CN100560581C - A kind of method for preparing caprolactone by cyclohexanone by catalytic oxidation - Google Patents
A kind of method for preparing caprolactone by cyclohexanone by catalytic oxidation Download PDFInfo
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- CN100560581C CN100560581C CNB2008100317406A CN200810031740A CN100560581C CN 100560581 C CN100560581 C CN 100560581C CN B2008100317406 A CNB2008100317406 A CN B2008100317406A CN 200810031740 A CN200810031740 A CN 200810031740A CN 100560581 C CN100560581 C CN 100560581C
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Abstract
The present invention relates to a kind of method for preparing caprolactone by cyclohexanone by catalytic oxidation, comprise following step: in reaction vessel, add raw material pimelinketone, oxygenant, solvent, catalyzer respectively, reaction vessel is heated to 40-100 ℃ and isothermal reaction 1-15 hour, and reaction finishes postcooling, separation promptly gets the caprolactone finished product; Wherein, described catalyzer contains other metal oxide of 50-100% zinc oxide and 50-0% by weight percentage; Described solvent is a nitrile; Described oxygenant is hydrogen peroxide or Peracetic Acid.Adopt method provided by the invention can obtain higher caprolactone productive rate and selectivity, and used catalyzer is cheap and easy to get, preparation simply, not halogen-containing element, stability is high and can be repeatedly used.
Description
[technical field]
The present invention relates to the Industrial Catalysis field of petrochemical industry, relate in particular to a kind of method that cyclohexanone by catalytic oxidation prepares caprolactone that is used for.
[background technology]
6-caprolactone is a kind of important organic synthesis intermediate, be mainly used in synthetic polycaprolactone and with other copolymerization of ester class or blending and modifying; 6-caprolactone can also dissolve many fluoropolymer resins as a kind of strong solvent, to the solvency power that the resin of some indissolubles is done well, can dissolve the urethane resin of chlorinated polyolefin resin and " ESTANE " as it.Wherein, polycaprolactone (PCL) is by 6-caprolactone (the linear aliphatic adoption ester of ring-opening polymerization gained of ε-CL).
There is the difficult problem of the aspects such as stability of the security of raw materials quality, production and product in 6-caprolactone synthetic, so its synthetic technology difficulty is big, have only seldom several companies of states such as American and Britain, day producing at present, and China mainly relies on import.
6-caprolactone just synthesized successfully in the laboratory as far back as the thirties in 20th century.Present industrial 6-caprolactone synthesis technique is synthetic through the Baeyer-Villiger reaction by pimelinketone: utilize ozone direct oxidation acetaldehyde in ethyl acetate solvent to obtain Peracetic Acid, the further oxidation pimelinketone of the Peracetic Acid that makes synthesizes thick 6-caprolactone, obtains pure product through vacuum distilling.The key of this technology is the preparation of Peracetic Acid.Because oxygen to directly oxidize acetaldehyde process must be strict controlled in temperature about 0 ℃, when temperature is higher than 20 ℃, acetaldehyde is oxidized to acetate, and what is more important will generate a kind of dangerously explosive intermediate product in oxidising process.In recent years, along with the continuous expansion of 6-caprolactone Application Areas, the market requirement also constantly increases thereupon, and the exploitation of 6-caprolactone synthetic technology is also more and more come into one's own.The synthetic method of the 6-caprolactone that present document has been reported also comprises employing peroxy acid oxidation style, lower concentration H
2O
2, O
2/ air etc. are synthetic ε-lactone of oxygenant oxidation pimelinketone and biological oxidation process, but these methods have the following disadvantages: activity of such catalysts is low, the productive rate of caprolactone and selectivity is relatively poor, catalyzer is not easy to be recycled, or the like.
At the deficiency of existing caprolactone synthesis technique, industry is just being put forth effort on and is being designed and developed out high reactivity, highly selective, low/pimelinketone oxidation pollution-free and that have strong development prospect prepares the effective catalyst and the novel process of caprolactone.
[summary of the invention]
Goal of the invention of the present invention provides and a kind ofly prepares the method for caprolactone by cyclohexanone by catalytic oxidation, to overcome above-mentioned defective of the prior art.
For reaching goal of the invention, the present invention proposes following technical scheme:
A kind of method for preparing caprolactone by cyclohexanone by catalytic oxidation, comprise following step: in reaction vessel, add raw material pimelinketone, oxygenant, solvent, catalyzer respectively, reaction vessel is heated to 40-100 ℃ and isothermal reaction 1-15 hour, and reaction finishes postcooling, separation promptly gets the caprolactone finished product; Wherein, described catalyzer contains other metal oxide of 50-100% zinc oxide and 50-0% by weight percentage; Described solvent is a nitrile; Described oxygenant is hydrogen peroxide or Peracetic Acid.
Preferably, the pimelinketone in the described adding reaction vessel and the weight ratio of catalyzer are 2-30: 1, and the mol ratio 1-15 of oxygenant and pimelinketone: 1, the volume ratio of solvent and pimelinketone is 1-30: 1.
Preferably, the pimelinketone in the described adding reaction vessel and the weight ratio of catalyzer are 4-20: 1, and the mol ratio 1-10 of oxygenant and pimelinketone: 1, the volume ratio of solvent and pimelinketone is 3-20: 1.
Preferably, described nitrile is to be selected from acetonitrile, cyanobenzene, propionitrile or benzyl cyanide.
Preferably, described other metal oxide is to be selected from chromic oxide, titanium oxide, aluminum oxide, zirconium white, cerium oxide, lanthanum trioxide, bismuth oxide or stannic oxide.
Preferably, the preferred titanium oxide of described other metal oxide, chromic oxide, zirconium white or cerium oxide.
Preferably, the condition optimization of described reaction is for being heated to reaction vessel 50-90 ℃ and isothermal reaction 2-10 hour.
Method provided by the present invention can obtain higher caprolactone productive rate and selectivity, and catalyzer is cheap and easy to get, preparation simply, not halogen-containing element, stability is high and can be repeatedly used.
[embodiment]
The present invention will be further described below in conjunction with embodiments of the invention and comparative example:
Embodiment 1
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 30wt% hydrogen peroxide 1.2 grams, 10 milliliters of acetonitriles and catalyzer (zinc oxide) 1.0 grams, closed reactor, reactor is heated to 100 ℃, and, treat that material is chilled to sampling analysis after the room temperature 100 ℃ of isothermal reactions 1 hour.Reaction result is: the transformation efficiency 75.7% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 6 times, do not see its active and selectivity decline yet.
Embodiment 2
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 30wt% hydrogen peroxide 4.0 grams, 6 milliliters of acetonitriles and catalyzer (90wt% zinc oxide+10wt% aluminum oxide) 0.5 gram, closed reactor, reactor is heated to 80 ℃, and, treat that material is chilled to sampling analysis after the room temperature 80 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 89.7% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 4 times, do not see its active and selectivity decline yet.
Embodiment 3
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 30wt% hydrogen peroxide 6.0 grams, 15 milliliters of acetonitriles and catalyzer (80wt% zinc oxide+20wt% lanthanum trioxide) 0.5 gram, closed reactor, reactor is heated to 40 ℃, and, treat that material is chilled to sampling analysis after the room temperature 40 ℃ of isothermal reactions 15 hours.Reaction result is: the transformation efficiency 72.3% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 4 times, do not see its active and selectivity decline yet.
Embodiment 4
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 30wt% hydrogen peroxide 6.0 grams, 10 milliliters of acetonitriles and catalyzer (50wt% zinc oxide+50wt% zirconium white) 0.25 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 82.3% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 5 times, do not see its active and selectivity decline yet.
Embodiment 5
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, Peracetic Acid 6.0 grams, 12 milliliters of propionitrile and catalyzer (90wt% zinc oxide+10wt% titanium oxide) 0.25 gram, closed reactor, reactor is heated to 50 ℃, and, treat that material is chilled to sampling analysis after the room temperature 50 ℃ of isothermal reactions 13 hours.Reaction result is: the transformation efficiency 88.3% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 5 times, do not see its active and selectivity decline yet.
Embodiment 6
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 37wt% hydrogen peroxide 8.0 grams, 12 milliliters of cyanobenzenes and catalyzer (85wt% zinc oxide+15wt% titanium oxide) 0.45 gram, closed reactor, reactor is heated to 60 ℃, and, treat that material is chilled to sampling analysis after the room temperature 60 ℃ of isothermal reactions 13 hours.Reaction result is: the transformation efficiency 89.6% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 5 times, do not see its active and selectivity decline yet.
Embodiment 7
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 37wt% hydrogen peroxide 8.0 grams, 29 milliliters of acetonitriles and catalyzer (95wt% zinc oxide+5wt% cerium oxide) 0.45 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 93.6% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 5 times, do not see its active and selectivity decline yet.
Embodiment 8
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 37wt% hydrogen peroxide 8.0 grams, 25 milliliters of cyanobenzenes and catalyzer (80wt% zinc oxide+20wt% cerium oxide) 0.35 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 83.2% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 7 times, do not see its active and selectivity decline yet.
Embodiment 9
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 37wt% hydrogen peroxide 6.0 grams, 12 milliliters of benzyl cyanides and catalyzer (70wt% zinc oxide+30wt% cerium oxide) 0.3 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 8 hours.Reaction result is: the transformation efficiency 80.5% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 5 times, do not see its active and selectivity decline yet.
Embodiment 10
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 30wt% hydrogen peroxide 8.0 grams, 10 milliliters of acetonitriles and catalyzer (70wt% zinc oxide+30wt% chromic oxide) 0.35 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 76.5% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 6 times, do not see its active and selectivity decline yet.
Embodiment 11
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 30wt% hydrogen peroxide 8.0 grams, 10 milliliters of acetonitriles and catalyzer (75wt% zinc oxide+25wt% bismuth oxide) 0.15 gram, closed reactor, reactor is heated to 90 ℃, and, treat that material is chilled to sampling analysis after the room temperature 90 ℃ of isothermal reactions 4 hours.Reaction result is: the transformation efficiency 73.5% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 4 times, do not see its active and selectivity decline yet.
Embodiment 12
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 30wt% hydrogen peroxide 4.0 grams, 5 milliliters of propionitrile and catalyzer (95wt% zinc oxide+5wt% chromic oxide) 0.05 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 7 hours.Reaction result is: the transformation efficiency 83.7% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 6 times, do not see its active and selectivity decline yet.
Embodiment 13
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 30wt% hydrogen peroxide 1.5 grams, 10 milliliters of acetonitriles and catalyzer (97wt% zinc oxide+3wt% chromic oxide) 0.25 gram, closed reactor, reactor is heated to 80 ℃, and, treat that material is chilled to sampling analysis after the room temperature 80 ℃ of isothermal reactions 4 hours.Reaction result is: the transformation efficiency 82.6% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 6 times, do not see its active and selectivity decline yet.
Embodiment 14
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 30wt% hydrogen peroxide 10.0 grams, 10 milliliters of acetonitriles and catalyzer (99wt% zinc oxide+1wt% zirconium white) 0.034 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 5 hours.Reaction result is: the transformation efficiency 86.7% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 6 times, do not see its active and selectivity decline yet.
Embodiment 15
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 30wt% hydrogen peroxide 10.0 grams, 10 milliliters of acetonitriles and catalyzer (95wt% zinc oxide+5wt% stannic oxide) 0.15 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 89.7% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 6 times, do not see its active and selectivity decline yet.
Embodiment 16
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 30wt% hydrogen peroxide 6.0 grams, 10 milliliters of acetonitriles and catalyzer (55wt% zinc oxide+45wt% zirconium white) 0.05 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 3 hours.Reaction result is: the transformation efficiency 79.7% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 6 times, do not see its active and selectivity decline yet.
Embodiment 17
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, Peracetic Acid 7.0 grams, 25 milliliters of cyanobenzenes and catalyzer (55wt% zinc oxide+45wt% stannic oxide) 1.0 grams, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 76.7% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 6 times, do not see its active and selectivity decline yet.
Embodiment 18
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, Peracetic Acid 4.0 grams, 15 milliliters of acetonitriles and catalyzer (85wt% zinc oxide+15wt% titanium oxide) 0.25 gram, closed reactor, reactor is heated to 80 ℃, and, treat that material is chilled to sampling analysis after the room temperature 80 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 81.7% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 6 times, do not see its active and selectivity decline yet.
Embodiment 19
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 30wt% hydrogen peroxide 8.0 grams, 14 milliliters of acetonitriles and catalyzer (98wt% zinc oxide+2wt% bismuth oxide) 0.35 gram, closed reactor, reactor is heated to 75 ℃, and, treat that material is chilled to sampling analysis after the room temperature 75 ℃ of isothermal reactions 1 hour.Reaction result is: the transformation efficiency 84.7% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 6 times, do not see its active and selectivity decline yet.
Embodiment 20
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 35wt% hydrogen peroxide 6.0 grams, 10 milliliters of acetonitriles and catalyzer (98wt% zinc oxide+2wt% titanium oxide) 0.25 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 80.4% of pimelinketone, the selectivity 100% of caprolactone.In addition, after catalyzer recycles repeatedly through 6 times, do not see its active and selectivity decline yet.
In order to further specify the superiority of catalyzer of the present invention, select following catalyzer for use as a comparison case.
Comparative example 1
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 35wt% hydrogen peroxide 6.0 grams, 10 milliliters of acetonitriles and catalyzer (magnesium oxide) 0.25 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 3.7% of pimelinketone, the selectivity 100% of caprolactone.
Comparative example 2
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 35wt% hydrogen peroxide 6.0 grams, 10 milliliters of acetonitriles and catalyzer (stannic oxide) 0.25 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 2.5% of pimelinketone, the selectivity 100% of caprolactone.
Comparative example 3
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 35wt% hydrogen peroxide 6.0 grams, 10 milliliters of acetonitriles and catalyzer (calcium oxide) 0.25 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 14.9% of pimelinketone, the selectivity 0% of caprolactone.
Comparative example 4
In the stainless steel cauldron of 30 milliliters of inner liner polytetrafluoroethylenes, add pimelinketone 1.0 grams successively, 35wt% hydrogen peroxide 6.0 grams, 10 milliliters of acetonitriles and catalyzer (aluminum oxide) 0.25 gram, closed reactor, reactor is heated to 70 ℃, and, treat that material is chilled to sampling analysis after the room temperature 70 ℃ of isothermal reactions 6 hours.Reaction result is: the transformation efficiency 40% of pimelinketone, the selectivity 2.5% of caprolactone.
Can find out by the foregoing description and comparative example, because technical scheme provided by the present invention has adopted the catalyzer of the transition metal oxide that contains 50-100% zinc oxide and 50-0%, in catalytic oxidation process, can improve the productive rate and the selectivity of caprolactone, cheap and easy to get, the preparation of this catalyzer simultaneously simply, not halogen-containing element, stability be high, and can be repeatedly used and reduce cost.
Claims (6)
1. method for preparing caprolactone by cyclohexanone by catalytic oxidation, comprise following step: in reaction vessel, add raw material pimelinketone, oxygenant, solvent, catalyzer respectively, reaction vessel is heated to 40-100 ℃ and isothermal reaction 1-15 hour, and reaction finishes postcooling, separation promptly gets the caprolactone finished product; Wherein, described catalyzer contains other metal oxide that is selected from chromic oxide, titanium oxide, aluminum oxide, zirconium white, cerium oxide, lanthanum trioxide, bismuth oxide or stannic oxide of 50-100% zinc oxide and 50-0% by weight percentage; Described solvent is a nitrile; Described oxygenant is hydrogen peroxide or Peracetic Acid.
2. the method for preparing caprolactone by cyclohexanone by catalytic oxidation according to claim 1, it is characterized in that, the pimelinketone in the described adding reaction vessel and the weight ratio of catalyzer are 2-30: 1, and the mol ratio 1-15 of oxygenant and pimelinketone: 1, the volume ratio of solvent and pimelinketone is 1-30: 1.
3. the method for preparing caprolactone by cyclohexanone by catalytic oxidation according to claim 2, it is characterized in that, the pimelinketone in the described adding reaction vessel and the weight ratio of catalyzer are 4-20: 1, and the mol ratio 1-10 of oxygenant and pimelinketone: 1, the volume ratio of solvent and pimelinketone is 3-20: 1.
4. according to claim 1ly prepare the method for caprolactone, it is characterized in that described nitrile is to be selected from acetonitrile, cyanobenzene, propionitrile or benzyl cyanide by cyclohexanone by catalytic oxidation.
5. the method for preparing caprolactone by cyclohexanone by catalytic oxidation according to claim 1, it is characterized in that described catalyzer contains other metal oxide that is selected from titanium oxide, chromic oxide, zirconium white or cerium oxide of 50-100% zinc oxide and 50-0% by weight percentage.
6. describedly prepare the method for caprolactone according to any one of claim 1-5, it is characterized in that the condition optimization of described reaction is for being heated to reaction vessel 50-90 ℃ and isothermal reaction 2-10 hour by cyclohexanone by catalytic oxidation.
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Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336734B (en) * | 2010-07-15 | 2013-11-06 | 中国石油化工股份有限公司 | Method for catalytic oxidation preparation of lactone from cycloalkane |
| CN102336620B (en) * | 2010-07-15 | 2014-03-12 | 中国石油化工股份有限公司 | Method for producing lactone by cyclic ketone |
| CN102335624B (en) * | 2010-07-15 | 2013-09-04 | 中国石油化工股份有限公司 | Method for preparing caprolactone and adipic acid |
| CN102452893B (en) * | 2010-10-29 | 2014-08-20 | 中国石油化工股份有限公司 | Method for oxidizing cyclic ketone by utilizing zinc-supported Beta molecular sieve |
| CN102989459B (en) * | 2011-09-16 | 2014-10-29 | 中国科学院大连化学物理研究所 | Catalyst for preparing epsilon-caprolactone by oxidizing cyclohexanone/oxygen under aldehyde-assisted oxidizing action |
| CN102391238B (en) * | 2011-09-28 | 2013-07-03 | 江苏飞翔化工股份有限公司 | Method for preparing epsilon-caprolactone by catalyzing oxidation of cyclohexanone |
| CN102351836A (en) * | 2011-10-14 | 2012-02-15 | 厦门大学 | Method for preparing caprolactone from cyclohexanone through catalytic oxidation |
| CN102408404B (en) * | 2011-11-21 | 2013-05-01 | 上海应用技术学院 | Method for preparing epsilon-caprolactone by oxidizing cyclohexanone through molecular oxygen |
| CN103204775B (en) * | 2012-01-13 | 2015-03-18 | 中国石油化工股份有限公司 | Oxidation method of acetophenone |
| CN102603446B (en) * | 2012-02-13 | 2014-08-06 | 湖南大学 | Method for preparing organic lactone by catalyzing and oxidizing organic ketone with carbon materials |
| CN102603447B (en) * | 2012-02-13 | 2014-09-03 | 湖南大学 | Method for preparing organic lactone |
| CN103274883B (en) * | 2013-06-08 | 2016-04-13 | 中山大学 | A kind of catalyzing ketone compound oxidation prepares the method for lactone |
| CN103951642B (en) * | 2014-04-23 | 2016-07-06 | 南京理工大学 | Method for synthesizing lactone compound by catalytic oxidation of cyclic ketone |
| CN104211675B (en) * | 2014-09-22 | 2016-06-08 | 四川大学 | A kind of method being prepared 6-caprolactone by Ketohexamethylene one step |
| CN105130947B (en) * | 2015-07-21 | 2018-04-17 | 刘小秦 | A kind of industrial process of ε-caprolactone |
| CN105315442A (en) * | 2015-12-01 | 2016-02-10 | 仇颖超 | Preparation method of starch modified polycaprolactone plastic material |
| CN109879853B (en) * | 2019-01-27 | 2020-10-20 | 台州市源众药业有限公司 | Fe2O3/CeO2Method for preparing caprolactone by catalyzing oxidation of cyclohexanone |
| CN110227444B (en) * | 2019-04-04 | 2022-01-07 | 河南能源化工集团研究总院有限公司 | Composite oxide carrier loaded tungsten oxide catalyst and preparation method thereof |
| CN113198472B (en) * | 2021-04-13 | 2023-01-03 | 南京工业大学 | Magnetic catalyst and preparation and application thereof |
| CN114835669A (en) * | 2022-03-23 | 2022-08-02 | 华东理工大学 | Microfluidic synthesis method of high-purity epsilon-caprolactone |
-
2008
- 2008-07-11 CN CNB2008100317406A patent/CN100560581C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| 环己酮氧化合成 -己内酯的研究进展. 程东恩等.武汉化工学院学报，第28卷第4期. 2006 |
| 环己酮氧化合成 -己内酯的研究进展. 程东恩等.武汉化工学院学报，第28卷第4期. 2006 * |
| 高活性MgO/SnO2复合金属氧化物催化剂的合成及其在双氧水选择氧化环己酮制 -己内酯反应中的应用. 李静霞等.化学学报，第66卷第1期. 2008 |
| 高活性MgO/SnO2复合金属氧化物催化剂的合成及其在双氧水选择氧化环己酮制 -己内酯反应中的应用. 李静霞等.化学学报，第66卷第1期. 2008 * |
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