CN108543548A - A kind of preparation method of liquid phase Beckmann rearrangement caprolactam resin catalyst - Google Patents
A kind of preparation method of liquid phase Beckmann rearrangement caprolactam resin catalyst Download PDFInfo
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- CN108543548A CN108543548A CN201810349872.7A CN201810349872A CN108543548A CN 108543548 A CN108543548 A CN 108543548A CN 201810349872 A CN201810349872 A CN 201810349872A CN 108543548 A CN108543548 A CN 108543548A
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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 present invention provides a kind of preparation methods of liquid phase Beckmann rearrangement caprolactam resin catalyst, include the following steps, 1) tetrapropylammonium hydroxide solution is weighed to be put into container, add aminated compounds, stirring is opened at room temperature, silicon-containing compound is added in tetrapropylammonium hydroxide solution, continues to stir, obtains mixed solution；2) mixed solution for weighing step 1) preparation is put into reaction kettle, strong acid type resin is added, 4 12h are reacted at 80 120 DEG C, gained resin is washed with deionized to neutrality after reaction, then it is dried at 80 150 DEG C, obtains siliceous composite resin catalyst.It is of the present invention.Preparation method of the present invention, it is compound by being carried out with silicon to resin catalyst so that liquid phase Beckmann rearrangement caprolactam yield significantly improves, and reduces cost.
Description
Technical field
The invention belongs to catalyst preparation technical fields, are used more particularly, to a kind of liquid phase Beckmann rearrangement caprolactam
The preparation method of resin catalyst.
Background technology
Caprolactam is a kind of important industrial chemicals, is the monomer of nylon 6 and engineering plastics processed.Current caprolactam processed
Process route mainly have two kinds of liquid and gas Beckmann rearrangement.At present in industrial production, sulfuric acid catalysis liquid is mainly used
Mutually reset technique.The technique is that cyclohexanone oxime is anti-in certain temperature generation Beckmann rearrangement under the concentrated sulfuric acid or oleum effect
It answers, then ammonia neutralization reaction system acidity is utilized to generate caprolactam.The technology is more mature, reaction condition mitigates, former
Expect that conversion ratio and selectivity of product are all higher, but there is also many disadvantages.First the concentrated sulfuric acid can etching apparatus, in production process
Meeting discharge harmful, does not meet environmentally protective idea of development；Simultaneously can also a large amount of cheap ammonium sulfate of by-product, economic benefit
It is poor.Therefore, become the weight studied recently with the novel caprolactam technique for the purpose of environmental benefit to increase economic efficiency
Want direction.Although since last century the eighties, people reduce making for sulfuric acid by changing reactor types and process conditions
With the generation with ammonium sulfate, but since sulfuric acid is not solved always using leading to the problem of at all.
To solve the above-mentioned problems, people begin one's study produces work by the gas phase beckmann rearrangement of catalyst of solid acid
Skill.The technique can completely avoid the use of sulfuric acid.But since vapor phase beckmann rearrangement reaction temperature is higher, generally at 360 DEG C
Left and right, and cyclohexanone oxime is heated to be easy coking in this temperature course being vaporized, therefore limits the industry of this technology
Change process.
Invention content
In view of this, the present invention is directed to propose a kind of preparation of liquid phase Beckmann rearrangement caprolactam resin catalyst
Method, with overcome the deficiencies in the prior art, catalyst prepared by the present invention is reacted for liquid phase Beckmann rearrangement caprolactam,
Good effect is obtained；
The present invention overcomes in existing sulfuric acid process liquid phase Beckmann rearrangement caprolactam technology a large amount of ammonium sulfate of by-product not
Foot provides a kind of low cost, not by-product low value ammonium sulfate liquid phase Beckmann rearrangement caprolactam preparation method.
In order to achieve the above objectives, the technical proposal of the invention is realized in this way：
A kind of preparation method of liquid phase Beckmann rearrangement caprolactam resin catalyst, includes the following steps,
1) it weighs tetrapropylammonium hydroxide solution to be put into container, adds aminated compounds, open stirring at room temperature,
Silicon-containing compound is added in tetrapropylammonium hydroxide solution, continues to stir, obtains mixed solution；
2) mixed solution for weighing step 1) preparation is put into reaction kettle, and strong acid type resin is added, anti-at 80-120 DEG C
4-12h is answered, gained resin is washed with deionized to neutrality after reaction, then dries, is contained at 80-150 DEG C
The composite resin catalyst of silicon.
Preferably, in step 1), in mixed solution tetrapropylammonium hydroxide, aminated compounds, silicon-containing compound with mole
Than 1：(0.01-0.2)：(2-5) is mixed；Preferably, in step 1), a concentration of 5- of tetrapropylammonium hydroxide solution
20wt%.
Preferably, in step 1), at 18~35 DEG C stirring prepare mixed solution, mixing time is 1~4h.
Preferably, in step 1), the aminated compounds is one kind in triethylamine, n-butylamine, Tri-n-Propylamine；It is described
Silicon-containing compound is one kind in silicon tetrachloride, Ludox, ethyl orthosilicate.
Preferably, in step 2), the strong acid type resin be strong acid ion exchange resin, it is preferred that 001 × 7, D61,
One kind of D62, D72, Amberlyst15, Amberlyst36.
Preferably, in step 2), the mass ratio of the mixed solution and strong acid type resin of the step 1) preparation that reaction kettle is added
For (6~10)：(1~4).
Preferably, in step 2), reaction carries out in the hydrothermal reaction kettle containing tetrafluoroethene liner.
The present invention also provides a kind of composite resin catalysts that preparation method as described above obtains in liquid phase Beckman weight
Application in row's caprolactam processed.
The present invention also provides a kind of method preparing caprolactam, the compound resin arrived using preparation method as described above
Catalyst, is added cyclohexanone oxime and dimethyl sulfoxide (DMSO), composite resin catalyst, cyclohexanone oxime and dimethyl sulfoxide (DMSO) quality
Than for (0.6~1.6)：(2~6)：(35~45), it is preferred that 1:4:40；It is stirred to react 2~6h at 120~140 DEG C.
How to prepare strong acid type resin catalyst and is not belonging to scope of the invention as claimed.Content according to the present invention is
Composite modified scope is carried out for resin catalyst.More specifically, previous use resin catalyst directly carries out liquid phase shellfish
Ke Man rearrangements caprolactam yield processed is relatively low, and it is higher that this allows for cost.The present invention is compound by carrying out it with silicon, improves
Resin catalyst performance makes caprolactam yield significantly improve, therefore reduces cost.
Compared with the existing technology, the preparation of liquid phase Beckmann rearrangement caprolactam resin catalyst of the present invention
Method has the advantage that：
(1) preparation method of the present invention, it is compound by being carried out with silicon to resin catalyst so that liquid phase Beckman weight
Row's caprolactam yield processed significantly improves, and reduces cost.
(2) preparation method of the present invention, avoids the use of sulfuric acid, thoroughly solves a large amount of secondary in existing sulfuric acid process
The problem of producing low value ammonium sulfate, therefore meet very much the developing direction of low-carbon environment-friendly.
Specific implementation mode
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
With reference to embodiment, the present invention will be described in detail.
Embodiment 1
The tetrapropylammonium hydroxide solution for weighing a certain amount of a concentration of 5wt% is put into flask, is then added certain
The triethylamine of amount, at room temperature open stirring, by a certain amount of silicon tetrachloride be added tetrapropylammonium hydroxide solution in, then after
Continuous stirring 1h, obtains mixed solution.Tetrapropylammonium hydroxide, triethylamine, silicon tetrachloride molar ratio are 1 in mixed solution：0.01：
2。
It weighs the above-mentioned mixed solutions of 60g to be put into the hydrothermal reaction kettle containing tetrafluoroethene liner, 10g 001 × 7 is added
Strong acid type resin reacts 4h at 80 DEG C, gained resin is washed with deionized to neutrality after reaction, then at 80 DEG C
Lower drying, obtains siliceous composite resin catalyst.
Embodiment 2
The tetrapropylammonium hydroxide solution for weighing a certain amount of a concentration of 20wt% is put into flask, is then added certain
The n-butylamine of amount opens stirring at room temperature, and a certain amount of Ludox is added in tetrapropylammonium hydroxide solution, is then proceeded to
4h is stirred, mixed solution is obtained.Tetrapropylammonium hydroxide, n-butylamine, Ludox molar ratio are 1 in mixed solution：0.2：5.
It weighs the above-mentioned mixed solutions of 100g to be put into the hydrothermal reaction kettle containing tetrafluoroethene liner, it is strong that 40g D62 is added
Acid type resin reacts 8h at 100 DEG C, gained resin is washed with deionized to neutrality after reaction, then at 100 DEG C
Lower drying, obtains siliceous composite resin catalyst.
Embodiment 3
The tetrapropylammonium hydroxide solution for weighing a certain amount of a concentration of 10wt% is put into flask, is then added certain
The Tri-n-Propylamine of amount opens stirring at room temperature, a certain amount of ethyl orthosilicate is added in tetrapropylammonium hydroxide solution, so
After continue stir 2h, obtain mixed solution.Tetrapropylammonium hydroxide, Tri-n-Propylamine, ethyl orthosilicate molar ratio in mixed solution
It is 1：0.1：4.
It weighs the above-mentioned mixed solutions of 80g to be put into the hydrothermal reaction kettle containing tetrafluoroethene liner, 40g 001 × 7 is added
Strong acid type resin reacts 12h at 120 DEG C, and gained resin is washed with deionized to neutrality after reaction, then exists
It is dried at 150 DEG C, obtains siliceous composite resin catalyst.
Embodiment 4
The tetrapropylammonium hydroxide solution for weighing a certain amount of a concentration of 8wt% is put into flask, is then added certain
The triethylamine of amount opens stirring at room temperature, a certain amount of ethyl orthosilicate is added in tetrapropylammonium hydroxide solution, then
Continue to stir 3h, obtains mixed solution.Tetrapropylammonium hydroxide, triethylamine, ethyl orthosilicate molar ratio are 1 in mixed solution：
0.05：4.
It weighs the above-mentioned mixed solutions of 90g to be put into the hydrothermal reaction kettle containing tetrafluoroethene liner, 30g D72 strong acid is added
Type resin reacts 10h at 110 DEG C, gained resin is washed with deionized to neutrality after reaction, then at 120 DEG C
Lower drying, obtains siliceous composite resin catalyst.
Embodiment 5
The tetrapropylammonium hydroxide solution for weighing a certain amount of a concentration of 8wt% is put into flask, is then added certain
The n-butylamine of amount opens stirring at room temperature, a certain amount of ethyl orthosilicate is added in tetrapropylammonium hydroxide solution, then
Continue to stir 3h, obtains mixed solution.Tetrapropylammonium hydroxide, n-butylamine, ethyl orthosilicate molar ratio are 1 in mixed solution：
0.15：4.
It weighs the above-mentioned mixed solutions of 70g to be put into the hydrothermal reaction kettle containing tetrafluoroethene liner, 30g is added
Amberlyst15 strong acid type resins react 12h at 100 DEG C, and gained resin is washed with deionized into after reaction
Property, it is then dried at 100 DEG C, obtains siliceous composite resin catalyst.
Embodiment 6
The tetrapropylammonium hydroxide solution for weighing a certain amount of a concentration of 8wt% is put into flask, is then added certain
The n-butylamine of amount, at room temperature open stirring, by a certain amount of silicon tetrachloride be added tetrapropylammonium hydroxide solution in, then after
Continuous stirring 3h, obtains mixed solution.Tetrapropylammonium hydroxide, n-butylamine, silicon tetrachloride molar ratio are 1 in mixed solution：0.05：
3.5。
It weighs the above-mentioned mixed solutions of 80g to be put into the hydrothermal reaction kettle containing tetrafluoroethene liner, 20g is added
Amberlyst36 strong acid type resins react 10h at 110 DEG C, and gained resin is washed with deionized into after reaction
Property, it is then dried at 80 DEG C, obtains siliceous composite resin catalyst.
Comparative example：The strong acid type resin used in embodiment 1-5 by purchase is respectively directly as catalyst.
The highly acidic resin bought in composite resin catalyst and comparative example prepared by Examples 1 to 6 carries out catalyst
Evaluation, using following methods：
It takes resin catalyst 1g to pour into 100ml round-bottomed flasks, cyclohexanone oxime 4g is then added, dimethyl sulfoxide (DMSO) 40g is opened
It opens stirring and oil bath heating is reacted to 130 DEG C, stop reaction after 4h, upper layer reaction solution is taken to carry out gas chromatographic analysis.
For the evaluating catalyst of liquid phase Beckmann rearrangement caprolactam, 1 the results are shown in Table：
1 different catalysts liquid phase Beckmann rearrangement caprolactam result of table
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (9)
1. a kind of preparation method of liquid phase Beckmann rearrangement caprolactam resin catalyst, it is characterised in that：Including as follows
Step,
1) it weighs tetrapropylammonium hydroxide solution to be put into container, adds aminated compounds, stirring is opened, by siliceous chemical combination
Object is added in tetrapropylammonium hydroxide solution, continues to stir, obtains mixed solution；
2) mixed solution for weighing step 1) preparation is put into reaction kettle, and strong acid type resin is added, reacts 4- at 80-120 DEG C
Gained resin is washed with deionized to neutrality, is then dried at 80-150 DEG C, obtained siliceous by 12h after reaction
Composite resin catalyst.
2. preparation method according to claim 1, it is characterised in that：In step 1), tetrapropyl hydroxide in mixed solution
Ammonium, aminated compounds, silicon-containing compound are with molar ratio 1：(0.01-0.2)：(2-5) is mixed；Preferably, in step 1), tetrapropyl
A concentration of 5-20wt% of ammonium hydroxide aqueous solution.
3. preparation method according to claim 1, it is characterised in that：In step 1), at 18~35 DEG C prepared by stirring to mix
Solution is closed, mixing time is 1~4h.
4. preparation method according to claim 1, it is characterised in that：In step 1), the aminated compounds is three second
One kind in amine, n-butylamine, Tri-n-Propylamine；The silicon-containing compound is one in silicon tetrachloride, Ludox, ethyl orthosilicate
Kind.
5. preparation method according to claim 1, it is characterised in that：In step 2), the strong acid type resin is strong-acid type
Ion exchange resin, it is preferred that 001 × 7, one kind of D61, D62, D72, Amberlyst15, Amberlyst36.
6. preparation method according to claim 1, it is characterised in that：In step 2), prepared by the step 1) that reaction kettle is added
Mixed solution and strong acid type resin mass ratio be (6~10)：(1~4).
7. preparation method according to claim 1, it is characterised in that：In step 2), reaction is containing tetrafluoroethene liner
Hydrothermal reaction kettle in carry out.
8. the composite resin catalyst obtained according to claim 1~7 any one of them preparation method is in liquid phase Beckman weight
Application in row's caprolactam processed.
9. a kind of method preparing caprolactam, it is characterised in that：Use such as claim 1~7 any one of them preparation side
Cyclohexanone oxime and dimethyl sulfoxide (DMSO), composite resin catalyst, cyclohexanone oxime and two are added in the composite resin catalyst that method arrives
The mass ratio of methyl sulfoxide is (0.6~1.6)：(2~6)：(35~45), it is preferred that 1:4:40；It is stirred at 120~140 DEG C
React 2~6h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651221A (en) * | 2018-12-27 | 2019-04-19 | 中国天辰工程有限公司 | A kind of processing method for the ion-exchange resin catalyst preparing caprolactam |
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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 |
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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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2018
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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 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651221A (en) * | 2018-12-27 | 2019-04-19 | 中国天辰工程有限公司 | A kind of processing method for the ion-exchange resin catalyst preparing caprolactam |
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