CN102643232B - Method for preparing caprolactam by beckmann rearrangement for cyclohexanone-oxime - Google Patents
Method for preparing caprolactam by beckmann rearrangement for cyclohexanone-oxime Download PDFInfo
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Abstract
The invention relates to a method for preparing caprolactam by beckmann rearrangement for cyclohexanone-oxime, which is characterized in that the cyclohexanone-oxime serving as the raw material and organic solvent are dissolved with each other, and then catalyst load heteropoly acid is added into the solution; under the condition of inert gas shielding, liquid-phase or gas-phase reaction is carried out, and the caprolactam can be prepared by the beckmann rearrangement; the load heteropoly acid is tungsten-containing heteropoly acid compound which is obtained by loading heteropoly acid on SiO2 and has a Keggin structure, wherein the molar ratio of P to W to V is 1:(5-15):(1-10); the liquid-phase reaction temperature is 30-150 DEG C, and the weight ratio of the cyclohexanone-oxime to the organic solvent is 1:(5-15); the gas-phase reaction temperature is 250-350 DEG C, and the weight ratio of the cyclohexanone-oxime to the organic solvent is 1:(5-10); and the weight space velocity of the cyclohexanone-oxime is 0.25-25h<-1>. The method is mild in reaction condition and simple in reaction operation, and the conversion rate of the cyclohexanone-oxime and the selectivity of the caprolactam are higher, so that the method is completely suitable for industrial production; and the reaction process is environment-friendly.
Description
Technical field
The present invention is a kind of preparation method of hexanolactam, and particularly the method for hexanolactam is prepared in a kind of cyclohexanone-oxime Beckmann rearrangement.
Background technology
Hexanolactam is a kind of important Organic Chemicals, is the important monomer of manufacturing nylon 6, plastics and film.Industrially generally with cyclohexanone-oxime, under the vitriol oil or nicotinic acid effect, carry out Beckmann rearrangement and prepare, the disadvantage of this method is that equipment corrosion and environmental pollution are serious, and the sulphur ammonium of a large amount of low values of by-product, has increased production cost.Therefore exploitation is the improved target of preparing process of caprolactam without the Beckmann rearrangement novel process of sulphur ammonium by product, also meets the direction of Green Chemistry development.
In order to solve the problem existing in preparing process of caprolactam, the rearrangement technique of oleum is not used in people's research, what research was many at present is the cyclohexanone-oxime gas phase beckmann rearrangement under solid acid catalyst condition, and catalyzer mainly comprises loading type boron oxide catalyzer and molecular sieve catalyst.Wherein SUMITOMO CHEMICAL company has obtained larger progress aspect vapor phase rearrangement, patent documentation USP3, and 574,193, USP5,914,398, USP5,942,613 grades all have take the report of the cyclohexanone-oxime gas phase beckmann rearrangement that oxide compound is catalyzer.Patent documentation USP5,403,801 have reported that the si molecular sieves of processing through inorganic alkali solution is at WHSV=8h
-1while reacting 6.25 h, the transformation efficiency of cyclohexanone-oxime is 99.5%, the selectivity 96.5% of hexanolactam, then pass into the saturated air regeneration 23h that contains methyl alcohol, proceed reaction, be so repeated to the 30th time, reaction 6.25 h, the transformation efficiency of cyclohexanone-oxime is 95.3%, the selectivity 95.3% of hexanolactam.
For cyclohexanone-oxime, through gas phase beckmann rearrangement, produce the reaction system that hexanolactam adopts, comprise fixed bed and fluidized-bed, J.Catal., 1992, the reaction result that 137:252 has reported application of pure si molecular sieves, the fixed bed of take is reaction system, its catalyst life is less than 30 h, and transformation efficiency is 90%, and selectivity is 81%.Use the technology of fluidized-bed at patent documentation US3,154,539, in DE2641408 and patent documentation CN1269360A, there is report, its Patent Literature CN1269360A discloses a kind of processing method of MFI structure molecular screen as Catalyst Production hexanolactam of take in fluidized-bed, in the method, catalyzer is sent to revivifier from reactor continuously or off and on, after the internal circulating load of catalyzer is 20g/h, reaction 200 h, the transformation efficiency of the cyclohexanone-oxime that the method obtains is 99.6%, the selectivity 95.7% of hexanolactam; After the internal circulating load of catalyzer is 200g/h, reaction 200 h, the transformation efficiency of the cyclohexanone-oxime that the method obtains is 97.8%, the selectivity 94.7% of hexanolactam.
Although above cyclohexanone-oxime gas phase beckmann rearrangement technique can avoid producing by product ammonium sulfate, also has wretched insufficiency, as catalyst activity and selectivity not, be unfavorable for existing installation to transform etc.By comparison, the Beckmann rearrangement of cyclohexanone-oxime liquid phase has reaction conditions gentleness, to equipment requirements advantages of higher not, is conducive to existing installation to undergo technological transformation.The technical study of liquid phase rearrangement also makes some progress in recent years, patent documentation GB1029201 discloses in a kind of catalyst system forming at anhydrous acetic acid, diacetyl oxide and sulfonic acid type ion exchange resin, cyclohexanone-oxime generation rearrangement reaction, the hexanolactam generating combines with the sulfonic group of ion exchange resin, then ion exchange resin is separated from rearrangement system, use the water treatment ion exchange resin lower than 5 ℃ to obtain hexanolactam, the productive rate of hexanolactam reaches 95.5% again; At patent documentation US5, with alkylating agent and DMF, do the liquid phase rearrangement system of solvent composition cyclohexanone-oxime in 225,547, the transformation efficiency 100% of cyclohexanone-oxime, the selectivity 99.8% of hexanolactam.
Ionic liquid is also applied in rearrangement of cyclohexanone-oxime reaction as a kind of emerging new catalytic agent material and green solvent, as Zhang Wei etc. utilizes ionic liquid at room temperature 1-butyl-3-Methylimidazole trifluoroacetate, 1-butyl-3-Methylimidazole fluoroborate and normal-butyl pyridine fluoroborate, at PCl
5, P
2o
5or POCl
3deng effect under studied cyclohexanone-oxime Beckmann rearrangement; The two-phase system that patent documentation CN1566089 adopts ionic liquid and organic solvent to form, usings P contained compound as catalyzer, and the transformation efficiency of cyclohexanone-oxime and the selectivity of hexanolactam all approach 100%.Separated owing to using ionic liquid to exist ionic liquid and product to be difficult to, be unfavorable for the shortcomings such as production of the refining and derived product of product thereby unrealized industrialization so far.
Summary of the invention
Technical problem to be solved by this invention is the problem for exploitation faces without the rearrangement of cyclohexanone-oxime technique of sulphur ammonium byproduct in prior art, propose that a kind of technological design is more reasonable, the transformation efficiency of cyclohexanone-oxime and the selectivity of hexanolactam all higher, may be used on the method that hexanolactam is prepared in the large cyclohexanone-oxime Beckmann rearrangement of producing of industry.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is a kind of method that rearrangement of cyclohexanone-oxime is prepared hexanolactam, be characterized in: after the method is dissolved each other raw material cyclohexanone-oxime and organic solvent, add catalyst cupport heteropolyacid or gasification after by the bed of carried heteropoly acid, under protection of inert gas condition, there is liquid phase or gas-phase reaction Beckmann rearrangement and prepare hexanolactam;
Described carried heteropoly acid refers to that loaded by heteropoly acid is at SiO
2on the heteropoly acid containing tungsten compound with Keggin structure, P:W:V(phosphorus wherein: tungsten: mol ratio vanadium) is 1:5 ~ 15:1 ~ 10;
While adopting liquid phase reaction, described organic solvent is polyhalid alkane, many halogen aromatic hydrocarbon or thiophene-based heterogeneous ring compound; During liquid phase reaction, temperature is 30 ~ 150 ℃, and the weight ratio of cyclohexanone-oxime and organic solvent is 1:5 ~ 15, and the reaction times is 1 ~ 10h;
While adopting gas-phase reaction, described organic solvent is the fatty alcohol of 1 ~ 5 carbon atom; During gas-phase reaction, temperature is 250 ~ 350 ℃, and the weight ratio of cyclohexanone-oxime and organic solvent is 1:5 ~ 10, the weight space velocity 0.25 ~ 25h of cyclohexanone-oxime
-1.
Above-described cyclohexanone-oxime Beckmann rearrangement is prepared in the method and technology scheme of hexanolactam: described carried heteropoly acid can be heteropolyacid or its esters of free acid form.
Above-described cyclohexanone-oxime Beckmann rearrangement is prepared in the method and technology scheme of hexanolactam: described rare gas element is preferably nitrogen, VIII A family gas.
Above-described cyclohexanone-oxime Beckmann rearrangement is prepared in the method and technology scheme of hexanolactam: during liquid phase reaction, reaction can adopt intermittence or continuous mode to carry out.During gas-phase reaction, preferably adopt the mode of successive reaction to carry out.
Above-described cyclohexanone-oxime Beckmann rearrangement is prepared in the method and technology scheme of hexanolactam: described carried heteropoly acid can adopt disclosed ordinary method preparation in prior art, also can adopt disclosed method preparation in the present invention.
Compared with prior art, the inventive method has following distinguishing feature:
1. the inventive method has adopted the carried heteropoly acid catalyst with excellent catalytic activity, this catalyzer is acid strong, good stability not only, and environmentally safe, it is genuine green catalyst, be applied in and when hexanolactam is prepared in cyclohexanone-oxime Beckmann rearrangement, can be used for liquid phase reaction, also can be used for gas-phase reaction, and catalytic activity is strong, by embodiment, verifies complete alternative oleum.
2. the inventive method reaction conditions is gentle, and operation is simple, and the transformation efficiency of cyclohexanone-oxime and the selectivity of hexanolactam are all higher, is applicable to suitability for industrialized production completely.
3. the inventive method equipment corrosion is little, by-product sulphur ammonium not, reaction process environmental friendliness.
Accompanying drawing explanation
The infrared spectrogram that Fig. 1 is the hexanolactam that adopts the inventive method and make.
Embodiment
Referring to accompanying drawing, further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not form the restriction to its right.
Embodiment 1, and a kind of rearrangement of cyclohexanone-oxime is prepared the method for hexanolactam, and the method adds catalyst cupport heteropolyacid after raw material cyclohexanone-oxime and organic solvent are dissolved each other, and under protection of inert gas condition, liquid phase reaction Beckmann rearrangement occurs and prepare hexanolactam;
Described carried heteropoly acid refers to that loaded by heteropoly acid is at SiO
2on the heteropoly acid containing tungsten compound with Keggin structure, wherein the mol ratio of P:W:V is 1:5:1;
While adopting liquid phase reaction, described organic solvent is polyhalid alkane, many halogen aromatic hydrocarbon or thiophene-based heterogeneous ring compound; During liquid phase reaction, temperature is 30 ℃, and the weight ratio of cyclohexanone-oxime and organic solvent is 1:5, and the reaction times is 1h.
Embodiment 2, and a kind of rearrangement of cyclohexanone-oxime is prepared the method for hexanolactam, and the method adds catalyst cupport heteropolyacid after raw material cyclohexanone-oxime and organic solvent are dissolved each other, and under protection of inert gas condition, liquid phase reaction Beckmann rearrangement occurs and prepare hexanolactam;
Described carried heteropoly acid refers to that loaded by heteropoly acid is at SiO
2on the heteropoly acid containing tungsten compound with Keggin structure, wherein the mol ratio of P:W:V is 1:15:10;
While adopting liquid phase reaction, described organic solvent is polyhalid alkane, many halogen aromatic hydrocarbon or thiophene-based heterogeneous ring compound; During liquid phase reaction, temperature is 150 ℃, and the weight ratio of cyclohexanone-oxime and organic solvent is 1:15, and the reaction times is 10h.
Embodiment 3, and a kind of rearrangement of cyclohexanone-oxime is prepared the method for hexanolactam, and the method adds catalyst cupport heteropolyacid after raw material cyclohexanone-oxime and organic solvent are dissolved each other, and under protection of inert gas condition, liquid phase reaction Beckmann rearrangement occurs and prepare hexanolactam;
Described carried heteropoly acid refers to that loaded by heteropoly acid is at SiO
2on the heteropoly acid containing tungsten compound with Keggin structure, wherein the mol ratio of P:W:V is 1:10:5;
While adopting liquid phase reaction, described organic solvent is polyhalid alkane, many halogen aromatic hydrocarbon or thiophene-based heterogeneous ring compound; During liquid phase reaction, temperature is 100 ℃, and the weight ratio of cyclohexanone-oxime and organic solvent is 1:10, and the reaction times is 5h.
Embodiment 4, rearrangement of cyclohexanone-oxime is prepared a method for hexanolactam, after the method is dissolved each other raw material cyclohexanone-oxime and organic solvent, after gasification by the bed of carried heteropoly acid, under protection of inert gas condition, there is gas-phase reaction Beckmann rearrangement and prepare hexanolactam;
Described carried heteropoly acid refers to that loaded by heteropoly acid is at SiO
2on the heteropoly acid containing tungsten compound with Keggin structure, wherein the mol ratio of P:W:V is 1:5:1;
While adopting gas-phase reaction, described organic solvent is the fatty alcohol of 1 ~ 5 carbon atom; During gas-phase reaction, temperature is 250 ℃, and the weight ratio of cyclohexanone-oxime and organic solvent is 1:5, the weight space velocity 0.25h of cyclohexanone-oxime
-1.
Embodiment 5, rearrangement of cyclohexanone-oxime is prepared a method for hexanolactam, after the method is dissolved each other raw material cyclohexanone-oxime and organic solvent, after gasification by the bed of carried heteropoly acid, under protection of inert gas condition, there is gas-phase reaction Beckmann rearrangement and prepare hexanolactam;
Described carried heteropoly acid refers to that loaded by heteropoly acid is at SiO
2on the heteropoly acid containing tungsten compound with Keggin structure, wherein the mol ratio of P:W:V is 1:15:10;
While adopting gas-phase reaction, described organic solvent is the fatty alcohol of 1 ~ 5 carbon atom; During gas-phase reaction, temperature is 350 ℃, and the weight ratio of cyclohexanone-oxime and organic solvent is 1:10, the weight space velocity 25h of cyclohexanone-oxime
-1.
Embodiment 6, rearrangement of cyclohexanone-oxime is prepared a method for hexanolactam, after the method is dissolved each other raw material cyclohexanone-oxime and organic solvent, after gasification by the bed of carried heteropoly acid, under protection of inert gas condition, there is gas-phase reaction Beckmann rearrangement and prepare hexanolactam;
Described carried heteropoly acid refers to that loaded by heteropoly acid is at SiO
2on the heteropoly acid containing tungsten compound with Keggin structure, wherein the mol ratio of P:W:V is 1:10:5;
While adopting gas-phase reaction, described organic solvent is the fatty alcohol of 1 ~ 5 carbon atom; During gas-phase reaction, temperature is 300 ℃, and the weight ratio of cyclohexanone-oxime and organic solvent is 1:7, the weight space velocity 2.5h of cyclohexanone-oxime
-1.
Embodiment 7, in the method for embodiment 1-6 described in any one: the heteropolyacid that described carried heteropoly acid is free acid form or its esters.
Embodiment 8, in the method for embodiment 1-7 described in any one: described rare gas element is nitrogen, VIII A family gas.
Embodiment 10, in the method for embodiment 1-3 described in any one: during liquid phase reaction, reaction adopts intermittently or continuous mode is carried out.
Embodiment 11, in the method for embodiment 4-6 described in any one: adopt the mode of successive reaction to carry out during gas-phase reaction.
Embodiment 12, and a kind of rearrangement of cyclohexanone-oxime is prepared the methods experiment of hexanolactam.
Analyse and adopt gas-chromatography (Agilent 7890A, OV-1 capillary column 60m * 0.25mm * 0.25 μ m), using toluene as interior mark, the method for temperature programming is come quantitatively.After finishing, reaction calculates by following formula: cyclohexanone-oxime mole number * 100% of the cyclohexanone-oxime mole number transforming in the transformation efficiency=reaction of cyclohexanone-oxime/add; Mole number * 100% of hexanolactam of the mole number of the selectivity of hexanolactam=actual hexanolactam obtaining/in theory.
In carried heteropoly acid, the mol ratio of P:W:V is 1:8:4.
By the NH of 15.5g
4vO
3na with 11.9g
2hPO
4﹒ 12H
2o is made into respectively the aqueous solution of 500ml and 150ml, regulates pH=6, by the Na of 87.4g with Glacial acetic acid
2wO
4﹒ 2H
2the O 165ml aqueous solution that is made into soluble in water, with the sulfuric acid adjusting pH=4 of 8mol/L, by Na
2hPO
4solution joins NH rallentando
4vO
3in, fully stir, then regulate pH=3 with the sulfuric acid of 8mol/L, in boiling water bath, continuing to be heated with stirring to liquor capacity is 1/5 of original volume, elimination throw out, filtrate is placed 24h, and recrystallization twice again after crystallization, makes (NH
4)
6hPV
4w
8o
40﹒ 14H
2the heteropolyacid of O.
Get 10g silica gel and grind, first dry 4h in 500 ℃ of baking ovens, coolingly soaks a night with deionized water afterwards, then at 180 ℃ dry 10h.
Heteropolyacid 10g 10% the solution that is made into soluble in water of getting above-mentioned preparation, adds the silica gel through above-mentioned processing, stirs 2 h under the condition of room temperature, then standing over night, after dipping, in water-bath, boil off unnecessary moisture content, finally dry for standby under 100 ℃ of conditions, makes carried heteropoly acid catalyst.
The carried heteropoly acid catalyst that adds the above preparation of 1g after the trichloromethane of the cyclohexanone-oxime of 1.13g and 9.04g is mixed is warming up to 50 ℃ of reaction 8 h under nitrogen protection.
Analytical results shows, the transformation efficiency of cyclohexanone-oxime is 99.8%, the selectivity 99.5% of hexanolactam.
Reaction finishes rear elimination catalyzer, under condition of normal pressure, steams trichloromethane, by the thing that steams under negative pressure 2Kpa, through infrared spectrum test, is then hexanolactam, and Fig. 1 is shown in by collection of illustrative plates.
The carried heteropoly acid catalyst that adds the above preparation of 1g after the tetramethylene sulfide of the cyclohexanone-oxime of 1.13g and 13.56g is mixed is warming up to 100 ℃ of reaction 5 h under helium protection.Analytical results shows, the transformation efficiency of cyclohexanone-oxime is 100%, the selectivity 99.7% of hexanolactam.
The carried heteropoly acid catalyst that adds the above preparation of 1g after the orthodichlorobenzene of the cyclohexanone-oxime of 1.13g and 11.30g is mixed is warming up to 120 ℃ of reaction 3h under helium protection.Analytical results shows, the transformation efficiency of cyclohexanone-oxime is 99.9%, the selectivity 99.6% of hexanolactam.
The carried heteropoly acid catalyst of getting the above preparation of 5g packs in the Glass tubing of Φ 10mm, is warming up to 300 ℃ under nitrogen protection, passes into the methanol solution containing 25% cyclohexanone-oxime, and air speed is 0.3 h
-1, sampling analysis after reaction 240 h.Analytical results shows, the transformation efficiency of cyclohexanone-oxime is 99.7%, the selectivity 99.5% of hexanolactam.
Claims (1)
1. a rearrangement of cyclohexanone-oxime is prepared the method for hexanolactam, it is characterized in that: after the method is dissolved each other raw material cyclohexanone-oxime and organic solvent, add catalyst cupport heteropolyacid, under protection of inert gas condition, liquid phase reaction Beckmann rearrangement occurs and prepare hexanolactam;
Described carried heteropoly acid refers to that loaded by heteropoly acid is at SiO
2on the heteropoly acid containing tungsten compound with Keggin structure, wherein the mol ratio of P:W:V is 1:8:4;
The preparation method of carried heteropoly acid catalyst is as follows:
By the NH of 15.5g
4vO
3na with 11.9g
2hPO
4﹒ 12H
2o is made into respectively the aqueous solution of 500ml and 150ml, regulates pH=6, by the Na of 87.4g with Glacial acetic acid
2wO
4﹒ 2H
2the O 165ml aqueous solution that is made into soluble in water, with the sulfuric acid adjusting pH=4 of 8mol/L, by Na
2hPO
4solution joins NH rallentando
4vO
3in, fully stir, then regulate pH=3 with the sulfuric acid of 8mol/L, in boiling water bath, continuing to be heated with stirring to liquor capacity is 1/5 of original volume, elimination throw out, filtrate is placed 24h, and recrystallization twice again after crystallization, makes (NH
4)
6hPV
4w
8o
40﹒ 14H
2the heteropolyacid of O;
Get 10g silica gel and grind, first dry 4h in 500 ℃ of baking ovens, coolingly soaks a night with deionized water afterwards, then at 180 ℃ dry 10h;
Heteropolyacid 10g 10% the solution that is made into soluble in water of getting above-mentioned preparation, adds the silica gel through above-mentioned processing, under the condition of room temperature, stirs 2h, then standing over night, after dipping, in water-bath, boil off unnecessary moisture content, finally dry for standby under 100 ℃ of conditions, makes carried heteropoly acid catalyst;
The carried heteropoly acid catalyst that adds the above preparation of 1g after the trichloromethane of the cyclohexanone-oxime of 1.13g and 9.04g is mixed is warming up to 50 ℃ of reaction 8h under nitrogen protection; Reaction finishes rear elimination catalyzer, under condition of normal pressure, steams trichloromethane, by the thing that steams under negative pressure 2Kpa, through infrared spectrum test, is then hexanolactam;
Or, by adding the carried heteropoly acid catalyst of the above preparation of 1g after the tetramethylene sulfide mixing of the cyclohexanone-oxime of 1.13g and 13.56g, under helium protection, be warming up to 100 ℃ of reaction 5h, obtain;
Or, by adding the carried heteropoly acid catalyst of the above preparation of 1g after the orthodichlorobenzene mixing of the cyclohexanone-oxime of 1.13g and 11.30g, under helium protection, be warming up to 120 ℃ of reaction 3h, obtain;
Or the carried heteropoly acid catalyst of getting the above preparation of 5g packs in the Glass tubing of Φ 10mm, is warming up to 300 ℃ under nitrogen protection, passes into the methanol solution containing 25% cyclohexanone-oxime, air speed is 0.3h
-1, reaction 240h, obtains.
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| EP2935210B1 (en) * | 2012-12-19 | 2016-11-16 | Basf Se | Process for the preparation of purified caprolactam from the beckman rearrangement of cyclohexanoxim |
| CN104725195A (en) * | 2015-04-13 | 2015-06-24 | 江苏三吉利化工股份有限公司 | Method for preparing o-cresol and 2, 6-xylenol by catalysis of heteropolyacid |
| CN114507171B (en) * | 2022-02-24 | 2024-07-23 | 江苏扬农化工集团有限公司 | Preparation method of caprolactam |
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|---|---|---|---|---|
| US2634269A (en) * | 1951-09-21 | 1953-04-07 | Du Pont | Process for manufacturing caprolactam |
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| CN1312133C (en) * | 2004-03-15 | 2007-04-25 | 中国石油化工股份有限公司 | Method for separating Beckmann rearrangement reaction products from ion liquid |
| CN101130167A (en) * | 2007-08-30 | 2008-02-27 | 湘潭大学 | Catalyzer for one-step synthesis of caprolactam |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2634269A (en) * | 1951-09-21 | 1953-04-07 | Du Pont | Process for manufacturing caprolactam |
Non-Patent Citations (6)
| Title |
|---|
| Beckmann rearrangement over phosphotungstic acid/SiMCM-41 cyclohexanone oxime to ε-caprolactam;R. Maheswari等;《Applied Catalysis A:General》;20030808;第248卷(第1-2期);第293页右栏第2.3节、左栏第2.1节 * |
| R. Maheswari等.Beckmann rearrangement over phosphotungstic acid/SiMCM-41 cyclohexanone oxime to ε-caprolactam.《Applied Catalysis A:General》.2003,第248卷(第1-2期),第293页右栏第2.3节、左栏第2.1节. |
| 固体磺酸催化环己酮肟液相Beckmann重排制己内酰胺;曾珍;《湘潭大学硕士学位论文》;20110630;第6-7页1.4.2.3节、第29-30页 * |
| 曾珍.固体磺酸催化环己酮肟液相Beckmann重排制己内酰胺.《湘潭大学硕士学位论文》.2011,第6-7页1.4.2.3节、第29-30页. |
| 曾远晖.有机无机复合杂多酸盐的制备及其催化环己酮氨肟化反应.《湘潭大学硕士学位论文》.2011,第1页第1-3段、第2页第1段、第3页第1.2.1节、第7页倒数第2段. |
| 有机无机复合杂多酸盐的制备及其催化环己酮氨肟化反应;曾远晖;《湘潭大学硕士学位论文》;20110630;第1页第1-3段、第2页第1段、第3页第1.2.1节、第7页倒数第2段 * |
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