CN102260157B - Method for preparing corresponding diacid by cyclone oxide - Google Patents
Method for preparing corresponding diacid by cyclone oxide Download PDFInfo
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- CN102260157B CN102260157B CN2010101843730A CN201010184373A CN102260157B CN 102260157 B CN102260157 B CN 102260157B CN 2010101843730 A CN2010101843730 A CN 2010101843730A CN 201010184373 A CN201010184373 A CN 201010184373A CN 102260157 B CN102260157 B CN 102260157B
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Abstract
The invention relates to a method for preparing corresponding diacid by cyclone oxide, and is characterized in that a composition composed of a titanium-silicon molecular sieve and multiple-metal oxyacid or a salt thereof are taken as a catalyst, under the temperature of 10 DEG C-160 DEG C and the pressure of 0.1-2.0 MPa, cyclic ketones, hydrogen peroxide, a solvent and the catalyst are reacted according to a mol ratio of 1: 0.1-10 of cyclic ketones to hydrogen peroxide, a mass ratio of 1-1000:1 of solvent to catalyst and a mass ratio of 1-100:1 of cyclic ketones to catalyst. The method has the advantages of high conversion rate of cyclic ketones, good selectivity of corresponding diacid, good catalytic activity and stability. The preparation method is an environment-friendly synthetic process, and has a simple production process which is suitable for industrial production and application.
Description
Technical field
The invention relates to a kind of method of catalytic oxidation of cyclic ketone, further say about a kind of and take HTS and as main composition as catalyzer, oxidizing cyclic ketone, prepare the method for corresponding diacid.
Background technology
Di-carboxylic acid is important industrial chemicals, and wherein important have succinic acid, pentanedioic acid, a hexanodioic acid etc., is the principal monomer of synthon-nylon 66 and the main raw material of nylon engineering plastic as hexanodioic acid.Hexanodioic acid is the main raw material of synthesis of polyurethane foam, synthetic leather (PU), synthetic rubber and film simultaneously.Hexanodioic acid can be used as food acidulant, ester plasticizer and textile treating agent, also can be used for the production of medicine, agricultural chemicals, spices, tackiness agent and soldering flux etc.
In traditional Production Processes of Adipic Acid, be mainly to take benzene to be starting raw material, Hydrogenation hexanaphthene at first, then air oxidation of cyclohexane becomes hexalin and pimelinketone (being commonly called as K-A oil), then with nitric acid, K-A oil is oxidized to hexanodioic acid.This route accounts for more than 90% of global aggregated capacity.At present industrial method by hexalin and oxidizing cyclohexanone production hexanodioic acid is derived from Du Pont's technique in the 1940's, namely under 70～90 ℃ with 40～60% concentrated nitric acid and copper, vanadium catalyst catalyzed oxidation hexalin and Cyclohexanone Production hexanodioic acid, yield is about 80% left and right, reaction needed is used concentrated nitric acid, seriously polluted to equipment corrosion, and can produce the nitrogenous compound that environment is had to severe contamination.And oxidizing ethyle alkyl is produced the technological process of hexalin and pimelinketone and often used homogeneous cobalt catalyst based, product yield is low, needs simultaneously with a large amount of strong acid and strong base solution etching apparatus, contaminate environment.In a word, current industrial the utilization in the multistep technique of hexanaphthene for the raw material production hexanodioic acid, intermediate steps is many, produces a large amount of waste lyes and oxynitrides, the operational condition harshness, cyclohexane oxidation become the transformation efficiency of KA oil general<10%, selectivity 80% left and right, cyclohexane conversion is low and the hexanaphthene internal circulating load is large, energy consumption is high, particularly in the decomposing cyclohexyl hydrogen peroxide process, the selectivity of pimelinketone is poor, and yield is low.Therefore, working out a kind of environmentally friendly and technique simply prepares the diacid novel process by the cyclic ketones environmental friendliness and is of great practical significance.
Last century early eighties, Italy Taramasso is in USP4410501, a kind of new catalytic oxidation material that is called as HTS (TS-1) is disclosed, it has good selective oxidation (EP0230949 to hydrocarbon, alcohol, phenol etc., USP4480135, USP4396783).
UlfSchuchardt etc. (J Catal, 1995,157:631-635) the titanium molecular sieve catalysis oxidizing ethyle alkyl has been carried out to a series of research.From research, drawing: hexanaphthene initial oxidation on TS-1 is hexalin, reoxidizes as pimelinketone.
Summary of the invention
The objective of the invention is the deficiency for existing technique, provide a kind of oxidizing cyclic ketone that is different from existing catalyst system to prepare the method for corresponding diacid.
Oxidizing cyclic ketone provided by the invention prepares the method for corresponding diacid, it is characterized in that adopting the composition of a kind of HTS and multiple-metal oxygen-containing acid or its salt is catalyzer, in temperature, being 10～160 ℃ is under the condition of 0.1～2.0MPa with pressure, by cyclic ketones, hydrogen peroxide, solvent and catalyzer, be 1: 0.1～10 according to the mol ratio of cyclic ketones and hydrogen peroxide, the mass ratio of solvent and catalyzer is 1～1000: 1, and cyclic ketones and the mass ratio of catalyzer are to react under 1～100: 1 ratio.
In method provided by the invention, said HTS can be selected from one or more in TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, Ti-ZSM-48, is preferably titanium-silicon molecular sieve TS-1, and this molecular sieve has the MFI crystalline structure.
In method provided by the invention, said multiple-metal oxygen-containing acid or salt, can be heteropllyacids or heteropoly blue class.Said heteropolyacid is well known to those skilled in the art, and heteropolyacid contains oxygen polyacid by certain structure by the class that the oxygen atom ligand bridging forms by heteroatoms (as P, Si, Fe, Co etc.) and polyatom (as Mo, W, V, Nb, Ta etc.).Heteropoly blue is the general name of the transition metal heteropolyacid salt of a large class lower valency.Heteropoly blue is obtained by the heteropolyacid salt reduction usually, and for example phosphato-molybdic heteropolyacid obtains blue phosphorus molybdenum blue with Reduction with Stannous Chloride.[SiWO for example again
39]
8-Reducible is [SiWO
40]
6-Blue compound, tungsten wherein be+5 with the mixed valence of+6 valencys.P
3+, Fe
3+And Cr
3+Also can replace the position of a tungsten atom.In method provided by the invention, said heteropolyacid or heteropoly blue can be phosphorus tungsten class heteropolyacid or heteropoly blue, molybdenum tungsten class heteropolyacid or heteropoly blue, phosphorus vanadium class heteropolyacid or heteropoly blue, molybdenum vanadium class heteropolyacid or heteropoly blue, tungsten silicon class heteropolyacid or heteropoly blue etc.
In method provided by the invention, said multiple-metal oxygen-containing acid or salt, can be also isopoly-acid or isopoly-acid salt.Said isopoly-acid is well known to those skilled in the art, and isopoly-acid, by the class acid that identical acid anhydrides forms, also can be thought the acid that two or more simple oxygen acid molecule of the same race condensations form.What in transition metal, easily form isopoly-acid has the elements such as Mo, W, V, Cr, for example a H
4V
2O
7, H
6V
4O
13, H
7V
5O
16, H
6V
10O
28H
6M
7O
24, H
4Mo
8O
26, H
10Mo
12O
41Deng.Hydrogen ion in isopoly-acid is replaced and can generate corresponding isopoly-acid salt by metal ion, or is called with how blue.
In method provided by the invention, in said catalyzer, the mass ratio of the acid of HTS and multiple-metal oxygen-containing or its salt is preferably 0.05～100: 1, more preferably 0.1～50: 1.
In method provided by the invention, the raw material optimum ratio is as follows: the mol ratio of cyclic ketones and hydrogen peroxide is preferably 1: 0.2～and 5, the mass ratio of solvent and catalyzer is preferably 5～200: 1.
In method provided by the invention, temperature of reaction is preferably 20～120 ℃, and reaction pressure is preferably 0.1～1.5MPa.
In method provided by the invention, said cyclic ketones can be corresponding methyl such as pimelinketone, cyclopentanone and methylcyclohexanone, methyl-cyclopentanone etc., ethyl, halogeno-group and other substituents.Be monomethyl pimelinketone, monomethyl cyclopentanone, single ethyl cyclohexanone, single ethyl cyclopentanone, 1,2-dimethylcyclohexanon, 1,3-dimethylcyclohexanon, halo pimelinketone, halo cyclopentanone etc.
In method provided by the invention, said solvent is selected from the alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, or the ketones such as acetone, butanone, or the nitrile such as acetonitrile, or multiple mixing in above-mentioned alcohol, ketone, nitrile, preferred solvent is one or more the mixing in methyl alcohol, acetonitrile, acetone.
In method provided by the invention, can adopt periodical operation or operate continuously mode.When andnon-continuous operation manner is carried out, after solvent, catalyzer are added to reactor, add continuously cyclic ketones, hydrogen peroxide; And continuous mode can adopt fixed-bed reactor while carrying out, and after the catalyzer of packing into, solvent, cyclic ketones, hydrogen peroxide is added continuously; Also can adopt slurry bed reactor, will catalyzer, add continuously cyclic ketones, hydrogen peroxide after the solvent making beating, continuous separated product simultaneously.
Method provided by the invention can also adopt closed still reaction, and soon catalyzer, solvent, cyclic ketones and hydrogen peroxide add simultaneously in still and mix afterreaction.
In method provided by the invention, preferred embodiment to be that 30～130 ℃ and pressure are under the condition of 0.2～1.5MPa in temperature, by cyclic ketones, hydrogen peroxide, solvent and catalyzer contact reacts, wherein, the mol ratio of cyclic ketones and hydrogen peroxide is 1: 0.2～5, the mass ratio of solvent and catalyzer is 5～200: 1, and the mass ratio of cyclic ketones and catalyzer is 5～80: 1, the ratio 0.5～50: 1 of the acid of HTS and multiple-metal oxygen-containing or its salt in catalyzer.
Oxidizing cyclic ketone provided by the invention prepares the method for corresponding diacid, and the cyclohexanone by catalytic oxidation of take prepares hexanodioic acid and is example, has following advantage:
1, reaction conditions gentleness;
2, its catalytic oxidation activity and stability of catalytic activity are better;
3, this preparation method is green synthesis process, whole production process environmental friendliness, and without the special producing equipment requirements, production process is simple, easily controls, and is beneficial to suitability for industrialized production and application.
Embodiment
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.
In embodiment and Comparative Examples, reagent used is commercially available chemically pure reagent.HTS used (TS-1) catalyzer is the method preparation by prior art (Zeolites, 943rd～950 pages of 1992, Vol.12).
In Comparative Examples and embodiment:
Comparative Examples 1
By pimelinketone, hydrogen peroxide and solvent, being 1: 2 according to the mol ratio of pimelinketone and hydrogen peroxide, is that 30 ℃ of pressure are to react under 1.5MPa in temperature.React after 2 hours, the transformation efficiency of pimelinketone is 2.5%; The hexanodioic acid selectivity is 6%.React after 15 hours, the transformation efficiency of pimelinketone is 2.4%; The hexanodioic acid selectivity is 8%.
Comparative Examples 2
By pimelinketone, hydrogen peroxide, solvent and catalyzer (TS-1), it is 1: 2 according to the mol ratio of pimelinketone and hydrogen peroxide, solvent methanol is 20 with the catalyst quality ratio, the mass ratio of pimelinketone and catalyzer is 20, is that 50 ℃ of pressure are to react under 1.5MPa in temperature.The result of reacting 2 hours is as follows: the pimelinketone transformation efficiency is 14%; The hexanodioic acid selectivity is 13%.The result of reacting 15 hours is as follows: the pimelinketone transformation efficiency is 12%; The hexanodioic acid selectivity is 16%.
Embodiment 1
By pimelinketone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 10), it is 1: 2 according to the mol ratio of pimelinketone and hydrogen peroxide, solvent methanol is 20 with the catalyst quality ratio, the mass ratio of pimelinketone and catalyzer is 20, is that 50 ℃ of pressure are to react under 1.5MPa in temperature.The result of reacting 2 hours is as follows: the pimelinketone transformation efficiency is 76%; The hexanodioic acid selectivity is 94%.The result of reacting 15 hours is as follows: the pimelinketone transformation efficiency is 74%; The hexanodioic acid selectivity is 92%.
Embodiment 2
By pimelinketone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and molybdenum tungsten heteropoly blue is 2), it is 1: 2 according to the mol ratio of pimelinketone and hydrogen peroxide, the mass ratio of solvent methanol and catalyzer is 120, the mass ratio of pimelinketone and catalyzer is 40, is that 30 ℃ of pressure are to react under 1.5MPa in temperature.The result of reacting 2 hours is as follows: the pimelinketone transformation efficiency is 53%; The hexanodioic acid selectivity is 92%.The result of reacting 15 hours is as follows: the pimelinketone transformation efficiency is 47%; The hexanodioic acid selectivity is 89%.
Embodiment 3
By 1,3-dimethylcyclohexanon, hydrogen peroxide, solvent and catalyzer (TS-1 is 50 with the mass ratio with the vanadium polyacid) are 1: 5 according to the mol ratio of cyclic ketones and hydrogen peroxide, the mass ratio of solvent acetone and catalyzer is 200, the mass ratio of cyclic ketones and catalyzer is 80, is that 60 ℃ of pressure are to react under 1.0MPa in temperature.The result of reacting 2 hours is as follows: the cyclic ketones transformation efficiency is 74%; The diacid selectivity is 94%.The result of reacting 15 hours is as follows: the cyclic ketones transformation efficiency is 72%; The diacid selectivity is 91%.
Embodiment 4
By pimelinketone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and phosphato-molybdic heteropolyacid is 8), it is 1: 4 according to the mol ratio of pimelinketone and hydrogen peroxide, the mass ratio of solvent tertiary butanol and catalyzer is 80, the mass ratio of pimelinketone and catalyzer is 2, is that 40 ℃ of pressure are to react under 0.5MPa in temperature.The result of reacting 2 hours is as follows: the pimelinketone transformation efficiency is 92%; The hexanodioic acid selectivity is 92%.The result of reacting 15 hours is as follows: the pimelinketone transformation efficiency is 88%; The hexanodioic acid selectivity is 90%.
Embodiment 5
By cyclopentanone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and phosphorus tungsten heteropoly blue is 20), it is 1: 3 according to the mol ratio of cyclic ketones and hydrogen peroxide, the mass ratio of aqueous solvent and catalyzer is 180, the mass ratio of cyclic ketones and catalyzer is 5, is that 90 ℃ of pressure are to react under 1.0MPa in temperature.The result of reacting 2 hours is as follows: the cyclic ketones transformation efficiency is 89%; The diacid selectivity is 96%.The result of reacting 15 hours is as follows: the cyclopentanone transformation efficiency is 86%; The pentanedioic acid selectivity is 92%.
Embodiment 6
By ethyl cyclopentanone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and ammonium phosphomolybdate is 0.1), it is 3: 1 according to the mol ratio of cyclic ketones and hydrogen peroxide, the mass ratio of solvent methanol and catalyzer is 10, the mass ratio of cyclic ketones and catalyzer is 10, is that 50 ℃ of pressure are to react under 0.5MPa in temperature.The result of reacting 2 hours is as follows: the cyclic ketones transformation efficiency is 32%; The diacid selectivity is 93%.The result of reacting 15 hours is as follows: ethyl cyclopentanone transformation efficiency is 31%; The ethylglutaric acid selectivity is 88%.
Embodiment 7
By pimelinketone, hydrogen peroxide, solvent and catalyzer (TS-1 with the mass ratio of molybdenum polyacid, be 100), it is 5: 1 according to the mol ratio of pimelinketone and hydrogen peroxide, the mass ratio of solvent acetone and catalyzer is 150, the mass ratio of pimelinketone and catalyzer is 100, is that 40 ℃ of pressure are to react under 0.5MPa in temperature.The result of reacting 2 hours is as follows: the pimelinketone transformation efficiency is 19%; The hexanodioic acid selectivity is 94%.The result of reacting 15 hours is as follows: the pimelinketone transformation efficiency is 15%; The hexanodioic acid selectivity is 93%.
Embodiment 8
By pimelinketone, hydrogen peroxide, solvent and catalyzer (TS-1 with the mass ratio of tungsten polyacid ammonium, be 40), it is 2: 1 according to the mol ratio of pimelinketone and hydrogen peroxide, the mass ratio of solvent acetonitrile and catalyzer is 40, the mass ratio of pimelinketone and catalyzer is 60, is that 70 ℃ of pressure are to react under 1.5MPa in temperature.The result of reacting 2 hours is as follows: the pimelinketone transformation efficiency is 61%; The hexanodioic acid selectivity is 93%.The result of reacting 15 hours is as follows: the pimelinketone transformation efficiency is 59%; The hexanodioic acid selectivity is 90%.
Embodiment 9
By methylcyclohexanone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and tungsten sila polyacid is 0.5), it is 1: 1 according to the mol ratio of cyclic ketones and hydrogen peroxide, solvent methanol is 60 with the catalyst quality ratio, the mass ratio of cyclic ketones and catalyzer is 1, is that 60 ℃ of pressure are to react under 1.0MPa in temperature.The result of reacting 2 hours is as follows: the cyclic ketones transformation efficiency is 83%; The diacid selectivity is 95%.The result of reacting 15 hours is as follows: the methylcyclohexanone transformation efficiency is 81%; Methyl hexanodioic acid selectivity is 93%.
Embodiment 10
The process that the present embodiment explanation utilizes catalyzer (TS-1 is 10 with the mass ratio of phosphorus heteropoly tungstic acid) to react in the tank reactor of sealing.
By pimelinketone, hydrogen peroxide, solvent acetone and catalyzer, it is 1: 4 according to the mol ratio of pimelinketone and acetone, hydrogen peroxide, the mass ratio of acetone and catalyzer is 50, the mass ratio of pimelinketone and catalyzer is 20, is that 60 ℃ of pressure are to react under 0.6MPa in temperature.The result of reacting 2 hours is as follows: the pimelinketone transformation efficiency is 26%; The hexanodioic acid selectivity is 96%.The result of reacting 15 hours is as follows: the pimelinketone transformation efficiency is 91%, and the hexanodioic acid selectivity is 92%.
Embodiment 11
By ethyl cyclohexanone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and molybdenum vanadium class heteropolyacid is 15), it is 2: 5 according to the mol ratio of pimelinketone and hydrogen peroxide, the mass ratio of solvent butanone and catalyzer is 60, the mass ratio of cyclic ketones and catalyzer is 80, is that 50 ℃ of pressure are to react under 0.2MPa in temperature.The result of reacting 2 hours is as follows: the ethyl cyclohexanone transformation efficiency is 73%; Ethyl hexyl diacid selectivity is 90%.The result of reacting 15 hours is as follows: the cyclic ketones transformation efficiency is 66%; The diacid selectivity is 87%.
Embodiment 12
By cyclopentanone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and the Phosphorus heteropoly blue of molybdenum is 20), it is 2: 7 according to the mol ratio of cyclic ketones and hydrogen peroxide, the mass ratio of etoh solvent and catalyzer is 30, the mass ratio of pimelinketone and catalyzer is 50, is that 80 ℃ of pressure are to react under 1.2MPa in temperature.The result of reacting 2 hours is as follows: the cyclic ketones transformation efficiency is 65%; The diacid selectivity is 88%.The result of reacting 15 hours is as follows: the cyclopentanone transformation efficiency is 59%; The pentanedioic acid selectivity is 83%.
Embodiment 13
By chloro pimelinketone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and tungsten silicon class heteropoly blue is 60), it is 2: 9 according to the mol ratio of pimelinketone and hydrogen peroxide, the mass ratio of solvent butanone and catalyzer is 40, the mass ratio of cyclic ketones and catalyzer is 90, is that 60 ℃ of pressure are to react under 0.1MPa in temperature.The result of reacting 2 hours is as follows: the cyclic ketones transformation efficiency is 79%; The diacid selectivity is 86%.The result of reacting 15 hours is as follows: chloro pimelinketone transformation efficiency is 75%; Chloro hexanodioic acid selectivity is 82%.
From embodiment and Comparative Examples, can find out: the inventive method catalytic activity is high, and selectivity is good, and especially stability of catalytic activity is better.Illustrate that the inventive method catalytic oxidation activity and selectivity are high, have simultaneously stability of catalytic activity preferably.
Claims (6)
1. a catalytic oxidation of cyclic ketone prepares the method for corresponding diacid, it is characterized in that adopting the composition of a kind of HTS and multiple-metal oxygen-containing acid or its salt is catalyzer, in temperature, being 10～160 ℃ is under the condition of 0.1～2.0MPa with pressure, by cyclic ketones, hydrogen peroxide, solvent and catalyzer are 1:0.1～10 according to the mol ratio of cyclic ketones and hydrogen peroxide, the mass ratio of solvent and catalyzer is 1～1000:1, cyclic ketones and the mass ratio of catalyzer are to react under the ratio of 1～100:1, wherein in catalyzer, the mass ratio of HTS and multiple-metal oxygen-containing acid or its salt is 0.05～100:1, said HTS is TS-1, said multiple-metal oxygen-containing acid is phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, with the molybdenum polyacid, tungsten sila polyacid or molybdenum vanadium heteropolyacid, said Polyoxometalate is molybdenum tungsten heteropoly blue, phosphorus tungsten heteropoly blue, molybdenum phosphorus heteropoly blue or tungsten silicon heteropoly blue.
2. according to the method for claim 1, in said catalyzer, the mass ratio of HTS and multiple-metal oxygen-containing acid or its salt is 0.1～50:1.
3. according to the method for claim 1, the mol ratio of said cyclic ketones and hydrogen peroxide is 1:0.2～5, and the mass ratio of solvent and catalyzer is 5～200:1.
4. according to the method for claim 1, it is characterized in that temperature of reaction is 20～120 ℃, reaction pressure is 0.1～1.5MPa.
5. according to the method for claim 1, it is characterized in that said cyclic ketones is pimelinketone, cyclopentanone, methylcyclohexanone, methyl-cyclopentanone, ethyl cyclohexanone, ethyl cyclopentanone, 1,2-dimethylcyclohexanon, 1,3-dimethylcyclohexanon, halo pimelinketone, halo cyclopentanone.
6. according to the method for claim 1, it is characterized in that in temperature, being 30～130 ℃ is under the condition of 0.2～1.5MPa with pressure, by cyclic ketones, hydrogen peroxide, solvent and catalyzer contact reacts, wherein, the mol ratio of cyclic ketones and hydrogen peroxide is 1:0.2～5, the mass ratio of solvent and catalyzer is 5～200:1, and the mass ratio of cyclic ketones and catalyzer is 5～80:1, and in catalyzer, the mass ratio of HTS and multiple-metal oxygen-containing acid or its salt is 0.5～50:1.
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| CN105272840A (en) * | 2014-06-28 | 2016-01-27 | 宋雪梅 | Method for preparing adipic acid with cyclohexanone |
| CN105622386A (en) * | 2014-10-27 | 2016-06-01 | 湖南师范大学 | Green process for synthesizing adipic acid from cyclohexanone |
| CN105622385A (en) * | 2014-10-27 | 2016-06-01 | 湖南师范大学 | Process for preparing adipic acid through cleaning catalytic oxidation of cyclohexanone, catalyst, and catalyst preparation method |
| CN104610040B (en) * | 2015-01-22 | 2016-04-27 | 郑州大学 | One prepares the method for 1,12-dodecanedioic acid |
| CN106883115B (en) * | 2015-12-15 | 2019-01-11 | 中国科学院大连化学物理研究所 | The method that one kettle way prepares adipic acid by cyclopentanone |
| CN107539999B (en) * | 2016-06-27 | 2020-01-10 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, preparation method and application thereof, and cyclic ketone oxidation method |
| CN109438312A (en) * | 2018-10-31 | 2019-03-08 | 湖南工程学院 | A kind of preparation method of ketone peroxide |
| CN111606798B (en) * | 2019-02-26 | 2022-10-21 | 中国石油化工股份有限公司 | Process for the catalytic oxidation of cyclic ketones |
| CN112441906B (en) * | 2019-08-30 | 2022-10-21 | 中国石油化工股份有限公司 | Process for oxidation of cyclic ketones |
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| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
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