CN1130181A - Method for producing amide acetate and caprolactam - Google Patents
Method for producing amide acetate and caprolactam Download PDFInfo
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- CN1130181A CN1130181A CN 95117244 CN95117244A CN1130181A CN 1130181 A CN1130181 A CN 1130181A CN 95117244 CN95117244 CN 95117244 CN 95117244 A CN95117244 A CN 95117244A CN 1130181 A CN1130181 A CN 1130181A
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- carboxylic acid
- oxime
- acid
- hexanolactam
- rearrangement
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Abstract
This invention relates to a process for the use of carboxylic acids in the Beckman transposition of chetoximes to amides with oleum and the production of caprolactam by the transposition of cyclohexanone oxime in the presence of cyclohexylcarboxylic acid. Reduced coproduction of ammonium sulphate, increases in the capacity of existing plants for the production of caprolactam, and the maintenance of a fluid and easily separable mass up to the end of the reaction without the need to use special solvents can be achieved.
Description
The bright method that in ketoxime, oleum Beckmann rearrangement, generates acid amides and in the presence of cyclohexane carboxylic acid, produce hexanolactam that relates to of we through rearrangement of cyclohexanone-oxime with carboxylic acid.
Monomer during hexanolactam can be produced as polyamide 6, so it is a kind of Chemicals of important and widespread use.It can be by the preparation of many methods, but industrial application have only several method, and this is owing to need obtain the product that its quality is applicable to polyreaction with suitable production cost.
Ullmann Encyclopedia of Industrial Chemistry the 5th edition, delivered one piece of up-to-date summary in the A5 volume about the chemical industry present situation of caprolactam production, exercise question is " Caprolactam ", and it has been discussed with the several different methods of cyclohexanone-oxime as intermediate product; Cyclohexanone-oxime changes into hexanolactam (for example referring to the article " The Beckmann Rearrange-ment " of L.G.Donaruma and W.Z.Heldt through Beckmann rearrangement under acidic conditions, be published in Organic Reactions, Vol.11, A.C.Cope, Ed., J.Wi-ley, NY, 1960).
The difference of these methods is to obtain the method difference of cyclohexanone-oxime, resets the reagent difference, the condition difference of resetting.
Rearrangement reagent commonly used is oleum, the concentration difference of its free sulphur trioxide; Also can use dilute sulphuric acid, but poor effect; Also can use spissated oleum, for example referring to O.Wichterle and J.Rocek, Coll.Czech.Chem.Communs., 16, (1951), 591-8.But, the shortcoming of using sulfuric acid or oleum is after reaction finishes, and can produce a large amount of ammonium sulfate, production process difference in recovery and the purifying hexanolactam process, the amount of ammonium sulfate can change to some extent, and hexanolactam per ton can generate with 1.7-5.0 tons vitriol.Though this material can be used as chemical fertilizer on agricultural, it has limited the growth of existing plant capacity as by product, or has limited the construction of new factory.
Therefore studied some new rearrangement reagent, and developed low or do not have the method that vitriol produces.Have in these novel methods recently a kind ofly to be called the method for HPO by DSM, it is recorded in DE-A-2 106385, does not produce the vitriol by product thereby wherein make to reset reagent with phosphoric acid; The BASF method of DE-2 508 247 record only produces a spot of vitriol, and the recirculation of part of sulfuric acid salt is used for the building-up reactions of cyclohexanone-oxime.These methods need complicated and expensive processing, lock out operation and recirculation flow process liquid to reach these effects, and the characteristics of these methods discussed in the article among the above-mentioned Ull-mann " Caprolactam ".
IT-603 606, IT-604 795 and IT-608 793 have introduced a kind of completely new approach of producing hexanolactam to SNIA Viscosa.This method is in sulphuric acid environment hydrogen sulfate nitrous and cyclohexane carboxylic acid reaction to be generated hexanolactam.Though the reagent of this method is different with building-up process, ammonium sulfate is still a kind of byproduct; It is with producing in the ammonia and as the sulfuric acid of solvent and the hydrogen sulfate ion in the hydrogen sulfate nitrous.With the factory that this method is produced, hexanolactam per ton has 4.5 tons of vitriol byproducts approximately.The reaction of hydrogen sulfate nitrous and cyclohexane carboxylic acid is a lactamization, must be at high density SO
3Carry out under existing, cyclohexane carboxylic acid and hydrogen sulfate nitrous mol ratio are 2: 3.Cyclohexane carboxylic acid just part transforms, and reaction contains when finishing and exists the high density should acid in the acid mixture of caprolactam product.
Known sulfurous gas and carboxylic acid can generate adduct, and its general formula is R-COO-SO
3H is referred to as acyl group sulfuric acid usually, and Saul Patai sets forth this with example in " The Chemistry of CarboxylGroups ".Also known hexanolactam is that the form with own lactim vitriol exists in the high-concentration sulfuric acid environment, and it is salifiable enol form hexanolactam.Therefore most of sulfuric acid and sulphur trioxide are in lactamization reaction latter stage, are used for being added to the adduct of organic component mixture, and acid is arranged in the organic component, as cyclohexane carboxylic acid, and alkali, as hexanolactam.
The objective of the invention is to produce hexanolactam with the method that reduces the ammonium sulfate byproduct.
Another object of the present invention is to improve existing throughput of producing hexanolactam factory according to SNIA Viscosa method, but do not increase the amount of byproduct of ammonium sulfate, and factory need not increase new investment in preparation with when subsequently cyclohexane carboxylic acid and hydrogen sulfate nitrous being reacted.
One of purpose of the present invention is at last stage reaction, keeps a kind of liquid mixture, and it can be able to simple separation without special reagent.
Surprisingly, the present invention contain 1-20 carbon atom aliphatic carboxylic acids and/or cycloaliphatic carboxylic acid in the presence of, ketoxime and oleum are generated acid amides through Beckmann rearrangement, thereby have reached above-mentioned purpose.
Particularly, if in containing cyclohexane carboxylic acid, hexanolactam, sulphur trioxide and vitriolic mixture, add cyclohexanone-oxime, cyclohexanone-oxime will become hexanolactam with high yield conversion so, and this addition is further to add on the cyclohexanone-oxime basis that exists in initial reaction mixture.
Especially surprisingly because this reaction conditions is unfavorable to the chemical reactivity of sulfuric acid in the reaction mixture and sulphur trioxide.
Obviously, the present invention has great practicality, and it can utilize can not be by adding the reaction mixture that the hydrogen sulfate nitrous produces hexanolactam again after the lactamization reaction again in the above-mentioned SNIAViscosa patented method in cyclohexane carboxylic acid that still exists and oleum.Thereby do not need to add again oleum and sulfuric acid,, just can further obtain hexanolactam by in the acid mixture that reacted, adding cyclohexanone-oxime again.By summary of the present invention and the more specifically operation of explanation afterwards,, can significantly reduce the ratio between sulphur consumption and the caprolactam product producing the factory of hexanolactam and the new factory of application mix technology with SNIA Viscosa method.
According to the present invention, can utilize a mixture length to produce hexanolactam, the reagent of its first reactions steps is cyclohexane carboxylic acid and hydrogen sulfate nitrous, and the reagent of second reactions steps is cyclohexanone-oxime, and the acid mixture that utilizes first step simultaneously is as resetting reagent.
Also can carry out in the reaction that Beckmann rearrangement generates acid amides with acyl group sulfuric acid as resetting reagent at oxime, wherein the advantage of rearrangement of cyclohexanone-oxime is to contain a kind of fluid and be easy to isolating mixture in the reaction later stage, and this will be more obvious after this.
Condition and range with the rearrangement reaction of acyl group vitriolic is very wide, and optimal acyl group sulfuric acid is low-melting acyl group sulfuric acid that oleum and carboxylic acid form, and just can be used as the good solvent and the liquid agent of reaction mixture like this at reaction remaining carboxylic acid of later stage.Therefore, recommend use to contain 1-20 carbon atoms, the aliphatic carboxylic acid of preferred 1-10 carbon atoms and cycloaliphatic carboxylic acid.The temperature of resetting is 20-150 ℃, preferred 50-100 ℃, considers whether to add the excessive oleum of carboxylic acid for existing.Oleum is estimated excessive use according to the ratio of the mole number of the grammeatom number of sulphur in sulphur trioxide or the sulfuric acid and carboxylic acid in this case.Ratio is excessive greater than 1 explanation oleum, and ratio is less than 1 explanation oleum deficiency.The ratio of mixture is 0.1-10, and preferred have activity 0.5-4 the time.Reaction can be carried out in the presence of suitable volatile compound, can remove in reaction heat by evaporation like this, for example can select aliphatic hydrocarbon such as normal hexane for use, or alicyclic hydrocarbon such as hexanaphthene.
Preferred cyclohexanone-oxime adds in the acid mixture that lactamization reaction produces with certain mol proportion, and it is 0.1-3.0 with the ratio of hexanolactam, and more preferably 0.5-2.5.
For security reasons, simultaneously also for controlled temperature better, can with cyclohexanone-oxime with half in batches form join one by one in the acid mixture that react, perhaps, the factory that produces for successive type can be with serial a plurality of reactors dispersion interpolation cyclohexanone-oximes.
Utilize the final blending product of the lactamization reaction of above-mentioned SNIA Viscosa patented method to carry out containing cyclohexane carboxylic acid in the waste liquid that lactamization reaction exhausts under this particular case of rearrangement of cyclohexanone-oxime, particularly have following mole and form:
Hexanolactam (own lactim vitriol)=1
Sulphur (SO
3And H
2SO
4)=2-4
Cyclohexane carboxylic acid=1-3
The normal hexane that also has non-quantitative in addition can be added to many 2 moles cyclohexanone-oxime in this acid mixture for every mole of initial hexanolactam that exists, thereby well be reset productive rate.In this case, according to the ratio of oxime with the initial hexanolactam that exists, reaction should be carried out under as the boiling temperature of the hydrocarbon of reaction heat conditioning agent at normal hexane or other, and the reaction times should be 1-60 minutes; The amount that adds oxime is many more, and the reaction times is long more.Under barometric point, temperature is 70-80 ℃.Be lower than under the barometric point, temperature can rise to 100 ℃ or high-temperature slightly.Under any circumstance, even at 70 ℃, the flowability of reaction mixture is still very high, can stir effectively and release reaction heat.
The following example describes synthetic method of the present invention but without any restriction.
Embodiment
The acid mixture 31.42g that cyclohexane carboxylic acid and hydrogen sulfate nitrous lactamization reaction are obtained is divided into two parts, every part heavy respectively 15g and 16.42g.That part of 15g analyzed without further handling, found that it contains following composition: the 2.85g hexanolactam; 4.97g unreacted cyclohexane carboxylic acid; 2.04g sulphur trioxide and 5.11g sulfuric acid.With ammonia this acid mixture that neutralizes, generate 11.1g ammonium sulfate, every g hexanolactam generates with 3.9g ammonium sulfate.
In the presence of the 3ml normal hexane, in 74 ℃ of acid mixtures that the 3.57g cyclohexanone-oxime added that part 16.42g, last 15 minutes.Actual measurement is the 6.65g hexanolactam, calculates by the oxime that adds, and productive rate is 98.9%.With ammonia this acid mixture that neutralizes, obtain 12.3g ammonium sulfate, every g hexanolactam is with 1.8g ammonium sulfate.
Claims (9)
1. containing 1-20 carbon atoms, the aliphatic series of preferred 1-10 carbon atoms and/or cycloaliphatic carboxylic acid exist down, and ketoxime and oleum are carried out the method that Beckmann rearrangement generates acid amides.
2. according to the process of claim 1 wherein that described ketoxime is a cyclohexanone-oxime, said acid amides is a hexanolactam.
3. at least one method in requiring according to aforesaid right, wherein said carboxylic acid is a cyclohexane carboxylic acid.
4. at least one method in requiring according to aforesaid right, wherein said cyclohexane carboxylic acid and oleum derive from cyclohexane carboxylic acid and hydrogen sulfate nitrous lactamization reaction.
5. according to the method for claim 4, wherein joining the cyclohexanone-oxime in the acid mixture that derives from described lactamization reaction and the mol ratio of hexanolactam is 0.1-3.0, preferred 0.5-2.5.
6. at least one method in requiring according to aforesaid right, wherein said rearrangement is to carry out under 20 ℃-150 ℃ temperature, preferred 50 ℃-100 ℃.
7. at least one method in requiring according to aforesaid right, wherein said rearrangement be with half in batches form carry out, described oxime is added in the described acid mixture that contains oleum and exhausted carboxylic acid one by one.
8. at least one method in requiring according to aforesaid right, wherein said rearrangement is that the dispersal of feed of described oxime is carried out in one or several reactor continuously.
9. at least one method in requiring according to aforesaid right, wherein said rearrangement is carried out in the presence of a kind of aliphatic solvents.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT001959A/94 | 1994-09-27 | ||
| ITMI941959A IT1270090B (en) | 1994-09-27 | 1994-09-27 | Process for the use of carboxylic acids in the Beckman transposition of chetoximes to amides with oleum and for the production of caprolactam by the transposition of cyclohexanone oxime in the presence of cyclohexylcarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1130181A true CN1130181A (en) | 1996-09-04 |
Family
ID=11369602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95117244 Pending CN1130181A (en) | 1994-09-27 | 1995-09-26 | Method for producing amide acetate and caprolactam |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1130181A (en) |
| IT (1) | IT1270090B (en) |
| RU (1) | RU2125556C1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168524B (en) * | 2007-11-01 | 2010-05-26 | 湘潭大学 | Method for preparing low sulfonated caprolactam |
| WO2024000848A1 (en) * | 2022-06-29 | 2024-01-04 | 中国天辰工程有限公司 | Caprolactam synthesis method free of by-production of ammonium sulfate |
-
1994
- 1994-09-27 IT ITMI941959A patent/IT1270090B/en active IP Right Grant
-
1995
- 1995-09-26 CN CN 95117244 patent/CN1130181A/en active Pending
- 1995-09-26 RU RU95116368A patent/RU2125556C1/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168524B (en) * | 2007-11-01 | 2010-05-26 | 湘潭大学 | Method for preparing low sulfonated caprolactam |
| WO2024000848A1 (en) * | 2022-06-29 | 2024-01-04 | 中国天辰工程有限公司 | Caprolactam synthesis method free of by-production of ammonium sulfate |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1270090B (en) | 1997-04-28 |
| ITMI941959A0 (en) | 1994-09-27 |
| RU2125556C1 (en) | 1999-01-27 |
| ITMI941959A1 (en) | 1996-03-27 |
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