CN100386307C - Method for preparing amide using nonhomogeneous phase oximation rearrangement - Google Patents
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Abstract
The present invention relates to a preparation method of amide by nonhomogeneous phase oximation and rearrangement, particularly to a preparation method of amide by using aliphatic or/and cycloaliphatic ketone as raw material through oximation and rearrangement. The preparation method comprises the following steps: under the condition of the existence of inert solvent, ketone, hydrogen peroxide and ammonia generate a ketoxime solution by catalysis, and oil phase products carry out a Beckmann rearrangement reaction under the action of fuming sulphuric acid to be hydrolyzed and neutralized to prepare amide. The preparation method can shorten the prior process of hydroxylamine oximation or ammonia oximation, reduce the temperature of cyclohexanone oxime rearrangement reaction, and further reduce sulphuric acid consumption and by-products.
Description
Technical field
The present invention relates to a kind of preparation method of acid amides, illustrating further is to be raw material with ketone, resets the preparation acid amides by heterogeneous amidoximeization and heterogeneous Beckmann.
Background technology
Acid amides is that hydroxyl also can be considered as the acyl derivative of ammonia, primary amine or secondary amine by amino or amido metathetical one compounds in the carboxylic acid molecules.Acid amides majority with RCONH2 general formula at room temperature is crystal form, has well water-solublely, is excellent solvent and polymer raw material.The preparation of acid amides has methods such as amine acylations, ammonium carboxylate salt dehydration, nitrile partial hydrolysis and ketoxime rearrangement usually.
Aliphatic ketone or aromatic ketone all can with the derivative such as the azanol generation condensation reaction of ammonia, generate corresponding ketoxime.With acidic substance such as the vitriol oil or phosphorus pentachlorides is catalyzer, and the group occurrence positions on the hydroxyl in the oxime molecule on the nitrogen-atoms and the two key heteropleural carbon atoms exchanges, and generates acid amides, and this class reaction is the Beckmann rearrangement.
By the synthetic ketoxime of ketone, use the Beckmann rearrangement again and can synthesize a series of acid amides.The simple acid amides of aliphatics is not very extensive in industrial purposes at present, but rearrangement of cyclohexanone-oxime system hexanolactam has important industrial significance.
Hexanolactam, the formal name used at school ε-Ji Neixianan is a kind of important petrochemicals, is widely used in making polyamide fibre and engineering plastics.The hexanolactam industrial process mainly contains pimelinketone-hydroxylamine assay, photo-nitrosation of cyclohexane process and toluene method etc.Wherein preceding two class methods are raw material with benzene, generate hexanaphthene by benzene hydrogenation, generate pimelinketone through oxidation again, and pimelinketone and azanol carry out oximation reaction and make cyclohexanone-oxime, then through resetting and treating process acquisition hexanolactam finished product.Prepare the technology difference of azanol by Chu, pimelinketone-azanol operational path mainly contains three kinds of oxammonium sulfate method (HSO method), nitric oxide reduction method (NO method) and phosphatic hydroxylamine methods (HPO method) again.
Above-mentioned three kinds of synthetic methods all have industrialized unit, but the shared ratio of HSO method and NO method is less, and the HSO legal system is equipped with azanol process complexity, and environment is had considerable influence; The NO method is used pure oxygen, and to the processing requirement harshness, even more important problem is all sulphur ammoniums of by-product low value of these two kinds of methods, and is subjected to the influence of market ability to accept.And the circulation of HPO method by inorganic process liquor by-product sulphur ammonium does not have discharge of wastewater, and technology is more reasonable, but exists control to require very fine deficiency equally.
Cyclohexanone oxamidinating technology is catalyzer with the HTS, adopt pimelinketone directly to synthesize with ammonia and hydrogen peroxide and obtain cyclohexanone-oxime, this method technical process is short, has avoided complicated azanol building-up process and the generation of SOx or NOx, and by-product sulphur ammonium is not environmentally friendly.EP0208311 discloses the process that adopts the titanium molecular sieve catalysis cyclohexanone oxamidinating, and EP0496385 and EP0561040 disclose two steps or multistep amidoxime metallization processes to improve the transformation efficiency and the yield of reaction.For solving problems such as amidoxime process catalyst separating and efficient, CN02100227 and CN02100228 disclose amidoxime product and the isolating method of catalyzer continuous sedimentation, and catalyst recirculation is used, and has improved the hydrogen peroxide utilization ratio.
In order to reduce the production cost of hydrogen peroxide and oxime, EP0690045 and US 5599987 disclose the integrated technique of isopropanol oxidation and cyclohexanone oxamidinating, with the HTS is catalyzer, the trimethyl carbinol is a solvent, hydrogen peroxide, ammoniacal liquor and pimelinketone carry out Ammoximation reaction, the gained pimelinketone needs extracting and refining, and solvent and excess of ammonia recycle through fractionation by distillation.
Above-mentioned amidoxime technology has a common feature, and reaction process need add the low-carbon alcohol (for example trimethyl carbinol) of dissolving each other with water as solvent, improves the solubleness of product in system, is beneficial to reaction and carries out.But, selected solvent can not stable existence in the oleum system, must before rearrangement reaction, separate process through repeatedly distilling with extraction etc., mainly have the following disadvantages:
(1) technical process complexity, energy consumption is big;
(2) distillation and extraction are all carried out under comparatively high temps, and the oxime stability of solution is relatively poor relatively, generates trace impurity in follow-up rearrangement, brings difficulty to treating process;
(3) material that enters follow-up rearrangement is the oxime of molten state, and pipeline need be incubated and accompany heat in the production, stops up easily, makes troubles for start-stop car and production operation.
On the other hand, the using cyclohexanone-oxime Beckmann rearrangement reaction process all consumes oleum, and by product ammonium sulfate is a kind of product of low value.U.S. Pat 4804754 and US5264571 disclose multistage rearrangement technology, react than nicotinic acid under the condition and most oxime at lesser temps with than the peracid oxime, to guarantee that viscosity is unlikely too high under the low temperature, suppress side reaction; Follow-up under a little more than previous stage temperature of reaction and low sour oxime mol ratio condition with the reaction of small portion oxime, react completely guaranteeing, reduce the consumption of acid, satisfy the requirement of low sulfuric acid consumption and high final product quality.
Propose to adopt the ammonium salt double decomposition to avoid consuming sulfuric acid among U.S. Pat 3991047 and the US4081442 and generate producing ammonium sulfate byproduct, rearrangement product with in the ammoniacal liquor and the time control reaction pH value, obtain hydrogen sulfate ammonia and hexanolactam.Hexanolactam is by extracting and separating, and hydrogen sulfate ammonia produces sulfurous gas, ammonia G﹠W by pyrolytic reaction, sulfurous gas is made sulfuric acid again and is recycled.The sulfuric acid circulation method has been proposed in the U.S. Pat 3912721, without the gas ammonia neutralization, contain 50% the aqueous solution but further be diluted to, by alkylphenol extraction hexanolactam, and with alkaline solution washing to remove residual sulfuric acid, the percentage extraction of hexanolactam is greater than 99.5%.The aqueous sulfuric acid that contains organic impurity is through concentrating, and thermo-cracking produces sulfurous gas, is used further to produce oleum behind the catalytic dehydration.
But, there is following problem from reaction with the method for separating aspect reduction sulfuric acid consumption and by-product at present:
(1) multistage rearrangement by-product decline scope is less, and under low acid amount and cold condition, material viscosity is big, and is unfavorable to mass transfer and reaction.
(2) ammonium salt metathesis and sulfuric acid circulation technology energy consumption are big, the cost height, thereby do not possess economy.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of technology more simple, be difficult in the production process resulting in blockage, improve reaction mass, reduce sulfuric acid consumption, the preparation method of the acid amides that the ammonium sulfate by-product is lower.
The objective of the invention is to realize in the following way:
Under the condition that is the existence of inert solvent under the oleum system, ketone, hydrogen peroxide and ammonia are carried out the heterogeneous catalysis oximation reaction generate ketoxime; The water-phase product of oximation reaction is equally with inert solvent extraction, its extraction phase and the inert solvent solution that obtains ketoxime after the organic phase product of oximation reaction mixes, and this solution carries out heterogeneous Beckmann rearrangement reaction generation acid amides under the effect of oleum.
Described inert solvent is alkane or naphthenic hydrocarbon, or their mixture.
Described ketone is aliphatic ketone, or cyclic aliphatic ketone, or aromatic ketone, preferred carbonatoms 3～10.
Under the condition that HTS exists, be raw material with pimelinketone, hydrogen peroxide and ammonia, be inert material alkane or naphthenic hydrocarbon under the oleum system, their mixture is an inert solvent, generates cyclohexanone-oxime by heterogeneous catalytic reaction; After product extracts by inert solvent, containing certain free SO
3The oleum effect Beckmann rearrangement reaction takes place down, be hydrolyzed after stopping certain hour, generate the weight two-phase; Gently be inert solvent mutually, heavy phase is hexanolactam-sulphuric acid soln, with in ammonia or the ammoniacal liquor and heavy phase, Crystallization Separation ammonium sulfate, hexanolactam.
Described is inert solvent mutually gently, can be circulated to oximation reaction.
Described inert solvent is taken from the alkane or the naphthenic hydrocarbon of carbonatoms 4～8, or their mixture.
Oximation process provided by the present invention will obtain the two-phase product, gently be solvent mutually, and heavy phase is a water, and cyclohexanone-oxime is distributed in two-phase according to a certain percentage.But rearrangement process must be carried out in anhydrous system, so the cyclohexanone-oxime of water need further separate.Simple effective method is that resulting extraction phase gently is of identical composition mutually with oximation reaction, can mix with the inert solvent aqueous phase extracted of reaction the most.Mixed cyclohexanone-oxime strength of solution is 5%～80% (weight), and is preferred 10～20%, need decide according to solvent types etc.
The present invention is directed to important improvement of original technology is: the contriver has changed thinking, two technologies that inhomogeneous reaction is integrated have been adopted in the present invention, Beckmann rearrangement reaction solvent for use and oximation reaction solvent phase are together, solvent is containing the rearrangement system energy stable existence of oleum, and self any reaction can not take place.So the oximate product need not to make pure oxime by conventional separation means such as distillation, extractions.
Although industrial rearrangement of cyclohexanone-oxime all carries out in oleum, method provided by the present invention mainly embodies following difference:
(1) cyclohexanone-oxime is dissolved in the inert solvent, with the charging of solution mode;
(2) solvent can all gasify in rearrangement process and condensation is reclaimed, perhaps partial gasification, and solvent and phlegma that the reaction posthydrolysis obtains reclaim in the lump;
(3) recovered solvent can be circulated to Ammoximation reaction.
Heterogeneous amidoximeization provided by the invention-solvent is reset integrated technique has bigger improvement and simplification with respect to original technology, and has saved cost widely, can produce economic worth well, particular embodiment in the following areas:
(1) having omitted is the processes such as the necessary alcohol distillation of amidoxime metallization processes, toluene extraction and toluene distillation of solvent with the low-carbon alcohol, and technology is simple, and is easy to operate.
(2) cyclohexanone-oxime that obtains of Ammoximation reaction enters follow-up rearrangement with solution mode rather than fusion mode, has overcome the susceptible to plugging shortcoming of existing technology, and Beckmann rearrangement reaction temperature is further reduced becomes possibility.
(3) solvent is reset and have been solved the low temperature low acid amount material viscosity problems such as the mass transfer effect that brings is not good that rise down, can improve reaction mass, further reduces sulfuric acid consumption and by-product.
Inhomogeneous reaction process provided by the present invention can obtain higher transformation efficiency and yield in following processing range:
Inert solvent and raw ketone are disposable charging;
Hydrogen peroxide and ammoniacal liquor is for progressively dripping mode respectively, perhaps mixes back dropping mode, and the dropping time is 10 minutes～5 hours, and preferred 30 minutes～2 hours, but the termination reaction again of termination reaction or prolong 10 minutes behind reinforced the finishing～after 2 hours;
The mol ratio of hydrogen peroxide and pimelinketone is 1.0～5.0, preferred 1.0～1.2;
In oximation reaction, the concentration of inert solvent is 20%～80%, by percentage to the quality; The oximation reaction temperature is 10～120 ℃, preferred 60～80 ℃.The mol ratio of ammonia and ketone is 0.5～10.
The mol ratio of oleum and the cyclohexanone-oxime (SO in the oleum in the heterogeneous rearrangement process
3Conversion is for sulphur acid meter) be 0.5～4.0, preferred 1.0～1.3, can be lower than existing industrial ratio, corresponding by-product amount reduces.Free SO in the used oleum
3Concentration is 2%～65%, and is preferred 5%～20%, can adjust according to the variation of total acid content.
The rearrangement reaction temperature is at 30～150 ℃, and preferred 60～80 ℃, this will depend on solvent types and working pressure; Reaction time is 1 minute～2 hours, preferred 10～30 minutes.
Embodiment
Just the present invention will be further described for the following examples, and should not be interpreted as limitation of the scope of the invention.
Embodiment 1: add normal hexane 45.0g in advance in the glass reaction still of 250ml band magnetic agitation, methylethylketone 15.2g, HTS 1.5g is warming up to 65 ℃ after the mixing fully, slowly drips the ammoniacal liquor 30.0g of 27.5% (weight ratio) hydrogen peroxide 28.0g and 25% (weight ratio).At the uniform velocity dripped 2.5 hours, and continued reaction 1 hour.Keep in the reaction process stirring, temperature is controlled at 65 ℃.After the cooling standing separation goes out heavy phase, divide three extractions with the 45.0g normal hexane, extraction phase mixes mutually with response light, obtain methyl ethyl ketoxime-hexane solution 105.6g, the gas chromatographic analysis mass concentration is 16.8%, and the methylethylketone transformation efficiency is 99.5%, and the methyl ethyl ketoxime selectivity is 97.1%.In another 250ml reactor, add SO
3Concentration is 5% oleum 15.8g, slowly drips methyl ethyl ketoxime oxime solution.Temperature of reaction is 68 ℃, the whole condensing refluxes of the normal hexane of gasification, total reaction time 30 minutes.Hydrolysis, in and water, obtain N-methyl propanamide 17.6g by liquid-phase chromatographic analysis, reset yield 99.2%.
Embodiment 2: add hexanaphthene, pimelinketone and titanium-silicon molecular sieve catalyst in advance in the glass reaction still of 250ml band magnetic agitation, the hexanaphthene consumption is a hexanaphthene: pimelinketone=3.0: 1 (mol ratio, down together), the HTS mass percent is 2.2%.Begin to drip hydrogen peroxide when being warming up to 70～71 ℃ and ammoniacal liquor carries out oximation reaction, total consumption of hydrogen peroxide and ammonia is a hydrogen peroxide: ammonia: pimelinketone=1.1: 1.9: 1.The dropping time is 2 hours, dropwises the back and continues reaction 1.1 hours.Keep in the reaction process stirring, temperature is controlled at 71 ℃.The water-phase product of reaction is used with the hexanaphthene that reacts equivalent and is divided three extractions, and its extraction phase mixes with the organic phase product of reaction, gets the cyclohexane solution of cyclohexanone-oxime.By the pimelinketone in this solution of gas chromatographic analysis and the content of cyclohexanone-oxime, and calculate transformation efficiency and selectivity.Pimelinketone transformation efficiency 99.4%, cyclohexanone-oxime selectivity are 98.3%.
Comparative Examples 2: repeat the reactive moieties of embodiment 2, difference is that solvent is the trimethyl carbinol.Because pure water dissolves each other, so do not need the extraction process of embodiment 2, by gas-chromatography direct analysis product, reaction result is a pimelinketone transformation efficiency 98.9%, cyclohexanone-oxime selectivity 98.2%.
Embodiment 3: add hexanaphthene 39.2g, pimelinketone 15.1g, titanium-silicon molecular sieve catalyst 3.8g in 250ml glass reaction still.Getting concentration respectively is 27.5% (weight ratio) hydrogen peroxide 23.5g and ammoniacal liquor 33.2g, at the uniform velocity drops in the reactor, and the reinforced time is 2.1 hours.Adopt magnetic agitation, the oil bath temperature control, temperature of reaction is about 72 ℃ under the normal pressure.Continue reaction 1 hour behind reinforced the finishing, cool off, leave standstill, isolate light phase 55.1g, with three extractions of 39.0g hexanaphthene five equilibrium heavy phase, extraction phase and gently mixing mutually obtain cyclohexanone-oxime solution 95.3g.In another 250ml reactor, add SO
3Concentration is 8% oleum 15.8g, slowly drips cyclohexanone-oxime solution.The oil bath temperature control is 80 ℃ under the normal pressure, mechanical stirring, and the hexanaphthene partial condensation of gasification refluxes, total reaction time 20 minutes.In ice-water bath, drip water 6.0g after the stopped reaction, the reaction that is hydrolyzed, controlled temperature is no more than 30 ℃.In and water, obtain hexanolactam 16.9g by stratographic analysis, reset yield 98.8%, the mol ratio of conversion sulfuric acid and hexanolactam is 1.10.
Comparative Examples 3: the oximate part is with embodiment 3, and difference is that solvent is the trimethyl carbinol.The oxime of gained-tertiary butanol and water solution contains cyclohexanone-oxime 15.8%, the trimethyl carbinol 35.5%, and water 46.5%, the trimethyl carbinol is removed in distillation, and the oxime aqueous solution divides three extractions with 51.0g toluene, and extraction phase is removed toluene by distillation again, obtains pure oxime 17.1g.In another 250ml reactor, add SO
3Concentration is 20% oleum 20.9g, slowly drips the molten state cyclohexanone-oxime.The oil bath temperature control is 120 ℃, mechanical stirring, total reaction time 20 minutes.Process such as hydrolysis, neutralization obtains hexanolactam 16.8g with embodiment 3 by liquid-phase chromatographic analysis, resets yield 98.5%, and the mol ratio of conversion sulfuric acid and hexanolactam is 1.50.
Embodiment 4: oximate and rearrangement step are with embodiment 3, and difference is that solvent is a normal heptane, and corresponding temperature of reaction is 98 ℃.The oximation reaction result is a pimelinketone transformation efficiency 99.8%, and cyclohexanone-oxime selectivity 97.3% is reset yield 99.0%.
Claims (14)
1. the method for a preparing amide using nonhomogeneous phase oximation rearrangement under the condition that is the existence of inert solvent under the oleum system, is carried out the heterogeneous catalysis oximation reaction with ketone, hydrogen peroxide and ammonia and is generated ketoxime; The water-phase product of oximation reaction is equally with inert solvent extraction, its extraction phase and the inert solvent solution that obtains ketoxime after the organic phase product of oximation reaction mixes, and this solution carries out heterogeneous Beckmann rearrangement reaction generation acid amides under the effect of oleum.
2. the method for a kind of preparing amide using nonhomogeneous phase oximation rearrangement according to claim 1, described inert solvent is alkane or naphthenic hydrocarbon, or their mixture.
3. the method for a kind of preparing amide using nonhomogeneous phase oximation rearrangement according to claim 1, described ketone is aliphatic ketone or cyclic aliphatic ketone or aromatic ketone.
4. the method for a kind of preparing amide using nonhomogeneous phase oximation rearrangement according to claim 1, under the condition that HTS exists, with pimelinketone, hydrogen peroxide and ammonia is raw material, be inert material alkane or naphthenic hydrocarbon under the oleum system, or their mixture is inert solvent, generates cyclohexanone-oxime by heterogeneous catalytic reaction; After product extracts by inert solvent, containing free SO
3The oleum effect Beckmann rearrangement reaction takes place down, stops and is hydrolyzed generation weight two-phase after 1 minute～2 hours; Gently be inert solvent mutually, heavy phase is hexanolactam-sulphuric acid soln, and with in ammonia or the ammoniacal liquor and heavy phase, crystallization divides ammonium persulfate, hexanolactam.
5. the method for a kind of preparing amide using nonhomogeneous phase oximation rearrangement according to claim 4, described light phase inert solvent is circulated to oximation reaction.
6. the method for a kind of preparing amide using nonhomogeneous phase oximation rearrangement according to claim 4, described inert solvent is taken from the alkane or the naphthenic hydrocarbon of carbonatoms 4～8, or their mixture.
7. the method for a kind of preparing amide using nonhomogeneous phase oximation rearrangement according to claim 4, in oximation reaction, the concentration of inert solvent is 20%～80%, by percentage to the quality; The mol ratio of hydrogen peroxide and pimelinketone is 1.0～5.0, and the mol ratio of ammonia and ketone is 0.5～10.
8. the method for a kind of preparing amide using nonhomogeneous phase oximation rearrangement according to claim 4, the oximation reaction temperature is 10～120 ℃.
9. according to the method for claim 7 or 8 described a kind of preparing amide using nonhomogeneous phase oximation rearrangements, the mol ratio of hydrogen peroxide and pimelinketone is 1.0～1.2; 60～80 ℃ of oximation reaction temperature.
10. according to the method for each described a kind of preparing amide using nonhomogeneous phase oximation rearrangement of claim 4-8, inert solvent and pimelinketone are disposable charging; Hydrogen peroxide and ammoniacal liquor is for progressively dripping mode respectively, perhaps mixes back dropping mode, and the dropping time is 10 minutes～5 hours, but the termination reaction again of termination reaction or prolong 10 minutes behind reinforced the finishing～after 2 hours.
11. the method for a kind of preparing amide using nonhomogeneous phase oximation rearrangement according to claim 4, the mol ratio of rearrangement reaction process oleum and cyclohexanone-oxime are 0.5～4.0, with the SO in the oleum
3Conversion is sulphur acid meter; Free SO in the used oleum
3Concentration is 2%～65%.
12. the method for a kind of preparing amide using nonhomogeneous phase oximation rearrangement according to claim 11, the mol ratio of rearrangement reaction process oleum and cyclohexanone-oxime are 1.0～1.3, with the SO in the oleum
3Conversion is sulphur acid meter; Free SO in the used oleum
3Concentration is 5%～20%.
13. the method for a kind of preparing amide using nonhomogeneous phase oximation rearrangement according to claim 4, rearrangement reaction temperature are at 30～150 ℃.
14. the method for a kind of preparing amide using nonhomogeneous phase oximation rearrangement according to claim 13, rearrangement reaction temperature are 60～80 ℃, reaction time is 10～30 minutes.
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| CNB2005100321840A CN100386307C (en) | 2005-09-23 | 2005-09-23 | Method for preparing amide using nonhomogeneous phase oximation rearrangement |
| JP2008531513A JP5249033B2 (en) | 2005-09-23 | 2006-09-18 | Process for producing amides by heterogeneous oximation and rearrangement |
| PCT/CN2006/002434 WO2007033582A1 (en) | 2005-09-23 | 2006-09-18 | A method for preparing amides by heterogeneous oximation and rearrangement |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10654795B2 (en) | 2017-03-03 | 2020-05-19 | Chemical Technology Academy Of Shandong Province | Method for synthesizing ketoxime |
| WO2022073525A1 (en) | 2020-11-02 | 2022-04-14 | 湖北金湘宁化工科技有限公司 | Method for integrating ammoximation reaction and separation and device thereof |
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| CN101891681B (en) * | 2010-07-09 | 2012-05-16 | 清华大学 | Novel Beckmann rearrangement method for preparing caprolactam from cyclohexanone oxime |
| JP2013129609A (en) * | 2011-12-20 | 2013-07-04 | Sumitomo Chemical Co Ltd | METHOD FOR PRODUCING ε-CAPROLACTAM |
| CN105315211B (en) * | 2014-08-01 | 2018-01-09 | 中国石油化工股份有限公司 | The method that high concentration fuming sulfuric acid catalysis of pimelinketone oxime prepares caprolactam |
| 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 |
| CN104910071A (en) * | 2015-05-08 | 2015-09-16 | 河北美邦工程科技股份有限公司 | Caprolactam preparation method |
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| CN111751471A (en) * | 2020-07-09 | 2020-10-09 | 山东方明化工股份有限公司 | Method for detecting impurity content in caprolactam Beckmann heavy liquid discharge |
| CN114471699B (en) * | 2020-10-28 | 2023-09-19 | 万华化学集团股份有限公司 | Catalyst composition for cyclododecanone ammoximation reaction and application thereof |
| CN112479925B (en) * | 2020-11-30 | 2023-01-20 | 中国天辰工程有限公司 | Method for ammoximation of large naphthenic ketone |
| CN115215307B (en) * | 2021-04-15 | 2024-03-29 | 华东师范大学 | Synthesis method of hydroxylamine solution |
| CN114671808A (en) * | 2022-04-28 | 2022-06-28 | 武亚梅 | Preparation method of caprolactam |
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| US5227525A (en) * | 1991-01-23 | 1993-07-13 | Enichem Anic S.R.L. | Multistep process for the liquid phase ammoximation of carbonyl compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10654795B2 (en) | 2017-03-03 | 2020-05-19 | Chemical Technology Academy Of Shandong Province | Method for synthesizing ketoxime |
| WO2022073525A1 (en) | 2020-11-02 | 2022-04-14 | 湖北金湘宁化工科技有限公司 | Method for integrating ammoximation reaction and separation and device thereof |
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| JP2009508884A (en) | 2009-03-05 |
| CN1762985A (en) | 2006-04-26 |
| WO2007033582A1 (en) | 2007-03-29 |
| JP5249033B2 (en) | 2013-07-31 |
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