CN112661620A - Preparation method of cyclopentanone - Google Patents
Preparation method of cyclopentanone Download PDFInfo
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- CN112661620A CN112661620A CN201910984944.XA CN201910984944A CN112661620A CN 112661620 A CN112661620 A CN 112661620A CN 201910984944 A CN201910984944 A CN 201910984944A CN 112661620 A CN112661620 A CN 112661620A
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- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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 21
- 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 20
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 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
- 239000007789 gas Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- 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 7
- 239000007868 Raney catalyst Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 5
- 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
- 208000005374 Poisoning Diseases 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 231100000572 poisoning Toxicity 0.000 claims description 3
- 230000000607 poisoning effect Effects 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 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
- 150000002815 nickel Chemical class 0.000 claims description 2
- 238000010992 reflux Methods 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
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910018054 Ni-Cu Inorganic materials 0.000 description 2
- 229910018481 Ni—Cu Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-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
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002249 anxiolytic agent Substances 0.000 description 1
- 230000000949 anxiolytic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
Abstract
The invention belongs to the technical field of organic chemical industry and discloses a preparation method of cyclopentanone. The method adopts three steps to meet the process requirement: (1) and (3) oxidation reaction: cyclopentene is taken as a raw material, hydrogen peroxide is taken as an oxidant, an oxidation catalyst, an auxiliary agent and a solvent are added, and oxidation reaction is carried out in a reactor to generate 1, 2-epoxycyclopentane; (2) hydrogenation reaction: 1, 2-epoxy cyclopentane is taken as a raw material, hydrogen and a nickel-based supported catalyst are added, and a hydrogenation reaction process is carried out in a reactor to generate cyclopentanol; (3) dehydrogenation reaction: taking cyclopentanol as a raw material, adding a dehydrogenation catalyst, and carrying out dehydrogenation reaction in a reaction rectifying device to generate cyclopentanone. The preparation method of cyclopentanone provided by the invention is environment-friendly, mild in operation condition and high in cyclopentanone yield, and reduces the pollution of a 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 method for preparing cyclopentanol from cyclopentene and then dehydrogenating the cyclopentanol to generate the cyclopentanone.
Background
Cyclopentanone is an intermediate of perfume and pharmaceutical industry, can be used for producing novel fine chemical products such as methyl dihydrojasmonate, albronone and buspirone as anxiolytic, and can also be used for synthesizing pesticides such as pesticide and herbicide. In addition, cyclopentanone has good solubility, and is widely used as a solvent in the electronic industry. The cyclopentene separated from the C5 fraction as the by-product of cracking naphtha to prepare ethylene can be used as raw material to produce cyclopentanone, and the main process is cyclopentene N2Two technical routes of an O direct oxidation method and a cyclopentene hydration-dehydrogenation method. Wherein N is2Although the process for producing cyclopentanone by O direct oxidation method is industrialized, the process can be limited to specific regions and can produce N as a byproduct2The production cost of cyclopentanone can be greatly reduced only by matching the O oxidant production devices; the cyclopentene is firstly hydrated to prepare the cyclopentanol, and then the cyclopentanone is prepared by dehydrogenation, so that the method is an environment-friendly technical route and has great advantages in technical and economic aspects.
Japanese patents JP60092234 and JP04312549 propose gas phase dehydrogenation of cyclopentanol using a zinc-copper catalyst with a conversion per pass of cyclopentanol of about 50%, a selectivity of about 97%, and a relatively low conversion. In the prior art, dehydrogenation catalysts using noble metals as alcohols are well established, and for example, japanese patent JP60115542 describes a method for preparing cyclopentanone from cyclopentanol by dehydrogenation of cyclopentanol by a gas phase reaction using a supported fixed bed catalyst such as palladium or platinum, with a per pass conversion of about 86% and a selectivity of about 96%.
Chinese patents ZL03142062.1 and 03142063.X propose a catalytic rectification method for preparing cyclopentanone from cyclopentanol, and the cyclopentanol as raw material is directly prepared into high-purity cyclopentanone through catalytic dehydrogenation and rectification reaction. The dehydrogenation reaction temperature is 130-140 ℃, the reaction pressure is normal pressure, and the dehydrogenation reaction adopts granular Raney nickel type metal alloy as a catalyst. Discharging the dehydrogenation reaction product in the gas phaseAnd directly enters rectification and purification. The purity of cyclopentanol is generally 98%. But WWH is only 0.3-1.5 hr due to cyclopentanol load of the catalyst-1The catalyst efficiency is low and the energy consumption is still high.
Chinese patent CN105461526A provides a method for preparing cyclopentanone by dehydrogenating cyclopentanol through Ni-Cu/Al2O3-SiO2Dehydrogenating the mixture in a fixed bed layer formed by the catalyst to prepare cyclopentanone, wherein the volume liquid hourly space velocity of the dehydrogenation reaction is 0.5-2.0 hr-1The system pressure is 0.05-1.0 bar, and the reaction temperature is 100-140 ℃; dehydrogenation catalyst Ni-Cu/Al2O3-SiO2The content of the active component nickel is 30-50 wt% of the mass of the carrier, the content of the cocatalyst copper is 1-5 wt% of the mass of the carrier, and the carrier is Al2O3With SiO2A mixture of (a); the conversion per pass of the dehydrogenation reaction is more than 70 percent, and the selectivity of cyclopentanone is close to 100 percent.
From the prior art, although the cyclopentanone can be effectively prepared by the method, the method still has the defects of low conversion rate and high energy consumption, and is not beneficial to industrial production.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of cyclopentanone. 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 to prepare cyclopentanol through hydrogenation process, and finally using cyclopentanol as raw material to prepare cyclopentanone through dehydrogenation reaction. The method can effectively solve the defects of low yield, equipment corrosion caused by the use of sulfuric acid in the preparation process of the intermediate product cyclopentanol and serious environmental pollution in the existing cyclopentanone preparation process. The method provided by the invention has the advantages of easily obtained raw materials, high yield of the oxidation process, high yield of the hydrogenation and dehydrogenation steps, simple operation, environmental safety and friendliness, easy operation, high yield of cyclopentanone, good selectivity and low energy consumption.
The following is a specific technical scheme of the invention:
a preparation method of cyclopentanone comprises the following steps:
(1) and (3) oxidation reaction: cyclopentene is taken as a raw material, hydrogen peroxide is taken as an oxidant, an oxidation catalyst, a solvent and an auxiliary agent are added, and oxidation reaction is carried out in a reactor to synthesize 1, 2-epoxycyclopentane;
(2) hydrogenation reaction: 1, 2-epoxy cyclopentane is taken as a raw material, and is subjected to hydrogenation reaction in a reactor under the action of a nickel-based supported catalyst to obtain cyclopentanol;
(3) dehydrogenation reaction: cyclopentanol is used as a raw material, a dehydrogenation catalyst is added, and dehydrogenation reaction is carried out in a reaction rectifying device to obtain cyclopentanone.
Further, in the step (1), the oxidation 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 (1), the reactor is a tank reactor.
Further, in the step (2), the hydrogenation reaction conditions are as follows: the temperature is 90-160 ℃, 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 95-125 ℃, 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 reactor is a fixed bed reactor.
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 (3), the dehydrogenation catalyst is Raney nickel.
Further, in the step (3), the dehydrogenation reaction conditions are as follows: the temperature is 138-139 ℃, the overhead temperature is 119-121 ℃, the feeding rate is 0.5-1.2 Kg/hr, and the reflux ratio is 8-18: 1.
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, NaHCO is used as an oxidant3As an auxiliary agent, acetone is a solvent and can be oxidized to generate 1, 2-epoxycyclopentane, under a mild condition, the conversion rate of cyclopentene is 60-70%, and the selectivity is close to 100%. In the hydrogenation reaction stage, the 1, 2-epoxycyclopentane can be subjected to one-step hydrogenation to generate cyclopentanol and cyclopentane, which belong to parallel competition reaction, the yield of the cyclopentanol depends on the activity and selectivity of the catalyst, and the further modification treatment of the nickel-based supported catalyst enables the active component part to exist in a sulfuration state, so that the selectivity of the catalyst is improved. In the dehydrogenation reaction stage, under the catalysis of Raney nickel, the conversion rate is high, the selectivity is high, the conversion rate of cyclopentanol can reach more than 97%, and the selectivity of cyclopentanone is more than 99%.
Compared with the prior art, the invention has the beneficial effects that:
after the oxidation reaction, the hydrogenation reaction and the dehydrogenation reaction are carried out, the method can effectively solve the defects of low yield of cyclopentanone, complex raw material source and serious corrosion to equipment and environmental pollution caused by using sulfuric acid in the preparation process of cyclopentanone in the conventional preparation process of cyclopentanone.
Detailed description of the preferred embodiments
The details of the present invention are further described below by way of examples. In examples 1 to 10, cyclopentanone was prepared by the following steps:
(1) and (3) oxidation reaction: by cyclopentylAlkene is taken as a raw material, hydrogen peroxide is taken as an oxidant, an oxidation catalyst is a TS-1 molecular sieve, a solvent is acetone, and an auxiliary agent is NaHCO3Carrying out oxidation reaction in a reactor to synthesize 1, 2-epoxycyclopentane;
(2) hydrogenation reaction: 1, 2-epoxy cyclopentane is taken as a raw material, and is subjected to hydrogenation reaction in a reactor under the action of a nickel-based supported catalyst to obtain cyclopentanol;
(3) dehydrogenation reaction: cyclopentanol is used as a raw material, Raney nickel is used as a dehydrogenation catalyst, and dehydrogenation reaction is carried out in a reaction rectifying device to obtain the cyclopentanone.
[ 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-epoxycyclopentane molar content) represents the 1, 2-epoxycyclopentane molar content in the reaction solution after the oxidation reaction; (cyclopentene molar content)inRepresents the inlet mole content of cyclopentene; (cyclopentene molar content)outRepresents the exit molar content of cyclopentene.
The oxidation reactor is a kettle type reactor, cyclopentene and acetone are added into the reaction kettle in proportion, and TS-1 molecular sieve catalyst provided by China Shanghai petrochemical institute is 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 1.
TABLE 1
Second, hydrogenation reaction
The conversion of 1, 2-epoxycyclopentane and the selectivity to cyclopentanol were calculated as follows:
wherein, the content of (1, 2-epoxy cyclopentane)inRepresents the inlet molar content of 1, 2-epoxy cyclopentane; (1, 2-Cyclopentalene oxide content)outRepresents the outlet mole content of 1, 2-epoxy cyclopentane; (cyclopentanol molar content)outRepresents the mole content of cyclopentanol in the reaction solution after the reaction; (1, 2-Cyclopentalene oxide molar content)inRepresents the inlet molar content of 1, 2-epoxy cyclopentane; (1, 2-Cyclopentalene oxide molar content)outRepresents the outlet molar content of 1, 2-epoxycyclopentane.
Is selected to have a size of
The stainless steel tubular fixed bed reactor is used as a reactor for hydrogenation reaction. The reactor was charged with 100ml of a hydrogenation catalyst, wherein examples 1 to 2 used a nickel-based supported catalyst, model number LY-2008, purchased from the landau petrochemical institute, and the physicochemical indices and chemical analyses thereof are shown in tables 2 and 3, respectively, and examples 3 to 10 used a modified nickel-based supported catalyst, obtained by modifying LY-2008 by partial sulfur poisoning treatment, the modification being carried out in a fixed bed reactor, and the atmospheric pressure, the system temperature, the content of sulfur-containing substances in the gas phase, and the 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
| Item | LY2008 |
| Shape of | Cylinder body |
| Active ingredient | Ni |
| A/m2/g | 92.4 |
| Vp/ml/g | 0.20 |
TABLE 3
TABLE 4
| Temperature/. degree.C | Sulfide content/ppm | Time/h | Fraction of sulfide/percent | |
| Example 3 | 40 | 80 | 12 | 0.20 |
| Example 4 | 60 | 10 | 9 | 0.19 |
| Example 5 | 100 | 50 | 7 | 0.22 |
| Example 6 | 70 | 120 | 10 | 0.35 |
| Example 7 | 85 | 100 | 12 | 0.4 |
| Example 8 | 45 | 60 | 6 | 0.21 |
| Example 9 | 96 | 40 | 8 | 0.22 |
| Example 10 | 80 | 30 | 7.5 | 0.34 |
TABLE 5
III, dehydrogenation reaction
The conversion of cyclopentanol and the selectivity of cyclopentanone were calculated as follows:
wherein, (cyclopentanol content)inRepresents the inlet mole content of cyclopentanol; (cyclopentanol content)outRepresents the cyclopentanol outlet molar content; (cyclopentanone molar content)outRepresents the molar content of cyclopentanone in the reaction solution after the dehydrogenation reaction; (cyclopentanol molar content)inRepresents the inlet mole content of cyclopentanol; (cyclopentanol molar content)outRepresents the cyclopentanol outlet molar content.
And adding cyclopentanol and Raney catalyst into a reaction rectification reactor for dehydrogenation reaction to obtain cyclopentanone. The dehydrogenation product was analyzed by gas chromatography. The reaction experiment condition parameters, reactant ratios and reaction results are shown in Table 6.
TABLE 6
Claims (12)
1. The preparation method of cyclopentanone 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, an oxidation catalyst, a solvent and an auxiliary agent are added, and oxidation reaction is carried out in a reactor to synthesize 1, 2-epoxycyclopentane;
(2) hydrogenation reaction: 1, 2-epoxy cyclopentane is taken as a raw material, and is subjected to hydrogenation reaction in a reactor under the action of a nickel-based supported catalyst to obtain cyclopentanol;
(3) dehydrogenation reaction: cyclopentanol is used as a raw material, a dehydrogenation catalyst is added, and dehydrogenation reaction is carried out in a reaction rectifying device to obtain cyclopentanone.
2. The process according to claim 1, wherein in the step (1), the oxidation catalyst is a tungstic acid catalyst or a 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 oxidation 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 90-160 ℃, 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 95-125 ℃, 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 in the step (2), the sulfide selected for preparing the sulfur-containing substance by the hydrogenation reaction modified nickel-based catalyst is one or more of hydrogen sulfide, methyl sulfide and/or ethyl sulfide.
11. The production method according to claim 1, wherein in the step (3), the dehydrogenation catalyst is Raney nickel.
12. The production method according to claim 1, wherein in the step (3), the dehydrogenation reaction conditions are as follows: the temperature is 138-139 ℃, the overhead temperature is 119-121 ℃, the feeding rate is 0.5-1.2 Kg/hr, and the reflux ratio is 8-18: 1.
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