CN102260157A - Method for preparing corresponding diacid by cyclone oxide - Google Patents
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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 catalyzed oxidation cyclic ketones, further say so about a kind of based on HTS composition be the method that catalyzer, oxidation cyclic ketones prepare corresponding diacid.
Background technology
Di-carboxylic acid is an 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 starting raw material with benzene, hydrogenation preparing cyclohexane at first, 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.This route accounts for more than 90% of global aggregated capacity.At present industrial method by hexalin and pimelinketone oxidation production hexanodioic acid is derived from Du Pont's technology in the 1940's, promptly at 70～90 ℃ of concentrated nitric acid and copper, vanadium catalyst catalyzed oxidation hexalin and Cyclohexanone Production hexanodioic acids that descend with 40～60%, yield is about about 80%, reaction needed is used concentrated nitric acid, seriously polluted to equipment corrosion, and can produce the nitrogenous compound that environment is had severe contamination.And oxidizing ethyle alkyl is produced the technological process of hexalin and pimelinketone and is often used homogeneous cobalt catalyst based, and product yield is low, needs with a large amount of strong acid and strong base solution etching apparatus, contaminate environment simultaneously.In a word, present industrial the utilization in the multistep technology 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 about 80%, cyclohexane conversion is low and the hexanaphthene internal circulating load is big, the energy consumption height, particularly in the cyclohexyl hydroperoxide decomposition course, the selectivity of pimelinketone is relatively poor, and yield is low.Therefore, working out a kind of environmentally friendly and technology simply prepares the diacid novel process by the cyclic ketones environmental friendliness and is of great practical significance.
Last century early eighties, Italy Taramasso discloses a kind of new catalytic oxidation material that is called as HTS (TS-1) in USP4410501, 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 a series of research.Draw from research: hexanaphthene initial oxidation on TS-1 is a hexalin, reoxidizes to be pimelinketone.
Summary of the invention
The objective of the invention is deficiency, provide a kind of oxidation cyclic ketones that is different from existing catalyst system to prepare the method for corresponding diacid at existing technology.
Oxidation cyclic ketones 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, being 10～160 ℃ in temperature is under the condition of 0.1～2.0MPa with pressure, is 1: 0.1～10 with cyclic ketones, hydrogen peroxide, solvent and catalyzer according to the mol ratio of cyclic ketones and hydrogen peroxide, the mass ratio of solvent and catalyzer is 1～1000: 1, and the mass ratio of cyclic ketones and catalyzer is to react under 1～100: 1 the ratio.
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, is preferably titanium-silicon molecular sieve 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.[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+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.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 acid of HTS and multiple-metal oxygen-containing or the mass ratio of its salt are preferably 0.05～100 in the said catalyzer: 1, more preferably 0.1～50: 1.
In the 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 the method provided by the invention, temperature of reaction is preferably 20～120 ℃, and reaction pressure is preferably 0.1～1.5MPa.
In the 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 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, can adopt periodical operation or operate continuously mode.When andnon-continuous operation manner is carried out, behind solvent, catalyzer adding reactor, add cyclic ketones, hydrogen peroxide continuously; And continuous mode can adopt fixed-bed reactor when carrying out, and behind the catalyzer of packing into solvent, cyclic ketones, hydrogen peroxide is added continuously; Also can adopt slurry bed reactor, catalyzer, solvent making beating back are added cyclic ketones, hydrogen peroxide continuously, the while is separated product constantly.
Method provided by the invention can also adopt closed still reaction, and soon catalyzer, solvent, cyclic ketones and hydrogen peroxide add simultaneously and mix afterreaction in the still.
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 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 the catalyzer.
Oxidation cyclic ketones provided by the invention prepares the method for corresponding diacid, and preparing hexanodioic acid with cyclohexanone by catalytic oxidation 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 a green synthesis process, the whole process of production environmental friendliness, and 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.Used HTS (TS-1) catalyzer is the method preparation by prior art (Zeolites, 1992, the 943rd～950 page of Vol.12).
In Comparative Examples and embodiment:
Comparative Examples 1
Is 1: 2 with pimelinketone, hydrogen peroxide and solvent according to the mol ratio of pimelinketone and hydrogen peroxide, is that 30 ℃ of pressure are to react under the 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
Is 1: 2 with pimelinketone, hydrogen peroxide, solvent and catalyzer (TS-1) 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 the 1.5MPa in temperature.The result who reacts 2 hours is as follows: the pimelinketone transformation efficiency is 14%; The hexanodioic acid selectivity is 13%.The result who reacts 15 hours is as follows: the pimelinketone transformation efficiency is 12%; The hexanodioic acid selectivity is 16%.
Embodiment 1
Is 1: 2 with pimelinketone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 10) 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 the 1.5MPa in temperature.The result who reacts 2 hours is as follows: the pimelinketone transformation efficiency is 76%; The hexanodioic acid selectivity is 94%.The result who reacts 15 hours is as follows: the pimelinketone transformation efficiency is 74%; The hexanodioic acid selectivity is 92%.
Embodiment 2
Is 1: 2 with pimelinketone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and molybdenum tungsten heteropoly blue is 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 the 1.5MPa in temperature.The result who reacts 2 hours is as follows: the pimelinketone transformation efficiency is 53%; The hexanodioic acid selectivity is 92%.The result who reacts 15 hours is as follows: the pimelinketone transformation efficiency is 47%; The hexanodioic acid selectivity is 89%.
Embodiment 3
With 1,3-dimethylcyclohexanon, hydrogen peroxide, solvent and catalyzer (TS-1 be 50 with the mass ratio of 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 the 1.0MPa in temperature.The result who reacts 2 hours is as follows: the cyclic ketones transformation efficiency is 74%; The diacid selectivity is 94%.The result who reacts 15 hours is as follows: the cyclic ketones transformation efficiency is 72%; The diacid selectivity is 91%.
Embodiment 4
Is 1: 4 with pimelinketone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and phosphato-molybdic heteropolyacid is 8) 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 the 0.5MPa in temperature.The result who reacts 2 hours is as follows: the pimelinketone transformation efficiency is 92%; The hexanodioic acid selectivity is 92%.The result who reacts 15 hours is as follows: the pimelinketone transformation efficiency is 88%; The hexanodioic acid selectivity is 90%.
Embodiment 5
Is 1: 3 with cyclopentanone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and phosphorus tungsten heteropoly blue is 20) 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 the 1.0MPa in temperature.The result who reacts 2 hours is as follows: the cyclic ketones transformation efficiency is 89%; The diacid selectivity is 96%.The result who reacts 15 hours is as follows: the cyclopentanone transformation efficiency is 86%; The pentanedioic acid selectivity is 92%.
Embodiment 6
Is 3: 1 with ethyl cyclopentanone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and ammonium phosphomolybdate is 0.1) 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 the 0.5MPa in temperature.The result who reacts 2 hours is as follows: the cyclic ketones transformation efficiency is 32%; The diacid selectivity is 93%.The result who reacts 15 hours is as follows: ethyl cyclopentanone transformation efficiency is 31%; The ethylglutaric acid selectivity is 88%.
Embodiment 7
Is 5: 1 with pimelinketone, hydrogen peroxide, solvent and catalyzer (TS-1 be 100 with the mass ratio of molybdenum polyacid) 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 the 0.5MPa in temperature.The result who reacts 2 hours is as follows: the pimelinketone transformation efficiency is 19%; The hexanodioic acid selectivity is 94%.The result who reacts 15 hours is as follows: the pimelinketone transformation efficiency is 15%; The hexanodioic acid selectivity is 93%.
Embodiment 8
Is 2: 1 with pimelinketone, hydrogen peroxide, solvent and catalyzer (TS-1 be 40 with the mass ratio of tungsten polyacid ammonium) 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 the 1.5MPa in temperature.The result who reacts 2 hours is as follows: the pimelinketone transformation efficiency is 61%; The hexanodioic acid selectivity is 93%.The result who reacts 15 hours is as follows: the pimelinketone transformation efficiency is 59%; The hexanodioic acid selectivity is 90%.
Embodiment 9
Is 1: 1 with methylcyclohexanone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and tungsten sila polyacid is 0.5) 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 the 1.0MPa in temperature.The result who reacts 2 hours is as follows: the cyclic ketones transformation efficiency is 83%; The diacid selectivity is 95%.The result who reacts 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 (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 10) to react in the tank reactor of sealing.
Is 1: 4 with pimelinketone, hydrogen peroxide, solvent acetone and catalyzer 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 the 0.6MPa in temperature.The result who reacts 2 hours is as follows: the pimelinketone transformation efficiency is 26%; The hexanodioic acid selectivity is 96%.The result who reacts 15 hours is as follows: the pimelinketone transformation efficiency is 91%, and the hexanodioic acid selectivity is 92%.
Embodiment 11
Is 2: 5 with ethyl cyclohexanone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and molybdenum vanadium class heteropolyacid is 15) 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 the 0.2MPa in temperature.The result who reacts 2 hours is as follows: the ethyl cyclohexanone transformation efficiency is 73%; Ethyl hexanodioic acid selectivity is 90%.The result who reacts 15 hours is as follows: the cyclic ketones transformation efficiency is 66%; The diacid selectivity is 87%.
Embodiment 12
Is 2: 7 with cyclopentanone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and the Phosphorus heteropoly blue of molybdenum is 20) 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 the 1.2MPa in temperature.The result who reacts 2 hours is as follows: the cyclic ketones transformation efficiency is 65%; The diacid selectivity is 88%.The result who reacts 15 hours is as follows: the cyclopentanone transformation efficiency is 59%; The pentanedioic acid selectivity is 83%.
Embodiment 13
Is 2: 9 with chloro pimelinketone, hydrogen peroxide, solvent and catalyzer (mass ratio of TS-1 and tungsten silicon class heteropoly blue is 60) 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 the 0.1MPa in temperature.The result who reacts 2 hours is as follows: the cyclic ketones transformation efficiency is 79%; The diacid selectivity is 86%.The result who reacts 15 hours is as follows: chloro pimelinketone transformation efficiency is 75%; Chloro hexanodioic acid selectivity is 82%.
From embodiment and Comparative Examples as can be seen: the inventive method catalytic activity height, selectivity is good, and especially stability of catalytic activity is better.The inventive method catalytic oxidation activity and selectivity height are described, have stability of catalytic activity preferably simultaneously.
Claims (10)
1. change the method that the oxidation cyclic ketones prepares corresponding diacid for one kind, it is characterized in that adopting the composition of a kind of HTS and multiple-metal oxygen-containing acid or its salt is catalyzer, being 10～160 ℃ in temperature is under the condition of 0.1～2.0MPa with pressure, with 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, the mass ratio of cyclic ketones and catalyzer is to react under 1～100: 1 the ratio, and wherein the mass ratio of the acid of HTS and multiple-metal oxygen-containing or its salt is 0.05～100: 1 in the catalyzer.
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, it is characterized in that said multiple-metal oxygen-containing acid is heteropolyacid or isopoly-acid, said multiple-metal oxygen-containing hydrochlorate is a heteropoly blue or with many salt.
4. according to the method for claim 3, wherein, said multiple-metal oxygen-containing acid is selected from phosphorus tungsten class heteropolyacid, the Phosphorus heteropolyacid of molybdenum, phosphorus vanadium class heteropolyacid, molybdenum vanadium class heteropolyacid, tungsten silicon class heteropolyacid, and said multiple-metal oxygen-containing hydrochlorate is 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.
5. according to the method for claim 3, wherein said isopoly-acid is molybdenum, tungsten, tantalum, niobium class isopoly-acid.
6. according to the method for claim 1, the mass ratio of the acid of HTS and multiple-metal oxygen-containing or its salt is 0.1～50: 1 in the said catalyzer.
7. 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.
8. 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.
9. 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, 1,2-dimethylcyclohexanon, 1,3-dimethylcyclohexanon, halo pimelinketone, halo cyclopentanone.
10. 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 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 the mass ratio of the acid of HTS and multiple-metal oxygen-containing or its salt is 0.5～50: 1 in the catalyzer.
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| CN104610040A (en) * | 2015-01-22 | 2015-05-13 | 郑州大学 | Preparation method of 1, 12-lauryl binary acid |
| 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 |
| CN106883115A (en) * | 2015-12-15 | 2017-06-23 | 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 |
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| CN111606798A (en) * | 2019-02-26 | 2020-09-01 | 中国石油化工股份有限公司 | Process for the catalytic oxidation of cyclic ketones |
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| 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 |
| CN104610040A (en) * | 2015-01-22 | 2015-05-13 | 郑州大学 | Preparation method of 1, 12-lauryl binary 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 |
| CN106883115A (en) * | 2015-12-15 | 2017-06-23 | 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 |
| CN107539999A (en) * | 2016-06-27 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of HTS and its preparation method and application and a kind of method of cyclic ketones oxidation |
| 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 |
| CN111606798A (en) * | 2019-02-26 | 2020-09-01 | 中国石油化工股份有限公司 | Process for the catalytic oxidation of cyclic ketones |
| 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 |
| CN112441906A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Process for 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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