CN117160530A - Preparation method of sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement - Google Patents
Preparation method of sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement Download PDFInfo
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 238000006237 Beckmann rearrangement reaction Methods 0.000 title claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 29
- 239000011593 sulfur Substances 0.000 title claims abstract description 29
- 239000007791 liquid phase Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 20
- 239000011574 phosphorus Substances 0.000 title claims abstract description 20
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 26
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000001291 vacuum drying Methods 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 230000003197 catalytic effect Effects 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 9
- GPULXEIKKFAUAW-UHFFFAOYSA-N 2,4-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C(O)=C1 GPULXEIKKFAUAW-UHFFFAOYSA-N 0.000 claims description 8
- VOEZCXMAYZOMRG-UHFFFAOYSA-N benzenethiol;phenol Chemical compound OC1=CC=CC=C1.SC1=CC=CC=C1 VOEZCXMAYZOMRG-UHFFFAOYSA-N 0.000 claims description 6
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- IULJSGIJJZZUMF-UHFFFAOYSA-N 2-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC=C1S(O)(=O)=O IULJSGIJJZZUMF-UHFFFAOYSA-N 0.000 claims description 2
- OAZFOYFTVWTHKK-UHFFFAOYSA-N C1(=CC=CC=C1)S.C1(O)=CC=C(O)C=C1 Chemical compound C1(=CC=CC=C1)S.C1(O)=CC=C(O)C=C1 OAZFOYFTVWTHKK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 8
- 235000011130 ammonium sulphate Nutrition 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- HYBIIGFUKKOJJM-UHFFFAOYSA-N cyclohexanone;hydroxylamine Chemical compound ON.O=C1CCCCC1 HYBIIGFUKKOJJM-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NJNQUTDUIPVROZ-UHFFFAOYSA-N nitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1 NJNQUTDUIPVROZ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- ZFQJFYYGUOXGRF-UHFFFAOYSA-N 2-sulfanylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(S)=C1 ZFQJFYYGUOXGRF-UHFFFAOYSA-N 0.000 description 1
- XBNOMKROXZGMFW-UHFFFAOYSA-N 3-[(3-hydroxyphenyl)disulfanyl]phenol Chemical compound OC1=CC=CC(SSC=2C=C(O)C=CC=2)=C1 XBNOMKROXZGMFW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004157 Nitrosyl chloride Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000009935 nitrosation Effects 0.000 description 1
- 238000007034 nitrosation reaction Methods 0.000 description 1
- VPCDQGACGWYTMC-UHFFFAOYSA-N nitrosyl chloride Chemical compound ClN=O VPCDQGACGWYTMC-UHFFFAOYSA-N 0.000 description 1
- 235000019392 nitrosyl chloride Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxime chloride Chemical class 0.000 description 1
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
Classifications
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- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of a sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement, which comprises the following steps: (1) Firstly, phosphorus chloride is weighed and dissolved in a solvent to prepare a solution A, and then sulfur-containing organic matters are dissolved in the solvent to prepare a solution B; (2) Mixing A and B in a reactor under the microwave reaction condition to react; (3) Washing the catalyst precursor obtained in the step (2) by a solvent and drying in vacuum to obtain a catalyst; (4) The catalyst is used for catalyzing the Beckmann rearrangement reaction of the cyclohexanone oxime to generate caprolactam. In the catalyst provided by the invention, in the Beckmann rearrangement catalytic reaction of the cyclohexanone oxime, the maximum value of the cyclohexanone oxime conversion rate is 100%, and the maximum value of the caprolactam selectivity is 99.5%.
Description
Technical Field
The invention relates to a catalyst, in particular to a preparation method of a sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement.
Background
Caprolactam is an important organic chemical raw material, and is mainly used for producing polyamide-6 fibers, polyamide resins and films. The caprolactam production process mainly comprises a cyclohexanone-hydroxylamine method, a toluene method, a cyclohexane nitrosation method and a cyclohexanone ammoximation method. The method has the advantages of simple process flow, mild reaction conditions, high reactant conversion rate, high selectivity and the like, and the cyclohexanone oxime liquid-phase Beckmann rearrangement (cyclohexanone ammoximation method) is the main process for producing caprolactam, but the concentrated sulfuric acid catalyst has strong corrosiveness and a large amount of low-value ammonium sulfate products as byproducts in the catalytic reaction process, which is a technical problem to be overcome. Therefore, the development of green catalytic research for producing caprolactam by rearrangement without ammonium sulfate is of great significance.
The existing caprolactam production method comprises the following steps: 1. the cyclohexanone-hydroxylamine process includes the reaction of cyclohexanone and hydroxylamine to produce quaternary contemporaneous cyclohexanone oxime, beckmann rearrangement in fuming sulfuric acid and neutralization to obtain caprolactam. The process has the defects that: the byproduct ammonium sulfate (1.8 tons of ammonium sulfate per 1 ton of caprolactam) and caprolactam are complex in refining process. 2. The process is carried out by oxidizing toluene to obtain benzoic acid, hydrogenating benzoic acid to obtain cyclohexanecarboxylic acid, reacting with nitrosoacylating agent in sulfuric acid medium to obtain caprolactam. The process has the defects that: the catalyst recovery difficulty is high, the byproduct ammonium sulfate is more (4.2 tons of ammonium sulfate per 1 ton of caprolactam) and the caprolactam refining process is complex. 3. The cyclohexane photonitrosation process includes the reaction of cyclohexane under the irradiation of mercury lamp, the formation of oxime chloride from cyclohexane, nitrosyl chloride and hydrogen chloride, and the subsequent Beckmann rearrangement in fuming sulfuric acid to obtain caprolactam. The method is to nitrify cyclohexane to prepare nitrocyclohexane, and then to reduce the nitrocyclohexane to cyclohexanone fat through hydrogenation. The disadvantage of this process is: high energy consumption, serious equipment corrosion and high equipment investment.
The catalyst provided by the invention has the beneficial effects in the Beckmann rearrangement catalytic reaction of cyclohexanone oxime: the catalyst has no ammonium sulfate byproduct, the catalyst is easy to separate from the product, the cyclohexanone oxime conversion rate of the catalyst is 100 percent at the maximum, and the caprolactam selectivity is 99.5 percent at the maximum.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement, wherein the maximum value of cyclohexanone oxime conversion rate of the catalyst is 100%, the maximum value of caprolactam selectivity is 99.5%, and the catalyst stability is good.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing a sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement, which comprises the following steps:
(1) Under certain reaction conditions, firstly, phosphorus chloride is weighed and dissolved in a solvent to prepare a solution A, and then sulfur-containing organic matters are dissolved in the solvent to prepare a solution B;
(2) Mixing A and B in a reactor under the microwave reaction condition to react;
(3) And (3) washing the catalyst precursor obtained in the step (2) by a solvent and drying in vacuum to obtain the catalyst.
And (2) dissolving phosphorus chloride in the solvent in the step (1) and magnetically stirring the solution in an open beaker to obtain a solution A, then dissolving sulfur-containing organic matters in the solvent in the open beaker and magnetically stirring the solution B, wherein the stirring temperature is 20-40 ℃, the stirring speed is 200-500r/min, the stirring time is 15-60 min, the mass ratio of the phosphorus chloride to the solvent is (1-3): 7, and the mass ratio of the sulfur-containing organic matters to the solvent is (1-3): 7.
Further, the phosphorus chloride is one of phosphorus trichloride and phosphorus pentachloride.
Further, the sulfur-containing organic matter in the step (1) is 4,4 '-dihydroxydiphenyl sulfide, 3' -dihydroxydiphenyl sulfide, thiol-polyethylene glycol-hydroxy, 4-hydroxybenzene thiophenol, 2-hydroxybenzene thiophenol, 3-hydroxybenzene thiophenol, 2, 5-dihydroxybenzene thiophenol, 2-hydroxybenzene sulfonic acid, 2, 4-dihydroxybenzene sulfonic acid or 2, 4-dihydroxybenzene sulfonic acid.
Further, the solvent in the step (1) is methanol, benzene, acetonitrile, toluene, acetone, ethanol, diethyl ether or carbon tetrachloride.
Further, in the step (2), under the microwave reaction condition, mixing the A and the B, and placing the mixture into a reactor for reaction. The microwave power is 800-1200W, the reaction temperature is 100-200 ℃, the reaction time is 0.5-12h, and the reaction atmosphere is nitrogen.
And (3) washing the catalyst precursor obtained in the step (2) by using a solvent, and then moving to a vacuum drying oven for drying to obtain the catalyst, wherein the drying temperature is 100-200 ℃ and the drying time is 2-48h, and the solvent is methanol, benzene, acetonitrile, toluene, acetone, ethanol, diethyl ether or carbon tetrachloride.
The invention also provides application of the sulfur-and phosphorus-based catalyst in the reaction of preparing caprolactam by liquid-phase Beckmann rearrangement, which takes cyclohexanone oxime as a raw material, synthesizes caprolactam under the catalysis of the sulfur-and phosphorus-based catalyst, the conversion rate of the cyclohexanone oxime reaches 100%, and the selectivity of caprolactam reaches 99.5%.
Further, adding cyclohexanone oxime and a catalyst into a catalytic reactor, heating to 80-140 ℃, and reacting at a pressure of 0.1KPa-1.0Kpa for 1-60min; wherein the mass ratio of the catalyst to the cyclohexanone oxime is (1-50): 50.
The invention has the beneficial effects that: heating in a specific solvent system, and carrying out condensation reaction between chlorine atoms of phosphorus chloride and hydroxyl groups in sulfur-containing organic matters to generate a phosphorus-sulfur compound. The cyclohexanone oxime is used as a raw material to synthesize caprolactam under the catalysis of a sulfur-containing and phosphorus-based catalyst, the solid catalyst has no corrosiveness, no byproduct of ammonium sulfate, the catalyst and the product are easy to separate, the cyclohexanone oxime conversion rate of the catalyst is 100%, and the caprolactam selectivity is 99.5%.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that numerous insubstantial modifications and adaptations can be made by those skilled in the art in light of the foregoing disclosure.
Example 1
The preparation method of the sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement is as follows:
(1) Firstly, 30g of phosphorus trichloride is weighed and dissolved in 70g of acetonitrile, the mixture is stirred for 15min at the temperature of 30 ℃ and the stirring rotation speed of 200r/min to prepare a solution A, then 30g of 4,4' -dihydroxydiphenyl sulfide is dissolved in 70g of acetonitrile solvent, and the mixture is stirred for 15min at the temperature of 30 ℃ and the stirring rotation speed of 200r/min to prepare a solution B;
(2) Then mixing A and B and placing the mixture into a reactor for microwave reaction for 0.5h under the microwave reaction condition that the microwave power is 800W and the reaction temperature is 120 ℃ to obtain a catalyst precursor;
(3) Washing the catalyst precursor obtained in the step (2) by ethanol, and vacuum drying for 0.5h at the vacuum drying temperature of 100 ℃ to obtain the catalyst 1.
Catalyst evaluation
Adding cyclohexanone oxime and a catalyst 1 into a catalytic reactor, heating to 140 ℃, and reacting for 30min; wherein the mass ratio of the catalyst to the cyclohexanone oxime is 1:1. The cyclohexanone oxime conversion was 100% and the caprolactam selectivity was 99.0%.
Example 2
The preparation method of the sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement is as follows:
(1) Firstly, 30g of phosphorus pentachloride is weighed and dissolved in 70g of acetonitrile, and stirred for 15min under the conditions of the temperature of 30 ℃ and the stirring rotation speed of 200r/min to prepare a solution A, then 30g of 4,4' -dihydroxydiphenyl sulfide is dissolved in 70g of acetonitrile solvent, and stirred for 15min under the conditions of the temperature of 30 ℃ and the stirring rotation speed of 200r/min to prepare a solution B;
(2) Then mixing A and B and placing the mixture into a reactor for microwave reaction for 0.5h under the microwave reaction condition that the microwave power is 800W and the reaction temperature is 120 ℃ to obtain a catalyst precursor;
(3) Washing the catalyst precursor obtained in the step (2) by ethanol, and vacuum drying for 0.5h at the vacuum drying temperature of 100 ℃ to obtain the catalyst 2.
Catalyst evaluation
Adding cyclohexanone oxime and a catalyst 2 into a catalytic reactor, heating to 140 ℃, and reacting for 30min; wherein the mass ratio of the catalyst to the cyclohexanone oxime is 1:1. The cyclohexanone oxime conversion was 99.7% and the caprolactam selectivity was 99.1%.
Example 3
The preparation method of the sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement is as follows:
(1) Firstly, 30g of phosphorus trichloride is weighed and dissolved in 70g of acetonitrile, and stirred for 15min under the conditions of 30 ℃ and 200r/min of stirring speed to prepare solution A, and then 30g of solution A is obtainedThiol-polyethylene glycol-hydroxy groupDissolving in 70g acetonitrile solvent, stirring for 15min at 30deg.C at stirring speed of 200r/min to obtain solution B;
(2) Then mixing A and B and placing the mixture into a reactor for microwave reaction for 0.5h under the microwave reaction condition that the microwave power is 800W and the reaction temperature is 120 ℃ to obtain a catalyst precursor;
(3) Washing the catalyst precursor obtained in the step (2) by ethanol, and vacuum drying for 0.5h at the vacuum drying temperature of 100 ℃ to obtain the catalyst 3.
Catalyst evaluation
Adding cyclohexanone oxime and a catalyst 3 into a catalytic reactor, heating to 140 ℃, and reacting for 30min; wherein the mass ratio of the catalyst to the cyclohexanone oxime is 1:1. The cyclohexanone oxime conversion was 99.8% and the caprolactam selectivity was 99.3%.
Example 4
The preparation method of the sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement is as follows:
(1) Firstly, 30g of phosphorus pentachloride is weighed and dissolved in 70g of acetonitrile, and stirred for 15min under the conditions of 30 ℃ and 500r/min of stirring speed to prepare solution A, and then 30g of solution A is obtained2, 4-dihydroxybenzenesulfonic acidDissolving in 70g acetonitrile solvent, stirring at 30deg.C and stirring speed of 500r/min for 15min to obtain solution B;
(2) Then mixing A and B and placing the mixture into a reactor for microwave reaction for 0.5h under the microwave reaction condition that the microwave power is 800W and the reaction temperature is 120 ℃ to obtain a catalyst precursor;
(3) Washing the catalyst precursor obtained in the step (2) by ethanol, and vacuum drying for 0.5h at the vacuum drying temperature of 100 ℃ to obtain the catalyst 4.
Catalyst evaluation
Adding cyclohexanone oxime and a catalyst 4 into a catalytic reactor, heating to 140 ℃, and reacting for 30min; wherein the mass ratio of the catalyst to the cyclohexanone oxime is 1:1. The cyclohexanone oxime conversion was 99.7% and the caprolactam selectivity was 99.5%.
Example 5
The preparation method of the sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement is as follows:
(1) Firstly, 25g of phosphorus trichloride is weighed and dissolved in 70g of acetonitrile, the mixture is stirred for 15min at the temperature of 30 ℃ and the stirring rotation speed of 500r/min to prepare a solution A, then 25g of 3,3' -dihydroxydiphenyl disulfide is dissolved in 70g of acetonitrile solvent, and the mixture is stirred for 15min at the temperature of 30 ℃ and the stirring rotation speed of 500r/min to prepare a solution B;
(2) Then mixing A and B and placing the mixture into a reactor for microwave reaction for 0.5h under the microwave reaction condition that the microwave power is 1200W and the reaction temperature is 200 ℃ to obtain a catalyst precursor;
(3) Washing the catalyst precursor obtained in the step (2) by ethanol, and vacuum drying for 0.5h at the vacuum drying temperature of 100 ℃ to obtain the catalyst 5.
Catalyst evaluation
Adding cyclohexanone oxime and a catalyst 5 into a catalytic reactor, heating to 140 ℃, and reacting for 30min; wherein the mass ratio of the catalyst 5 to the cyclohexanone oxime is 1:1. The cyclohexanone oxime conversion was 99.3% and the caprolactam selectivity was 99.0%.
Example 6
The preparation method of the sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement is as follows:
(1) Firstly, 15g of phosphorus pentachloride is weighed and dissolved in 70g of acetonitrile, and stirred for 15min under the conditions of 30 ℃ and 500r/min of stirring speed to prepare solution A, and then 15g of solution A is obtained2, 4-dihydroxybenzenesulfonic acidDissolving in 70g acetonitrile solvent, stirring at 30deg.C and stirring speed of 500r/min for 15min to obtain solution B;
(2) Then mixing A and B and placing the mixture into a reactor for microwave reaction for 0.5h under the microwave reaction condition that the microwave power is 800W and the reaction temperature is 120 ℃ to obtain a catalyst precursor;
(3) Washing the catalyst precursor obtained in the step (2) by ethanol, and vacuum drying for 0.5h at the vacuum drying temperature of 100 ℃ to obtain the catalyst 6.
Catalyst evaluation
Adding cyclohexanone oxime and a catalyst 6 into a catalytic reactor, heating to 140 ℃, and reacting for 30min; wherein the mass ratio of the catalyst to the cyclohexanone oxime is 1:1. The cyclohexanone oxime conversion was 99.6% and the caprolactam selectivity was 99.4%.
Example 7
The preparation method of the sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement is as follows:
(1) Firstly, 10g of phosphorus pentachloride is weighed and dissolved in 70g of acetonitrile, and stirred for 60min under the conditions of 30 ℃ and 500r/min of stirring speed to prepare solution A, and then 30g of solution A is obtained2, 4-dihydroxybenzenesulfonic acidDissolving in 70g acetonitrile solvent, stirring at 30deg.C and stirring speed of 500r/min for 15min to obtain solution B;
(2) Then mixing A and B and placing the mixture into a reactor for microwave reaction for 0.5h under the microwave reaction condition that the microwave power is 800W and the reaction temperature is 140 ℃ to obtain a catalyst precursor;
(3) Washing the catalyst precursor obtained in the step (2) by ethanol, and vacuum drying for 120 hours at the vacuum drying temperature of 120 ℃ to obtain the catalyst 7.
Catalyst evaluation
Adding cyclohexanone oxime and a catalyst 7 into a catalytic reactor, heating to 140 ℃, and reacting for 60min; wherein the mass ratio of the catalyst to the cyclohexanone oxime is 1:1. The cyclohexanone oxime conversion was 98.9% and the caprolactam selectivity was 98.8%.
Example 8
The preparation method of the sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement is as follows:
(1) Firstly, 20g of phosphorus pentachloride is weighed and dissolved in 70g of acetonitrile, the mixture is stirred for 60min under the conditions of the temperature of 30 ℃ and the stirring rotation speed of 500r/min to prepare a solution A, then 30g of 2, 5-dihydroxythiophenol is dissolved in 70g of acetonitrile solvent, and the mixture is stirred for 15min under the conditions of the temperature of 30 ℃ and the stirring rotation speed of 500r/min to prepare a solution B;
(2) Then mixing A and B and placing the mixture into a reactor for microwave reaction for 0.5h under the microwave reaction condition that the microwave power is 800W and the reaction temperature is 120 ℃ to obtain a catalyst precursor;
(3) Washing the catalyst precursor obtained in the step (2) by ethanol, and vacuum drying for 0.5h at the vacuum drying temperature of 120 ℃ to obtain the catalyst 8.
Catalyst evaluation
Adding cyclohexanone oxime and a catalyst 8 into a catalytic reactor, heating to 130 ℃, and reacting for 60min; wherein the mass ratio of the catalyst to the cyclohexanone oxime is 1:1. The cyclohexanone oxime conversion was 99.4% and the caprolactam selectivity was 99.1%.
Example 9
The preparation method of the sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement is as follows:
(1) Firstly, 30g of phosphorus pentachloride is weighed and dissolved in 70g of acetonitrile, and stirred for 60min under the conditions of the temperature of 30 ℃ and the stirring rotation speed of 500r/min to prepare a solution A, and then 30g of dihydroxydiphenyl sulfide is dissolved in 70g of acetonitrile solvent and stirred for 15min under the conditions of the temperature of 30 ℃ and the stirring rotation speed of 500r/min to prepare a solution B;
(2) Then mixing A and B and placing the mixture into a reactor for microwave reaction for 0.5h under the microwave reaction condition that the microwave power is 800W and the reaction temperature is 120 ℃ to obtain a catalyst precursor;
(3) Washing the catalyst precursor obtained in the step (2) by ethanol, and vacuum drying for 0.5h at the vacuum drying temperature of 100 ℃ to obtain 9.
Catalyst evaluation
Adding cyclohexanone oxime and a catalyst 9 into a catalytic reactor, heating to 120 ℃, and reacting for 30min; wherein the mass ratio of the catalyst to the cyclohexanone oxime is 1:1. The cyclohexanone oxime conversion was 99.1% and the caprolactam selectivity was 99.1%.
Example 10
The preparation method of the sulfur-containing and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement is as follows:
(1) Firstly, 30g of phosphorus pentachloride is weighed and dissolved in 70g of carbon tetrachloride, and stirred for 15min under the conditions of 30 ℃ and 500r/min of stirring speed to prepare solution A, and then 30g of solution A is obtained2, 4-dihydroxybenzenesulfonic acidDissolving in 70g of carbon tetrachloride solvent, and stirring at 30deg.C and stirring speed of 500r/min for 15min to obtain solution B;
(2) Then mixing A and B and placing the mixture into a reactor for microwave reaction for 0.5h under the microwave reaction condition that the microwave power is 1200W and the reaction temperature is 120 ℃ to obtain a catalyst precursor;
(3) Washing the catalyst precursor obtained in the step (2) by ethanol, and vacuum drying for 0.5h at the vacuum drying temperature of 100 ℃ to obtain the catalyst 10.
Catalyst evaluation
Adding cyclohexanone oxime and a catalyst 10 into a catalytic reactor, heating to 140 ℃, and reacting for 60min; wherein the mass ratio of the catalyst to the cyclohexanone oxime is 1:1. The cyclohexanone oxime conversion was 98.8% and the caprolactam selectivity was 99.4%.
| Catalyst name | Conversion (%) | Selectivity (%) |
| Catalyst 1 | 100 | 99.0 |
| Catalyst 2 | 99.7 | 99.1 |
| Catalyst 3 | 99.8 | 99.3 |
| Catalyst 4 | 99.7 | 99.5 |
| Catalyst 5 | 99.3 | 99.0 |
| Catalyst 6 | 99.6 | 99.4 |
| Catalyst 7 | 98.9 | 98.8 |
| Catalyst 8 | 99.4 | 99.1 |
| Catalyst 9 | 99.1 | 99.1 |
| Catalyst 10 | 98.8 | 99.4 |
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A process for preparing a sulfur-and phosphorus-based catalyst for preparing caprolactam by liquid-phase Beckmann rearrangement, comprising the steps of:
(1) Under certain reaction conditions, firstly, phosphorus chloride is weighed and dissolved in a solvent to prepare a solution A, and then sulfur-containing organic matters are dissolved in the solvent to prepare a solution B;
(2) Under the microwave reaction condition, mixing the solution A and the solution B, and placing the mixture into a reactor for reaction to prepare a catalyst precursor;
(3) And (3) washing the catalyst precursor obtained in the step (2) by a solvent and drying in vacuum to obtain the liquid-phase Beckmann rearrangement catalyst containing sulfur and phosphorus for preparing caprolactam.
2. The process for preparing sulfur-and phosphorus-based catalysts for the preparation of caprolactam by liquid-phase Beckmann rearrangement according to claim 1, wherein: in the step (1), phosphorus chloride is dissolved in a solvent and placed in an open beaker for magnetic stirring to prepare a solution A, then sulfur-containing organic matters are dissolved in the solvent and placed in the open beaker for magnetic stirring to prepare a solution B, the stirring temperature is 20-40 ℃, the stirring speed is 200-500r/min, the stirring time is 15-60 min, wherein the mass ratio of the phosphorus chloride to the solvent is (1-3): 7, and the mass ratio of the sulfur-containing organic matters to the solvent is (1-3): 7.
3. The process for preparing sulfur-and phosphorus-based catalysts for the preparation of caprolactam by liquid-phase Beckmann rearrangement according to claim 1, wherein: the phosphorus chloride in the step (1) is phosphorus trichloride or phosphorus pentachloride.
4. The process for preparing sulfur-and phosphorus-based catalysts for the preparation of caprolactam by liquid-phase Beckmann rearrangement according to claim 1, wherein: the sulfur-containing organic matters in the step (1) are 4,4 '-dihydroxydiphenyl sulfide, 3' -dihydroxydiphenyl sulfide, thiol-polyethylene glycol-hydroxy, 4-hydroxybenzene thiophenol, 2-hydroxybenzene thiophenol, 3-hydroxybenzene thiophenol, 2, 5-dihydroxybenzene thiophenol, 2-hydroxybenzene sulfonic acid, 2, 4-dihydroxybenzene sulfonic acid or 2, 4-dihydroxybenzene sulfonic acid.
5. The process for preparing sulfur-and phosphorus-based catalysts for the preparation of caprolactam by liquid-phase Beckmann rearrangement according to claim 1, wherein: the solvent in the step (1) is methanol, benzene, acetonitrile, toluene, acetone, ethanol, diethyl ether or carbon tetrachloride.
6. The process for preparing sulfur-and phosphorus-based catalysts for the preparation of caprolactam by liquid-phase Beckmann rearrangement according to claim 1, wherein: the microwave power of the step (2) is 800-1200W, the reaction temperature is 80-150 ℃, the reaction time is 0.5-12h, and the reaction atmosphere is nitrogen.
7. The process for preparing sulfur-and phosphorus-based catalysts for the preparation of caprolactam by liquid-phase Beckmann rearrangement according to claim 1, wherein: and (3) washing the catalyst precursor obtained in the step (2) by using a solvent, then moving to a vacuum drying oven, and drying to obtain the catalyst, wherein the drying temperature is 100-200 ℃ and the drying time is 2-48h, and the solvent is methanol, benzene, acetonitrile, toluene, acetone, ethanol, diethyl ether or carbon tetrachloride.
8. Use of the sulfur-and phosphorus-based catalyst prepared by the preparation process of any one of claims 1 to 7 in a liquid-phase Beckmann rearrangement reaction to produce caprolactam.
9. Use according to claim 8, characterized in that caprolactam is synthesized starting from cyclohexanone oxime with a conversion of 100% and a selectivity of caprolactam of 99.5% under the catalysis of a catalyst comprising sulfur and phosphorus.
10. Use according to claim 9, characterized in that cyclohexanone oxime and a catalyst containing sulphur and phosphorus are added to the catalytic reactor, heated to 80-140 ℃, at a pressure of 0.1KPa-1.0KPa, and for a reaction time of 1-60min; wherein the mass ratio of the sulfur-and phosphorus-based catalyst to cyclohexanone oxime is (1-50): 50.
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