CN102206149B - Method for preparing corresponding diacid by catalytic oxidization of naphthene - Google Patents
Method for preparing corresponding diacid by catalytic oxidization of naphthene Download PDFInfo
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Abstract
The invention discloses a method for preparing a corresponding diacid by catalytic oxidization of naphthene, which is characterized by comprising: contacting a diacid by catalytic oxidization of naphthene, hydrogen peroxide, a solvent and a catalyst to perform a reaction at 0 to 180 DEG C and under 0.1 to 3.0MPa, wherein the molar ratio of the naphthene to the hydrogen peroxide to the solvent is 1:(1-50):(0-1,000), and the mass ratio of the naphthene to the catalyst is (0.1-500):1. The catalyst is a composition of titanium silicalite and multimetallic oxygen acid or salt thereof. When the method is used, the conversion ratio of the naphthene is high, the selectivity of the corresponding diacid is high, and the catalytic activity and stability are high. The method is a green synthetic process and does not require production equipment; the production process is simple and easy to control; and the method is suitable for industrial production and use.
Description
Technical field
The invention relates to the method that a kind of catalyzed oxidation cycloalkanes prepares corresponding diacid.
Background technology
Di-carboxylic acid is important chemical material, 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, mainly be to be the production route of starting raw material with benzene, account for the hydrogenation preparing cyclohexane at first more than 90% of global aggregated capacity, air oxidation of cyclohexane becomes hexalin and pimelinketone (being commonly called as K-A oil) then, then with nitric acid K-A oil is oxidized to hexanodioic acid.The first step cyclohexane oxidation be the transformation efficiency of K-A oil general＜10%, in the selectivity about 80%, particularly intermediate product cyclohexyl hydroperoxide decomposition course, the pimelinketone selectivity is not high; Produce the oxynitrides that environment is had severe contamination in the second step nitric acid oxidation process, equipment corrosion is serious, the operational condition harshness.
" method of oxidation synthesis of adipic acid by epoxy cyclohexane " of CN101177390A, the method that relates to a kind of oxidation synthesis of adipic acid by epoxy cyclohexane, this method is catalyzer with tungsten, molybdenum multi-metal oxygen hydrochlorate, and aqueous hydrogen peroxide solution is made oxygenant, the catalysis oxidation synthesis of adipic acid by epoxy cyclohexane.The principal feature of this method is no longer with an organic solvent to make reaction medium, avoids the pollution of using nitric acid as oxidant that environment is produced.
" method of a kind of synthesizing cyclohexanol, pimelinketone, hexanodioic acid " of CN1062718A, disclosing a kind of organic high conductivity polymer molecular clustering of transition metal catalyzer is applied to the hexanaphthene is the method for initial feed synthesizing cyclohexanol, pimelinketone, hexanodioic acid.
CN1193009A disclosed " a kind of method of obtaining hexanodioic acid and diprotic acid ", produce in pimelinketone and the hexalin process with air oxidation of cyclohexane, the washing sour water that mainly contains the caproic acid organic hydroper oxide, heating evaporation concentrates under normal pressure or decompression, concentrated solution is to carry out thermolysis between 90 ℃～105 ℃ or is that catalyzer carries out cartalytic decomposition effect with the variable valency metal ions in normal pressure, temperature, mixed solution after the decomposition, be to carry out oxidizing reaction with nitric acid under 35 ℃～78 ℃ conditions in normal pressure or decompression, temperature, generate hexanodioic acid and diprotic acid mixed solution.Obtain smart hexanodioic acid through enrichment, crystallization, filtration, drying and activated carbon treatment again; Crystalline mother solution gets diprotic acid through enrichment, crystallization.
CN101337879A discloses technology and the equipment that a kind of catalytic air oxidation hexanaphthene prepares hexanodioic acid.In hexanaphthene, be dissolved with the mixed catalyst that the catalyzer monometallic porphyrin of 1-50ppm or M-oxygen bimetallic porphyrin or they and transition metal salt or oxide compound constitute, in having the multi-stage oxidizing reactor of gas distributor, the air of feeding 5-12atm or oxygen enrichment, oxygen-denuded air, the control temperature of reaction was 140-160 ℃, with cyclohexane oxidation 45-120 minute; Oxidation mixtures enters flash separator, and at temperature 78-155 ℃, flash distillation under the pressure 0.1-1.0atm condition makes low-boiling products hexanaphthene, hexalin and pimelinketone become gas, surpasses 80% hexanodioic acid with content and separates; Again with the continuous cyclic oxidation of low-boiling products, with the separation and purification of high boiling point oxidation products: carry out purifies and separates by prior art, obtain smart adipic acid product.
CN1556088A relates to the method that a kind of bionically catalyzing and oxidizing hexanaphthene prepares hexanodioic acid, select for use metal phthalocyanine, monokaryon metalloporphyrin or μ-oxygen-dinuclear metalloporphyrin compounds with the biological enzyme structural similitude as catalyzer, its consumption is 0.1 of hexanaphthene weight～1 ‰, with hexanaphthene itself as solvent, feed the oxygen of 0.5～3.5MPa, the control temperature of reaction is 110～160 ℃, reaction times 4～32h.
CN1535947A discloses the method for atmospheric oxidation hydrogenation of six carbocyclic compound hexanodioic acid, relates under catalysis of metalloporphyrin, and the mixture oxidation by air of hexanaphthene, hexalin, pimelinketone, tetrahydrobenzene or hexalin and pimelinketone becomes the novel process of hexanodioic acid.Under the 1-20atm air conditions, temperature of reaction is 50-200 ℃, select for use μ-oxygen-bimetallic porphyrin and monometallic porphyrin or their immobilized thing to make catalyzer separately, also can select for use metalloporphyrin or their immobilized thing as Primary Catalysts, as co-catalyst, metalloporphyrin can be efficient as biological enzyme under biological concentration, the highly selective catalytic air directly becomes hexanodioic acid with cyclohexane oxidation with transition metal salt or oxide compound.
CN101337878A discloses a kind of method of directly producing adipic acid by cyclohexane catalytic oxidation, and this method forms mixed suspension with hexanaphthene, solvent, initiator and carbon material catalyst mix, and the carbon material catalyzer is carbon nanotube, graphite or gac; Mixing suspension is warming up to 50-250 ℃ again, aerating oxygen or air are as oxygenant, and the maintenance reacting kettle inner pressure is 0.1-5MPa, reaction 0.1-20h; To obtain reaction mixture and separate, can obtain the product hexanodioic acid.
CN101239899A discloses a kind of method of preparing adipic acid by using cyclohexane catalytic oxidation one-step, and this method first just hexanaphthene, solvent, initiator join in the reactor with the catalyzer of solid and mix, and form mixed suspension; Then the gained mixing suspension is warming up to 50-250 ℃, the oxygen of feeding sufficient quantity or air are as oxygenant, and reactor pressure is 0.1-5MPa, reaction 0.1-20h; And reaction mixture separated, obtain solid catalyst and contain the liquid mixture of reaction product, unreacted reactant and solvent; Isolate hexanodioic acid in the last isolated liquid phase mixture.
CN1157605A is direct oxidation into the method for recycling cobalt-containing catalyst in the reaction of hexanodioic acid at hexanaphthene, it is characterized in that comprising that a processing becomes the step of the reaction mixture that generates in the hexanodioic acid process at cyclohexane oxidation, this step comprises that extraction is at least partially in the pentanedioic acid and the Succinic Acid that produce in the reaction.
CN1850756A discloses the method for a kind of cyclohexane air dioxide prepare cyclohexanol, pimelinketone and hexanodioic acid: in the reactive system of the bubbling column reactor cascade reaction system of the tank reactor cascade reaction system of a 4-8 level belt stirrer or the outer circulation of 3-7 band or 2-6 dissimilar reactors in series, feeding is dissolved with hexanaphthene that the 1-100ppm metalloporphyrin is catalyzer and air or oxygen or oxygen-rich air or the oxygen-denuded air of 0.1-2.0ppm, temperature 120-160 ℃ of reaction 45-120 minute down.
A kind of catalyzed oxidation material that is called as HTS (TS-1) is disclosed in USP4410501, document (J Catal, 1995,157:631-635) its catalyzed oxidation hexanaphthene has been carried out a series of research, draw: hexanaphthene initial oxidation on TS-1 is hexalin, reoxidizes to be pimelinketone.Selecting the shape selectivity makes hexalin will be oxidized to pimelinketone further in the TS-1 zeolite cages.
Do not see the composition catalyst that utilizes HTS and multiple-metal oxygen-containing acid and salts substances thereof so far, be the research report that oxidizer catalytic oxidation cycloalkanes prepares corresponding diacid aspect with the hydrogen peroxide.
Summary of the invention
The purpose of this invention is to provide the method that a kind of oxidation cycloalkanes that is different from existing catalyst system prepares corresponding diacid.
Oxidation cycloalkanes provided by the invention prepares the method for corresponding diacid, it is characterized in that being 0～180 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure, with cycloalkanes, hydrogen peroxide, solvent and catalyzer contact reacts, wherein, the mol ratio of cycloalkanes, hydrogen peroxide and solvent is 1: 0.2～50: 0～1000, the mass ratio of cycloalkanes and catalyzer is 0.1～500: 1, and said catalyzer is the composition of HTS and multiple-metal oxygen-containing acid or its salt.
In the method provided by the invention, said HTS can be selected from one or more among TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, the Ti-ZSM-48, wherein preferred HTS is TS-1, and this molecular sieve has the MFI crystalline structure.
In the 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 the class that heteropolyacid is made up of by the oxygen atom ligand bridging by certain structure heteroatoms (as P, Si, Fe, Co etc.) and polyatom (as Mo, W, V, Nb, Ta etc.) contains the oxygen polyacid.Heteropoly blue is the general name of the transition metal heteropolyacid salt of a big class lower valency.Heteropoly blue is obtained by heteropolyacid salt reduction usually, and for example phosphato-molybdic heteropolyacid reduces bluely with tin protochloride the phosphorus molybdenum blue.Reduzate generally still keeps original structure, and the delocalized electron that reduction obtains makes its blueness with different depths, therefore again such electronics is called " blue electronics ".[SiWO for example
39]
8-Can under low temperature and inert atmosphere, be reduced to [SiWO
40]
6-Blue compound, tungsten wherein be+5 with the mixed valence of+6 valencys.P
3+, Fe
3+And Cr
3+The position that also can replace a tungsten atom.In the 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 the method provided by the invention, said multiple-metal oxygen-containing acid or salt also can be isopoly-acid or isopoly-acid salt.Said isopoly-acid is well known to those skilled in the art, and the class acid that isopoly-acid is made up of identical acid anhydrides also can be thought: the acid that two or more simple oxygen acid molecule of the same race condensations form.What easily form isopoly-acid in transition metal has 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.Factors such as the concentration of their formation condition and solution, temperature, acidity are relevant, and generally along with the increase of acidity, the degree of condensation increases.Hydrogen ion in the isopoly-acid is replaced by metal ion can generate corresponding isopoly-acid salt, or is called with how blue.
In the method provided by the invention, the mass ratio of HTS and multiple-metal oxygen-containing acid or salt is 0.01～150 in the said catalyzer, preferred 0.1～50.
In the method provided by the invention, the raw material optimum ratio is as follows: the mol ratio of cycloalkanes, hydrogen peroxide and solvent is 1: 1～10: 0～200, and the mass ratio of cycloalkanes and catalyzer is 0.1～100: 1.
In the method provided by the invention, cycloalkanes can be hexanaphthene, pentamethylene or their substituent, said substituent is methylcyclopentane, normenthane, 1 for example, 2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1-methyl-4-tertiary butyl hexanaphthene etc.
In the method provided by the invention, temperature of reaction is preferably 20～120 ℃, and reaction pressure is preferably 0.1～2.5MPa.
In the method provided by the invention, said solvent is selected from alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, or ketones such as acetone, butanone, or nitrile such as acetonitrile, or multiple mixing in the above-mentioned alcohol, ketone, nitrile, preferred solvent is one or more the mixing in methyl alcohol, acetonitrile, the acetone.
In the method provided by the invention, preferred embodiment be to be that 30～130 ℃ and pressure are under the condition of 0.2～1.5MPa in temperature, with cycloalkanes, hydrogen peroxide, solvent and catalyzer contact reacts, wherein, the mol ratio of cycloalkanes, hydrogen peroxide and solvent is 1: 0.5～20: 0～50, the mass ratio of cycloalkanes and catalyzer is 5～80: 1, the ratio 0.1～50 of the acid of HTS and multiple-metal oxygen-containing or its salt in the catalyzer.
Catalyzed oxidation cycloalkanes provided by the invention prepares the method for diacid, has following advantage:
1, reaction conditions gentleness;
2, its catalytic oxidation activity and stability of catalytic activity are better;
3, be green synthesis process, the whole process of production environmental friendliness, no special producing equipment requirements, production process is simple, and control is beneficial to suitability for industrialized production and application easily.
Embodiment
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.
In embodiment and the Comparative Examples, used reagent is commercially available chemically pure reagent, and used titanium-silicon molecular sieve TS-1 is that TS-2 prepares according to the CN1167081A method by the preparation of prior art (Zeolites, the 943rd～950 page of 1992, Vol.12) method.Ti-MCM-41 prepares according to document (Chem.Commun., 1994,147～148) method.
In Comparative Examples and embodiment:
Comparative Examples
Being 1: 2: 10 with hexanaphthene, hydrogen peroxide and solvent acetone according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.React after 2 hours, conversion of cyclohexane is 0%.React after 15 hours, conversion of cyclohexane is 0%.
Embodiment 1
Be 1: 2: 20 with hexanaphthene, hydrogen peroxide, solvent methanol and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 100) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 20, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 36%; The hexanodioic acid selectivity is 93%.The result who reacts 15 hours is as follows: cyclohexane conversion is 35%; The hexanodioic acid selectivity is 91%.
Embodiment 2
Be 1: 2: 27 with hexanaphthene, hydrogen peroxide, solvent methanol and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 0.1) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 30, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 13%; The hexanodioic acid selectivity is 91%.The result who reacts 15 hours is as follows: cyclohexane conversion is 15%; The hexanodioic acid selectivity is 90%.
Embodiment 3
Be 1: 6: 18 with hexanaphthene, hydrogen peroxide, solvent acetone and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 50) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 12, is that 60 ℃ of pressure are to react under the 1.0MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 84%; The hexanodioic acid selectivity is 91%.The result who reacts 15 hours is as follows: cyclohexane conversion is 72%; The hexanodioic acid selectivity is 90%.
Embodiment 4
Be 1: 8: 16 with hexanaphthene, hydrogen peroxide, solvent tertiary butanol and catalyzer (mass ratio of TS-1 and phosphato-molybdic heteropolyacid is 10) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 80, is that 40 ℃ of pressure are to react under the 0.2MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 82%; The hexanodioic acid selectivity is 94%.The result who reacts 15 hours is as follows: cyclohexane conversion is 78%; The hexanodioic acid selectivity is 91%.
Embodiment 5
Be 1: 3: 5 with hexanaphthene, hydrogen peroxide, aqueous solvent and catalyzer (mass ratio of Ti-MCM-41 and phosphorus tungsten heteropoly blue is 20) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 180, is that 90 ℃ of pressure are to react under the 1.0MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 19%; The hexanodioic acid selectivity is 96%.The result who reacts 15 hours is as follows: cyclohexane conversion is 16%; The hexanodioic acid selectivity is 92%.
Embodiment 6
Be 3: 1 with hexanaphthene, hydrogen peroxide and catalyzer (mass ratio of TS-1 and tungsten isopoly-acid is 40) according to the mol ratio of hexanaphthene and hydrogen peroxide, the mass ratio of hexanaphthene and catalyzer is 25, is that 130 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 13%; The hexanodioic acid selectivity is 93%.The result who reacts 15 hours is as follows: cyclohexane conversion is 12%; The hexanodioic acid selectivity is 90%.
Embodiment 7
Be 1: 8 with hexanaphthene, hydrogen peroxide and catalyzer (mass ratio of TS-1 and phosphorus molybdenum heteropoly blue is 0.5) according to the mol ratio of hexanaphthene and hydrogen peroxide, the mass ratio of hexanaphthene and catalyzer is 15, is that 60 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 64%; The hexanodioic acid selectivity is 95%.The result who reacts 15 hours is as follows: cyclohexane conversion is 62%; The hexanodioic acid selectivity is 92%.
Embodiment 8
Be 1: 2 with hexanaphthene, hydrogen peroxide and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 10) according to the mol ratio of hexanaphthene and hydrogen peroxide, the mass ratio of hexanaphthene and catalyzer is 5, is that 60 ℃ of pressure are to react under the 0.8MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 78%; The hexanodioic acid selectivity is 94%.The result who reacts 15 hours is as follows: cyclohexane conversion is 76%; The hexanodioic acid selectivity is 93%.
Embodiment 9
Be 8: 1: 32 with hexanaphthene, hydrogen peroxide, solvent methanol and catalyzer (mass ratio of TS-2 and molybdenum isopoly-acid is 20) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 10, is that 40 ℃ of pressure are to react under the 0.5MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 12%; The hexanodioic acid selectivity is 94%.The result who reacts 15 hours is as follows: cyclohexane conversion is 11%; The hexanodioic acid selectivity is 91%.
Embodiment 10
Be 10: 1: 20 with hexanaphthene, hydrogen peroxide, solvent acetone and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 15) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 80, is that 40 ℃ of pressure are to react under the 1.0MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 9%; The hexanodioic acid selectivity is 96%.The result who reacts 15 hours is as follows: cyclohexane conversion is 8.5%; The hexanodioic acid selectivity is 93%.
Embodiment 11
Be 2: 1: 30 with hexanaphthene, hydrogen peroxide, solvent methanol and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 50) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 40, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 11%; The hexanodioic acid selectivity is 93%.The result who reacts 15 hours is as follows: cyclohexane conversion is 9%; The hexanodioic acid selectivity is 91%.
Embodiment 12
Be 1: 1: 15 with methylcyclohexane, hydrogen peroxide, solvent methanol and catalyzer (mass ratio of TS-1 and tungsten sila polyacid is 0.3) according to the mol ratio of cycloalkanes, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 60, is that 60 ℃ of pressure are to react under the 1.0MPa in temperature.The result who reacts 2 hours is as follows: the methylcyclohexane transformation efficiency is 13%; The diacid selectivity is 94%.The result who reacts 15 hours is as follows: the methylcyclohexane transformation efficiency is 12%; The diacid selectivity is 91%.
Embodiment 13
The process that the present embodiment explanation utilizes catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 10) to react in the tank reactor of sealing.
Be 1: 5: 20 with pentamethylene, hydrogen peroxide, solvent acetone and catalyzer according to the mol ratio of cycloalkanes, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 50, is that 60 ℃ of pressure are to react under the 0.6MPa in temperature.The result who reacts 2 hours is as follows: the pentamethylene transformation efficiency is 26%; The pentanedioic acid selectivity is 95%.The result who reacts 12 hours is as follows: the pentamethylene transformation efficiency is 65%, and the pentanedioic acid selectivity is 88%.
Embodiment 14
The process that the present embodiment explanation utilizes catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 40) to react in the tank reactor of sealing.
Be 1: 2: 50 with hexanaphthene, hydrogen peroxide, solvent methanol and catalyzer according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 20, and temperature is that 80 ℃ of pressure are to react under the 1.5MPa.The result who reacts 2 hours is as follows: cyclohexane conversion is 17%, and the hexanodioic acid selectivity is 94%.The result who reacts 12 hours is as follows: cyclohexane conversion is 48%; The hexanodioic acid selectivity is 90%.
From embodiment and Comparative Examples as can be seen: method catalytic activity height provided by the invention, selectivity is good, and especially stability of catalytic activity is better.
Claims (5)
1. a catalyzed oxidation cycloalkanes prepares the method for corresponding diacid, it is characterized in that being 0～180 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure, with cycloalkanes, hydrogen peroxide, solvent and catalyzer contact reacts, wherein, cycloalkanes, the mol ratio of hydrogen peroxide and solvent is 1: 0.2～50: 0～1000, the mass ratio of cycloalkanes and catalyzer is 0.1～500: 1, said catalyzer is that mass ratio is the composition of 0.01～150 HTS and multiple-metal oxygen-containing acid or its salt, said multiple-metal oxygen-containing acid is heteropolyacid or isopoly-acid, said multiple-metal oxygen-containing hydrochlorate is heteropoly blue or with many salt, wherein, said heteropolyacid is selected from phosphorus tungsten class heteropolyacid, the Phosphorus heteropolyacid of molybdenum, phosphorus vanadium class heteropolyacid, molybdenum vanadium class heteropolyacid, tungsten silicon class heteropolyacid, said isopoly-acid is molybdenum, tungsten, tantalum, niobium class isopoly-acid, said heteropoly blue are selected from phosphorus tungsten class heteropoly blue, the Phosphorus heteropoly blue of molybdenum, phosphorus vanadium class heteropoly blue, molybdenum vanadium class heteropoly blue, tungsten silicon class heteropoly blue; Said cycloalkanes is hexanaphthene, pentamethylene or their substituent, and wherein substituent is methylcyclopentane, normenthane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1-methyl-4-tertiary butyl hexanaphthene.
2. according to the method for claim 1, it is characterized in that said HTS is one or more among TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, the Ti-ZSM-48.
3. according to the method for claim 1, the mol ratio of cycloalkanes, hydrogen peroxide and solvent is 1: 1～10: 0～200, and the mass ratio of cycloalkanes and catalyzer is 0.1～100: 1.
4. according to the process of claim 1 wherein, said temperature of reaction is 20～120 ℃, and reaction pressure is 0.1～2.5MPa.
5. according to the method for claim 1, it is characterized in that being 30～130 ℃ in temperature is under the condition of 0.2～1.5MPa with pressure, with cycloalkanes, hydrogen peroxide, solvent and catalyzer contact reacts, wherein, the mol ratio of cycloalkanes, hydrogen peroxide and solvent is 1: 0.5～20: 0～50, the mass ratio of cycloalkanes and catalyzer is 5～80: 1, the ratio 0.1～50 of the acid of HTS and multiple-metal oxygen-containing or its salt in the catalyzer.
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| CN103373915B (en) * | 2012-04-27 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of catalytic oxidation prepares the method for di-carboxylic acid |
| CN103920530B (en) * | 2014-04-10 | 2015-12-09 | 四川之江高新材料股份有限公司 | The preparation method of 2-hydroxyl-5-alkylacetophenone oxime and used catalyst |
| CN111099572B (en) * | 2018-10-29 | 2021-12-17 | 中国石油化工股份有限公司 | Carbon oxide-based material, method for oxidizing carbon-based material, and method for catalytically oxidizing cyclic hydrocarbon |
| CN111097405B (en) * | 2018-10-29 | 2023-01-13 | 中国石油化工股份有限公司 | Process for catalytic oxidation of cyclic hydrocarbons |
| CN116120157A (en) * | 2023-02-24 | 2023-05-16 | 山东京博石油化工有限公司 | Method for preparing cyclopentanone by selective oxidation of cyclopentane |
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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 |
| TW200621676A (en) * | 2004-10-22 | 2006-07-01 | United States Borax Inc | Selective oxidation of organic compounds |
| CN101177390A (en) * | 2007-09-26 | 2008-05-14 | 江苏大学 | Method for oxidation synthesis of adipic acid by epoxy cyclohexane |
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