CN115608416A - Preparation method and application of caprolactam catalyst produced by liquid-phase Beckmann rearrangement - Google Patents
Preparation method and application of caprolactam catalyst produced by liquid-phase Beckmann rearrangement Download PDFInfo
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- CN115608416A CN115608416A CN202211340724.1A CN202211340724A CN115608416A CN 115608416 A CN115608416 A CN 115608416A CN 202211340724 A CN202211340724 A CN 202211340724A CN 115608416 A CN115608416 A CN 115608416A
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- liquid
- caprolactam
- beckmann rearrangement
- catalyst
- sulfonic acid
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000007791 liquid phase Substances 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000006237 Beckmann rearrangement reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000003756 stirring Methods 0.000 claims abstract description 59
- 238000005303 weighing Methods 0.000 claims abstract description 39
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 phosphine sulfonic acid compound Chemical class 0.000 claims abstract description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000012263 liquid product Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- JHNLZOVBAQWGQU-UHFFFAOYSA-N 380814_sial Chemical compound CS(O)(=O)=O.O=P(=O)OP(=O)=O JHNLZOVBAQWGQU-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- WVPKAWVFTPWPDB-UHFFFAOYSA-N dichlorophosphinic acid Chemical compound OP(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-N 0.000 claims description 4
- DSQCNXSPLHDLED-UHFFFAOYSA-M methanesulfonate;tetrabutylphosphanium Chemical compound CS([O-])(=O)=O.CCCC[P+](CCCC)(CCCC)CCCC DSQCNXSPLHDLED-UHFFFAOYSA-M 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229940032950 ferric sulfate Drugs 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 54
- 239000000047 product Substances 0.000 description 21
- 238000004817 gas chromatography Methods 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 18
- 239000002608 ionic liquid Substances 0.000 description 10
- 229910000365 copper sulfate Inorganic materials 0.000 description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 230000008707 rearrangement Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000011831 acidic ionic liquid Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- HYBIIGFUKKOJJM-UHFFFAOYSA-N cyclohexanone;hydroxylamine Chemical compound ON.O=C1CCCCC1 HYBIIGFUKKOJJM-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0264—Phosphorus acid amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
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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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Abstract
The invention belongs to the technical field of caprolactam production, and discloses a preparation method of a caprolactam catalyst produced by liquid-phase Beckmann rearrangement, which comprises the following steps: weighing an organic solvent, putting the organic solvent into a flask, adding a metal salt and an organic phosphine sulfonic acid compound, mixing at 10-50 ℃, and simultaneously carrying out microwave stirring at the rotation speed of 15-800r/min for 1-120min to obtain a liquid product, namely a caprolactam catalyst produced by liquid-phase Beckmann rearrangement. The invention takes metal salt and organic phosphine sulfonic acid compounds as raw materials to prepare the catalyst for producing caprolactam through Beckmann rearrangement, which can effectively improve the catalytic activity in the liquid-phase Beckmann rearrangement reaction and improve the conversion rate of cyclohexanone oxime and the selectivity of caprolactam.
Description
Technical Field
The invention belongs to the technical field of caprolactam production, and particularly relates to a preparation method and application of a caprolactam catalyst produced by liquid-phase Beckmann rearrangement.
Background
Caprolactam is an important organic chemical raw material, which is mainly used for producing polyamide-6 fibers, polyamide resins and films through polymerization. The caprolactam production process mainly comprises the following steps: cyclohexanone-hydroxylamine process, toluene process, cyclohexane photonitrosation process, and cyclohexanone ammoximation process. The cyclohexanone ammoximation method (cyclohexanone oxime liquid phase Beckmann rearrangement) is the mainstream process for producing caprolactam at present due to the advantages of simple process flow, mild reaction conditions, high reactant conversion rate, high selectivity and the like. However, the concentrated sulfuric acid catalyst has strong corrosivity, and a large amount of low-value ammonium sulfate products are by-produced in the catalytic reaction process, which is a technical problem that the process is urgently needed to overcome. Therefore, the development of the green catalysis research for producing caprolactam by rearrangement without ammonium sulfate has important significance.
The ionic liquid as a novel catalyst has wide liquid temperature range, good solubility, can be separated and recycled, and has the function ofThe double functions of the medium and the catalyst and the like draw great attention in the field of cyclohexanone oxime liquid phase Beckmann rearrangement catalysis. Guo Qiang et al found that the chloroaluminate ionic liquid can catalyze beckmann rearrangement of cyclohexanone oxime to generate caprolactam, and the maximum values of the conversion rate of cyclohexanone oxime and the selectivity of caprolactam are 99.7% and 98.0%, respectively. Jinxinlei and the like are designed to synthesize the silica gel bonded imidazole type acidic ionic liquid catalyst, and the catalyst is used for catalyzing liquid phase rearrangement of cyclohexanone oxime to synthesize caprolactam. After the catalyst is used for five times, the caprolactam yield is still maintained to be more than 85 percent. Zhaojiangyu through acidic ionic liquid and ZnCl 2 The catalyst system can realize the liquid phase rearrangement of the catalytic cyclohexanone-oxime to prepare caprolactam, wherein the conversion rate of the cyclohexanone-oxime is 100 percent, and the selectivity of the caprolactam is 94.9 percent. Although the ionic liquid catalyst shows excellent cyclohexanone oxime conversion rate (100%) in the reaction of catalyzing the liquid-phase Beckmann rearrangement of cyclohexanone oxime to prepare caprolactam, the caprolactam selectivity needs to be further improved. In conclusion, the ionic liquid shows excellent cyclohexanone conversion rate and caprolactam selectivity in catalyzing the liquid-phase rearrangement reaction of cyclohexanone-oxime. Compared with other catalysts (molecular sieve and high molecular resin), the ionic liquid catalyst has two advantages of low reaction temperature and short reaction time. However, the ionic liquid catalyst has the following technical problems to be solved: (1) The liquid phase rearrangement mechanism of cyclohexanone oxime catalyzed by the ionic liquid catalyst is not clear; (2) The separation process of the ionic liquid catalyst and the liquid phase product is complex; (3) poor ionic liquid catalyst recoverability; (4) The raw material part synthesized by the ionic liquid catalyst is not environment-friendly.
Therefore, in the process for producing caprolactam by cyclohexanone oxime liquid phase Beckmann rearrangement, a new catalyst needs to be developed so as to obtain good reaction conversion rate and selectivity.
Disclosure of Invention
The invention aims to provide a preparation method and application of a caprolactam catalyst produced by liquid-phase Beckmann rearrangement, wherein the catalyst can effectively improve the catalytic activity in the liquid-phase Beckmann rearrangement reaction and improve the cyclohexanone oxime conversion rate and caprolactam selectivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a caprolactam catalyst produced by liquid-phase Beckmann rearrangement, which comprises the following steps: weighing an organic solvent, putting the organic solvent into a flask, adding a metal salt and an organic phosphine sulfonic acid compound, mixing at 10-50 ℃, and simultaneously carrying out microwave stirring at the rotation speed of 15-800r/min for 1-120min to obtain a liquid product, namely a caprolactam catalyst produced by liquid-phase Beckmann rearrangement.
Preferably, the mass ratio of the organic solvent to the organic phosphonic sulfonic acid compound is 1-100, and the mass ratio of the metal salt to the organic phosphonic acid compound is 1-100.
Preferably, the organic solvent is selected from one of ethanol, methanol, benzene, toluene, dimethyl sulfoxide, cyclohexane, isopropanol, tert-butanol and n-butylamine.
Preferably, the metal salt is selected from stannous chloride, stannic sulfate, cupric chloride, zinc sulfate and ferric sulfate.
Preferably, the organic phosphine sulfonic acid compound is one of organic phosphorus sulfonic acid, N-benzene sulfonamide dichlorophosphoric acid, tetrabutyl phosphorus methanesulfonate and phosphorus pentoxide methane sulfonic acid.
Preferably, the microwave power is 500-2000 w.
The invention also provides application of the liquid-phase Beckmann rearrangement caprolactam production catalyst prepared by the preparation method in caprolactam production.
Preferably, the process for producing caprolactam comprises: weighing a catalyst and cyclohexanone oxime, mixing, putting into a reactor, reacting for 0.5-100 min at 50-130 ℃, and performing centrifugal separation to obtain a liquid-phase mixed solution.
Preferably, the mass ratio of the catalyst to the cyclohexanone oxime is 1-100.
Compared with the prior art, the invention has the beneficial effects that:
the catalyst for producing caprolactam through liquid-phase Beckmann rearrangement takes metal salt and organic phosphonic and sulfonic acid compounds as raw materials, and researches on the synergistic effect of the organic phosphonic and sulfonic acid compounds and metal ions systematically, so that the catalytic activity in the liquid-phase Beckmann rearrangement reaction can be effectively improved, and the cyclohexanone oxime conversion rate and caprolactam selectivity can be improved; meanwhile, the catalyst of the invention is adopted to prepare caprolactam, thus overcoming the defects (long reaction time and high reaction temperature) of the caprolactam prepared by Beckmann rearrangement reaction of the solid acid catalyst at present, and leading the caprolactam prepared by no ammonium sulfate rearrangement to have a new path.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The test methods in the following examples are conventional methods unless otherwise specified.
Example 1
Weighing 10g of ethanol, putting the ethanol into a flask, adding 4g of copper sulfate and 20g of organic phosphine sulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 1000w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain a liquid A1.
20g of liquid A1 and 10g of cyclohexanone oxime are weighed and placed in a reactor to react for 30min at 100 ℃, the obtained product is subjected to centrifugal separation, and a liquid-phase mixed solution is taken to perform gas chromatography analysis, and the results are shown in Table 1.
Example 2
Weighing 10g of ethanol, putting the ethanol into a flask, adding 4g of zinc sulfate and 20g of organic phosphine sulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 1000w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain liquid A2.
20g of liquid A2 and 10g of cyclohexanone oxime are weighed and put into a reactor to react for 30min at 100 ℃, the obtained product is centrifugally separated, and a liquid-phase mixed solution is taken to carry out gas chromatography analysis, and the result is shown in Table 1.
Example 3
Weighing 10g of ethanol, putting the ethanol into a flask, adding 4g of ferric sulfate and 20g of organic phosphine sulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 1000w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain liquid A3.
Weighing 20g of liquid A3 and 10g of cyclohexanone oxime, putting the liquid A3 and the cyclohexanone oxime into a reactor, reacting for 30min at 100 ℃, centrifugally separating the obtained product, and taking a liquid-phase mixed solution for gas chromatography analysis, wherein the results are shown in Table 1.
Example 4
Weighing 10g of ethanol, putting the ethanol into a flask, adding 4g of copper nitrate and 20g of organic phosphonic sulfonic acid, and starting and stirring the mixture at room temperature by using microwaves at the power of 1000w, at the stirring speed of 200r/min and for 20min to obtain liquid B1.
Weighing 20g of liquid B1 and 10g of cyclohexanone oxime, putting the liquid B1 and the cyclohexanone oxime into a reactor, reacting for 30min at 100 ℃, performing centrifugal separation on the obtained product, and performing gas chromatography analysis on the liquid-phase mixed solution, wherein the results are shown in Table 1.
Example 5
Weighing 10g of ethanol, putting the ethanol into a flask, adding 4g of copper chloride and 20g of organic phosphine sulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 1000w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain liquid B2.
Weighing 20g of liquid B2 and 10g of cyclohexanone oxime, putting the liquid B2 and the cyclohexanone oxime into a reactor, reacting for 30min at 100 ℃, performing centrifugal separation on the obtained product, and taking a liquid-phase mixed solution for gas chromatography analysis, wherein the results are shown in Table 1.
Example 6
Weighing 10g of ethanol, putting the ethanol into a flask, adding 4g of copper phosphate and 20g of organic phosphine sulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 1000w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain liquid B3.
Weighing 20g of liquid B3 and 10g of cyclohexanone oxime, putting the liquid B3 and the cyclohexanone oxime into a reactor, reacting for 30min at 100 ℃, performing centrifugal separation on the obtained product, and taking a liquid-phase mixed solution for gas chromatography analysis, wherein the results are shown in Table 1.
Example 7
Weighing 10g of ethanol, putting the ethanol into a flask, adding 4g of copper sulfate and 20g of phosphorus pentoxide methanesulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 1000w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain a liquid C1.
Weighing 20g of liquid C1 and 5g of cyclohexanone oxime, putting the liquid C1 and the cyclohexanone oxime into a reactor, reacting for 30min at 100 ℃, performing centrifugal separation on the obtained product, and taking a liquid-phase mixed solution for gas chromatography analysis, wherein the results are shown in Table 1.
Example 8
Weighing 10g of methanol, putting the methanol into a flask, adding 4g of copper sulfate and 20g of phosphorus pentoxide methanesulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 1000w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain a liquid C2.
Weighing 20g of liquid C2 and 5g of cyclohexanone oxime, putting the liquid C and the cyclohexanone oxime into a reactor, reacting for 30min at 100 ℃, performing centrifugal separation on the obtained product, and taking a liquid-phase mixed solution for gas chromatography analysis, wherein the results are shown in Table 1.
Example 9
Weighing 10g of dimethyl sulfoxide, putting the dimethyl sulfoxide into a flask, adding 4g of copper sulfate and 20g of phosphorus pentoxide methanesulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 1000w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain a liquid C3.
Weighing 20g of liquid C3 and 5g of cyclohexanone oxime, putting the liquid C3 and the cyclohexanone oxime into a reactor, reacting for 30min at 100 ℃, performing centrifugal separation on the obtained product, and taking a liquid-phase mixed solution for gas chromatography analysis, wherein the results are shown in Table 1.
Example 10
Weighing 10g of toluene, putting the toluene into a flask, adding 4g of copper sulfate and 20g of phosphorus pentoxide methanesulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 1000w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain liquid C4.
Weighing 20g of liquid C4 and 5g of cyclohexanone oxime, putting the liquid C4 and the cyclohexanone oxime into a reactor, reacting for 30min at 100 ℃, performing centrifugal separation on the obtained product, and taking a liquid-phase mixed solution for gas chromatography analysis, wherein the results are shown in Table 1.
Example 11
Weighing 10g of ethanol, putting the ethanol into a flask, adding 4g of copper sulfate and 20g of phosphorus pentoxide methanesulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 500w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain a liquid D1.
20g of liquid D1 and 5g of cyclohexanone oxime were weighed and placed in a reactor to react at 100 ℃ for 30min, the obtained product was subjected to centrifugal separation, and a liquid-phase mixed solution was taken to perform gas chromatography, and the results are shown in Table 1.
Example 12
Weighing 10g of ethanol, putting the ethanol into a flask, adding 4g of copper sulfate and 20g of phosphorus pentoxide methanesulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 1500w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain a liquid D2.
Weighing 20g of liquid D2 and 5g of cyclohexanone oxime, putting the liquid D2 and the cyclohexanone oxime into a reactor, reacting for 30min at 100 ℃, performing centrifugal separation on the obtained product, and taking a liquid-phase mixed solution for gas chromatography analysis, wherein the results are shown in Table 1.
Example 13
Weighing 10g of ethanol, putting the ethanol into a flask, adding 4g of copper sulfate and 20g of phosphorus pentoxide methanesulfonic acid, and starting microwave stirring at room temperature, wherein the microwave power is 2000w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain a liquid D3.
Weighing 20g of liquid D3 and 5g of cyclohexanone oxime, putting the liquid D3 and the cyclohexanone oxime into a reactor, reacting for 30min at 100 ℃, performing centrifugal separation on the obtained product, and taking a liquid-phase mixed solution for gas chromatography analysis, wherein the results are shown in Table 1.
Example 14
Weighing 12g of methanol, putting the methanol into a flask, adding 6g of zinc sulfate and 18g of N-benzenesulfonamide dichlorophosphoric acid, starting microwave stirring at room temperature, wherein the microwave power is 1200w, the stirring speed is 800r/min, and the stirring time is 50min, so as to obtain a liquid E1.
Weighing 10g of liquid E1 and 20g of cyclohexanone oxime, putting the liquid E1 and the cyclohexanone oxime into a reactor, reacting for 60min at 120 ℃, performing centrifugal separation on the obtained product, and performing gas chromatography analysis on the liquid-phase mixed solution, wherein the results are shown in Table 1.
Example 15
Weighing 15g of ethanol, putting the ethanol into a flask, adding 6g of tin sulfate and 30g of tetrabutyl phosphonium methanesulfonate, starting microwave stirring at room temperature, wherein the microwave power is 500w, the stirring speed is 1000r/min, and the stirring time is 60min, so as to obtain a liquid F1.
Weighing 20g of liquid F1 and 5g of cyclohexanone oxime, putting the liquid F1 and the cyclohexanone oxime into a reactor, reacting for 90min at 110 ℃, performing centrifugal separation on the obtained product, and performing gas chromatography analysis on the liquid-phase mixed solution, wherein the results are shown in Table 1.
Comparative example 1
Weighing 10g of ethanol, putting the ethanol into a flask, adding 20g of organic phosphine sulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 1000w, the stirring speed is 200r/min, and the stirring time is 20min, so as to obtain liquid A4.
20g of liquid A4 and 10g of cyclohexanone oxime are weighed and put into a reactor to react for 30min at 100 ℃, the obtained product is centrifugally separated, and a liquid-phase mixed solution is taken to carry out gas chromatography analysis, and the result is shown in Table 1.
Comparative example 2
Weighing 15g of benzene, putting the benzene into a flask, adding 22g of phosphorus pentoxide methanesulfonic acid, starting microwave stirring at room temperature, wherein the microwave power is 1500w, the stirring speed is 200r/min, and the stirring time is 40min, so as to obtain a liquid D4.
Weighing 25g of liquid D4 and 5g of cyclohexanone oxime, putting the liquid D4 and the cyclohexanone oxime into a reactor, reacting for 50min at 100 ℃, performing centrifugal separation on the obtained product, and taking a liquid-phase mixed solution for gas chromatography analysis, wherein the results are shown in Table 1.
Comparative example 3
Weighing 12g of methanol, putting the methanol into a flask, adding 18g of N-benzenesulfonamide dichlorophosphoric acid, starting microwave stirring at room temperature, wherein the microwave power is 1200w, the stirring speed is 800r/min, and the stirring time is 50min, so as to obtain a liquid E2.
Weighing 10g of liquid E2 and 20g of cyclohexanone oxime, putting the liquid E2 and the cyclohexanone oxime into a reactor, reacting for 60min at 120 ℃, performing centrifugal separation on the obtained product, and performing gas chromatography analysis on the liquid-phase mixed solution, wherein the results are shown in Table 1.
Comparative example 4
Weighing 15g of ethanol, putting the ethanol into a flask, adding 30g of tetrabutyl phosphonium methanesulfonate, and starting microwave stirring at room temperature, wherein the microwave power is 500w, the stirring speed is 1000r/min, and the stirring time is 60min, so as to obtain a liquid F2.
Weighing 20g of liquid F2 and 5g of cyclohexanone oxime, putting the liquid F2 and the cyclohexanone oxime into a reactor, reacting for 90min at 110 ℃, performing centrifugal separation on the obtained product, and performing gas chromatography analysis on the liquid-phase mixed solution, wherein the results are shown in Table 1.
TABLE 1 main parameters and results of examples 1 to 15 and comparative examples 1 to 4
As can be seen from Table 1, the catalyst prepared by combining the metal salt and the organic phosphonic sulfonic acid compound can significantly improve the conversion rate of cyclohexanone oxime and the selectivity of caprolactam when caprolactam is prepared by liquid phase rearrangement, wherein the catalyst prepared by copper sulfate and phosphorus pentoxide methane sulfonic acid has the best effect when caprolactam is prepared.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are merely illustrative and not restrictive, and it should be understood that other embodiments may be easily made by those skilled in the art by replacing or changing the technical contents disclosed in the specification, and therefore, all changes and modifications that are made on the principle of the present invention should be included in the scope of the claims of the present invention.
Claims (9)
1. The preparation method of the caprolactam catalyst produced by liquid-phase Beckmann rearrangement is characterized by comprising the following steps: weighing an organic solvent, putting the organic solvent into a flask, adding a metal salt and an organic phosphonic sulfonic acid compound, mixing at 10 to 50 ℃, and simultaneously stirring for 1 to 120min under the rotation speed of 15 to 800r/min by microwave to obtain a liquid product, namely a caprolactam catalyst produced by liquid-phase Beckmann rearrangement.
2. The preparation method according to claim 1, wherein the mass ratio of the organic solvent to the organic phosphonic sulfonic acid compound is 1 to 100, and the mass ratio of the metal salt to the organic phosphonic sulfonic acid compound is 1 to 100.
3. The method according to claim 1, wherein the organic solvent is one selected from ethanol, methanol, benzene, toluene, dimethyl sulfoxide, cyclohexane, isopropanol, tert-butanol, and n-butylamine.
4. The method of claim 1, wherein the metal salt is selected from stannous chloride, stannic sulfate, cupric chloride, zinc sulfate, and ferric sulfate.
5. The preparation method according to claim 1, wherein the organic phosphine sulfonic acid compound is one of organic phosphorus sulfonic acid, N-benzene sulfonamide dichlorophosphoric acid, tetrabutyl phosphorus methanesulfonate, and phosphorus pentoxide methanesulfonic acid.
6. The preparation method according to claim 1, wherein the microwave power is 500 to 2000w.
7. Use of a liquid phase Beckmann rearrangement caprolactam production catalyst prepared by the preparation method according to any one of claims 1 to 6 for producing caprolactam.
8. Use according to claim 7, characterized in that the process for producing caprolactam is as follows: weighing a catalyst and cyclohexanone oxime, mixing, putting into a reactor, reacting for 0.5-100min at 50-130 ℃, and performing centrifugal separation to obtain a liquid phase mixed solution.
9. The use according to claim 8, wherein the mass ratio of the catalyst to the cyclohexanone oxime is 1 to 100.
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