CN112661619A - Method for preparing cyclopentanone - Google Patents
Method for preparing cyclopentanone Download PDFInfo
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- CN112661619A CN112661619A CN201910983932.5A CN201910983932A CN112661619A CN 112661619 A CN112661619 A CN 112661619A CN 201910983932 A CN201910983932 A CN 201910983932A CN 112661619 A CN112661619 A CN 112661619A
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- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 56
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 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 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 27
- 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 23
- 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 20
- 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 16
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims description 18
- 229910052797 bismuth Inorganic materials 0.000 claims description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- 238000002791 soaking Methods 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
- 150000002940 palladium Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000007935 neutral 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 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
- 238000001354 calcination Methods 0.000 claims 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 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
- 239000007789 gas Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 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
- 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
- 239000000203 mixture Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000012071 phase 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
- 239000004593 Epoxy Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 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
- 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
- 229910052759 nickel Inorganic materials 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
- 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
- 230000002195 synergetic effect Effects 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 method for preparing 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, and cyclopentanol is generated by a hydrogenation reaction process in a kettle type or fixed bed reactor under the action of a palladium catalyst; (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 method for preparing 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. By-product C of ethylene production by naphtha cracking5The cyclopentene separated from the fraction 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. Dehydrogenation reaction product and gasDischarging the phase, and directly carrying out 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 method for preparing 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, complex raw material source, and serious equipment corrosion and environmental pollution caused by using sulfuric acid in the preparation process of the intermediate product cyclopentanol 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 process for the preparation of cyclopentanone, comprising the steps of:
(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 kettle type or fixed bed reactor under the action of a palladium 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 20-50 ℃, and preferably 30-40 ℃.
Further, in the step (1), the oxidation reactor is a tank reactor.
Further, in the step (2), the conditions of the hydrogenation reaction are as follows: the temperature is 75-150 ℃, 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 85-120 ℃, the pressure is preferably 4-8 MPa, and the liquid hourly space velocity is 0.2-0.6 h-1。
Further, in the step (2), the palladium-based catalyst is a modified palladium-based catalyst and is obtained by impregnating a small amount of lead and bismuth into the palladium-based catalyst.
Further, in the step (2), the preparation of the modified palladium-based catalyst includes the steps of:
(a) loading a modified component and a coagent:
preparing a precursor of a modified component lead and a precursor of an active additive bismuth into a solution, and soaking a palladium catalyst in the solution for 2-6 hours at the temperature of 60-80 ℃ by adopting an isometric soaking method to obtain a palladium catalyst precursor; drying the precursor at the temperature of 90-110 ℃ for 2-4 h; roasting the precursor by stages, wherein the temperature of the first stage is 225 ℃, the time is 1.5-2.5 h, the temperature of the second stage is 280-310 ℃, and the time is 3-6 h, so as to obtain the palladium catalyst loaded with the modified component and the active assistant;
(b) and (3) catalyst reduction:
adding a certain amount of 20 wt% hydrazine hydrate solution into the catalyst obtained in the step (a), reducing for 1-4 h at 60-80 ℃, washing the reduced material with deionized water until the pH value of washing liquor is close to neutral, and drying to obtain the modified palladium catalyst.
Further, in the step (a), the precursor of the modified component lead is one or more of lead sulfate, lead nitrate or lead acetate; the precursor of the active auxiliary agent bismuth is one or more of bismuth nitrate, bismuth acetate or bismuth sulfate.
In the step (a), the soaking time is preferably 3-5 h, the drying temperature is preferably 100-105 ℃, the temperature of the staged roasting second stage is preferably 290-300 ℃, and the time of the staged roasting second stage is preferably 4-5 h.
Further, in the step (a), the concentrations of the solutions prepared from the precursor of the lead as the active component and the precursor of the bismuth as the active additive are both 0.4-1.0 mol/L, so that the molar ratio of the lead to the palladium is 0.1: 1-0.4: 1, and the molar ratio of the lead to the bismuth is kept at 1: 1.
Further, in the step (2), the hydrogenation reactor is a fixed bed reactor.
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 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 oxidant3Is used as an auxiliary agent, and acetone is used as a solvent and can be oxidized to generate 1, 2-epoxy ringThe conversion rate of cyclopentene is 60-70% under mild conditions, the selectivity is close to 100%, and the selectivity of the palladium catalyst is obviously improved under the synergistic effect of lead and bismuth by further modifying the palladium catalyst. In the hydrogenation reaction stage, the 1, 2-epoxy cyclopentane can be hydrogenated into the cyclopentanol and the cyclopentane in one step, which belongs to parallel competition reaction, and the yield of the cyclopentanol depends on the activity and the selectivity of the catalyst. 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 96%, and the selectivity of cyclopentanone is more than 98%.
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 and serious equipment corrosion and environmental pollution caused by using sulfuric acid in the preparation process of cyclopentanone in the prior 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: cyclopentene is used as a raw material, hydrogen peroxide is used as an oxidant, an oxidation catalyst is a TS-1 molecular sieve, and an auxiliary agent is NaHCO3The solvent is acetone, and the 1, 2-epoxy cyclopentane is synthesized by oxidation reaction in a reactor;
(2) hydrogenation reaction: 1, 2-epoxy cyclopentane is used as a raw material, and the cyclopentanol is obtained by hydrogenation reaction in a fixed bed reactor under the action of a palladium catalyst.
(3) Dehydrogenation reaction: cyclopentanol is used as a raw material, a Raney catalyst is added, 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) 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 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
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-epoxycyclopentane molar content) in represents the 1, 2-epoxycyclopentane inlet molar content; (molar content of 1, 2-Cyclopentalene oxide) out represents the molar content of 1, 2-Cyclopentalene oxide at the outlet.
Is selected to have a size of
The stainless steel tubular fixed bed reactor is used as a reactor for hydrogenation reaction. The method is characterized in that 100ml of hydrogenation catalyst is filled in a reactor, wherein the palladium catalyst is adopted in the examples 1-2, the palladium catalyst is purchased from Shandong Ke mechanical and chemical research institute, the model is WSH-01, the modified palladium catalyst is adopted in the examples 3-10, and the palladium catalyst is obtained by dipping a small amount of lead and bismuth in the palladium catalyst, and the method specifically comprises the following steps: (a) loading a modified component and a coagent: preparing a solution with the concentration of 0.4-1.0 mol/L from lead sulfate and bismuth nitrate, keeping the molar ratio of lead to palladium at 0.1: 1-0.4: 1 and the molar ratio of lead to bismuth at 1:1, and soaking a palladium catalyst in the solution at the temperature of 60-80 ℃ for 2-6 hours by adopting an isometric soaking method to obtain a palladium catalyst precursor; drying the precursor at the temperature of 90-110 ℃ for 2-4 h; roasting the precursor by stages, wherein the temperature of the first stage is 225 ℃, the time is 1.5-2.5 h, the temperature of the second stage is 280-310 ℃, and the time is 3-6 h, so as to obtain the palladium catalyst loaded with the modified component and the active assistant; (b) and (3) catalyst reduction: adding a certain amount of 20 wt% hydrazine hydrate solution into the catalyst obtained in the step (a), reducing for 1-4 h at 60-80 ℃, washing the reduced material with deionized water until the pH value of washing liquor is close to neutral, and drying to obtain the modified palladium catalyst. The experimental parameters of the preparation process are shown in Table 2.
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 hydrogenation reactor from top at set speed, hydrogen entering into reactor through gas distributor, mixing 1, 2-cyclopentane epoxide with hydrogen, entering into 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 3.
TABLE 2
TABLE 3
III, dehydrogenation reaction
The conversion of cyclopentanol and the selectivity of cyclopentanone were calculated as follows:
wherein (cyclopentanol content)inRepresents the inlet content of cyclopentanol; (cyclopentanol content)outRepresents the cyclopentanol outlet content; (cyclopentanone molar content)outRepresents the molar content of cyclopentanone in the reaction solution after the dehydrogenation reaction; (cyclopentanol molar content) in represents the cyclopentanol inlet molar content; (cyclopentanol molar content) out represents 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 4.
TABLE 4
Claims (15)
1. A process for the preparation of cyclopentanone, comprising the steps of:
(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 kettle type or fixed bed reactor under the action of a palladium 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 method according to claim 1, wherein in 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 process of claim 2, wherein in 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 method according to claim 1, wherein in step (1), the oxidation reactor is a tank reactor.
7. The method according to claim 1, wherein in the step (2), the conditions of the hydrogenation reaction are as follows: the temperature is 75-150 ℃, the pressure is 3-10 MPa, and the liquid hourly space velocity is 0.1-0.8 h-1。
8. The method according to claim 7, wherein in the step (2), the conditions of the hydrogenation reaction are as follows: the temperature is 85-120 ℃, the pressure is preferably 4-8 MPa, and the liquid hourly space velocity is 0.2-0.6 h-1。
9. The production method according to claim 1, wherein in the step (2), the palladium-based supported catalyst is a modified palladium-based supported catalyst obtained by impregnating a palladium-based supported catalyst with a small amount of lead and bismuth.
10. The method according to claim 9, wherein the preparation of the modified palladium-based supported catalyst in the step (2) comprises the steps of:
(a) loading a modified component and a coagent:
preparing a precursor of a modified component lead and a precursor of an active additive bismuth into a solution, and soaking the palladium supported catalyst in the solution for 2-6 hours at the temperature of 60-80 ℃ by adopting an isometric soaking method to obtain a palladium supported catalyst precursor; drying the precursor at the temperature of 90-110 ℃ for 2-4 h; roasting the precursor by stages, wherein the temperature of the first stage is 225 ℃, the time is 1.5-2.5 h, the temperature of the second stage is 280-310 ℃, and the time is 3-6 h, so as to obtain the palladium supported catalyst loaded with the modified component and the active additive;
(b) and (3) catalyst reduction:
adding a certain amount of 20 wt% hydrazine hydrate solution into the catalyst obtained in the step (a), reducing for 1-4 h at 60-80 ℃, washing the reduced material with deionized water until the pH value of a washing solution is close to neutral, and drying to obtain the modified palladium supported catalyst.
11. The preparation method according to claim 10, wherein in the step (a), the precursor of the modified component lead is one or more of lead sulfate, lead nitrate or lead acetate; the precursor of the active auxiliary agent bismuth is one or more of bismuth nitrate, bismuth acetate or bismuth sulfate.
12. The method according to claim 10, wherein in the step (a), the dipping time is 3 to 5 hours, the drying temperature is 100 to 105 ℃, the temperature of the second stage of the staged calcination is 290 to 300 ℃, and the time of the second stage of the staged calcination is 4 to 5 hours.
13. The preparation method of claim 10, wherein in the step (a), the concentration of the solution prepared from the precursor of lead as the active component and the precursor of bismuth as the active additive is 0.4-1.0 mol/L, so that the molar ratio of lead to palladium is 0.1: 1-0.4: 1, and the molar ratio of lead to bismuth is kept at 1: 1.
14. The process of claim 1, wherein in step (3), the dehydrogenation catalyst is Raney nickel.
15. The 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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