CN117886730A - Preparation method of caprolactam - Google Patents
Preparation method of caprolactam Download PDFInfo
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- CN117886730A CN117886730A CN202410047579.0A CN202410047579A CN117886730A CN 117886730 A CN117886730 A CN 117886730A CN 202410047579 A CN202410047579 A CN 202410047579A CN 117886730 A CN117886730 A CN 117886730A
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 138
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 100
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 67
- 230000005496 eutectics Effects 0.000 claims abstract description 57
- 239000002904 solvent Substances 0.000 claims abstract description 57
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000000284 extract Substances 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 12
- 125000003295 alanine group Chemical group N[C@@H](C)C(=O)* 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 9
- 235000019743 Choline chloride Nutrition 0.000 claims description 9
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical group [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 9
- 229960003178 choline chloride Drugs 0.000 claims description 9
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 9
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 6
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 6
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 5
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 5
- 235000004279 alanine Nutrition 0.000 claims description 5
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical group Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 4
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 4
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 3
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 3
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004474 valine Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 229910021617 Indium monochloride Inorganic materials 0.000 description 22
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 22
- 238000007789 sealing Methods 0.000 description 17
- 238000003760 magnetic stirring Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000370 acceptor Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 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
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PPOHPUOKXMNCCI-UHFFFAOYSA-N n-(3,4,5,6-tetrahydro-2h-azepin-7-yl)hydroxylamine Chemical compound ONC1=NCCCCC1 PPOHPUOKXMNCCI-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07D201/06—Preparation of lactams from or via oximes by Beckmann rearrangement from ketones by simultaneous oxime formation and rearrangement
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/16—Separation or purification
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of caprolactam preparation, in particular to a preparation method of caprolactam, which comprises the steps of putting a hydrogen bond donor, a hydrogen bond acceptor and a third component into a reaction bottle, heating to prepare a eutectic solvent, putting cyclohexanone, hydroxylamine hydrochloride and the eutectic solvent into a reaction kettle, replacing the reaction kettle with nitrogen for several times, stirring materials in the reaction kettle at 10-40 ℃ for reaction for 0.5-3 h, heating to 40-100 ℃ and stirring for reaction for 1-6 h at a constant temperature, cooling the reaction kettle to room temperature after the reaction is finished, extracting with dichloromethane for three times, merging extract liquid, and distilling under reduced pressure to remove extractant, thus obtaining the product caprolactam with the yield of 80.7-85.7%. Therefore, the invention can effectively shorten the reaction flow, reduce the discharge of three wastes, improve the product yield, has mild reaction conditions, easy separation of products, simple and convenient operation, and convenient recovery and repeated use of the eutectic solvent and the organic solvent.
Description
Technical Field
The invention relates to the technical field of caprolactam preparation, in particular to a preparation method of caprolactam.
Background
In recent years, the main development trend of the green strategy is to reduce the three-waste emission and energy consumption by reducing the working procedure operation flow, the main process of producing caprolactam at the present stage is to prepare cyclohexanone oxime by cyclohexanone and hydroxylamine hydrochloride under the action of an alkaline acid binding agent or deacidification agent, and prepare the caprolactam oxime by Beckmann rearrangement reaction by taking concentrated sulfuric acid or fuming sulfuric acid as a catalyst and a reaction medium, but the process is complex in working procedure, serious in equipment corrosion, large in acid binding agent and catalyst consumption and serious in three-waste emission.
The eutectic solvent is generally formed by combining hydrogen bond acceptors and hydrogen bond donors in a certain stoichiometric ratio, has the advantages of good solubility, no toxicity or low toxicity, good thermal stability, biodegradability, simple preparation, easy recovery, repeated use and the like, and has wide application in substitution reaction, esterification reaction, addition reaction, condensation reaction, cyclization reaction, elimination reaction, reduction reaction and other reactions as a catalyst.
Therefore, how to effectively shorten the reaction flow, reduce the three wastes discharge, improve the product yield, and the reaction condition is mild, the product is easy to separate, and the operation is simple and convenient, thus becoming a technical problem needing breakthrough.
In summary, it is clear that the prior art has inconvenience and defects in practical use, so that improvement is needed.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a preparation method of caprolactam, which can effectively shorten the reaction flow, reduce the discharge of three wastes, improve the product yield, has mild reaction conditions, is easy to separate products, is simple and convenient to operate, and can conveniently recover and reuse the eutectic solvent and the organic solvent.
In order to achieve the above object, the present invention provides a method for preparing caprolactam, comprising the steps of:
preparation of the eutectic solvent in step one
And (3) putting the hydrogen bond donor, the hydrogen bond acceptor and the third component into a reaction bottle according to a molar ratio of 3:1:1-1:3:3, heating to 40 ℃, and carrying out heat preservation and stirring reaction for 1-3 hours to prepare the eutectic solvent.
Process for the preparation of biscaprolactam
Adding 0.01-0.1 mol of cyclohexanone, 0.01-0.1 mol of hydroxylamine hydrochloride and 0.01-0.1 mol of eutectic solvent into a reaction kettle, replacing the reaction kettle with nitrogen for a plurality of times, stirring materials in the reaction kettle for reaction for 0.5-3 h at 10-40 ℃, heating to 40-100 ℃ and preserving heat and stirring for reaction for 1-6 h, cooling the reaction kettle to room temperature after the reaction is finished, extracting with dichloromethane for three times, merging extract liquid, decompressing and distilling to remove extractant, thus obtaining the product caprolactam, wherein the yield is 80.7-85.7%.
According to the preparation method of caprolactam, residual extractant dichloromethane is removed from the extracted raffinate phase through reduced pressure distillation, the temperature is raised to 80 ℃ and nitrogen is purged for 2 hours, and the eutectic solvent is obtained.
According to the method for preparing caprolactam of the invention, the hydrogen bond donor is alanine, valine, leucine, proline, tryptophan or phenylalanine.
According to the preparation method of caprolactam, the hydrogen bond acceptor is scandium chloride or zinc chloride or indium chloride.
According to the process for the preparation of caprolactam according to the invention, the third component is choline chloride or urea.
According to the preparation method of caprolactam, the number of times of nitrogen replacement of the reaction kettle is three.
According to the preparation method of caprolactam, the method of cooling the reaction kettle to room temperature is water bath cooling.
The invention aims to provide a preparation method of caprolactam, which comprises the steps of putting a hydrogen bond donor, a hydrogen bond acceptor and a third component into a reaction bottle, heating to prepare a eutectic solvent, putting cyclohexanone, hydroxylamine hydrochloride and the eutectic solvent into a reaction kettle, extracting with methylene dichloride three times after the reaction is finished, combining extract liquor, distilling under reduced pressure to remove extractant, and obtaining the product caprolactam. In summary, the beneficial effects of the invention are as follows: can effectively shorten the reaction flow, reduce the discharge of three wastes, improve the product yield, has mild reaction conditions, easy separation of products, simple and convenient operation, and convenient recovery and repeated use of the eutectic solvent and the organic solvent.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
To verify a process for the preparation of caprolactam according to the invention, the invention provides the following examples:
example 1
Adding indium chloride, choline chloride and alanine into a reaction bottle provided with a stirrer, a thermometer and a reflux condenser according to a molar ratio of 1:1:1, heating to 40 ℃, and carrying out heat preservation, stirring and reaction for 1h to obtain an acid-base amphoteric eutectic solvent [ InCl 3 ][ChCl][Ala]。
0.01mol of cyclohexanone, 0.01mol of hydroxylamine hydrochloride and 0.02mol of eutectic solvent [ InCl 3 ][ChCl][Ala]Putting the mixture into a pressure reaction kettle with a magnetic stirring and thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring the materials in the kettle at 30 ℃ for reaction for 1h, heating to 80 ℃ and preserving heat for stirring for reaction for 3h, after the reaction is finished, rapidly cooling the reaction kettle to room temperature in a water bath, extracting with dichloromethane of equal volume for three times, combining the extracts, and distilling under reduced pressure to remove the extractant, thereby obtaining the caprolactam product with the yield of 85.7%; the residual extractant dichloromethane is removed from the raffinate DES by reduced pressure distillation, the temperature is raised to 80 ℃ and nitrogen is purged for 2 hours, and the eutectic solvent [ InCl ] is obtained 3 ][ChCl][Ala]Can be repeatedly used.
To verify the effect of the eutectic solvent in example 1 above, the present invention provides the following comparative examples, which are convenient for comparison:
comparative example 1
Adding 0.01mol of cyclohexanone, 0.01mol of hydroxylamine hydrochloride and 0.02mol of 70% concentrated sulfuric acid into a pressure reaction kettle provided with a stirrer and a thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring materials in the kettle at 30 ℃ for reaction for 1h, heating to 80 ℃ and stirring for reaction for 3h, after the reaction is finished, rapidly cooling the reaction kettle to room temperature in a water bath, extracting with an equal volume of dichloromethane for three times, merging extract liquid, and distilling under reduced pressure to remove extractant, thus obtaining the product caprolactam, wherein the yield is 25.4%.
Comparative example 2
Adding 0.01mol of cyclohexanone, 0.01mol of hydroxylamine hydrochloride and 0.02mol of indium chloride into a pressure reaction kettle provided with a stirrer and a thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring materials in the kettle at 30 ℃ for reaction for 1h, heating to 80 ℃ and carrying out heat preservation and stirring for reaction for 3h, after the reaction is finished, rapidly cooling the reaction kettle to room temperature in a water bath, extracting with an equal volume of dichloromethane for three times, merging extract liquid, and distilling under reduced pressure to remove extractant, thus obtaining the product caprolactam, wherein the yield is 32.6%.
Comparative example 3
Adding 0.01mol of cyclohexanone, 0.01mol of hydroxylamine hydrochloride and 0.02mol of alanine into a pressure reaction kettle provided with a stirrer and a thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring materials in the kettle at 30 ℃ for reaction for 1h, heating to 80 ℃ and carrying out heat preservation and stirring for reaction for 3h, after the reaction is finished, rapidly cooling the reaction kettle to room temperature in a water bath, extracting with equal volume of dichloromethane for three times, merging extract liquid, and distilling under reduced pressure to remove extractant, thus obtaining the product caprolactam, wherein the yield is 23.6%.
Comparative example 4
Adding 0.01mol of cyclohexanone, 0.01mol of hydroxylamine hydrochloride and 0.02mol of zinc chloride into a pressure reaction kettle provided with a stirrer and a thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring materials in the kettle at 30 ℃ for reaction for 1h, heating to 80 ℃ and carrying out heat preservation and stirring for reaction for 3h, after the reaction is finished, rapidly cooling the reaction kettle to room temperature in a water bath, extracting with an equal volume of dichloromethane for three times, merging extract liquid, and distilling under reduced pressure to remove extractant, thus obtaining the product caprolactam, wherein the yield is 29.1%.
Comparative example 5
Adding 0.01mol of cyclohexanone, 0.01mol of hydroxylamine hydrochloride and 0.02mol of scandium chloride into a pressure reaction kettle provided with a stirrer and a thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring materials in the kettle at 30 ℃ for reaction for 1h, heating to 80 ℃ and carrying out heat preservation and stirring for reaction for 3h, after the reaction is finished, rapidly cooling the reaction kettle to room temperature in a water bath, extracting with an equal volume of dichloromethane for three times, merging extract liquid, and distilling under reduced pressure to remove extractant, thus obtaining the product caprolactam, wherein the yield is 35.9%.
Comparing the data of the comparative example with the data of example 1, the yield of caprolactam product is greatly different, and the effect of improving the yield of caprolactam product after the eutectic solvent participates in the reaction is verified.
Example 2
Adding indium chloride, choline chloride and valine into a reaction bottle provided with a stirrer, a thermometer and a reflux condenser according to a molar ratio of 3:1:1, heating to 40 ℃, and carrying out heat preservation, stirring and reaction for 3 hours to obtain the acid-base amphoteric eutectic solvent [ InCl 3 ] 3 [ChCl][Val]。
0.01mol of cyclohexanone, 0.02mol of hydroxylamine hydrochloride and 0.02mol of eutectic solvent [ InCl 3 ] 3 [ChCl][Val]Putting the mixture into a pressure reaction kettle with a magnetic stirring and thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring the materials in the kettle at 30 ℃ for reaction for 1h, heating to 90 ℃ and preserving heat for stirring for reaction for 2h, after the reaction is finished, rapidly cooling the reaction kettle to room temperature in a water bath, extracting with dichloromethane of equal volume for three times, combining the extracts, and distilling under reduced pressure to remove the extractant, thereby obtaining the caprolactam product with the yield of 83.8%; the residual extractant dichloromethane is removed from the raffinate DES by reduced pressure distillation, the temperature is raised to 80 ℃ and nitrogen is purged for 2 hours, and the eutectic solvent [ InCl ] is obtained 3 ] 3 [ChCl][Val]Can be repeatedly used.
Example 3
Adding indium chloride, choline chloride and tryptophan into a reaction bottle provided with a stirrer, a thermometer and a reflux condenser according to a molar ratio of 2:1:1, heating to 40 ℃, and carrying out heat preservation, stirring and reaction for 2 hours to obtain an acid-base amphoteric eutectic solvent [ InCl 3 ] 2 [ChCl][Trp]。
0.10mol of cyclohexanone, 0.10mol of hydroxylamine hydrochloride and 0.01mol of eutectic solvent [ InCl 3 ] 2 [ChCl][Trp]Putting the mixture into a pressure reaction kettle with a magnetic stirring thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring the materials in the kettle at 40 ℃ for reaction for 0.5h, heating to 100 ℃ and preserving heat for stirring for reaction for 1h, after the reaction is finished, rapidly cooling the reaction kettle to room temperature in a water bath, extracting with dichloromethane of equal volume for three times, merging the extracting solutions, and distilling under reduced pressure to remove the extracting agent to obtain the caprolactam product, wherein the yield is 80.7%; the residual extractant dichloromethane is removed from the raffinate DES by reduced pressure distillation, the temperature is raised to 80 ℃ and nitrogen is purged for 2 hours, and the eutectic solvent [ InCl ] is obtained 3 ] 2 [ChCl][Trp]Can be repeatedly used.
Example 4
Adding indium chloride, choline chloride and leucine into a reaction bottle provided with a stirrer, a thermometer and a reflux condenser according to a molar ratio of 1:3:3, heating to 40 ℃, and carrying out heat preservation, stirring and reaction for 3 hours to obtain the acid-base amphoteric eutectic solvent [ InCl 3 ][ChCl] 3 [Leu] 3 。
0.01mol of cyclohexanone, 0.02mol of hydroxylamine hydrochloride and 0.10mol of eutectic solvent [ InCl 3 ][ChCl] 3 [Leu] 3 Putting the mixture into a pressure reaction kettle with a magnetic stirring and thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring the materials in the kettle at 10 ℃ for reaction for 3 hours, heating to 40 ℃ and preserving heat for stirring for reaction for 6 hours, rapidly cooling the reaction kettle to room temperature in a water bath after the reaction is finished, extracting with dichloromethane with the same volume for three times, combining the extracting solutions, and distilling under reduced pressure to remove the extracting agent to obtain the caprolactam product, wherein the yield is 81.3%; the residual extractant dichloromethane is removed from the raffinate DES by reduced pressure distillation,heating to 80 ℃ and nitrogen purging for 2 hours to obtain the eutectic solvent [ InCl ] 3 ][ChCl] 3 [Leu] 3 Can be repeatedly used.
Example 5
Adding indium chloride, choline chloride and proline into a reaction bottle provided with a stirrer, a thermometer and a reflux condenser according to a molar ratio of 1:2:2, heating to 40 ℃, and carrying out heat preservation, stirring and reaction for 2 hours to obtain an acid-base amphoteric eutectic solvent [ InCl 3 ][ChCl] 2 [Pro] 2 。
0.01mol of cyclohexanone, 0.03mol of hydroxylamine hydrochloride and 0.02mol of eutectic solvent [ InCl 3 ][ChCl] 2 [Pro] 2 Putting the mixture into a pressure reaction kettle with a magnetic stirring and thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring the materials in the kettle at 20 ℃ for 2 hours, heating to 60 ℃ and preserving heat for 4 hours, rapidly cooling the reaction kettle to room temperature in a water bath after the reaction is finished, extracting with equal volume of dichloromethane for three times, combining the extracts, and distilling under reduced pressure to remove the extractant, thereby obtaining the caprolactam product with the yield of 83.6%; the residual extractant dichloromethane is removed from the raffinate DES by reduced pressure distillation, the temperature is raised to 80 ℃ and nitrogen is purged for 2 hours, and the eutectic solvent [ InCl ] is obtained 3 ][ChCl] 2 [Pro] 2 Can be repeatedly used.
Example 6
Adding indium chloride, urea and tryptophan into a reaction bottle provided with a stirrer, a thermometer and a reflux condenser according to a molar ratio of 1:1:1, heating to 40 ℃, and carrying out heat preservation, stirring and reaction for 1h to obtain an acid-base amphoteric eutectic solvent [ InCl 3 ][Urea][Trp]。
0.01mol of cyclohexanone, 0.01mol of hydroxylamine hydrochloride and 0.02mol of eutectic solvent [ InCl 3 ][Urea][Trp]Putting the mixture into a pressure reaction kettle with a magnetic stirring thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring and reacting materials in the kettle at 30 ℃ for 1h, heating to 80 ℃ and preserving heat and stirring for 3h, after the reaction is finished, rapidly cooling the reaction kettle to room temperature in a water bath, extracting with dichloromethane with the same volume for three times, merging extract liquid, and distilling under reduced pressure to remove extractant, thus obtaining the product caprolactam with the yield of 84.2%; the residual extractant dichloromethane is removed from the raffinate DES by reduced pressure distillation, the temperature is raised to 80 ℃ and nitrogen is purged for 2 hours, and the eutectic solvent [ InCl ] is obtained 3 ][Urea][Trp]Can be repeatedly used.
Example 7
Zinc chloride, choline chloride and alanine are put into a reaction bottle provided with a stirrer, a thermometer and a reflux condenser according to the mol ratio of 1:2:1, heated to 40 ℃, and stirred and reacted for 1h under heat preservation, thus obtaining the acid-base amphoteric eutectic solvent [ ZnCl 2 ][ChCl] 2 [Ala]。
0.01mol of cyclohexanone, 0.02mol of hydroxylamine hydrochloride and 0.03mol of eutectic solvent [ ZnCl ] 2 ][ChCl] 2 [Ala]Putting the mixture into a pressure reaction kettle with a magnetic stirring and thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring the materials in the kettle at 30 ℃ for 2 hours, heating to 60 ℃ and preserving heat for 5 hours, rapidly cooling the reaction kettle to room temperature in a water bath after the reaction is finished, extracting with equal volume of dichloromethane for three times, combining the extracts, and distilling under reduced pressure to remove the extractant, thereby obtaining the caprolactam product, wherein the yield is 80.7%; the residual extractant dichloromethane is removed from the raffinate DES by reduced pressure distillation, the temperature is raised to 80 ℃ and nitrogen is purged for 2 hours, and the eutectic solvent [ ZnCl ] is obtained 2 ][ChCl] 2 [Ala]Can be repeatedly used.
Example 8
Zinc chloride, urea and tryptophan are put into a reaction bottle provided with a stirrer, a thermometer and a reflux condenser according to the mol ratio of 1:2:2, heated to 40 ℃, and stirred and reacted for 1h under heat preservation, thus obtaining the acid-base amphoteric eutectic solvent [ ZnCl 2 ][Urea] 2 [Trp] 2 。
0.01mol of cyclohexanone, 0.03mol of hydroxylamine hydrochloride and 0.10mol of eutectic solvent [ ZnCl 2 ][Urea] 2 [Trp] 2 Putting into a pressure reaction kettle with magnetic stirring and thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring and reacting the materials in the kettle at 40 ℃ for 1h, heating to 60 ℃ and keeping the temperature and stirring and reacting for 4h, rapidly cooling the reaction kettle to room temperature in a water bath after the reaction is finished, extracting with equal volume of dichloromethane for three times, combining the extracts, and decompressingDistilling to remove extractant to obtain caprolactam product with yield of 83.5%; the residual extractant dichloromethane is removed from the raffinate DES by reduced pressure distillation, the temperature is raised to 80 ℃ and nitrogen is purged for 2 hours, and the eutectic solvent [ ZnCl ] is obtained 2 ][Urea] 2 [Trp] 2 Can be repeatedly used.
Example 9
Scandium chloride, choline chloride and proline are put into a reaction bottle provided with a stirrer, a thermometer and a reflux condenser according to the mol ratio of 3:1:1, heated to 40 ℃, and stirred for reaction for 3 hours under heat preservation, thus obtaining the acid-base amphoteric eutectic solvent [ ScCl 3 ] 3 [ChCl][Pro]。
0.01mol of cyclohexanone, 0.02mol of hydroxylamine hydrochloride and 0.01mol of eutectic solvent [ ScCl ] 3 ] 3 [ChCl][Pro]Putting the mixture into a pressure reaction kettle with a magnetic stirring and thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring the materials in the kettle at 40 ℃ for reaction for 1h, heating to 60 ℃ and preserving heat for stirring for reaction for 4h, after the reaction is finished, rapidly cooling the reaction kettle to room temperature in a water bath, extracting with dichloromethane of equal volume for three times, combining the extracts, and distilling under reduced pressure to remove the extractant, thereby obtaining the caprolactam product with the yield of 85.4%; the residual extractant dichloromethane is removed from the raffinate DES by reduced pressure distillation, the temperature is raised to 80 ℃ and nitrogen is purged for 2 hours, and the eutectic solvent [ ScCl ] is obtained 3 ] 3 [ChCl][Pro]Can be repeatedly used.
Example 10
Scandium chloride, urea and phenylalanine are put into a reaction bottle provided with a stirrer, a thermometer and a reflux condenser according to the mol ratio of 1:1:1, heated to 40 ℃, and stirred and reacted for 1h under heat preservation, thus obtaining the acid-base amphoteric eutectic solvent [ ScCl 3 ][Urea][Phe]。
0.01mol of cyclohexanone, 0.03mol of hydroxylamine hydrochloride and 0.10mol of eutectic solvent [ ScCl ] 3 ][Urea][Phe]Putting into a pressure reaction kettle with magnetic stirring and thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring and reacting the materials in the kettle at 30deg.C for 2h, heating to 100deg.C, keeping the temperature and stirring and reacting for 1h, rapidly cooling the reaction kettle to room temperature in water bath after the reaction is finished, and using equal volumeExtracting with dichloromethane for three times, mixing the extractive solutions, and distilling under reduced pressure to remove extractant to obtain caprolactam product with yield of 80.8%; the residual extractant dichloromethane is removed from the raffinate DES by reduced pressure distillation, the temperature is raised to 80 ℃ and nitrogen is purged for 2 hours, and the eutectic solvent [ ScCl ] is obtained 3 ][Urea][Phe]Can be repeatedly used.
From the above examples and comparative examples, the eutectic solvent can provide the necessary acidic and alkaline environments for the reaction, shortening the flow path and simplifying the process.
Example 11
The eutectic solvent [ InCl ] obtained in example 1 was recovered 3 ][ChCl][Ala]Adding 0.01mol of cyclohexanone and 0.01mol of hydroxylamine hydrochloride into a pressure reaction kettle with a magnetic stirring thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring and reacting the materials in the kettle at 30 ℃ for 1h, heating to 80 ℃ and preserving heat and stirring for 3h, rapidly cooling the reaction kettle to room temperature in a water bath after the reaction is finished, extracting with equal volume of dichloromethane for three times, combining the extracting solution, distilling under reduced pressure to remove the extracting agent, thus obtaining the product caprolactam, the yield is 84.5%, and recovering the obtained eutectic solvent [ InCl ] for the example 3 ][ChCl][Ala]Repeated use for 10 times under the same experimental conditions, and the obtained caprolactam yields are all more than 81.6%.
Example 12
Example 2 recovery of the resulting eutectic solvent [ InCl ] 3 ] 3 [ChCl][Val]Adding 0.01mol of cyclohexanone and 0.02mol of hydroxylamine hydrochloride into a pressure reaction kettle with a magnetic stirring thermometer, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, stirring materials in the kettle at 30 ℃ for reaction for 1h, heating to 90 ℃ and stirring for reaction for 2h, after the reaction is finished, rapidly cooling the reaction kettle to room temperature in a water bath, extracting with equal volume of dichloromethane for three times, merging extract liquid, and distilling under reduced pressure to remove extractant, thereby obtaining a product caprolactam with the yield of 82.7%; and recovering the resulting eutectic solvent [ InCl ] for this example 3 ] 3 [ChCl][Val]Repeated use for 10 times under the same experimental conditions, and the obtained caprolactam yields are all more than 80.2%.
From the above examples, the eutectic solvent and the product are easily separated, and the operation is simple.
The invention provides a preparation method of caprolactam, which comprises the steps of putting a hydrogen bond donor, a hydrogen bond acceptor and a third component into a reaction bottle, heating to prepare a eutectic solvent, putting cyclohexanone, hydroxylamine hydrochloride and the eutectic solvent into a reaction kettle, extracting with methylene dichloride three times after the reaction is finished, merging extract liquid, and distilling under reduced pressure to remove extractant, thus obtaining the product caprolactam. In summary, the beneficial effects of the invention are as follows: can effectively shorten the reaction flow, reduce the discharge of three wastes, improve the product yield, has mild reaction conditions, easy separation of products, simple and convenient operation, and convenient recovery and repeated use of the eutectic solvent and the organic solvent.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A process for the preparation of caprolactam comprising the steps of:
preparation of the eutectic solvent in step one
Putting a hydrogen bond donor, a hydrogen bond acceptor and a third component into a reaction bottle according to a molar ratio of 3:1:1-1:3:3, heating to 40 ℃, and carrying out heat preservation and stirring reaction for 1-3 hours to prepare a eutectic solvent;
process for the preparation of biscaprolactam
Adding 0.01-0.1 mol of cyclohexanone, 0.01-0.1 mol of hydroxylamine hydrochloride and 0.01-0.1 mol of eutectic solvent into a reaction kettle, replacing the reaction kettle with nitrogen for a plurality of times, stirring materials in the reaction kettle for reaction for 0.5-3 h at 10-40 ℃, heating to 40-100 ℃ and preserving heat and stirring for reaction for 1-6 h, cooling the reaction kettle to room temperature after the reaction is finished, extracting with dichloromethane for three times, merging extract liquid, decompressing and distilling to remove extractant, thus obtaining the product caprolactam, wherein the yield is 80.7-85.7%.
2. The method for preparing caprolactam according to claim 1, wherein the residual extractant dichloromethane is removed from the extracted raffinate phase by reduced pressure distillation, the temperature is raised to 80 ℃ and nitrogen is purged for 2 hours, and the eutectic solvent is obtained.
3. The method for producing caprolactam according to claim 1, wherein the hydrogen bond donor is alanine, valine, leucine, proline, tryptophan or phenylalanine.
4. The method for preparing caprolactam according to claim 1, wherein the hydrogen bond acceptor is scandium chloride or zinc chloride or indium chloride.
5. The method for producing caprolactam according to claim 1, wherein the third component is choline chloride or urea.
6. The method for producing caprolactam according to claim 1, wherein the number of times of nitrogen substitution reaction in the autoclave is three.
7. The method for preparing caprolactam according to claim 1, wherein the method of cooling the reaction kettle to room temperature is water bath cooling.
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