2019-03-20 | 2019-06-18 | 甘肃农业大学 | A kind of synthesis of indole amides analog derivative and its application as plant growth regulator |
-
2021
- 2021-03-24 CN CN202110312753.6A patent/CN112973714B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3853830A (en) * | 1973-03-02 | 1974-12-10 | Goodrich Co B F | Process for preparing polymers of cyclopentene |
| WO2010022001A1 (en) * | 2008-08-18 | 2010-02-25 | Im&T Research, Inc. | Methods for preparing fluoroalkyl arylsulfinyl compounds and fluorinated compounds thereto |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112973714A (en) | 2021-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE102011083116B4 (en) | Catalyst for the hydrogenation of unsaturated hydrocarbons, production and application thereof | |
| JP5514668B2 (en) | Process for the preparation of Ni / Sn supported catalysts for the selective hydrogenation of polyunsaturated hydrocarbons | |
| US8178735B2 (en) | Process for the preparation of multimetallic catalysts that can be used in reactions for transformation of hydrocarbons | |
| JP5579534B2 (en) | Process for the preparation of supported catalysts based on Ni and Group IB metals for the selective hydrogenation of polyunsaturated hydrocarbons | |
| CN1665761B (en) | Selective hydrogenation of acetylenes | |
| CN113939548B (en) | Process for preparing hydrogenated petroleum resin | |
| TW200418790A (en) | Process for the selective hydrogenation of alkynes | |
| EP1560647B1 (en) | Method for regenerating a hydrogenation catalyst | |
| CN112973714B (en) | Catalyst for preparing cyclopentene, preparation method and application thereof | |
| US5464802A (en) | Process for preparing a supported metal catalyst for the selective hydrogenation of hydrocarbons by means of such a process and process for selective hydrogenation of hydrocarbons using such a catalyst | |
| US20060155154A1 (en) | Process for the selective hydrogenation of alkynes | |
| CN105732274B (en) | Ethylene selective hydrogenation refining method | |
| CN101209415B (en) | Catalyst for preparing linalyl acetate by hydrogenation of dehydrogenated linalyl acetate | |
| DE2412191A1 (en) | METHOD OF PURIFYING BUTADIENE AND ISOPRENE BY SELECTIVE HYDROGENATION OF THE ACETYLENIC CONTAMINATES | |
| JPH07223983A (en) | Hydrogenation of acetylenic compound | |
| KR101478398B1 (en) | Catalyst for selective hydrogenation of acetylene compounds in 1,3-butadiene, method for producing the same and method of using the same | |
| EP0013286B1 (en) | Hydrogenation catalyst, its preparation and use | |
| US6049012A (en) | Catalyst and process for the production of alkyl tert alkyl ether from hydrocarbon feedstocks with high levels of sulfur | |
| CN106582780B (en) | Alloy-type heavy aromatics lightening catalyst and preparation method thereof | |
| TW200404822A (en) | Process for production of hydrogenated petroleum resins | |
| CN115805081B (en) | Catalyst, preparation method thereof and application of catalyst in cyclopentadiene selective hydrogenation | |
| CN105777476B (en) | Ethylene selective hydrogenation refining method | |
| CN117160479A (en) | Preparation method of polymerization-grade ethylene catalyst prepared by selective hydrogenation | |
| KR101048964B1 (en) | Alkin's Selective Hydrogenation Method | |
| CN117160475A (en) | Method for preparing polymerization grade ethylene by selective hydrogenation |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |