CN101117326B - Method for preparing aminocaprolactam by catalysis of nicotinic acid in ionic liquid - Google Patents

Method for preparing aminocaprolactam by catalysis of nicotinic acid in ionic liquid Download PDF

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CN101117326B
CN101117326B CN2006100890367A CN200610089036A CN101117326B CN 101117326 B CN101117326 B CN 101117326B CN 2006100890367 A CN2006100890367 A CN 2006100890367A CN 200610089036 A CN200610089036 A CN 200610089036A CN 101117326 B CN101117326 B CN 101117326B
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ionic liquid
oleum
oxime
cyclohexanone
hexanolactam
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CN101117326A (en
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张伟
赵燕
胡合新
吴巍
闵恩泽
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention discloses a process that epsilon-Caprolactam is catalyzed and prepared by nicotinic acid in ionic liquid which is characterized in that the solvent function of the nicotinic acid is replaced or partially replaced by the ionic liquid, and the nicotinic acid only or mainly plays a role of catalyzer. The process can decrease the use of the nicotinic acid, decrease thiamine by-products, and is easy to realize the connection of the repeating use of the ionic liquid and the prior art.

Description

The method of oleum preparing aminocaprolactam by catalysis in a kind of ionic liquid
Technical field
The present invention relates to a kind of preparation method of petrochemical materials, particularly the Beckmann rearrangement reaction of nicotinic acid catalysis of pimelinketone oxime prepares the method for hexanolactam.
Background technology
Hexanolactam is a kind of important Organic Chemicals of widespread use, and about in the world 90% hexanolactam is prepared by the Beckmann rearrangement reaction by cyclohexanone-oxime.Traditional B eckmann rearrangement reaction process is: adopt nicotinic acid (oleum) to make cyclohexanone-oxime form vitriolic hexanolactam salt, and be that the high yield that obtains hexanolactam need add excessive nicotinic acid, use the ammoniacal liquor neutralise mixt then, obtain sulphur ammonium and hexanolactam.In the typical industry rearrangement process, the transformation efficiency of cyclohexanone-oxime is almost 100%, is 99% to the selectivity of hexanolactam, produces 1.3-1.8kg sulphur ammonium/kg oxime (or 1.0-1.3mol oxime).This traditional technology uses oleum to be catalyzer and solvent, consumes the sulfuric acid and the ammonia of high value, and the sulphur ammonium of a large amount of low values of by-product has increased production cost, and environment is also caused certain harm.Therefore the Beckmann of no sulphur ammonium of exploitation or low-sulfur ammonium by-product rearrangement novel process meets the Green Chemistry developing direction, is one of improved major objective of preparing process of caprolactam.
Reset technology from the begin one's study improvement of no sulphur ammonium or low-sulfur ammonium by-product of later 1960s, comprise vapor phase rearrangement and liquid phase rearrangement technology.In recent years, Sumitomo company is obtaining bigger progress aspect the vapor phase rearrangement research, but vapor phase rearrangement technology is unsuitable for existing installation is carried out technological transformation; Liquid phase rearrangement technology has the reaction conditions gentleness, to equipment requirements advantages of higher and coming into one's own not, and obtain some achievements in research.
Inventa company discloses in GB1029201 with anhydrous acetic acid, diacetyl oxide and sulfonic acid type ion-exchange resins and forms catalyst system, and the hexanolactam productive rate reaches 95.5%; Sumitomo company is at US5, discloses with alkylating reagent and N in 225,547, and dinethylformamide is made the liquid phase rearrangement catalyst system of solvent composition cyclohexanone-oxime, and the cyclohexanone-oxime transformation efficiency is 100%, the hexanolactam selectivity is 99.8%; Dong Li company opens to disclose among flat 9-227509 and the flat 9-227510 of Te Kai the spy and adopts N, dinethylformamide is a solvent, form catalyst system with HCl and hydroxyl phosphorus trichloride, the cyclohexanone-oxime transformation efficiency can reach 100%, hexanolactam selectivity and yield can reach 95%; DSM N. V. is at US5, and 571,913 and EP0,639, disclose the cation exchange resin as catalyst that uses the sulfo group benzene ring structure among the 565A1, hexanoyl imido grpup-O-sulfonic acid is made cocatalyst, and the hexanolactam yield is 100%, and the amount of vitriol by product is lower than 5%; People such as Jha are at US 5,401,843 and US 5,594, in dilute sulphuric acid, form micellar solution with tensio-active agent and cosurfactant in 137, only need in the small amount of alkali after the rearrangement reaction and excessive acid, significantly reduce sulphur ammonium by-product, the cyclohexanone-oxime transformation efficiency is 80-90%, hexanolactam yield 68-90%.
In recent years, ionic liquid is subjected to the great attention of academia and industry member as a kind of new catalytic material and green solvent.(petrochemical complex 2001,30 (2) 91-92) adopts butyl-pyridinium a tetrafluoro borate ([bupy] BF to Deng Youquan 4) and PCl 5Form catalyst system, the transformation efficiency of cyclohexanone-oxime and the selectivity of hexanolactam all approach 100%.
Though the selectivity of the transformation efficiency of cyclohexanone-oxime and hexanolactam is higher in the partial monopoly, because economy and technology, the catalytic liquid phase rearrangement technology of non-oleum fails to realize industrialization so far.
Summary of the invention
In the nicotinic acid rearrangement technological process that suitability for industrialized production adopts at present, nicotinic acid plays catalyzer and solvent simultaneously, if find a kind of material to replace or partly replace the solvent action of nicotinic acid, nicotinic acid only plays a part or mainly plays catalyzer, just might reduce the usage quantity of nicotinic acid greatly, reduce the consumption of ammoniacal liquor in the N-process, thereby reduce the amount of sulphur ammonium by-product greatly.
Ionic liquid is a kind of novel green solvent, and the contriver finds that ionic liquid can replace or part replaces the solvent action of nicotinic acid to be used for the preparation process of preparing aminocaprolactam by catalysis of nicotinic acid.
The objective of the invention is to reset the problem of a large amount of sulphur ammoniums of technology by-product, propose a kind of novel method that in ionic liquid, prepares hexanolactam with the Beckmann rearrangement reaction of nicotinic acid catalysis of pimelinketone oxime at nicotinic acid.
Method provided by the invention is characterized in that this method comprises the steps:
(1) adopt one of following three kinds of modes to carry out rearrangement reaction: (a) at first mixed ionic liquid and nicotinic acid, obtain the ionic liquid solution of nicotinic acid, add cyclohexanone-oxime then and carry out rearrangement reaction; (b) at first mixed ionic liquid and cyclohexanone-oxime obtain the ionic liquid solution of cyclohexanone-oxime, add nicotinic acid then and carry out rearrangement reaction; (c) at first mixed ionic liquid and nicotinic acid, obtain the ionic liquid solution of nicotinic acid, mixed ionic liquid and cyclohexanone-oxime then obtain the ionic liquid solution of cyclohexanone-oxime, and the ionic liquid solution of remix nicotinic acid and the ionic liquid solution of cyclohexanone-oxime carry out rearrangement reaction;
(2) add the ammoniacal liquor neutralization, obtain the ammonia soln and the ionic liquid two-phase of hexanolactam, phase-splitting;
(3) return the rearrangement reaction process after the ionic liquid washing;
(4) ammonia soln of hexanolactam enters the FF of hexanolactam in the conventional Industrial processes, is connected with existing commercial run.
In the method provided by the invention, described ionic liquid adopts hydrophobic ionic liquid, is dimerous by positively charged ion and negatively charged ion, plays solvent action in the rearrangement reaction system.
Said cationic moiety can be selected from alkyl imidazole positively charged ion (C 3H 0-4N 2R 1-5 +, promptly on the 1-5 position carbon of imidazole ring 2-5 alkyl substituent can be arranged), alkyl pyridine positively charged ion (C 5H 5NR +), quaternary ammonium salt cationic (R 1R 2R 3R 4N +), season phosphonium salt positively charged ion (R 1R 2R 3R 4P +), and above-mentioned cationic derivative or with one of similar organic cation of above-mentioned cationic structural, wherein, R, R 1, R 2, R 3, R 4, R 5For containing the alkyl of carbon number 1-12.
Said anionicsite is selected from (CF 3SO 2) 2N -, PF 6 -Deng one of negatively charged ion.
In the method provided by the invention, nicotinic acid is catalyzer, wherein SO 3Weight percentage is 2-50%, preferred 5-25%.In the nicotinic acid mole number of element sulphur (according to SO in the nicotinic acid 3Weight percentage calculate) with the ratio of cyclohexanone-oxime mole number be 0.1-0.95, preferred 0.3-0.6.
In the method provided by the invention, the percent by volume of the ionic liquid solution of said nicotinic acid is 5%-90%, preferred 20%-50%.The volumetric molar concentration of the ionic liquid solution of said cyclohexanone-oxime is 0.01-4.0mol/L, preferred 0.5-2.0mol/L.
Method provided by the invention be by liquid phase Beckmann rearrangement reaction by preparing caprolactam with cyclohexanone-oxime, temperature of reaction is 80-150 ℃, preferred 100-130 ℃.
Method provided by the invention can adopt intermittent mode or continuously feeding, discharge method operation.The rearrangement reaction time is 1-60 minute, preferred 5-30 minute when adopting the intermittent mode operation; When adopting the continuous mode operation is 0.01-300 second.
Method provided by the invention has following advantage: (1) per unit hexanolactam by-product sulphur ammonium is few, compares with existing industrial production by-product 1.3-1.8T sulphur ammonium/T hexanolactam, can reduce sulphur ammonium by-product 16% (embodiment 3) to 80% (embodiment 5); (2) in the ammoniacal liquor and after, hydrophobic ionic liquid and ammonia soln phase-splitting realize ion liquid recycling easily; (3) realize easily and being connected of existing technology.
Embodiment
Below by embodiment the present invention is further described, but not thereby limiting the invention.
Embodiment 1
Present embodiment explanation ionic liquid is [bmim]-(CF 3SO 2) 2N] ([bmim] +Be 1-butyl-3-Methylimidazole positively charged ion) time implementation process.
At first in the 100ml round-bottomed flask, add [bmim] [(CF 3SO 2) 2N] ionic liquid 10ml and 4.0g cyclohexanone-oxime, 100 ℃ of oil bath temperature controls, magnetic agitation drips nicotinic acid (SO then 3Quick strong exothermal reaction takes place in 1.09g percentage composition 20-23%), continues to stir 20min, with 10% ammoniacal liquor 10ml neutralization reaction liquid, obtains the profit two-phase, is respectively ammonia soln and [bmim] [(CF of hexanolactam 3SO 2) 2N] ionic liquid, static phase-splitting, the ammonia soln of hexanolactam adopts the process for purification of conventional Industrial processes hexanolactam to obtain hexanolactam, [bmim] [(CF 3SO 2) 2N] ionic liquid uses as the solvent of rearrangement reaction after washing with water once more.
Ammonia soln with 10ml chloroform extraction hexanolactam, use the gas chromatographic analysis chloroform soln again, the transformation efficiency of cyclohexanone-oxime reaches 97.9%, and the selectivity of hexanolactam is 86.8%, the selectivity of pimelinketone is 11.2%, and other matter selectives are 2.0%.
The amount of by-product sulphur ammonium can be calculated by the nicotinic acid that consumes, and S (sulphur) element that every consumption is a mole produces a molar sulphur ammonium, n in the present embodiment S: n Oxime(mol ratio)=0.328, by-product 0.375T sulphur ammonium/T hexanolactam.Compare with existing industrial production by-product 1.3-1.8T sulphur ammonium/T hexanolactam, can reduce sulphur ammonium by-product 71%-79%.
Embodiment 2
Present embodiment explanation ionic liquid is [bmim] [(CF 3SO 2) 2N] implementation process.
At first in the 250ml round-bottomed flask, add [bmim] [(CF 3SO 2) 2N] ionic liquid 100ml and 4.0g cyclohexanone-oxime, 100 ℃ of oil bath temperature controls, magnetic agitation drips nicotinic acid (SO then 3Quick strong exothermal reaction takes place in 2.13g percentage composition 20-23%), continues to stir 10min, with 10% ammoniacal liquor 10ml neutralization reaction liquid, obtains the profit two-phase, is respectively ammonia soln and [bmim] [(CF of hexanolactam 3SO 2) 2N] ionic liquid, static phase-splitting, ammonia soln with 10ml chloroform extraction hexanolactam, use the gas chromatographic analysis chloroform soln again, the transformation efficiency of cyclohexanone-oxime reaches 100.0%, the selectivity of hexanolactam is 83.3%, and the selectivity of pimelinketone is 14.1%, and other matter selectives are 2.6%.[bmim] [(CF 3SO 2) 2N] ionic liquid uses as the solvent of rearrangement reaction after washing with water once more.
N in the present embodiment S: n Oxime(mol ratio)=0.641, by-product 0.717T sulphur ammonium/T hexanolactam.Compare with existing industrial production by-product 1.3-1.8T sulphur ammonium/T hexanolactam, can reduce sulphur ammonium by-product 45%-60%.
Embodiment 3
Present embodiment explanation ionic liquid is [C 3 1C 2 3C 4Im] [PF 6 -] ([C wherein 3 1C 2 3C 4Im] +Be 1-propyl group-3-ethyl-4-methylimidazole positively charged ion) implementation process.
At first in the 250ml round-bottomed flask, add the 4.0g cyclohexanone-oxime, 150 ℃ of oil bath temperature controls, magnetic agitation drips nicotinic acid (SO then 3Percentage composition 2%-3%) [C 3 1C 2 3C 4Im] [PF 6 -] solution (mixing 3.23g nicotinic acid and 70ml[C 3 1C 2 3C 4Im] [PF 6 -]), quick strong exothermal reaction takes place, continue to stir 2min, with 10% ammoniacal liquor 10ml neutralization reaction liquid, obtain the profit two-phase, be respectively the ammonia soln and the [C of hexanolactam 3 1C 2 3C 4Im] [PF 6 -] ionic liquid, static phase-splitting, ammonia soln with 10ml chloroform extraction hexanolactam, use the gas chromatographic analysis chloroform soln again, the transformation efficiency of cyclohexanone-oxime reaches 100.0%, the selectivity of hexanolactam is 88.6%, and the selectivity of pimelinketone is 9.3%, and other matter selectives are 2.1%.[C 3 1C 2 3C 4Im] [PF 6 -] ionic liquid washes the back with water and use as the solvent of rearrangement reaction.
N in the present embodiment S: n Oxime(mol ratio)=0.935, by-product 1.09T sulphur ammonium/T hexanolactam.Compare with existing industrial production by-product 1.3-1.8T sulphur ammonium/T hexanolactam, can reduce sulphur ammonium by-product 16%-39%.
Embodiment 4
Present embodiment explanation ionic liquid is [C 5H 5NC 12] [(CF 3SO 2) 2N] ([C wherein 5H 5NC 12] +Be 12 carbon pyridyliums) implementation process.
At first in the 100ml round-bottomed flask, add [C 5H 5NC 12] [(CF 3SO 2) 2N] ionic liquid 6.0ml and 4.0g cyclohexanone-oxime, 80 ℃ of oil bath temperature controls, magnetic agitation drips nicotinic acid (SO then 3Percentage composition 46%-50%) [C 5H 5NC 12] [(CF 3SO 2) 2N] solution (mixing 1.85g nicotinic acid and 6.0ml[C 5H 5NC 12] [(CF 3SO 2) 2N]), quick strong exothermal reaction takes place, continue to stir 60min, with 10% ammoniacal liquor 20ml neutralization reaction liquid, obtain the profit two-phase, be respectively the ammonia soln and the [C of hexanolactam 5H 5NC 12] [(CF 3SO 2) 2N] ionic liquid, static phase-splitting, extract the ammonia soln of hexanolactam at twice with the 20ml trichloromethane, use the gas chromatographic analysis chloroform soln again, the transformation efficiency of cyclohexanone-oxime reaches 100.0%, the selectivity of hexanolactam is 80.6%, and the selectivity of pimelinketone is 16.7%, and other matter selectives are 2.7%.[C 5H 5NC 12] [(CF 3SO 2) 2N] ionic liquid uses as the solvent of rearrangement reaction after washing with water once more.
N in the present embodiment S: n Oxime(mol ratio)=0.590, by-product 0.685T sulphur ammonium/T hexanolactam.Compare with existing industrial production by-product 1.3-1.8T sulphur ammonium/T hexanolactam, can reduce sulphur ammonium by-product 47%-62%.
Embodiment 5
Present embodiment explanation ionic liquid is [(C 2H 5) 4N] [(CF 3SO 2) 2N] implementation process.
At first in the 100ml round-bottomed flask, add the 10.0g cyclohexanone-oxime, 150 ℃ of oil bath temperature controls, magnetic agitation drips nicotinic acid (SO then 3Percentage composition 20%-23%) [(C 2H 5) 4N] [(CF 3SO 2) 2N] solution (mixing 0.95g nicotinic acid and 20ml[(C 2H 5) 4N] [(CF 3SO 2) 2N]), quick strong exothermal reaction takes place, continue to stir 10min, with 10% ammoniacal liquor 10ml neutralization reaction liquid, obtain the profit two-phase, be respectively [(C 2H 5) 4N] [(CF 3SO 2) 2N] ammonia soln of ionic liquid and hexanolactam, static phase-splitting, ammonia soln with 10ml chloroform extraction hexanolactam, use the gas chromatographic analysis chloroform soln again, the transformation efficiency of cyclohexanone-oxime reaches 35.8%, the hexanolactam selectivity is 78.4%, and the pimelinketone selectivity is 14.1%, and other matter selectives are 7.5%.[(C 2H 5) 4N] [(CF 3SO 2) 2N] ionic liquid washes the back with water and uses as the solvent of rearrangement reaction.
N in the present embodiment S: n Oxime(mol ratio)=0.114, by-product 0.372T sulphur ammonium/T hexanolactam.Compare with existing industrial production by-product 1.3-1.8T sulphur ammonium/T hexanolactam, can reduce sulphur ammonium by-product 72%-80%.The consumption of nicotinic acid is less in the present embodiment, and the transformation efficiency of cyclohexanone-oxime is lower, should not adopt low nicotinic acid consumption.
Embodiment 6
Present embodiment explanation ionic liquid is [(C 4H 9) 4P] [(CF 3SO 2) 2N] implementation process.
At first in the 100ml round-bottomed flask, add [(C 4H 9) 4P] [(CF 3SO 2) 2N] ionic liquid 20ml and 5.0g cyclohexanone-oxime, 100 ℃ of oil bath temperature controls, magnetic agitation drips nicotinic acid (SO then 3Quick strong exothermal reaction takes place in 2.52g percentage composition 20-23%), continues to stir 15min, with 10% ammoniacal liquor 10ml neutralization reaction liquid, obtains the profit two-phase, is respectively the ammonia soln and the [(C of hexanolactam 4H 9) 4P] [(CF 3SO 2) 2N] ionic liquid, static phase-splitting, ammonia soln with 10ml chloroform extraction hexanolactam, use the gas chromatographic analysis chloroform soln again, the transformation efficiency of cyclohexanone-oxime reaches 100.0%, the selectivity of hexanolactam is 85.4%, and the selectivity of pimelinketone is 11.3%, and other matter selectives are 3.3%.[(C 4H 9) 4P] [(CF 3SO 2) 2N] ionic liquid uses as the solvent of rearrangement reaction after washing with water once more.
N in the present embodiment S: n Oxime(mol ratio)=0.608, by-product 0.710T sulphur ammonium/T hexanolactam.Compare with existing industrial production by-product 1.3-1.8T sulphur ammonium/T hexanolactam, can reduce sulphur ammonium by-product 45%-61%.

Claims (14)

1. the method for oleum preparing aminocaprolactam by catalysis in the ionic liquid is characterized in that this method comprises the steps:
(1) adopt one of following three kinds of modes to carry out rearrangement reaction: (a) at first mixed ionic liquid and oleum, obtain the ionic liquid solution of oleum, add cyclohexanone-oxime then and carry out rearrangement reaction; (b) at first mixed ionic liquid and cyclohexanone-oxime obtain the ionic liquid solution of cyclohexanone-oxime, add oleum then and carry out rearrangement reaction; (c) at first mixed ionic liquid and oleum, obtain the ionic liquid solution of oleum, mixed ionic liquid and cyclohexanone-oxime then obtain the ionic liquid solution of cyclohexanone-oxime, and the ionic liquid solution of remix oleum and the ionic liquid solution of cyclohexanone-oxime carry out rearrangement reaction;
(2) add the ammoniacal liquor neutralization, obtain the ammonia soln and the ionic liquid two-phase of hexanolactam, phase-splitting;
(3) return the rearrangement reaction process after the ionic liquid washing;
(4) ammonia soln of hexanolactam enters the FF of hexanolactam in the conventional Industrial processes, is connected with existing commercial run.
2. according to the method for claim 1, it is characterized in that said ionic liquid is a hydrophobic ionic liquid.
3. according to the method for claim 2, the cationic moiety that it is characterized in that said hydrophobic ionic liquid is selected from alkyl imidazole positively charged ion, alkyl pyridine positively charged ion, quaternary ammonium salt cationic, season phosphonium salt positively charged ion.
4. according to the method for claim 2, it is characterized in that the anionicsite of said hydrophobic ionic liquid is selected from (CF 3SO 2) 2N -Or PF 6 -
5. according to the method for claim 1, it is characterized in that said rearrangement reaction temperature is 80-150 ℃.
6. according to the method for claim 1, it is characterized in that said rearrangement reaction temperature is 100-130 ℃.
7. according to the method for claim 1, it is characterized in that SO in the said oleum 3Weight percentage be 2%～50%.
8. according to the method for claim 7, it is characterized in that SO in the said oleum 3Weight percentage be 5%～25%.
9. according to the method for claim 1, it is characterized in that the ratio in the oleum mole number of element sulphur and cyclohexanone-oxime mole number is 0.1～0.95, the oleum mole number is according to SO in the oleum 3Weight percentage calculate.
10. according to the method for claim 9, the oleum mole number is 0.3～0.6 with the ratio of cyclohexanone-oxime mole number.
11. according to the method for claim 1, the percent by volume that it is characterized in that the ionic liquid solution of said oleum is 5%～90%.
12. according to the method for claim 1, the percent by volume that it is characterized in that the ionic liquid solution of said oleum is 20%～50%.
13. according to the method for claim 1, the volumetric molar concentration that it is characterized in that the ionic liquid solution of said cyclohexanone-oxime is 0.01～4.0mol/L.
14. according to the method for claim 1, the volumetric molar concentration that it is characterized in that the ionic liquid solution of said cyclohexanone-oxime is 0.5～2.0mol/L.
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EP2445896A2 (en) * 2009-06-25 2012-05-02 VTU Holding GmbH Method of synthesizing organic molecules in ionic liquids
TWI414508B (en) * 2011-01-17 2013-11-11 China Petrochemical Dev Corp Taipei Taiwan A catalyst composition and a method for preparing an amide using the composition
CN103288734B (en) * 2012-02-29 2015-04-29 北京安耐吉能源工程技术有限公司 Catalyst system for Beckmann rearrangement and method for preparing caprolactam thereof
CN103073405B (en) * 2013-02-04 2015-08-19 河北工业大学 A kind of method of catalysis of pimelinketone oxime hydrolysis reaction in acidic ionic liquid
CN109503484A (en) * 2018-12-29 2019-03-22 清华大学 A method of caprolactam is prepared using higher boiling atent solvent

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