CN101485999B - Lewis acid catalyst as well as preparation method and application thereof in technique for producing acetylacetone by isopropenyl acetate displacement method - Google Patents
Lewis acid catalyst as well as preparation method and application thereof in technique for producing acetylacetone by isopropenyl acetate displacement method Download PDFInfo
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- CN101485999B CN101485999B CN2008101637115A CN200810163711A CN101485999B CN 101485999 B CN101485999 B CN 101485999B CN 2008101637115 A CN2008101637115 A CN 2008101637115A CN 200810163711 A CN200810163711 A CN 200810163711A CN 101485999 B CN101485999 B CN 101485999B
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Abstract
The invention provides a Lewis acid catalyst, a preparation method and application thereof in a process for producing acetylacetone by an isopropenyl acetate dislocation method. The catalyst consists of a complex of aluminum, a complex of tin or a complex of iron and a sulfur element, wherein ratio of the complex of aluminum to the complex of tin or the complex of iron to the sulfur element is 80-20:50-5:20-1. The Lewis acid catalyst can be used for replacing the prior lead tetraethyl or tetramethyllead catalyst with stronger toxicity in a process for preparing the acetylacetone by the isopropenyl acetate dislocation method so as to improve production condition and working environment, improve reaction conversion rate of isopropenyl acetate to 4 to 10 percent, effectively reduce charring coke amount and content of a side product of a high-boiling product in the reaction, and improve quality of the product. The application of the catalyst does not adopt water as a reaction addition agent, so that decomposition of the isopropenyl acetate can be reduced.
Description
Technical field
The present invention relates to a kind of lewis acid catalyst, particularly contain lewis acid catalyst of metal coordination complexs such as aluminium, tin, iron and its production and application.
Background technology
Acetylacetone,2,4-pentanedione is a kind of important chemical intermediate, mainly as chemical pharmacy industry, specifically can be used for the synthetic of antimicrobial LIJUNJING for animals, sulfa drug; Solvent, gasoline and the lubricated oil additive, synthetic intermediate, the metal ion extractant that also can be used as acetate fiber; The metal complex of acetylacetone,2,4-pentanedione is widely used as catalyst etc.
A kind of method that present production acetylacetone,2,4-pentanedione comparatively generally adopts is ketenes-acetone method, and its processing step is: one, adopt acetone or acetic acid cracking at high temperature to generate ketenes; Two, generate isopropenyl acetate (being called for short IPA) with the acetone ketenes; Three, IPA is sent into vaporizer, add lead tetraethide simultaneously or tetramethyl lead is made catalyst, and add entry and make auxiliary agent, IPA after the vaporization and water enter the transposition stove, at high temperature carry out molecular rearrangement reaction and obtain the acetylacetone,2,4-pentanedione crude product; Four, the acetylacetone,2,4-pentanedione crude product obtains the acetylacetone,2,4-pentanedione product through rectification and purification.The major defect that above-mentioned processing step three usefulness isopropenyl acetate transposition legal systems are equipped with the acetylacetone,2,4-pentanedione existence is: the plumbous series catalysts toxicity that is adopted is big, easy contaminated environment, the IPA reaction conversion ratio is low, the charing loss is serious, equipment corrosion is big, and the high-boiling components too high levels makes the separation and purification of products difficulty in the product.
Summary of the invention
Purpose of the present invention, be to be equipped with the existing shortcoming of acetylacetone,2,4-pentanedione technology, and provide a kind of novel Catalysts and its preparation method and this catalyst to be equipped with application process in the acetylacetone,2,4-pentanedione technology in isopropenyl acetate transposition legal system for overcoming above-mentioned isopropenyl acetate transposition legal system.
Technical solution of the present invention is: a kind of lewis acid (Lewis acid) composition metal position rotaring catalyst, complex by aluminium, the complex of tin or the complex of iron and element sulphur are formed, and the complex of aluminium: the complex of tin or the complex of iron: element sulphur=80～20: 50～5: 20～1.
The complex of described aluminium is triethyl aluminum or alchlor.
The complex of described tin is tin octylate or stannous chloride.
The complex of described iron is ferric salicylate or ferric trichloride.
Described element sulphur is a sublimed sulfur.
The preparation method of above-mentioned lewis acid composition metal position rotaring catalyst comprises following process steps:
1., the complex of the complex of tin or iron is dissolved in the alcohols solvent standby, its material proportion is counted by weight, the complex of tin or the complex of iron: alcohols solvent=1: 2～3;
2., in reactor, add isopropenyl acetate, under agitation slowly add the complex of aluminium, feed molar ratio is counted by weight: isopropenyl acetate: the complex of aluminium=100: 3, and 60～70 ℃ of temperature of control;
3., the 1. middle gained material of step is slowly added in the step reactor 2. 60～70 ℃ of control temperature;
4., again in aforesaid reaction vessel, add sublimed sulfur, stir and to be cooled to 50 ℃ after half an hour and promptly to get this catalyst prod with bottom discharge.
Above-mentioned lewis acid composition metal position rotaring catalyst is equipped with application process in the acetylacetone,2,4-pentanedione technology in isopropenyl acetate transposition legal system, comprise following process steps: in isopropenyl acetate (IPA), add catalyst mix and send into vaporizer after evenly, IPA after the vaporization enters the transposition stove, at high temperature carry out molecular rearrangement reaction and obtain the acetylacetone,2,4-pentanedione crude product, reaction equation is: CH
3COOCCH
2CH
3→ CH
3COCH
2COCH
3, and described catalyst is by the complex of aluminium, complex or the complex of iron and the lewis acid composition metal position rotaring catalyst that element sulphur is formed of tin, the reaction temperature of transposition stove is controlled at 610～630 ℃.
The suitable proportion of described catalyst and raw material IPA is IPA: lewis acid composition metal position rotaring catalyst=500: 1～3.
The invention has the beneficial effects as follows: this catalyst is applied to isopropenyl acetate transposition legal system and is equipped with stronger lead tetraethide or the tetramethyl lead catalyst of toxicity that substitutes former conventional use in the acetylacetone,2,4-pentanedione technology, has improved working condition and working environment; The reaction conversion ratio that has improved isopropenyl acetate reaches 4～10%; Reduce simultaneously charing coking amount and the high-boiling components byproduct content in the reaction effectively, improved product quality; Use this catalyst and also removed and use water as reaction promoter, thereby reduced the decomposition of isopropenyl acetate.
The specific embodiment
The invention will be further described with embodiment below.
Embodiment 1, a kind of lewis acid composition metal position rotaring catalyst, by alchlor, stannous chloride and sulphur are formed, and proportion of composing is: alchlor: the inferior tin of chloroethene: element sulphur=80: 50: 20.Its preparation method is:
1., anhydrous stannous chloride under agitation is dissolved in the absolute ethyl alcohol of qdx standby;
2., in reactor, add isopropenyl acetate, under agitation slowly add aluminum trichloride (anhydrous), feed molar ratio is counted by weight, isopropenyl acetate: aluminum trichloride (anhydrous)=100: 3, and 60～70 ℃ of temperature of control;
3., the 1. middle gained material of step is slowly added in the step reactor 2. 60～70 ℃ of control temperature;
4., again in aforesaid reaction vessel, add sublimed sulfur, stir and to be cooled to 50 ℃ after half an hour and promptly to get this catalyst prod with bottom discharge
Above-mentioned lewis acid composition metal position rotaring catalyst is equipped with application process in the acetylacetone,2,4-pentanedione technology in isopropenyl acetate transposition legal system, comprises with acetic acid cracking generating ketenes, obtains isopropenyl acetate with the acetone ketenes then, and concrete processing step is as follows:
1., cracking operation, with 1600 kg of ice acetic acid allocate to concentration be 92%, and under vacuum state, send in the pyrolysis furnace after the vaporization, add 40 kilograms of triethyl phosphates simultaneously and make catalyst, cracking reaction takes place in pyrolysis furnace at 840～925 ℃ of following acetic acid, generate ketene gas and water, the cracking reaction equation is:
CH
3COOH→CH
2CO+H
2O；
2., absorb esterification step, in absorbing esterifying kettle, come the ketene gas of autothermic cracking operation to carry out esterification and generate isopropenyl acetate (abbreviation IPA) with 2000 kilograms of absorptions of acetone, its reaction equation is: CH
3COCH
3+ CH
2CO → CH
3COOCCH
2CH
3, the esterifying liquid in the above-mentioned esterifying kettle is obtained 1590 kilograms of pure IPA through the rectifying separation;
3., transposition operation, 2. adding above-mentioned prepared catalyst among the IPA of gained in step mixes for 3.2 kilograms and sends into vaporizer, enter the transposition stove after the vaporization, carry out molecular rearrangement reaction and obtain 1280 kilograms of acetylacetone,2,4-pentanedione crude products under 610 ± 5 ℃ of temperature, reaction equation is:
CH
3COOCCH
2CH
3→ CH
3COCH
2COCH
3Transposition acetylacetone,2,4-pentanedione yield is 80.5%;
4., the acetylacetone,2,4-pentanedione crude product obtains 1152 kilograms of acetylacetone,2,4-pentanedione products through rectification and purification.
Embodiment 2, a kind of lewis acid composition metal position rotaring catalyst, by triethyl aluminum, tin octylate and sulphur are formed, and proportion of composing is: triethyl aluminum: tin octylate: element sulphur=20: 5: 1.Its preparation method is:
1., anhydrous tin octylate under agitation is dissolved in the absolute ethyl alcohol of qdx standby;
2., in reactor, add isopropenyl acetate, under agitation slowly add anhydrous triethyl aluminum, feed molar ratio is counted by weight: isopropenyl acetate: anhydrous triethyl aluminum=100: 3, and 60～70 ℃ of control temperature;
3., the 1. middle gained material of step is slowly added in the step reactor 2. 60～70 ℃ of control temperature;
4., again in aforesaid reaction vessel, add sublimed sulfur, stir and to be cooled to 50 ℃ after half an hour and promptly to get this catalyst prod with bottom discharge
Above-mentioned lewis acid composition metal position rotaring catalyst is equipped with application process in the acetylacetone,2,4-pentanedione technology in isopropenyl acetate transposition legal system, comprises following process steps:
1., in 1600 kilograms of IPA raw materials, add above-mentioned prepared catalyst and mix for 4.8 kilograms and send into vaporizer, enter the transposition stove after the vaporization, under 625 ± 5 ℃ of temperature, carry out molecular rearrangement reaction and obtain 1280 kilograms of acetylacetone,2,4-pentanedione crude products, reaction equation is:
CH
3COOCCH
2CH
3→ CH
3COCH
2COCH
3Transposition acetylacetone,2,4-pentanedione yield is 80%;
2., the acetylacetone,2,4-pentanedione crude product obtains 1148 kilograms of acetylacetone,2,4-pentanedione products through rectification and purification.
Embodiment 3, a kind of lewis acid composition metal position rotaring catalyst, by alchlor, ferric salicylate and sulphur are formed, and proportion of composing is: alchlor: ferric salicylate: element sulphur=60: 30: 12.Its preparation method is:
1., anhydrous ferric salicylate under agitation is dissolved in the absolute ethyl alcohol of triplication standby;
2., in reactor, add isopropenyl acetate, under agitation slowly add aluminum trichloride (anhydrous), feed molar ratio is counted by weight, isopropenyl acetate: aluminum trichloride (anhydrous)=100: 3, and 60～70 ℃ of temperature of control;
3., the 1. middle gained material of step is slowly added in the step reactor 2. 60～70 ℃ of control temperature;
4., again in aforesaid reaction vessel, add sublimed sulfur, stir and to be cooled to 50 ℃ after half an hour and promptly to get this catalyst prod with bottom discharge
Above-mentioned lewis acid composition metal position rotaring catalyst is equipped with application process in the acetylacetone,2,4-pentanedione technology in isopropenyl acetate transposition legal system, comprises following process steps:
1., in 2000 kilograms of IPA raw materials, add above-mentioned prepared catalyst and mix for 12 kilograms and send into vaporizer, enter the transposition stove after the vaporization, under 616 ± 5 ℃ of temperature, carry out molecular rearrangement reaction and obtain 1622 kilograms of acetylacetone,2,4-pentanedione crude products, reaction equation is:
CH
3COOCCH
2CH
3→ CH
3COCH
2COCH
3Transposition acetylacetone,2,4-pentanedione yield is 81.1%;
2., the acetylacetone,2,4-pentanedione crude product obtains 1460 kilograms of acetylacetone,2,4-pentanedione products through rectification and purification.
Embodiment 4, a kind of lewis acid composition metal position rotaring catalyst, by triethyl aluminum, ferric trichloride and sulphur are formed, and proportion of composing is: triethyl aluminum: ferric trichloride: element sulphur=40: 20: 8.Its preparation method is:
1., anhydrous ferric trichloride under agitation is dissolved in the absolute ethyl alcohol of triplication standby;
2., in reactor, add isopropenyl acetate, under agitation slowly add anhydrous triethyl aluminum, feed molar ratio is counted by weight, isopropenyl acetate: anhydrous triethyl aluminum=100: 3, and 60～70 ℃ of control temperature;
3., the 1. middle gained material of step is slowly added in the step reactor 2. 60～70 ℃ of control temperature;
4., again in aforesaid reaction vessel, add sublimed sulfur, stir and to be cooled to 50 ℃ after half an hour and promptly to get this catalyst prod with bottom discharge
Above-mentioned lewis acid composition metal position rotaring catalyst is equipped with application process in the acetylacetone,2,4-pentanedione technology in isopropenyl acetate transposition legal system, comprises following process steps:
1., in 1800 kilograms of IPA raw materials, add above-mentioned prepared catalyst and mix for 7.2 kilograms and send into vaporizer, enter the transposition stove after the vaporization, under 622 ± 5 ℃ of temperature, carry out molecular rearrangement reaction and obtain 1463 kilograms of acetylacetone,2,4-pentanedione crude products, reaction equation is:
CH
3COOCCH
2CH
3→ CH
3COCH
2COCH
3Transposition acetylacetone,2,4-pentanedione yield is 81.3%;
2., the acetylacetone,2,4-pentanedione crude product obtains 1310 kilograms of acetylacetone,2,4-pentanedione products through rectification and purification.
Claims (8)
1. a lewis acid composition metal position rotaring catalyst is characterized in that the complex by aluminium, and the complex of tin or the complex of iron and element sulphur are formed, and the complex of aluminium: the complex of tin or the complex of iron: element sulphur=80～20: 50～5: 20～1.
2. by the described lewis acid composition metal of claim 1 position rotaring catalyst, the complex that it is characterized in that described aluminium is triethyl aluminum or alchlor.
3. by the described lewis acid composition metal of claim 1 position rotaring catalyst, the complex that it is characterized in that described tin is tin octylate or stannous chloride.
4. by the described lewis acid composition metal of claim 1 position rotaring catalyst, the complex that it is characterized in that described iron is ferric salicylate or ferric trichloride.
5. by the described lewis acid composition metal of claim 1 position rotaring catalyst, it is characterized in that described element sulphur is a sublimed sulfur.
6. the preparation method of a lewis acid composition metal position rotaring catalyst as claimed in claim 1 is characterized in that comprising following process steps:
1., the complex of the complex of tin or iron is dissolved in the alcohols solvent standby, its material proportion is counted by weight, the complex of tin or the complex of iron: alcohols solvent=1: 2～3;
2., in reactor, add isopropenyl acetate, under agitation slowly add the complex of aluminium, feed molar ratio is counted by weight: isopropenyl acetate: the complex of aluminium=100: 3, and 60～70 ℃ of temperature of control;
3., the 1. middle gained material of step is slowly added in the step reactor 2. 60～70 ℃ of control temperature;
4., again in aforesaid reaction vessel, add sublimed sulfur, stir and to be cooled to 50 ℃ after half an hour and promptly to get this catalyst prod with bottom discharge.
7. a lewis acid composition metal position rotaring catalyst as claimed in claim 1 is equipped with application process in the acetylacetone,2,4-pentanedione technology in isopropenyl acetate transposition legal system, comprises following process steps:
Add catalyst mix and send into vaporizer after evenly in isopropenyl acetate (IPA), the IPA after the vaporization enters the transposition stove, at high temperature carries out molecular rearrangement reaction and obtains the acetylacetone,2,4-pentanedione crude product, and reaction equation is: CH
3COOCCH
2CH
3→ CH
3COCH
2COCH
3, it is characterized in that described catalyst is the complex by aluminium, the lewis acid composition metal position rotaring catalyst that the complex of tin or the complex of iron and element sulphur are formed, the reaction temperature of transposition stove is controlled at 610～630 ℃.
8. be equipped with application process in the acetylacetone,2,4-pentanedione technology by the described lewis acid composition metal of claim 7 position rotaring catalyst in isopropenyl acetate transposition legal system, the additional proportion that it is characterized in that described catalyst is IPA: lewis acid composition metal position rotaring catalyst=500: 1～3.
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| CN1850763A (en) * | 2006-05-25 | 2006-10-25 | 宁波王龙集团有限公司 | Process for preparing high-purity acetylacetone |
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| CN1850763A (en) * | 2006-05-25 | 2006-10-25 | 宁波王龙集团有限公司 | Process for preparing high-purity acetylacetone |
Non-Patent Citations (1)
| Title |
|---|
| 梁丽等.气相色谱法测定醋酸异丙烯酯的高温转化反应产物.《化学世界》.2006,88-89页. * |
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