CN108543548B - Preparation method of resin catalyst for preparing caprolactam through liquid phase Beckmann rearrangement - Google Patents
Preparation method of resin catalyst for preparing caprolactam through liquid phase Beckmann rearrangement Download PDFInfo
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- CN108543548B CN108543548B CN201810349872.7A CN201810349872A CN108543548B CN 108543548 B CN108543548 B CN 108543548B CN 201810349872 A CN201810349872 A CN 201810349872A CN 108543548 B CN108543548 B CN 108543548B
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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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
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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
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- 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
Abstract
The invention provides a preparation method of a resin catalyst for preparing caprolactam through liquid-phase Beckmann rearrangement, which comprises the following steps of 1) weighing tetrapropyl ammonium hydroxide aqueous solution, putting the tetrapropyl ammonium hydroxide aqueous solution into a container, adding an amine compound, starting stirring at room temperature, adding a silicon-containing compound into the tetrapropyl ammonium hydroxide aqueous solution, and continuing stirring to obtain a mixed solution; 2) weighing the mixed solution prepared in the step 1), putting the mixed solution into a reaction kettle, adding strong acid resin, reacting for 4-12h at 80-120 ℃, washing the obtained resin to be neutral by deionized water after the reaction is finished, and drying at 80-150 ℃ to obtain the silicon-containing composite resin catalyst. The invention is described. The preparation method of the invention obviously improves the yield of caprolactam prepared by liquid phase Beckmann rearrangement and reduces the cost by compounding the resin catalyst and silicon.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a resin catalyst for preparing caprolactam through liquid-phase Beckmann rearrangement.
Background
Caprolactam is an important chemical raw material and a monomer for preparing nylon 6 and engineering plastics. The current process route for preparing caprolactam mainly comprises two kinds of liquid-phase Beckmann rearrangement and gas-phase Beckmann rearrangement. At present, in industrial production, a liquid phase rearrangement process is mainly catalyzed by sulfuric acid. The process comprises the steps of carrying out Beckmann rearrangement reaction on cyclohexanone oxime under the action of concentrated sulfuric acid or fuming sulfuric acid at a certain temperature, and then neutralizing the acidity of a reaction system by ammonia to generate caprolactam. The process technology is mature, the reaction conditions are mild, the conversion rate of raw materials and the selectivity of products are high, but the process also has a plurality of defects. Firstly, concentrated sulfuric acid can corrode equipment, harmful substances can be discharged in the production process, and the development concept of green environmental protection is not met; meanwhile, a large amount of cheap ammonium sulfate is produced as a byproduct, and the economic benefit is poor. Therefore, a new caprolactam production process for the purpose of improving economic and environmental benefits has become an important direction of recent research. Although the use of sulfuric acid and the production of ammonium sulfate have been reduced by changing the reactor form and process conditions since the eighties of the last century, the problems due to the use of sulfuric acid have not been fundamentally solved.
In order to solve the above problems, a gas phase beckmann rearrangement process using a solid acid as a catalyst has been studied. The process can completely avoid the use of sulfuric acid. However, the gas phase Beckmann rearrangement reaction temperature is high, generally about 360 ℃, and cyclohexanone oxime is easy to coke during being vaporized and heated to the temperature, so that the industrialization process of the technology is limited.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a resin catalyst for preparing caprolactam through liquid-phase Beckmann rearrangement, so as to overcome the defects of the prior art, and the prepared catalyst is used for the reaction of preparing caprolactam through liquid-phase Beckmann rearrangement, so that a good effect is obtained;
the invention overcomes the defect of producing a large amount of ammonium sulfate as a byproduct in the process of preparing caprolactam by the existing sulfuric acid method liquid phase Beckmann rearrangement, and provides a low-cost liquid phase Beckmann rearrangement caprolactam preparation method without producing a low-value ammonium sulfate as a byproduct.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a resin catalyst for preparing caprolactam by liquid phase Beckmann rearrangement comprises the following steps,
1) weighing tetrapropyl ammonium hydroxide aqueous solution, putting the tetrapropyl ammonium hydroxide aqueous solution into a container, adding an amine compound, starting stirring at room temperature, adding a silicon-containing compound into the tetrapropyl ammonium hydroxide aqueous solution, and continuously stirring to obtain a mixed solution;
2) weighing the mixed solution prepared in the step 1), putting the mixed solution into a reaction kettle, adding strong acid resin, reacting for 4-12h at 80-120 ℃, washing the obtained resin to be neutral by deionized water after the reaction is finished, and drying at 80-150 ℃ to obtain the silicon-containing composite resin catalyst.
Preferably, in the step 1), the molar ratio of tetrapropylammonium hydroxide, the amine compound and the silicon-containing compound in the mixed solution is 1: (0.01-0.2): (2-5) mixing; preferably, in step 1), the concentration of the aqueous tetrapropylammonium hydroxide solution is 5 to 20 wt.%.
Preferably, in the step 1), the mixed solution is prepared by stirring at 18-35 ℃, and the stirring time is 1-4 hours.
Preferably, in the step 1), the amine compound is one of triethylamine, n-butylamine, and tri-n-propylamine; the silicon-containing compound is one of silicon tetrachloride, silica sol and ethyl orthosilicate.
Preferably, in step 2), the strong acid type resin is a strong acid type ion exchange resin, preferably, one of 001 × 7, D61, D62, D72, Amberlyst15 and Amberlyst 36.
Preferably, in the step 2), the mass ratio of the mixed solution prepared in the step 1) and the strong acid type resin added into the reaction kettle is (6-10): (1-4).
Preferably, in step 2), the reaction is carried out in a hydrothermal reaction kettle containing a tetrafluoroethylene lining.
The invention also provides application of the composite resin catalyst obtained by the preparation method in preparing caprolactam through liquid-phase Beckmann rearrangement.
The invention also provides a method for preparing caprolactam, which comprises the steps of adding cyclohexanone oxime and dimethyl sulfoxide into the composite resin catalyst prepared by the preparation method, wherein the mass ratio of the composite resin catalyst to the cyclohexanone oxime to the dimethyl sulfoxide is (0.6-1.6): (2-6): (35-45), preferably, 1:4: 40; stirring and reacting for 2-6 h at 120-140 ℃.
How to prepare the strong acid type resin catalyst does not fall within the scope of the claims of the present invention. The invention relates to a composite modification category of a resin catalyst. More specifically, the conventional method for preparing caprolactam by directly performing liquid phase beckmann rearrangement by using a resin catalyst has low yield, which leads to high cost. The invention improves the performance of the resin catalyst by compounding the catalyst with silicon, obviously improves the yield of caprolactam and reduces the cost.
Compared with the prior art, the preparation method of the resin catalyst for preparing caprolactam by liquid phase Beckmann rearrangement has the following advantages:
(1) the preparation method of the invention obviously improves the yield of caprolactam prepared by liquid phase Beckmann rearrangement and reduces the cost by compounding the resin catalyst and silicon.
(2) The preparation method of the invention avoids the use of sulfuric acid, and thoroughly solves the problem of a large amount of byproduct low-value ammonium sulfate in the existing sulfuric acid process, thereby being very in line with the development direction of low carbon and environmental protection.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
Weighing a certain amount of tetrapropyl ammonium hydroxide aqueous solution with the concentration of 5 wt% into a flask, then adding a certain amount of triethylamine, starting stirring at room temperature, adding a certain amount of silicon tetrachloride into the tetrapropyl ammonium hydroxide aqueous solution, and then continuing stirring for 1h to obtain a mixed solution. The molar ratio of tetrapropylammonium hydroxide, triethylamine and silicon tetrachloride in the mixed solution is 1: 0.01: 2.
and weighing 60g of the mixed solution, putting the mixed solution into a hydrothermal reaction kettle containing a tetrafluoroethylene lining, adding 10g of 001 x 7 strong acid type resin, reacting for 4 hours at 80 ℃, washing the obtained resin to be neutral by using deionized water after the reaction is finished, and drying at 80 ℃ to obtain the silicon-containing composite resin catalyst.
Example 2
Weighing a certain amount of 20 wt% tetrapropylammonium hydroxide aqueous solution, putting the tetrapropylammonium hydroxide aqueous solution into a flask, then adding a certain amount of n-butylamine, starting stirring at room temperature, adding a certain amount of silica sol into the tetrapropylammonium hydroxide aqueous solution, and then continuously stirring for 4 hours to obtain a mixed solution. The molar ratio of tetrapropylammonium hydroxide, n-butylamine and silica sol in the mixed solution is 1: 0.2: 5.
weighing 100g of the mixed solution, putting the mixed solution into a hydrothermal reaction kettle containing a tetrafluoroethylene lining, adding 40g D62 strong acid type resin, reacting for 8 hours at 100 ℃, washing the obtained resin to be neutral by deionized water after the reaction is finished, and drying at 100 ℃ to obtain the silicon-containing composite resin catalyst.
Example 3
Weighing a certain amount of tetrapropylammonium hydroxide aqueous solution with the concentration of 10 wt% into a flask, then adding a certain amount of tri-n-propylamine, starting stirring at room temperature, adding a certain amount of ethyl orthosilicate into the tetrapropylammonium hydroxide aqueous solution, and then continuously stirring for 2 hours to obtain a mixed solution. The molar ratio of tetrapropylammonium hydroxide, tri-n-propylamine and ethyl orthosilicate in the mixed solution is 1: 0.1: 4.
weighing 80g of the mixed solution, putting the mixed solution into a hydrothermal reaction kettle containing a tetrafluoroethylene lining, adding 40g of 001 x 7 strong acid type resin, reacting for 12 hours at 120 ℃, washing the obtained resin to be neutral by deionized water after the reaction is finished, and drying at 150 ℃ to obtain the silicon-containing composite resin catalyst.
Example 4
Weighing a certain amount of tetrapropyl ammonium hydroxide aqueous solution with the concentration of 8 wt% and putting the tetrapropyl ammonium hydroxide aqueous solution into a flask, then adding a certain amount of triethylamine, starting stirring at room temperature, adding a certain amount of tetraethoxysilane into the tetrapropyl ammonium hydroxide aqueous solution, and then continuing stirring for 3 hours to obtain a mixed solution. The molar ratio of tetrapropylammonium hydroxide, triethylamine and ethyl orthosilicate in the mixed solution is 1: 0.05: 4.
weighing 90g of the mixed solution, putting the mixed solution into a hydrothermal reaction kettle containing a tetrafluoroethylene lining, adding 30g D72 strong acid type resin, reacting for 10 hours at 110 ℃, washing the obtained resin to be neutral by deionized water after the reaction is finished, and drying at 120 ℃ to obtain the silicon-containing composite resin catalyst.
Example 5
Weighing a certain amount of tetrapropylammonium hydroxide aqueous solution with the concentration of 8 wt% into a flask, then adding a certain amount of n-butylamine, starting stirring at room temperature, adding a certain amount of ethyl orthosilicate into the tetrapropylammonium hydroxide aqueous solution, and then continuing stirring for 3 hours to obtain a mixed solution. The molar ratio of tetrapropylammonium hydroxide, n-butylamine and ethyl orthosilicate in the mixed solution is 1: 0.15: 4.
weighing 70g of the mixed solution, putting the mixed solution into a hydrothermal reaction kettle containing a tetrafluoroethylene lining, adding 30g of Amberlyst15 strong acid type resin, reacting for 12 hours at 100 ℃, washing the obtained resin to be neutral by deionized water after the reaction is finished, and drying at 100 ℃ to obtain the silicon-containing composite resin catalyst.
Example 6
Weighing a certain amount of tetrapropylammonium hydroxide aqueous solution with the concentration of 8 wt% into a flask, then adding a certain amount of n-butylamine, starting stirring at room temperature, adding a certain amount of silicon tetrachloride into the tetrapropylammonium hydroxide aqueous solution, and then continuously stirring for 3 hours to obtain a mixed solution. The molar ratio of tetrapropylammonium hydroxide, n-butylamine and silicon tetrachloride in the mixed solution is 1: 0.05: 3.5.
weighing 80g of the mixed solution, putting the mixed solution into a hydrothermal reaction kettle containing a tetrafluoroethylene lining, adding 20g of Amberlyst36 strong acid type resin, reacting for 10 hours at 110 ℃, washing the obtained resin to be neutral by deionized water after the reaction is finished, and drying at 80 ℃ to obtain the silicon-containing composite resin catalyst.
Comparative example: the commercially available strongly acidic resins used in examples 1 to 5 were each used directly as a catalyst.
The composite resin catalysts prepared in examples 1 to 6 and the strongly acidic resins purchased in comparative examples were subjected to catalyst evaluation by the following methods:
pouring 1g of resin catalyst into a 100ml round bottom flask, then adding 4g of cyclohexanone oxime and 40g of dimethyl sulfoxide, starting stirring, heating in an oil bath to 130 ℃ for reaction, stopping the reaction after 4h, and taking the upper reaction liquid for gas chromatography analysis.
Evaluation of the catalyst for the liquid phase beckmann rearrangement to caprolactam, the results are shown in table 1:
TABLE 1 results of liquid phase Beckmann rearrangement of different catalysts to caprolactam
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A preparation method of a resin catalyst for preparing caprolactam by liquid phase Beckmann rearrangement is characterized in that: comprises the following steps of (a) carrying out,
1) weighing tetrapropyl ammonium hydroxide aqueous solution, putting the tetrapropyl ammonium hydroxide aqueous solution into a container, adding an amine compound, starting stirring, adding a silicon-containing compound into the tetrapropyl ammonium hydroxide aqueous solution, and continuously stirring to obtain a mixed solution;
2) weighing the mixed solution prepared in the step 1), putting the mixed solution into a reaction kettle, adding strong acid resin, reacting for 4-12h at 80-120 ℃, washing the obtained resin to be neutral by deionized water after the reaction is finished, and drying at 80-150 ℃ to obtain a silicon-containing composite resin catalyst;
in the step 1), the molar ratio of tetrapropylammonium hydroxide, amine compound and silicon-containing compound in the mixed solution is 1: (0.01-0.2): (2-5) mixing; the concentration of the tetrapropyl ammonium hydroxide aqueous solution is 5-20 wt%; the amine compound is one of triethylamine, n-butylamine and tri-n-propylamine; the silicon-containing compound is one of silicon tetrachloride, silica sol and ethyl orthosilicate; the strong acid type resin is strong acid type ion exchange resin;
in the step 2), the mass ratio of the mixed solution prepared in the step 1) and the strong acid type resin added into the reaction kettle is (6-10): (1-4).
2. The method of claim 1, wherein: in the step 1), stirring at 18-35 ℃ to prepare a mixed solution, wherein the stirring time is 1-4 h.
3. The method of claim 1, wherein: in step 2), the strong acid type resin is one of 001 × 7, D61, D62, D72, Amberlyst15 and Amberlyst 36.
4. The method of claim 1, wherein: in the step 2), the reaction is carried out in a hydrothermal reaction kettle containing a tetrafluoroethylene lining.
5. The application of the composite resin catalyst obtained by the preparation method according to any one of claims 1 to 4 in preparing caprolactam through liquid-phase Beckmann rearrangement.
6. A process for preparing caprolactam, characterized in that: the composite resin catalyst obtained by the production method according to any one of claims 1 to 4, wherein cyclohexanone oxime and dimethyl sulfoxide are added, and the mass ratio of the composite resin catalyst to the cyclohexanone oxime to the dimethyl sulfoxide is (0.6-1.6): (2-6): (35-45); stirring and reacting for 2-6 h at 120-140 ℃.
7. Process for the preparation of caprolactam according to claim 6, characterized in that: the mass ratio of the composite resin catalyst to the cyclohexanone oxime to the dimethyl sulfoxide is 1:4: 40.
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| JP2559903B2 (en) * | 1990-11-21 | 1996-12-04 | 宇部興産株式会社 | Ion-exchange resin purification method for caprolactam aqueous solution |
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| CN102120589A (en) * | 2010-12-30 | 2011-07-13 | 中国天辰工程有限公司 | S-1 full-silicon molecular sieve and preparation method thereof as well as application of S-1 full-silicon molecular sieve in caprolactam preparation |
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| JP2559903B2 (en) * | 1990-11-21 | 1996-12-04 | 宇部興産株式会社 | Ion-exchange resin purification method for caprolactam aqueous solution |
| CN1366517A (en) * | 2000-04-21 | 2002-08-28 | 三菱化学株式会社 | Process for producing amide compound |
| CN1621405A (en) * | 2003-11-28 | 2005-06-01 | 中国石油化工股份有限公司 | Process for preparing caprolactam by cyclohexanone-oxime gas phase rearrangement |
| CN102120589A (en) * | 2010-12-30 | 2011-07-13 | 中国天辰工程有限公司 | S-1 full-silicon molecular sieve and preparation method thereof as well as application of S-1 full-silicon molecular sieve in caprolactam preparation |
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