CN112661618B - Copper catalysis preparation method of cyclopentanone - Google Patents
Copper catalysis preparation method of cyclopentanone Download PDFInfo
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- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 title claims abstract description 68
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000010949 copper Substances 0.000 title claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 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 41
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 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
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 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 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims description 18
- 229910052797 bismuth Inorganic materials 0.000 claims description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 239000007868 Raney catalyst Substances 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 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 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000012018 catalyst precursor Substances 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
- 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
- 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
- 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
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 2
- 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 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
- 238000004519 manufacturing process Methods 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
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-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
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 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
- -1 brandone Chemical compound 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
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 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
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 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
- 239000004009 herbicide Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 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
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical group O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 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 copper catalysis preparation method of cyclopentanone. The method adopts three steps to meet the process requirements: (1) oxidation reaction: taking cyclopentene as a raw material, adopting hydrogen peroxide as an oxidant, adding an oxidation catalyst, an auxiliary agent and a solvent, and performing oxidation reaction in a reactor to generate 1, 2-cyclopentane epoxide; (2) hydrogenation reaction: taking 1, 2-epoxy cyclopentane as a raw material, and carrying out hydrogenation reaction in a kettle type or fixed bed reactor under the action of a copper catalyst to generate cyclopentanol; (3) dehydrogenation reaction: cyclopentanol is used as a raw material, a dehydrogenation catalyst is added, and a dehydrogenation reaction is carried out in a reaction rectifying device to generate cyclopentanone. The copper catalysis preparation method of cyclopentanone provided by the invention is environment-friendly, mild in operation condition, high in cyclopentanone yield, and capable of reducing pollution of strong acid preparation technology 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 generating cyclopentanone from cyclopentanol by dehydrogenation.
Background
Cyclopentanone is an intermediate in the perfume and pharmaceutical industry, can be used for producing novel fine chemical products such as methyl dihydrojasmonate, brandone, and buspirone, which are anxiolytic drugs, and can also be used for synthesizing pesticides such as pesticides and herbicides. The cyclopentenone can be produced by taking cyclopentene separated from C5 fraction of ethylene byproduct produced by naphtha cracking as raw material, and the main process comprises cyclopentene N 2 Two technical routes of an O direct oxidation method and a cyclopentene hydration-dehydrogenation method. Wherein N is 2 Although the process for producing cyclopentanone by O direct oxidation realizes industrialization, the process is limited to specific regions and can be used for producing byproducts N 2 The O oxidant production device is matched with the device, so that the production cost of cyclopentanone can be greatly reduced; the preparation of cyclopentanol by hydration of cyclopentene and then dehydrogenation is an environment-friendly technical route, and has great advantages in technical and economic aspects.
Japanese patent JP60092234 and JP04312549 propose a process for gas phase dehydrogenation of cyclopentanol using a zinc-copper catalyst, the cyclopentanol single pass conversion being about 50%, the selectivity being about 97%, the conversion being relatively low. In the prior art, noble metals are adopted as dehydrogenation catalysts of alcohols, for example, japanese patent JP60115542 describes a method for preparing cyclopentanone from cyclopentanol by gas phase reaction using supported fixed bed catalysts of palladium, platinum and the like, wherein the single pass conversion is about 86% and the selectivity is about 96%.
The Chinese patent ZL03142062.1 and 03142063.X propose a catalytic distillation method for preparing cyclopentanone from cyclopentanol, and the cyclopentanol is directly prepared into high-purity cyclopentanone through catalytic dehydrogenation and rectification. The dehydrogenation reaction temperature is 130-140 ℃, the reaction pressure is normal pressure, and the dehydrogenation reaction adopts granular Raney nickel metal alloy as a catalyst. The dehydrogenation reaction product is discharged in a gas phase and directly enters rectification and purification. Cyclopentanol typically has a purity of 98%. However, the WWH load of cyclopentanol on the catalyst is only 0.3-1.5 hr -1 The efficiency of the catalyst is lower and the energy consumption is still higher.
Chinese patent CN105461526a provides a process for the preparation of cyclopentanone by dehydrogenation of cyclopentanol by passing cyclopentanol through a catalyst consisting of Ni-Cu/Al 2 O 3 -SiO 2 Dehydrogenation is carried out on a fixed bed layer formed by the catalyst to obtain cyclopentanone, and the volume liquid hourly space velocity of the dehydrogenation reaction is 0.5-2.0 hr -1 The system pressure is 0.05 to 1.0bar, and the reaction temperature is 100 to 140 ℃; dehydrogenation catalyst Ni-Cu/Al 2 O 3 -SiO 2 The content of active component nickel is 30-50wt% of the carrier mass, the content of copper as promoter is 1-5wt% of the carrier mass, and the carrier is Al 2 O 3 With SiO 2 Is a mixture of (a) and (b); the single pass conversion rate of dehydrogenation reaction is above 70%, and the selectivity of cyclopentanone is close to 100%.
From the prior art, the method can be used for effectively preparing cyclopentanone, but the method still has the defects of low conversion rate, high raw material cost, complex source 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 copper catalysis preparation method of cyclopentanone. The method takes cyclopentene as a raw material, firstly adopts an oxidation process to prepare 1, 2-cyclopentane epoxide; then taking 1, 2-epoxy cyclopentane as a raw material to prepare cyclopentanol through a hydrogenation process, and finally taking the cyclopentanol as the raw material to prepare cyclopentanone through a dehydrogenation reaction. The method can effectively solve the problems of low yield, complex raw material sources, high cost and serious equipment corrosion and environmental pollution caused by sulfuric acid in the process of preparing the intermediate cyclopentanol in the existing cyclopentanone preparation process. The method provided by the invention has the advantages of high oxidation process yield, high hydrogenation and dehydrogenation reaction yields, simple operation, environmental protection, easy operation, high cyclopentanone yield, good selectivity and low energy consumption.
The following is a specific technical scheme of the invention:
a copper catalysis preparation method of cyclopentanone comprises the following specific steps:
(1) Oxidation reaction: taking cyclopentene as a raw material, taking hydrogen peroxide as an oxidant, adding an oxidation catalyst, a solvent and an auxiliary agent, and performing oxidation reaction in a reactor to synthesize 1, 2-cyclopentane epoxide;
(2) Hydrogenation reaction: taking 1, 2-cyclopentane epoxide as a raw material, and carrying out hydrogenation reaction in a kettle type or fixed bed reactor under the action of a copper 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 NaHCO 3 The hydrogen peroxide is preferably 50wt% 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 kettle reactor.
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 hydrogenation reaction conditions 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 copper-based catalyst is a modified copper-based catalyst, and is obtained by impregnating a small amount of lead and bismuth with the copper-based catalyst.
Further, in the step (2), the preparation of the modified copper-based catalyst includes the steps of:
(a) Modified component and active auxiliary agent load:
preparing a precursor of modified component lead and a precursor of active auxiliary agent bismuth into a solution, and soaking a copper-based catalyst in the solution at 60-80 ℃ for 2-6 hours by adopting an equal volume soaking method to obtain a copper-based catalyst precursor; drying the precursor for 2-4 hours at the temperature of 90-110 ℃; roasting the precursor in stages, wherein the temperature of the first stage is 225 ℃ for 1.5-2.5 h, the temperature of the second stage is 280-310 ℃ for 3-6 h, and the copper catalyst loaded with the modified component and the active assistant is obtained;
(b) Catalyst activation:
and (c) activating the catalyst obtained in the step (a) at the temperature of 240 ℃ and under normal pressure, wherein the hydrogen flow rate is 150ml/min, and the activation time is 12h, so as to obtain the modified copper 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 bismuth is one or more of bismuth nitrate, bismuth acetate or bismuth sulfate.
Further, in the step (a), the impregnation time is preferably 3 to 5 hours, the drying temperature is preferably 100 to 105 ℃, and the stage-wise roasting second stage time is preferably 4 to 5 hours.
Further, in the step (a), the concentration of the precursor of the active component lead and the precursor of the active auxiliary agent bismuth are both between 0.4 and 1.0mol/L, so that the molar ratio of lead to palladium is between 0.1:1 and 0.4:1, and the molar ratio of lead to bismuth is kept at 1:1.
Further, in the step (2), the 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 tower top 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, 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 a catalyst 3 The method is characterized in that acetone is used as an auxiliary agent, and can be oxidized to generate 1, 2-cyclopentane epoxide, the cyclopentene conversion rate is 60-70% under a milder condition, the selectivity is close to 100%, the copper catalyst is further modified, the selectivity of the catalyst is improved, and the yield of cyclopentanol is improved. In the hydrogenation stage, 1, 2-epoxycyclopentane is passed through a single stepHydrogenation can produce cyclopentanol and cyclopentane, which belong to parallel competing reactions, and the yield of cyclopentanol depends on the activity and selectivity of the catalyst. In the dehydrogenation stage, the conversion rate is high, the selectivity is high, the cyclopentanol conversion rate can reach more than 97%, and the cyclopentanone selectivity is more than 99% under Raney nickel catalysis.
Compared with the prior art, the invention has the beneficial effects that:
after oxidation reaction, hydrogenation reaction and dehydrogenation reaction are carried out, the method can effectively solve the defects of low cyclopentanone yield, high raw material cost, complex sources, serious equipment corrosion and environmental pollution caused by sulfuric acid in the cyclopentanol preparation process in the existing cyclopentanone preparation process.
Detailed description of the preferred embodiments
The details of the invention are further described below by way of examples. Cyclopentanone was prepared in examples 1-10 by the following steps:
(1) Oxidation reaction: cyclopentene is used as raw material, hydrogen peroxide is used as oxidant, TS-1 molecular sieve is used as oxidation catalyst, acetone is used as solvent, and NaHCO is used as auxiliary agent 3 Oxidizing in a kettle reactor to synthesize 1, 2-cyclopentane epoxide;
(2) Hydrogenation reaction: taking 1, 2-epoxy cyclopentane as a raw material, and carrying out hydrogenation reaction in a fixed bed reactor under the action of a copper catalyst to obtain cyclopentanol;
(3) Dehydrogenation reaction: cyclopentanol is used as a raw material, raney nickel is used as a dehydrogenation catalyst, and a dehydrogenation reaction is carried out in a reaction rectifying device to obtain cyclopentanone.
Examples 1 to 10
1. Oxidation reaction
The cyclopentene conversion and the 1, 2-cyclopentane selectivity were calculated as follows:
wherein, (cyclopentene content) in Represents the inlet mole content of cyclopentene; (cyclopentene content) out Represents the molar content of the cyclopentene outlet; (1, 2-epoxycyclopentane molar content) represents the molar content of 1, 2-epoxycyclopentane in the reaction liquid 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 reactor for oxidation reaction is kettle reactor, cyclopentene and acetone are added into the reactor in proportion, and catalyst TS-1 molecular sieve catalyst is added in proportion, and the catalyst is provided by China petrochemical Shanghai petrochemical institute, auxiliary agent NaHCO 3 And hydrogen peroxide, and carrying out oxidation reaction. The oxidized product was analyzed by gas chromatography. The reaction temperature, the ratio of the reactants and the reaction results are shown in Table 1.
TABLE 1
Hydrogenation reaction
The 1, 2-cyclopentane epoxide conversion and cyclopentanol selectivity were calculated as follows:
wherein (1, 2-epoxycyclopentane content) in Represents the inlet molar content of the 1, 2-cyclopentane epoxide; (1, 2-Cyclopentane content) out Represents the outlet mole of 1, 2-cyclopentane epoxideThe molar content; (cyclopentanol molar content) out Representing the molar content of cyclopentanol in the reaction solution after the reaction; (1, 2-cyclopentane epoxide molar content) in represents the 1, 2-cyclopentane epoxide inlet molar content; (1, 2-cyclopentane epoxide molar content) out represents the 1, 2-cyclopentane epoxide outlet molar content.
Selecting the size asThe stainless steel tube type fixed bed reactor is used as a hydrogenation reactor. 100ml of a hydrogenation catalyst was charged in the reactor, wherein examples 1 to 2 were obtained by impregnating a copper-based catalyst, commercially available from Zhuang Xinmo Feng catalyst Co., ltd., prica Cu 60/35T, and examples 3 to 10 were obtained by impregnating a copper-based catalyst with a small amount of lead and bismuth, and specifically comprising the steps of: (a) modifying component and coagent loading: preparing lead sulfate and bismuth nitrate into a solution with the concentration of 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, and soaking a copper-based catalyst in the solution at the temperature of 60-80 ℃ for 2-6 hours by adopting an isovolumetric soaking method to obtain a copper-based catalyst precursor; drying the precursor for 2-4 hours at the temperature of 90-110 ℃; roasting the precursor in stages, wherein the temperature of the first stage is 225 ℃ for 1.5-2.5 h, the temperature of the second stage is 280-310 ℃ for 3-6 h, and the copper catalyst loaded with the modified component and the active assistant is obtained; (b) catalyst activation: and (c) activating the catalyst obtained in the step (a) at the temperature of 240 ℃ and under normal pressure, wherein the hydrogen flow rate is 150ml/min, and the activation time is 12h, so as to obtain the modified copper 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 system is raised to the required temperature, the reaction feeding amount is controlled by a feeding pump, and the system pressure is regulated by a back pressure valve arranged in the high-pressure separation tank. The 1, 2-epoxycyclopentane is preheated and then is sent into the reactor from the top by a pump at a set speed, hydrogen enters the reactor through a gas distributor, and the 1, 2-epoxycyclopentane and the hydrogen are mixed and then enter a catalyst bed layer for hydrogenation reaction. The hydrogenation product enters a gas-liquid separator from the bottom of the reactor, and the liquid-phase product enters a product storage tank. Unreacted hydrogen separated by the gas-liquid separator is decompressed by the regulating valve, enters the wet gas meter for metering and is then emptied, or is compressed and then returns to the reaction system. The hydrogenated product was analyzed by gas chromatography. The reaction experimental conditions, the reactant ratio and the reaction result are shown in table 3.
TABLE 2
TABLE 3 Table 3
3. Dehydrogenation reaction
Cyclopentanol conversion and cyclopentanone selectivity were calculated as follows:
wherein (cyclopentanol content) in Representing the molar content of cyclopentanol inlet; (cyclopentanol content) out Represents the molar content of cyclopentanol outlet; (cyclopentanone molar content) out Representing the molar content of cyclopentanone in the reaction solution after dehydrogenation; (cyclopentanol molar content) in represents 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 dehydrogenated product was analyzed by gas chromatography. The reaction experimental conditions, the reactant ratio and the reaction result are shown in table 4. .
TABLE 4 Table 4
Claims (10)
1. The copper catalysis preparation method of cyclopentanone is characterized by comprising the following specific steps:
(1) Oxidation reaction: taking cyclopentene as a raw material, taking hydrogen peroxide as an oxidant, adding an oxidation catalyst, a solvent and an auxiliary agent, and performing oxidation reaction in a reactor to synthesize 1, 2-cyclopentane epoxide;
(2) Hydrogenation reaction: taking 1, 2-epoxy cyclopentane as a raw material, and carrying out hydrogenation reaction in a reactor under the action of a copper catalyst to obtain cyclopentanol;
(3) Dehydrogenation reaction: cyclopentanol is taken as a raw material, a dehydrogenation catalyst is added, and dehydrogenation reaction is carried out in a reaction rectifying device to obtain cyclopentanone;
in the step (1), the oxidation catalyst is a TS-1 molecular sieve catalyst, the solvent is acetone, and the auxiliary agent is NaHCO 3 The hydrogen peroxide is 50wt% hydrogen peroxide;
in the step (2), the copper-based catalyst is a modified copper-based catalyst, and is obtained by impregnating a small amount of lead and bismuth with the copper-based catalyst;
in the step (2), the preparation of the modified copper-based catalyst comprises the following steps:
(a) Modified component and active auxiliary agent load:
preparing a precursor of modified component lead and a precursor of active auxiliary agent bismuth into a solution, and soaking a copper-based catalyst in the solution at 60-80 ℃ for 2-6 hours by adopting an equal volume soaking method to obtain a copper-based catalyst precursor; drying the precursor for 2-4 hours at the temperature of 90-110 ℃; roasting the precursor in stages, wherein the temperature of the first stage is 225 ℃ for 1.5-2.5 h, the temperature of the second stage is 280-310 ℃ for 3-6 h, and the copper catalyst loaded with the modified component and the active assistant is obtained;
(b) Catalyst activation:
activating the catalyst obtained in the step (a) at the temperature of 240 ℃ and under normal pressure, wherein the hydrogen flow rate is 150ml/min, and the activation time is 12 hours, so as to obtain a modified copper catalyst;
in the step (3), the dehydrogenation catalyst is Raney nickel.
2. The process according to claim 1, wherein in step (1), the temperature of the oxidation reaction is 20 to 50 ℃.
3. The method according to claim 2, wherein in the step (1), the temperature of the oxidation reaction is 30 to 40 ℃.
4. The process of claim 1, wherein in step (1), the reactor is a tank reactor.
5. The process according to claim 1, wherein in 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 。
6. The process according to claim 5, wherein in step (2), the hydrogenation reaction is carried out under the following conditions: the temperature is 90-120 ℃, the pressure is 4-8 MPa, and the liquid hourly space velocity is 0.2-0.6 h -1 。
7. The method of claim 1, wherein in 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 bismuth is one or more of bismuth nitrate, bismuth acetate or bismuth sulfate.
8. The method according to claim 1, wherein in the step (a), the dipping time is 3 to 5 hours, the drying temperature is 100 to 105 ℃, the staged roasting second stage temperature is 290 to 300 ℃, and the staged roasting second stage time is 4 to 5 hours.
9. The method of claim 1, wherein in step (a), the precursor of the active component lead and the precursor of the co-agent bismuth are both formulated in a solution at a concentration of between 0.4 and 1.0mol/L such that the molar ratio of lead to bismuth is maintained at 1:1.
10. The method of claim 1, wherein in step (3), the dehydrogenation reaction conditions are as follows: the temperature is 138-139 ℃, the tower top 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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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002020503A1 (en) * | 2000-09-11 | 2002-03-14 | Basf Aktiengesellschaft | Method for producing an epoxide |
| CN102202788A (en) * | 2008-08-04 | 2011-09-28 | 斯里赛科公司 | Metal-containing organosilica catalyst |
| CN102603506A (en) * | 2012-02-26 | 2012-07-25 | 上海派尔科化工材料有限公司 | Method for preparing cyclopentanone through cyclopentanol dehydrogenation |
| WO2017144336A1 (en) * | 2016-02-26 | 2017-08-31 | BASF Agro B.V. | Process for preparing terpinene-4-ol |
| CN108264448A (en) * | 2017-01-03 | 2018-07-10 | 万华化学集团股份有限公司 | A kind of reaction system, catalyst and its process for preparing bata-phenethyl alcohol |
| CN108821941A (en) * | 2018-07-19 | 2018-11-16 | 南京工业大学 | A kind of method that catalyzed conversion biomass prepares cyclopentanol or cyclopentanone |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101052385B1 (en) * | 2002-10-18 | 2011-07-28 | 몬산토 테크놀로지 엘엘씨 | Use of Metal Supported Copper Catalysts for Alcohol Reforming |
-
2019
- 2019-10-16 CN CN201910983923.6A patent/CN112661618B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002020503A1 (en) * | 2000-09-11 | 2002-03-14 | Basf Aktiengesellschaft | Method for producing an epoxide |
| CN102202788A (en) * | 2008-08-04 | 2011-09-28 | 斯里赛科公司 | Metal-containing organosilica catalyst |
| CN102603506A (en) * | 2012-02-26 | 2012-07-25 | 上海派尔科化工材料有限公司 | Method for preparing cyclopentanone through cyclopentanol dehydrogenation |
| WO2017144336A1 (en) * | 2016-02-26 | 2017-08-31 | BASF Agro B.V. | Process for preparing terpinene-4-ol |
| CN108264448A (en) * | 2017-01-03 | 2018-07-10 | 万华化学集团股份有限公司 | A kind of reaction system, catalyst and its process for preparing bata-phenethyl alcohol |
| CN108821941A (en) * | 2018-07-19 | 2018-11-16 | 南京工业大学 | A kind of method that catalyzed conversion biomass prepares cyclopentanol or cyclopentanone |
Non-Patent Citations (3)
| Title |
|---|
| Fiseha B. Gebretsadik et al..Hydrogenolysis of Glycidol as an Alternative Route to Obtain 1,3-Propanediol Selectively Using MOx-Modified Nickel-Copper Catalysts Supported on Acid Mesoporous Saponite.《ChemCatChem》.2017,第9卷第3670-3680页. * |
| PdCl_2-CuCl_2体系催化氧化环戊烯合成环戊酮;段元超等;《石油化工》;第40卷(第03期);第289-294页 * |
| 异戊二烯制备及精制技术概述;常慧等;《石油化工技术与经济》;第32卷(第06期);第53-56页 * |
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