CN112661604A - Preparation method of cyclopentanol based on nickel-based supported catalyst - Google Patents
Preparation method of cyclopentanol based on nickel-based supported catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 18
- GJEZBVHHZQAEDB-SYDPRGILSA-N (1s,5r)-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC[C@H]2O[C@H]21 GJEZBVHHZQAEDB-SYDPRGILSA-N 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 208000005374 Poisoning Diseases 0.000 claims description 3
- 231100000572 poisoning Toxicity 0.000 claims description 3
- 230000000607 poisoning effect Effects 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical group O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000003729 cation exchange resin Substances 0.000 description 6
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 5
- 230000036571 hydration Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000043 antiallergic agent Substances 0.000 description 1
- 229940124350 antibacterial drug Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRTFVKHPEHKBQF-UHFFFAOYSA-N bromocyclopentane Chemical compound BrC1CCCC1 BRTFVKHPEHKBQF-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- NDTCXABJQNJPCF-UHFFFAOYSA-N chlorocyclopentane Chemical compound ClC1CCCC1 NDTCXABJQNJPCF-UHFFFAOYSA-N 0.000 description 1
- QRWQMTKLBHUFJO-UHFFFAOYSA-N cyclopentene hydrate Chemical compound O.C1=CCCC1 QRWQMTKLBHUFJO-UHFFFAOYSA-N 0.000 description 1
- YFPCLQKFNXUAAK-UHFFFAOYSA-N cyclopentyl acetate Chemical compound CC(=O)OC1CCCC1 YFPCLQKFNXUAAK-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
The invention belongs to the technical field of organic chemical industry, and discloses a preparation method of cyclopentanol based on a nickel-based supported catalyst. The method comprises the following specific steps: (1) and (3) oxidation reaction: cyclopentene is used as a raw material, hydrogen peroxide is used as an oxidant, and a catalyst, an auxiliary agent and a solvent are added for oxidation reaction to generate 1, 2-epoxycyclopentane; (2) hydrogenation reaction: 1, 2-epoxy cyclopentane is taken as a raw material, hydrogen is introduced under the action of a nickel-based supported catalyst, and hydrogenation reaction is carried out in a kettle type or fixed bed reactor to obtain cyclopentanol; the preparation method of cyclopentanol provided by the invention is environment-friendly, has mild operation conditions, can effectively improve the yield of cyclopentanol, and reduces the pollution of the traditional strong acid preparation process to equipment and environment.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and particularly relates to a preparation method of cyclopentanol based on a nickel-based supported catalyst, in particular to a method for oxidizing cyclopentene to generate 1, 2-epoxycyclopentane, and then further hydrogenating the 1, 2-epoxycyclopentane to generate the cyclopentanol in the presence of the nickel-based supported catalyst.
Background
Cyclopentanol is colorless viscous liquid, has aromatic smell, is an important intermediate of fine chemical products of medicines and pesticides, and is mainly used for preparing bromocyclopentane, chlorocyclopentane, antibacterial drugs, antiallergic drugs and the like. At present, cyclopentanol is only produced abroad by Indian alkali metal company and Japanese Zeon company, and domestic reports are only smooth Tianzhu chemical manufacturing company, the capacity is 1000 tons/year, and the device is in a production stop state at present, mainly because the product cost of the reduction process adopting cyclopentanone as the raw material is high. At present, the global yield of cyclopentanol is about ten thousand tons, the market vacancy is large, and China needs to import about 3000 tons every year.
In the traditional cyclopentanol production, adipic acid is mainly used as a raw material, cyclopentanone is prepared through high-temperature decarboxylation and then is obtained through hydrogenation, but the generation of a large amount of pollutants and the limited raw material source limit the further development of the process. In recent years, due to the wide source and low price of the C5 olefin fraction, the research on the production of cyclopentanol by using the C5 fraction as a raw material has attracted great interest. The C5 fraction is a byproduct of ethylene production by naphtha steam cracking, has rich resources and low cost, and can obtain cyclopentene from dicyclopentadiene fraction through depolymerization and selective hydrogenation. Cyclopentene can be either indirectly hydrated or directly hydrated to produce cyclopentanol, and can also be directly oxidized to produce cyclopentanol and cyclopentanone. Wherein, cyclopentene is directly oxidized into homogeneous reaction, the conversion rate is low, and the selectivity is poor; although the indirect hydration method has the advantages of high conversion rate and good selectivity, the sulfuric acid has serious corrosion to equipment, the energy consumption of the concentration process is large when the sulfuric acid is recovered and reused, and the environmental pollution is serious; the direct hydration method solves the problems of equipment corrosion and large energy consumption, and a plurality of documents report the technology for preparing organic alcohol by directly hydrating olefin, wherein a catalyst is acidic substances such as strong-acid cation exchange resin, solid acid, zeolite and the like, so that the olefin and the water directly react to generate the alcohol.
Japanese patent JP2003212803 uses strong acid cation exchange resin to hydrate cyclopentene to prepare cyclopentanol, under the condition that the charging molar ratio of cyclopentene and water is 1.2-3.0, the conversion per pass of cyclopentene is about 3.5%, and the selectivity is about 98%.
The mesopetrochemical patent CN1676506A proposes a method for preparing cyclopentanol by hydration of cyclopentene, which comprises using cyclopentene and water as raw materials, and carrying out hydration reaction on the cyclopentene and the water under the combined catalysis of a main catalyst and a cocatalyst to prepare the cyclopentanol by a fixed bed hydration reaction, wherein the feeding molar ratio of the cyclopentene to the water is 0.8-5.0, and the volume space velocity is 1-10 hr-1The reaction temperature is 130-180 ℃, the reaction pressure is 1.0-3.0 MPa, the main catalyst is strong acid cation resin, the cocatalyst is trialkyl hexylamine, the conversion per pass of cyclopentene is 2.3-8.9%, and the selectivity is 98%.
Patent CN106674003A discloses a method for preparing cyclopentanol by hydration of cyclopentene, which comprises the following steps: (1) cyclopentene and acetic acid are subjected to addition reaction under the action of modified sulfonic cation exchange resin to generate cyclopentyl acetate, and the modified sulfonic cation exchange resin is prepared by sequentially soaking conventional sulfonic cation exchange resin in toluene and methyl isobutyl ketone; (2) and (2) feeding the material obtained in the step (1) into a rectifying tower, forming an azeotrope with water at the lower part of the rectifying tower, carrying out hydrolysis reaction with water under the action of a sulfonic cation exchange resin catalyst filled at the upper part of the rectifying tower, extracting a product cyclopentanol at the tower top, and extracting acetic acid at the tower bottom.
In the prior art, both CN1676506A and CN106674003A can be used for preparing cyclopentanol, but the conversion per pass of cyclopentene is not high, so that the yield per pass of cyclopentanol is low, or the reaction system uses strong acid to corrode equipment seriously, which causes environmental pollution, high requirement on equipment, high operation difficulty, and increased operation cost and energy consumption, which is not suitable for industrial production.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of cyclopentanol based on a modified nickel-based supported catalyst. The method uses cyclopentene as raw material, firstly adopts oxidation process to prepare 1, 2-epoxy cyclopentane; then using 1, 2-epoxy cyclopentane as raw material and adopting hydrogenation process to prepare cyclopentanol. The method can effectively solve the defects of low yield, equipment corrosion caused by using sulfuric acid, serious environmental pollution and the like in the existing cyclopentanol preparation process.
The following is a specific technical scheme of the invention:
a preparation method of cyclopentanol based on a nickel-based supported catalyst comprises the following steps:
(1) and (3) oxidation reaction: cyclopentene is taken as a raw material, hydrogen peroxide is taken as an oxidant, and a catalyst, a solvent and an auxiliary agent are added for oxidation reaction to obtain 1, 2-epoxycyclopentane;
(2) hydrogenation reaction: 1, 2-epoxy cyclopentane is used as a raw material, hydrogen is introduced under the action of a nickel-based supported catalyst, and hydrogenation reaction is carried out in a kettle-type or fixed bed reactor to obtain cyclopentanol.
Further, in the step (1), the catalyst is a tungstic acid catalyst or a molecular sieve catalyst, preferably a TS-1 molecular sieve catalyst, the solvent is acetone, and the auxiliary agent is NaHCO3The hydrogen peroxide is preferably 50 wt% hydrogen peroxide.
Further, in the step (1), the temperature of the oxidation reaction is 20 to 50 ℃, preferably 30 to 40 ℃.
Further, in the step (2), the hydrogenation reaction conditions are as follows: the temperature is 80-150 ℃, the pressure is 3-10 MPa, and the liquid hourly space velocity is 0.1-0.8 h-1. Preferably, the conditions of the hydrogenation reaction are as follows: the temperature is 90-120 ℃, the pressure is 4-8 MPa, and the liquid hourly space velocity is 0.2-0.6 h-1。
Further, in the step (2), the nickel-based supported catalyst is a modified nickel-based supported catalyst obtained by modifying the nickel-based supported catalyst through partial sulfur poisoning treatment under the following modification conditions: the method is carried out in a fixed bed reactor, the pressure is normal, the system temperature is 40-100 ℃, and the optimal temperature is 60-80 ℃; the content of the sulfur-containing substances in the gas phase is 10-120 ppm, preferably 40-100 ppm; the time is 6-12 h, preferably 8-10 h; the sulfur-containing substance is one or more of hydrogen sulfide, dimethyl sulfide or ethyl sulfide.
Further, in the step (2), the hydrogenation reaction is carried out in a fixed bed reactor.
In the technical scheme provided by the invention, in the oxidation reaction stage, a TS-1 molecular sieve is used as a catalyst, cyclopentene is used as a raw material, hydrogen peroxide is used as an oxidant, and NaHCO is used as an oxidant3The acetone is used as an auxiliary agent and is used as a solvent to be oxidized to generate 1, 2-epoxycyclopentane, under a mild condition, the conversion rate of cyclopentene is 60-75%, and the selectivity is close to 100%. In the hydrogenation reaction stage, the 1, 2-epoxycyclopentane can generate cyclopentanol and cyclopentane through further hydrogenation, which belongs to parallel competition reaction, the yield of cyclopentanol depends on the activity and selectivity of the catalyst, the further modification treatment of the nickel-based supported catalyst makes the active component part exist in a sulfuration state, and the selectivity of the catalyst is greatly improved. By using cyclopentene as a raw material and combining an oxidation reaction and a hydrogenation reaction, the technical scheme provided by the invention avoids the problems of high raw material cost, low conversion rate, poor selectivity, equipment corrosion and environmental pollution in the prior art.
Compared with the prior art, the invention has the beneficial effects that:
after the oxidation reaction and the hydrogenation reaction are carried out, the method can effectively solve the defects existing in the prior art: the yield of cyclopentanol is low, and the equipment corrosion and environmental pollution are serious by using sulfuric acid. In the method provided by the invention, the yield of the oxidation reaction stage is high, the operation is simple, and the method is safe and friendly to the environment; the hydrogenation reaction stage has mild conditions, easy operation, high yield of cyclopentanol and good selectivity.
Detailed description of the preferred embodiments
The details of the present invention are further described below by way of examples. Cyclopentanol was prepared in examples 1 to 10 by the following procedure:
(1) and (3) oxidation reaction: cyclopentene is used as a raw material, hydrogen peroxide is used as an oxidant, a catalyst is a TS-1 molecular sieve catalyst, acetone is used as a solvent, and NaHCO is used as an auxiliary agent3And carrying out oxidation reaction to prepare the 1, 2-epoxy cyclopentane.
(2) Hydrogenation reaction: 1, 2-epoxy cyclopentane is used as a raw material, hydrogen is introduced under the action of a nickel-based supported catalyst, and hydrogenation reaction is carried out in a kettle-type or fixed bed reactor to obtain cyclopentanol.
The TS-1 molecular sieve catalysts in the embodiments 1-10 are provided by China Shanghai petrochemical institute, and specific experimental parameters and result characterization of oxidation reaction and hydrogenation reaction and characterization results of nickel-based supported catalysts are respectively shown in tables 1-4.
[ examples 1 to 10 ]
First, oxidation reaction
The cyclopentene conversion and 1, 2-epoxycyclopentane selectivity were calculated as follows:
wherein (cyclopentene content)inRepresents the inlet mole content of cyclopentene; (cyclopentene content)outRepresents the cyclopentene outlet molar content; (1, 2-Cyclopentalene oxide molar content)outRepresents the molar content of 1, 2-epoxycyclopentane in the reaction solution after the oxidation reaction; (cyclopentene molar content) in represents the cyclopentene inlet molar content; (cyclopentene molar content) out represents the cyclopentene outlet molar content.
The oxidation reactor is a kettle type reactor, cyclopentene and acetone are added into the reaction kettle in proportion, and then TS-1 molecular sieve catalyst and auxiliary agent NaHCO are added in proportion3And hydrogen peroxide for oxidation reaction. The oxidation products were analyzed by gas chromatography. The reaction temperature, the reactant ratio and the reaction results are shown in Table 1Shown in the figure.
TABLE 1
Hydrogenation reaction
The conversion of 1, 2-epoxycyclopentane and the selectivity to cyclopentanol were calculated as follows:
is selected to have a size of
The stainless steel tubular fixed bed reactor is used as a reactor for hydrogenation reaction. 100ml of a hydrogenation catalyst was filled in the reactor, wherein examples 1 to 3 used a nickel-based supported catalyst, model number LY-2008, purchased from the landau petrochemical institute, whose physicochemical indices and chemical analyses are shown in tables 2 and 3, respectively, and examples 4 to 10 used a modified nickel-based supported catalyst, obtained by modifying LY-2008 by partial sulfur poisoning treatment, and the modification was performed in a fixed bed reactor, and the atmospheric pressure, system temperature, and the content of sulfur-containing substances in a gas phase and time are shown in table 4.
Before feeding, nitrogen is used for replacing, oxygen in the reactor is removed, the temperature of the system is raised to a required temperature, the reaction feeding amount is controlled by a feeding pump, and the pressure of the system is regulated by a back pressure valve arranged in a high molecular tank. Preheating 1, 2-cyclopentane epoxide, pumping into a reactor from the top at a set speed, introducing hydrogen into the reactor through a gas distributor, and mixing the 1, 2-cyclopentane epoxide with the hydrogen, and introducing the mixture into a catalyst bed layer for hydrogenation reaction. The hydrogenated product enters a gas-liquid separator from the bottom of the reactor, and the liquid-phase product enters a product storage tank. The unreacted hydrogen separated by the gas-liquid separator is decompressed by an adjusting valve, enters a wet gas meter for metering, is emptied, or is returned to the reaction system after being compressed. The hydrogenation product was analyzed by gas chromatography. The reaction experiment condition parameters, reactant ratios and reaction results are shown in Table 5.
TABLE 2
TABLE 3
| Item | LY2008 |
| Ni content wt% | 40±4 |
| Organic sulfur | 0 |
| Bulk density g/ml | 0.65±0.05 |
TABLE 4
| Temperature/. degree.C | Sulfide content/ppm | Time/h | Fraction of sulfide/percent | |
| Example 4 | 40 | 40 | 8 | 0.1 |
| Example 5 | 100 | 50 | 7 | 0.22 |
| Example 6 | 70 | 120 | 10 | 0.35 |
| Example 7 | 45 | 10 | 6 | 0.2 |
| Example 8 | 60 | 100 | 12 | 0.25 |
| Example 9 | 96 | 40 | 8 | 0.2 |
| Example 10 | 80 | 30 | 7.5 | 0.3 |
TABLE 5
Claims (10)
1. A preparation method of cyclopentanol based on a nickel-based supported catalyst is characterized by comprising the following steps:
(1) and (3) oxidation reaction: cyclopentene is taken as a raw material, hydrogen peroxide is taken as an oxidant, and a catalyst, a solvent and an auxiliary agent are added for oxidation reaction to obtain 1, 2-epoxycyclopentane;
(2) hydrogenation reaction: 1, 2-epoxy cyclopentane is used as a raw material, hydrogen is introduced under the catalysis of a nickel-based supported catalyst, and hydrogenation reaction is carried out in a kettle-type or fixed bed reactor to obtain cyclopentanol.
2. The process according to claim 1, wherein in the step (1), the catalyst is tungstic acid catalyst or molecular sieve catalyst, the solvent is acetone, and the auxiliary agent is NaHCO3The hydrogen peroxide is 50 wt% of hydrogen peroxide.
3. The method according to claim 2, wherein in the step (1), the catalyst is a TS-1 molecular sieve catalyst.
4. The method according to claim 1, wherein the temperature of the oxidation reaction in the step (1) is 20 to 50 ℃.
5. The method according to claim 4, wherein the temperature of the oxidation reaction in the step (1) is 30 to 40 ℃.
6. The production method according to claim 1, wherein in the step (2), the conditions of the hydrogenation reaction are as follows: the temperature is 80-150 ℃, the pressure is 3-10 MPa, and the liquid hourly space velocity is 0.1-0.8 h-1。
7. The production method according to claim 6, wherein in the step (2), the conditions of the hydrogenation reaction are as follows: the temperature is 90-120 ℃, the pressure is 4-8 MPa, and the liquid hourly space velocity is 0.2-0.6 h-1。
8. The method according to claim 1, wherein in the step (2), the nickel-based supported catalyst is a modified nickel-based supported catalyst obtained by modifying the nickel-based supported catalyst by a partial sulfur poisoning treatment under the following modification conditions: the method is carried out in a fixed bed reactor at normal pressure and the system temperature of 40-100 ℃; the content of the sulfur-containing substances in the gas phase is 10-120 ppm; the time is 6-12 h.
9. The method according to claim 8, wherein the modification conditions are as follows: the method is carried out in a fixed bed reactor at normal pressure and the system temperature of 60-80 ℃; the content of the sulfur-containing substances in the gas phase is 40-100 ppm; the time is 8-10 h.
10. The method according to claim 8, wherein the sulfur-containing substance is one or more of hydrogen sulfide, methyl sulfide, or ethyl sulfide.
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