CN101709053A - Process for preparing caprolactam - Google Patents
Process for preparing caprolactam Download PDFInfo
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- CN101709053A CN101709053A CN200910175322A CN200910175322A CN101709053A CN 101709053 A CN101709053 A CN 101709053A CN 200910175322 A CN200910175322 A CN 200910175322A CN 200910175322 A CN200910175322 A CN 200910175322A CN 101709053 A CN101709053 A CN 101709053A
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Abstract
The invention discloses a process for preparing caprolactam, which comprises the following steps: after mixing cyclohexanone and cyclohexane evenly, carrying out an oxamidine reaction to obtain a cyclohexane solution of cyclohexanone oxime; enabling the cyclohexane solution of the cyclohexanone oxime and oleum to react to generate a caprolactam sulfate solution, curing the caprolactam sulfate solution, then carrying out a neutralization reaction on the cured caprolactam sulfate solution and ammonia, afterwards separating the two materials to obtain a crude product of caprolactam and then carrying out extraction and water back extraction respectively to prepare a finished product. Because of the existence of a cyclohexane inert solvent, rectification and separation do not need to be carried out after the oxamidine reaction, and only a rearrangement reaction needs to be carried out after the water phase of a catalyst is separated, thereby saving a rectification device and the steam consumption; as a result, a caprolactam enterprise with an annual yield of a hundred thousand tons can save energy worth approximately 60000000 yuan every year and can also save the one-off equipment investment totaling 60000000 yuan, the technological process of caprolactam is simplified, the procedures of water washing, extraction, distillation and the like are reduced, the production period is shortened, and the annual yield is enhanced.
Description
Technical field:
The present invention relates to a kind of process for preparing caprolactam, further saying so prepares the technology of hexanolactam in the presence of the hexanaphthene inert solvent.
Background technology
Hexanolactam is a raw material of producing nylon-6.Prepare at present hexanolactam in the world to mainly contain with benzene be the ketone one azanol route of raw material, be that the hexahydrobenzene benzoic acid amides method and the photo-nitrosation of cyclohexane process of raw material directly prepares caprolactam technology with toluene.
Ketone-azanol the route that wherein with benzene is raw material is maximum, accounts for more than 90% of aggregated capacity.
Ketone-azanol route is again because the operational path difference of azanol, is divided into three kinds of HSO methods (oxammonium sulfate method), NO method (nitric oxide reduction method), HPO method (phosphatic hydroxylamine method).
But no matter above-mentioned three kinds of methods are HSO, NO or HPO method, equal long flow path, complex technical process.Reason mainly is after each intermediates (pimelinketone, cyclohexanone-oxime, hexanolactam crude product) prepare, and the treating process of a cover rectifying separation is all arranged, and causes not only that technical process is long, facility investment is many, and the energy consumption height.For the hexanolactam enterprise that produces 100000 tons per year, the energy consumption of preparing back rectifying separation process at intermediates accounts for 40% of hexanolactam manufacturing cost.
In sum, for reducing production costs, cut down the consumption of energy, the production technique of improving hexanolactam is a caprolactam production enterprise urgent problem.
Summary of the invention:
The present invention seeks to deficiency, the process for preparing caprolactam that a kind of flow process is simpler, energy consumption is lower, quality is more excellent is provided at existing Technology.
Be to realize the object of the invention, this in the presence of the hexanaphthene inert solvent preparation technology of combined preparation hexanolactam it is characterized in that may further comprise the steps:
A. with pimelinketone and hexanaphthene with 1: 3～1: 4 volume ratio mixing after, with ammonia, hydrogen peroxide in the presence of catalyzer, under 80～90 ℃, normal pressure, carry out Ammoximation reaction, after separating, obtain the cyclohexane solution of cyclohexanone-oxime then;
B. under 85～95 ℃, normal pressure, the cyclohexane solution and the oleum of above-mentioned cyclohexanone-oxime carried out Beckmann rearrangement, reaction generates hexanolactam sulfuric ester solution, wherein by cyclically utilizing after the cyclohexane solvent condensation of rearrangement reaction thermal evaporation;
C. after the above-mentioned rearrangement reaction, hexanolactam sulfuric ester solution under 100～150 ℃, normal pressure, is carried out the slaking of 0.5～3h;
D. the hexanolactam sulfuric ester solution after the slaking carries out neutralization reaction with ammoniacal liquor under 0.01～0.02MPa, 40～65 ℃, 4.5～5.5pH, then through separating the hexanolactam crude product that obtains containing micro-cyclohexane solvent;
E. above-mentioned hexanolactam crude product is extracted respectively and make the hexanolactam finished product after stripping with water.
Adopting benzene, toluene or trieline in the described extraction process is extraction agent.
The volume ratio of described benzene extraction agent and crude caprolactam is 2.3: 1～3: 1.
The volume ratio of described toluene extraction agent and crude caprolactam is 2.3: 1～3: 1.
The volume ratio of described trieline extraction agent and crude caprolactam is 2.3: 1～3: 1.
The volume ratio of the benzole soln of water and hexanolactam was 0.2: 1～0.4: 1 during described water was stripped.
Described catalyzer adopts the Ti/Si molecular sieve catalyst.
The technical progress that the present invention is obtained:
(1) owing to adopts technology of the present invention, in the preparing process of caprolactam process, after preparing cyclohexanone-oxime, because the existence of hexanaphthene inert solvent is arranged, needn't carry out rectifying separation, carry out Beckmann rearrangement after only need isolating the water that contains catalyzer, thereby rectifier unit and steam energy consumption have been saved, hexanolactam enterprise for producing 100000 tons per year can save the steam energy consumption every year and amount to 6,000 ten thousand yuan, and can save disposable apparatus and invest 6,000 ten thousand yuan.
(2) because the existence of hexanaphthene inert solvent, in hexanolactam crude product extraction process, because micro-hexanaphthene enters the benzene phase, form the stronger benzol-cyclohexane composite extractant of removal of impurities ability with benzene, make that the extracting power of benzol-cyclohexane composite extractant is stronger, make the hexanolactam phase-splitting better, thereby make quality of caprolactam purer.In water reextraction process, can make caprolactam water solution than traditional technology concentration high 15%, not only saved 50% reextraction de-salted water, also saved 50% steam in the follow-up treating process, for the hexanolactam enterprise that produces 100000 tons per year, this extraction process can be reduced expenses and reach 2,000 ten thousand yuan every year.
Technology of the present invention makes the caprolactam technology flow process be simplified, operations such as washing, extraction, distillation behind Ammoximation reaction, have been reduced, shorten technical process, shortened the production cycle, and the hexanaphthene inert solvent can cycling and reutilization in production process, on the existing equipment basis, improve annual production, had tangible economic results in society.
The present invention describes in detail:
The pimelinketone preparation section:
A, in the cyclohexane oxidation device, under 150～185 ℃ of controlled temperature, the pressure 0.8～1.9MPa condition, use air oxidation of cyclohexane, generate and to contain the cyclohexane oxidation mixture that cyclohexyl hydroperoxide is a primary product.
B, the oxidation mixture that will contain cyclohexyl hydroperoxide decompose, and cyclohexyl hydroperoxide is decomposed generate hexalin and pimelinketone.
C, in rectifying tower, isolate hexanaphthene, hexalin, pimelinketone.Obtain pimelinketone after the cyclohexanol dehydrogenation.
D, with purity be 99.88% pimelinketone and purity be 99.9% hexanaphthene with 1: 3～1: 4 ratio mixing after, as the raw material of subsequent processing Ammoximation reaction.
The cyclohexanone-oxime preparation section:
A, at the Ammoximation reaction device, controlled temperature is 80～90 ℃, pressure is normal pressure 0.4MPa, the cyclohexane solution of pimelinketone and hydrogen peroxide, ammonia react in the presence of the Ti/Si molecular sieve catalyst, generate the cyclohexane solution of cyclohexanone-oxime.
The water that contains catalyzer is separated, filters, separated to B, the reaction product of coming out from the Ammoximation reaction device by spinning liquid, the cyclohexane solution that contains micro-brinish cyclohexanone-oxime falls salt solution through the coalescer branch again and obtains the cyclohexane solution that content is 20～30% cyclohexanone-oximes, uses for the subsequent processing Beckmann rearrangement.
The crude caprolactam preparation section:
A, in rearrangement reactor, controlled temperature is at 85～95 ℃, the pressure normal pressure stopped 10～60 minutes, content is the cyclohexane solution of 20～30% cyclohexanone-oxime and 8～20% oleum generation Beckmann rearrangement, generates the hexanolactam sulfuric ester.
B, the slaking reaction device, carry out slaking from resetting the hexanolactam sulfuric ester that comes, 100～150 ℃ of controlled temperature, preferred 110～130 ℃, normal pressure stopped preferred 1～2 hour 0.5～3 hour.
C, the hexanolactam sulfuric ester that comes out from the slaking reaction device enter the thiamines crystallization and in the separator at 0.01～0.02MPa, 40～65 ℃ of temperature, carry out neutralization reaction with ammoniacal liquor under pH value 4.5～5.5 conditions, isolate the hexanolactam crude product that contains micro-hexanaphthene then.
Finished product hexanolactam preparation section:
A, from the thiamines crystallization and the hexanolactam crude product of separating in the separator that contains micro-hexanaphthene, in the benzene extraction tower, carry out counter-current extraction with benzene, be in a ratio of benzene: hexanolactam crude product=2.3: 1～3: 1,40～50 ℃ of temperature, normal pressure.Extraction obtains containing the benzole soln of the hexanolactam of a small amount of hexanaphthene, and this solution and water are stripped.Control water: the benzole soln of hexanolactam=0.24: 1～0.4: 1,30～40 ℃ of temperature, normal pressure obtains 30～45% caprolactam water solution.
B, caprolactam water solution are made highly purified hexanolactam finished product through after friendship, hydrogenation, triple effect evaporation, flash distillation and distillation.
Description of drawings
The present invention will be further described below in conjunction with accompanying drawing.
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Embodiment 1: as shown in Figure 1,99.9% the hexanaphthene of 99.88% (wt) pimelinketone that comes from the pimelinketone preparation section with same operation is mixed with the cyclohexane solution of 20～30% pimelinketone with 1: 3～1: 4 volume ratio, with the flow of 40.4～50.5t/h, enter the Ammoximation reaction device then.
The NH that in the Ammoximation reaction device, adds 2.0～2.2t/h simultaneously
3, 15.1～15.7t/hH
2O
2In concentration is in the presence of the Ti/Si molecular sieve catalyst of 2～4% (wt), in temperature is that 80～90 ℃, pressure are to carry out Ammoximation reaction under the condition of normal pressure of 0.4MPa, fall to contain the water of catalyzer then through the spinning liquid separating and filtering, after controlling its flow 42.5t/h～52.5t/h and down removing micro-salt solution, obtain the cyclohexane solution of cyclohexanone-oxime through coalescer.
The cyclohexane solution of cyclohexanone-oxime enters the Beckmann rearrangement device, and the catalyzer water of separating that contains the Ti/Si molecular sieve loops back the Ammoximation reaction device and continues to participate in reaction.
In the Beckmann rearrangement device, flow is that the cyclohexane solution of 8%～20% oleum of 14.1～18.4t/h and the cyclohexanone-oxime that flow is 42.5t/h～52.5t/h is with 1.3～1.7 mol ratio generation rearrangement reaction, reset 85～95 ℃ of temperature, pressure is normal pressure, stopped 10～60 minutes, the rearrangement reaction product is the hexanolactam sulfuric ester, wherein by cyclically utilizing after the cyclohexane solvent condensation of rearrangement reaction thermal evaporation.
Hexanolactam sulfuric ester solution continues to enter the slaking reaction device, 100～150 ℃ of curing temperatures, and under the normal pressure, 0.5～3 hour residence time.
Hexanolactam sulfuric ester solution after overcuring enters in the thiamines evaporation and crystallizer, under control pressure 0.01～0.02MPa, 40～65 ℃ of temperature, pH value 4.5～5.5 conditions, with flow be 20% the NH of 24.5～25.2t/h
3H
2Neutralization reaction takes place in O, and evaporative crystallization separates the hexanolactam crude product (caprolactam content 63～69% (wt), hexanaphthene 1～7% (wt) and water 30%) that obtains containing micro-hexanaphthene.
The hexanolactam crude product and the benzene that will contain micro-hexanaphthene carry out counter-current extraction with the flow of 18.10～18.30t/h and 45.2～45.4t/h at the benzene extraction tower respectively, obtaining flow is the benzole soln (containing micro-hexanaphthene) of the hexanolactam that contains hexanolactam 20% of 62～64t/h, entering the water extraction tower, to obtain flow be the aqueous solution that 42～28t/h contains hexanolactam 30～45%, wherein the volume ratio of the benzole soln of water and hexanolactam is 0.2～0.4: 1, the benzene that contains micro-hexanaphthene turns back to the recycle of benzene extraction tower, the aqueous solution process that contains hexanolactam is from friendship, hydrogenation, triple effect evaporation, treating process such as flash distillation and distillation finally obtains highly purified hexanolactam finished product.And micro-hexanaphthene enters in the benzene, forms benzene, hexanaphthene composite extractant with benzene, to be used to the hexanolactam of purifying.
Embodiment 2: the present embodiment difference from Example 1 is to replace the benzene extraction agent with the toluene extraction agent.
Embodiment 3: the present embodiment difference from Example 1 is to replace the benzene extraction agent with the trieline extraction agent.
Claims (7)
1. process for preparing caprolactam is characterized in that may further comprise the steps:
A. with pimelinketone and hexanaphthene with 1: 3～1: 4 volume ratio mixing after, with ammonia, hydrogen peroxide in the presence of catalyzer, under 80～90 ℃, normal pressure, carry out Ammoximation reaction, after separating, obtain the cyclohexane solution of cyclohexanone-oxime then;
B. under 85～95 ℃, normal pressure, the cyclohexane solution and the oleum of above-mentioned cyclohexanone-oxime carried out Beckmann rearrangement, reaction generates hexanolactam sulfuric ester solution, wherein by cyclically utilizing after the cyclohexane solvent condensation of rearrangement reaction thermal evaporation;
C. after the above-mentioned rearrangement reaction, hexanolactam sulfuric ester solution under 100～150 ℃, normal pressure, is carried out the slaking of 0.5～3h;
D. the hexanolactam sulfuric ester solution after the slaking carries out neutralization reaction with ammoniacal liquor under 0.01～0.02MPa, 40～65 ℃, 4.5～5.5pH, then through separating the hexanolactam crude product that obtains containing micro-cyclohexane solvent;
E. above-mentioned hexanolactam crude product is extracted respectively and make the hexanolactam finished product after stripping with water.
2. process for preparing caprolactam according to claim 1 is characterized in that it is extraction agent that benzene, toluene or trieline are adopted in described extraction.
3. process for preparing caprolactam according to claim 2, the volume ratio that it is characterized in that described benzene extraction agent and crude caprolactam is 2.3: 1～3: 1.
4. process for preparing caprolactam according to claim 2, the volume ratio that it is characterized in that described toluene extraction agent and crude caprolactam is 2.3: 1～3: 1.
5. process for preparing caprolactam according to claim 2, the volume ratio that it is characterized in that described trieline extraction agent and crude caprolactam is 2.3: 1～3: 1.
6. process for preparing caprolactam according to claim 1, it is characterized in that described water strip in the volume ratio of benzole soln of water and hexanolactam be 0.2: 1～0.4: 1.
7. process for preparing caprolactam according to claim 1 is characterized in that described catalyzer adopts the Ti/Si molecular sieve catalyst.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311386A (en) * | 2010-07-02 | 2012-01-11 | 天华化工机械及自动化研究设计院 | Caprolactam suspension filtering and washing method |
| CN102675176A (en) * | 2012-05-31 | 2012-09-19 | 中国天辰工程有限公司 | Method for producing caprolactam by taking high-purity benzene as raw material |
| CN103896838A (en) * | 2012-12-28 | 2014-07-02 | 帝斯曼知识产权资产管理有限公司 | Method and equipment for continuously producing epsilon-hexanolactam |
| CN104204145A (en) * | 2012-03-26 | 2014-12-10 | 环球油品公司 | Process for removing nitrogen from fuel streams with caprolactamium ionic liquids |
| CN105837507A (en) * | 2015-01-15 | 2016-08-10 | 湖北金湘宁化工科技有限公司 | Preparation method for caprolactam |
| CN107556213A (en) * | 2016-08-16 | 2018-01-09 | 沧州旭阳化工有限公司 | A kind of technique of cyclohexanone oxamidinating and the technique for manufacturing caprolactam |
| CN111635348A (en) * | 2020-06-22 | 2020-09-08 | 聊城鲁西聚酰胺新材料科技有限公司 | Application and system of screw vacuum pump in caprolactam refining process production |
| CN116199609A (en) * | 2023-02-10 | 2023-06-02 | 杭州湘云化工有限公司 | Process for preparing caprolactam and use thereof |
-
2009
- 2009-12-14 CN CN200910175322A patent/CN101709053A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311386B (en) * | 2010-07-02 | 2013-05-15 | 天华化工机械及自动化研究设计院有限公司 | Caprolactam suspension filtering and washing method |
| CN102311386A (en) * | 2010-07-02 | 2012-01-11 | 天华化工机械及自动化研究设计院 | Caprolactam suspension filtering and washing method |
| CN104204145A (en) * | 2012-03-26 | 2014-12-10 | 环球油品公司 | Process for removing nitrogen from fuel streams with caprolactamium ionic liquids |
| CN104204145B (en) * | 2012-03-26 | 2015-11-25 | 环球油品公司 | By the method except denitrification from fuel streams of acyl ammonium ion liquid in oneself |
| CN102675176B (en) * | 2012-05-31 | 2016-12-14 | 中国天辰工程有限公司 | A kind of be raw material production caprolactam with high pure benzene method |
| CN102675176A (en) * | 2012-05-31 | 2012-09-19 | 中国天辰工程有限公司 | Method for producing caprolactam by taking high-purity benzene as raw material |
| CN103896838B (en) * | 2012-12-28 | 2018-03-23 | Cap Iii 有限公司 | The method and apparatus of continuous production ε caprolactams |
| CN103896838A (en) * | 2012-12-28 | 2014-07-02 | 帝斯曼知识产权资产管理有限公司 | Method and equipment for continuously producing epsilon-hexanolactam |
| CN105837507A (en) * | 2015-01-15 | 2016-08-10 | 湖北金湘宁化工科技有限公司 | Preparation method for caprolactam |
| CN107556213A (en) * | 2016-08-16 | 2018-01-09 | 沧州旭阳化工有限公司 | A kind of technique of cyclohexanone oxamidinating and the technique for manufacturing caprolactam |
| CN107556213B (en) * | 2016-08-16 | 2019-11-22 | 沧州旭阳化工有限公司 | A kind of technique of cyclohexanone oxamidinating and the technique for manufacturing caprolactam |
| CN111635348A (en) * | 2020-06-22 | 2020-09-08 | 聊城鲁西聚酰胺新材料科技有限公司 | Application and system of screw vacuum pump in caprolactam refining process production |
| CN116199609A (en) * | 2023-02-10 | 2023-06-02 | 杭州湘云化工有限公司 | Process for preparing caprolactam and use thereof |
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Open date: 20100519 |