CN103204769B - Method for production of cyclohexanone from cyclohexanol - Google Patents
Method for production of cyclohexanone from cyclohexanol Download PDFInfo
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Abstract
The invention discloses a method for production of cyclohexanone from cyclohexanol. Under oxidation reaction conditions, the cyclohexanol, an oxidant and a catalyst are subjected to a contact reaction. The method is characterized in that the catalyst is the roasting product of a composition of a zinc compound and a heteroatom molecular sieve.
Description
Technical field
The invention relates to a kind of method of producing pimelinketone, be furtherly about a kind of with zinc compound and hetero-atom molecular-sieve composition for catalyst is oxidized the method for cyclohexanol production pimelinketone.
Background technology
Pimelinketone is a kind of important industrial chemicals, is widely used in the industry of fiber, synthetic rubber, industrial coating, medicine, agricultural chemicals, organic solvent.Developing rapidly particularly due to polymeric amide industry, the demand as the pimelinketone preparing nylon 6 and nylon66 fiber intermediate is annual all more than 1,000,000 tons in the whole world.Now, cyclohexanone production process route mainly contains three kinds: cyclohexane liquid-phase oxidation method, phenol hydrogenation method and partial hydrogenation of benzene method, and cyclohexane oxidation process is the main process of industrial production pimelinketone, accounts for more than 90%.But this production process is also considered to minimum one of efficiency in all chemical industry processes.Cyclohexane oxidation synthesizing cyclohexanone process is one of the key and bottleneck of restriction caprolactam production.The industrial cyclohexane oxidation production pimelinketone that utilizes generally has three kinds of methods: a kind of is adopt cobalt salt to be the catalyzed oxidation of catalyzer, and this method cyclohexane conversion is higher, but makes the easy fouling of reactor owing to forming hexanodioic acid cobalt, is now substantially eliminated.Two is boric acid class catalytic oxidations, and this method initial cost is high, and energy consumption is high, and in product, the ratio of hexalin is too high, increases the burden of postorder cyclohexanol dehydrogenation.And technique is very complicated, operation easier is large, is easy to cause e-quipment and pipe Severe blockage.Three is the non-catalyst oxidations with air direct oxidation, this method effectively prevent the problem of reactor fouling, industrially widely applies, but this complex process, intermediate steps is many, cyclohexane conversion is low, and hexanaphthene internal circulating load is large, and energy consumption is high, pollute also larger, particularly in decomposing cyclohexyl hydrogen peroxide process, pimelinketone selectivity is poor, and yield is low.In addition, a large amount of waste lyes that air oxidation of cyclohexane process produces, difficult treatment, is still global the difficult problem of environmental protection so far.
In above-mentioned pimelinketone preparation process, all companion produces hexalin, and then hexalin is converted into pimelinketone through oxidative dehydrogenation process process again, and this process adopts zinc oxide etc. to make oxygenant, and react under about 300 DEG C, energy consumption is high, and process is complicated.
Therefore, it is possible to for the deficiency of existing technique, work out a kind of environmentally friendly and technique and simply prepare pimelinketone novel process by hexalin environmental friendliness and be of great practical significance.
Italy Taramasso etc. are in USP4410501, and make public for the first time the new catalytic oxidation material that one is called as HTS (TS-1), it has good selective oxidation to hydrocarbon, alcohol, phenol etc.
Ulf Schuchardt etc. (J Catal, 1995,157:631 ~ 635) have carried out a series of research to titanium molecular sieve catalysis oxidizing ethyle alkyl.Draw from research: hexanaphthene initial oxidation on TS-1 is hexalin, reoxidizes as pimelinketone.Because of the reason of selective activization, hexalin will be oxidized to pimelinketone further in TS-1 zeolite cages.(the J Natural Gas Chem 2001 such as Tao Jialin, 10:295 ~ 307) and Ulf Schuchardt etc. (Applied Catal A:Gen 2001,211:1 ~ 17) also all titanium molecular sieve catalysis oxidizing ethyle alkyl is studied.
Summary of the invention
The object of the invention is on the basis of existing technology, provide a kind of in high hexalin transformation efficiency situation, pimelinketone selectivity produces the method for pimelinketone preferably.
The present inventor carries out deep research, be surprised to find that: hetero-atom molecular-sieve (as HTS) and the mixture of zn cpds are carried out roasting, and in element, in the product of roasting obtained, when whole heteroatomic mol ratio in zinc atom and described hetero-atom molecular-sieve is 0.05 ~ 50: 1, under the existence of this product of roasting and oxidation reaction condition, by cyclohexanol production pimelinketone, can obtain in high hexalin transformation efficiency situation, the good reaction effect of pimelinketone selectivity.This completes the present invention.
Therefore, method by cyclohexanol production pimelinketone provided by the invention, be under oxidation reaction condition, hexalin, oxygenant and catalyst exposure reacted, it is characterized in that described catalyzer is the product of roasting of the composition of zn cpds and hetero-atom molecular-sieve.
In method provided by the invention, described catalyzer is the product of roasting of the composition of zn cpds and hetero-atom molecular-sieve.In described composition, the mass ratio of zn cpds and hetero-atom molecular-sieve is 0.01 ~ 20: 1, preferably 0.05 ~ 10: 1; In described zn cpds, in element, whole heteroatomic mol ratio in zinc atom and described hetero-atom molecular-sieve is 0.05 ~ 50: 1, preferably 0.1 ~ 20: 1, and in described hetero-atom molecular-sieve, silicon and whole heteroatomic mol ratio are 5 ~ 250: 1, preferably 25 ~ 150: 1.
In method provided by the invention, described zn cpds can for various can after firing for catalyzer provides the zinc compound of zinc element.
Such as, described zn cpds can be selected from one or more in the oxyhydroxide of the oxide compound of zinc, the oxysalt of zinc, the anaerobic hydrochlorate of zinc and zinc.In the present invention, the oxysalt of described zinc comprises the organic oxygen-containing hydrochlorate of zinc and the inorganic oxysalt of zinc.The organic oxygen-containing hydrochlorate of described zinc can be such as C
2~ C
20the zinc salt of organic carboxyl acid.In the present invention, the inorganic oxysalt of described zinc can be such as the zinc salt of nonmetal oxyacid acid and/or the zinc salt of metal oxygen-containing acid, and described metal oxygen-containing acid refers to the acidic substance be made up of the acid group containing metallic element and hydrogen, as: isopoly-acid and heteropolyacid.In the present invention, the example of described isopoly-acid can be but be not limited to: wolframic acid, molybdic acid, metatungstic acid, ethyl metatungstic acid, para-molybdic acid, ammonium molybdate, ammonium paramolybdate, ammonium metawolframate and ethyl ammonium metawolframate; The example of described heteropolyacid can be but be not limited to: phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid, silicomolybdic acid, P-Mo-Wo acid and silicon molybdenum wolframic acid.In the present invention, the example of zn cpds includes but not limited to one or more the mixture be selected from zinc oxide, zinc nitrate, zinc carbonate, zinc taurine, zinc hydroxide, zinc uranyl acetate, zinc potassium cyanide, zine fluosilicate, zinc hydride, zinc cyanide, zinc sulphide, zinc thiocyanide, Zinic stearas, zinc iodide, zinc phosphide, zinc peroxide, zinc dithionite, zinc molybdate, zinc chlorate, zinc chromate, zinc pyrophosphate, zinc phosphate, zinc chloride, zinc sulfate, Zinc Gluconate, zinc acetate, zinc bromide, zinc fluoride and zinc hydrogen phosphate; Preferably, described zn cpds is one or more in the organic oxygen-containing hydrochlorate of zinc and the inorganic oxysalt of zinc; Further preferably, described zn cpds is one or more in zinc phosphate, zinc nitrate, zinc chloride, zinc sulfate, Zinc Gluconate, zinc acetate, zinc bromide, zinc fluoride and zinc hydrogen phosphate.
In method provided by the invention, described hetero-atom molecular-sieve refers to the molecular sieve that the skeletal atom of molecular sieve (such as: Siliciumatom and/or aluminium atom) is formed by heteroatoms isomorphous substitution.The present invention is not particularly limited for the heteroatomic kind in described hetero-atom molecular-sieve, can be the common various heteroatomss that can replace the skeletal atom of molecular sieve in this area.Preferably, the heteroatoms in described hetero-atom molecular-sieve is the atom of metallic element.Further preferably, the heteroatoms in described hetero-atom molecular-sieve is the atom of one or more metals be selected from IVB race metal, VB race metal, group VIII metal, IVA race metal and lanthanide series metal.In the present invention, the heteroatomic example in described hetero-atom molecular-sieve can be but be not limited to: titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, iron atom, cobalt atom, nickle atom, tin atom, lanthanum atom and cerium atom.More preferably, the heteroatoms in described hetero-atom molecular-sieve is one or more in titanium atom, vanadium atom, iron atom, tin atom and cerium atom.Further preferably, the heteroatoms in described hetero-atom molecular-sieve is titanium atom and/or vanadium atom.Most preferably, the heteroatoms in described hetero-atom molecular-sieve is titanium atom.Heteroatomic content in described hetero-atom molecular-sieve can change within wide in range scope.Preferably, in element, the whole heteroatomic mol ratio in the Siliciumatom in described hetero-atom molecular-sieve and described hetero-atom molecular-sieve is 5 ~ 250: 1.Further preferably, in element, the whole heteroatomic mol ratio in the Siliciumatom in described hetero-atom molecular-sieve and described hetero-atom molecular-sieve is 25 ~ 150: 1.
One of the present invention preferred embodiment in, described hetero-atom molecular-sieve is HTS (that is, the heteroatoms in described hetero-atom molecular-sieve is titanium atom).Described HTS can be various HTS well known to those skilled in the art, the example of described HTS can be but be not limited to: the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, at least one in the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.
One of the present invention more preferred embodiment in, described hetero-atom molecular-sieve is the HTS of MFI structure.Preferably, described hetero-atom molecular-sieve is the HTS of the MFI structure of hollow structure crystal grain, and the radical length of the chamber portion of its hollow structure is 5 ~ 300 nanometers, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.Hereinafter, the HTS with said structure is called hollow HTS.According to method of the present invention, adopt hollow HTS can obtain higher pimelinketone selectivity on the one hand, the transformation efficiency of hexalin can also be improved on the other hand further.
In another preferred embodiment of the present invention, described hetero-atom molecular-sieve be V-Si molecular sieve (namely, heteroatoms in described hetero-atom molecular-sieve is vanadium atom), and described zn cpds is one or more in zinc fluoride, zinc chloride and zinc bromide.
Catalyzer described in method of the present invention, its preparation is not particularly limited, as long as described catalyzer is the product by the raw material containing zn cpds and hetero-atom molecular-sieve being carried out roasting.
According to one embodiment of the present invention, the preparation method of described catalyzer can comprise: contacted with the solution containing described zn cpds by described hetero-atom molecular-sieve, drying is carried out after described solution loadings is on described hetero-atom molecular-sieve, to obtain the raw material containing described zn cpds and hetero-atom molecular-sieve, and described raw material is carried out roasting, thus obtain the catalyzer according to using in method of the present invention.The described solution containing zn cpds, its solvent can be the various solvent that can dissolve described zn cpds.According to the present invention, described zn cpds can be dissolved in the water usually, and therefore from the angle of environment protection and save energy, described solvent is preferably water.According to the present invention, described hetero-atom molecular-sieve and the described way of contact containing the solution of zn cpds can be that the routine of this area is selected, without particular requirement, such as: at the temperature of 15 ~ 40 DEG C, described hetero-atom molecular-sieve can be flooded with the described solution containing zn cpds; Also can at the temperature of 15 ~ 40 DEG C, by the described solution spraying containing zn cpds on described hetero-atom molecular-sieve.According to the present invention, the described concentration of solution containing zn cpds, the number of times of described contact were not particularly limited with the described time contacted, as long as the charge capacity of described zn cpds on described hetero-atom molecular-sieve makes in the catalyzer finally obtained, the whole heteroatomic mol ratio on zinc atom and described hetero-atom molecular-sieve meets previously described requirement.According to the present invention, the condition of described drying is not particularly limited, and can carry out appropriate selection according to the kind of described solvent.Such as, the temperature of described drying can be 25 ~ 200 DEG C, and the time can be 1 ~ 8 hour.Described drying can be carried out under air conditions; also can carry out under protection of inert gas; can there is not chemically interactive gas for various in described rare gas element, such as: neutral element gas (as argon gas), nitrogen with described hetero-atom molecular-sieve and zn cpds.Described drying can be carried out at ambient pressure, also can decompression or vacuum condition under carry out.
According to another embodiment of the invention, the preparation method of described catalyzer can comprise: mix (namely by described hetero-atom molecular-sieve with described zn cpds, described hetero-atom molecular-sieve for solid is mixed with the described zn cpds for solid), to obtain the raw material containing described hetero-atom molecular-sieve and described zn cpds, and described raw material is carried out roasting, to obtain the catalyzer according to using in method of the present invention.
In the present invention, the condition that the described raw material containing hetero-atom molecular-sieve and zn cpds carries out roasting be not particularly limited, described roasting can be carried out under the normal condition of this area.Usually, the temperature of described roasting can be 200 ~ 800 DEG C, and the time can be 1 ~ 12 hour.Described roasting can be carried out under air or oxygen atmosphere.
Method provided by the invention is preferably carried out in the presence of solvent, such one side can regulate the severe degree of reaction more easily, thus make method according to the present invention have higher security, the contact of reactant and catalyzer can also be made more abundant on the other hand.The present invention is not particularly limited for the kind of described solvent, all kinds of SOLVENTS can commonly used for this area.Preferably, described solvent is water, benzene, hexanaphthene, C
1~ C
10alcohol, C
3~ C
10ketone and C
2~ C
10nitrile in one or more, more preferably, described solvent is C
1~ C
5fatty alcohol, C
3~ C
5aliphatic ketone, C
2~ C
5aliphatic nitrile and C
7~ C
10aromatic nitriles in one or more.Such as: described solvent can be one or more in water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone, acetonitrile, propionitrile and benzyl cyanide.
In the present invention, described oxygenant is hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid, Perpropionic Acid etc.
In method provided by the invention, raw material optimum ratio is as follows: the mol ratio of hexalin and oxygenant is preferably 1: 1 ~ 10, and the mass ratio of solvent and catalyzer is preferably 0 ~ 200: 1.
In method provided by the invention, the amount between raw material hexalin and catalyzer is without clear limit, can realize the present invention, and the mass ratio of general hexalin and catalyzer is 0.1 ~ 150: 1.
In method provided by the invention, temperature of reaction is preferably 20 ~ 120 DEG C, and reaction pressure is preferably 0.1 ~ 2.5MPa.
In method provided by the invention, reinforced order, without special requirement, first can add hexalin, also can first add oxygenant or solvent.
The method of cyclohexanol production pimelinketone provided by the invention, has following advantage:
1, catalyst composition preparation is simple, by zinc compound and the roasting of hetero-atom molecular-sieve mechanical mixture and can get final product, reproducible;
2, in high hexalin transformation efficiency situation, pimelinketone selectivity is better;
3, this preparation method is green synthesis process, and without special producing equipment requirements, production process is simple, is beneficial to suitability for industrialized production and application.
Embodiment
Following examples will be further described the present invention, but therefore not limit content of the present invention.
In embodiment and comparative example, agents useful for same is commercially available chemically pure reagent, and wherein oxygenant is the aqueous solution of 30%.HTS (TS-1) used is by prior art Zeolites, (TS-1) sieve sample that the method described in 1992, Vol.12 943rd ~ 950 pages is prepared.Hollow HTS HTS used is prepared according to method disclosed in Chinese patent CN1132699C, this HTS is MFI structure, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, crystal grain is hollow crystal grain and the radical length of chamber portion is 15 ~ 180 nanometers; This HTS sample is at 25 DEG C, and P/PO=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is 78 milligrams/gram).Composition catalyzer compositional analysis adopts fluorescence analysis method, and Rigaku 3271E type Xray fluorescence spectrometer records.
In comparative example and embodiment:
Comparative example 1
This comparative example illustrates is not having catalyzer to deposit in case, the reaction conditions of hexalin and hydrogen peroxide and result.
Be 1: 2 by hexalin, hydrogen peroxide and solvent according to the mol ratio of hexalin and hydrogen peroxide, wherein solvent methanol quality is 20g, reacts under be 30 DEG C of pressure being 1.5MPa in temperature.React after 4 hours, the transformation efficiency of hexalin is 7.6%, and pimelinketone selectivity is 16%.
Comparative example 2
This comparative example illustrates when catalyst Ti-si molecular sieves TS-1 Individual existence, the reaction conditions of hexalin and hydrogen peroxide and result.
Be 2: 1 by hexalin, hydrogen peroxide, solvent and TS-1 according to the mol ratio of hexalin and hydrogen peroxide, the mass ratio of solvent methanol and catalyzer is 20: 1, the mass ratio of hexalin and catalyzer is 5: 1, reacts under be 30 DEG C of pressure being 1.5MPa in temperature.The result of reacting 2 hours is as follows: hexalin transformation efficiency is 33%, and pimelinketone selectivity is 35%.
Comparative example 3
This comparative example illustrates when catalyst oxidation zinc Individual existence, the reaction conditions of hexalin and hydrogen peroxide and result.
Be 1: 1 by hexalin, hydrogen peroxide, solvent and catalyzer (zinc oxide) according to the mol ratio of hexalin and hydrogen peroxide, the mass ratio of solvent acetone and catalyzer is 50: 1, the mass ratio of hexalin and catalyzer is 20: 1, reacts under be 60 DEG C of pressure being 2.5MPa in temperature.The result of reacting 2 hours is as follows: hexalin transformation efficiency is 7%, and pimelinketone selectivity is 28%.
Preparation example 1
This preparation example illustrates the preparation process of used catalyst in the present invention.
By zinc oxide and 10g titanium-silicon molecular sieve TS-1 mechanically mixing at normal temperatures and pressures, roasting 5h under 550 DEG C of air atmospheres.Characterize through compositional analysis, wherein the mass ratio of zinc compound and hetero-atom molecular-sieve is 0.2: 1, Zn/ heteroatoms mol ratio be 5: 1, Si/ heteroatoms mol ratio is 56: 1.
Preparation example 2
This preparation example illustrates the preparation process of used catalyst in the present invention.
Zinc nitrate is soluble in water, then add 10g HTS HTS, mix at normal temperatures and pressures, after drying at room temperature, roasting 2h under 650 DEG C of air atmospheres.Characterize through compositional analysis, wherein the mass ratio of zinc compound and hetero-atom molecular-sieve is 1: 1, Zn/ heteroatoms mol ratio be 2: 1, Si/ heteroatoms mol ratio is 37: 1.
Preparation example 3
This preparation example illustrates the preparation process of used catalyst in the present invention.
By zinc hydroxide and 10g titanium-silicon molecular sieve TS-1 mechanically mixing at normal temperatures and pressures, roasting 5h under 550 DEG C of air atmospheres.Characterize through compositional analysis, wherein the mass ratio of zinc compound and hetero-atom molecular-sieve is 5: 1, Zn/ heteroatoms mol ratio be 18: 1, Si/ heteroatoms mol ratio is 49: 1.
Embodiment 1
Be 1: 2 by hexalin, hydrogen peroxide, solvent and catalyzer (composition that preparation example 1 obtains) according to the mol ratio of hexalin and hydrogen peroxide, the mass ratio of solvent methanol and catalyzer is 20: 1, the mass ratio of hexalin and catalyzer is 10: 1, reacts under be 30 DEG C of pressure being 1.2MPa in temperature.The result of reacting 2 hours is as follows: hexalin transformation efficiency is 46%, and pimelinketone selectivity is 78%.
Embodiment 2
Be 1: 1 by hexalin, hydrogen peroxide, solvent and catalyzer (composition that preparation example 2 obtains) according to the mol ratio of hexalin and hydrogen peroxide, the mass ratio of solvent acetone and catalyzer is 5: 1, the mass ratio of hexalin and catalyzer is 50: 1, reacts under be 60 DEG C of pressure being 2.0MPa in temperature.The result of reacting 2 hours is as follows: hexalin transformation efficiency is 83%, and pimelinketone selectivity is 89%.
Embodiment 3
Be 2: 5 by cyclopentanone, tertbutyl peroxide, solvent and catalyzer (composition that preparation example 3 obtains) according to the mol ratio of hexalin and tertbutyl peroxide, the mass ratio of solvent methanol and catalyzer is 80: 1, the mass ratio of hexalin and catalyzer is 120: 1, reacts under be 50 DEG C of pressure being 0.5MPa in temperature.The result of reacting 2 hours is as follows: hexalin transformation efficiency is 64%, and pimelinketone selectivity is 76%.
The method for preparing catalyst that following embodiment is used is except zinc compound kind and amount difference thereof, other condition is with preparation example 1, and wherein the mass ratio of hetero-atom molecular-sieve and zinc compound, Zn/ heteroatoms mol ratio, Si/ heteroatoms mol ratio refer to each embodiment.
Embodiment 4
By hexalin, hydrogen peroxide, solvent and catalyzer, (mass ratio 0.2: 1, the Zn/ heteroatoms mol ratio of zinc iodide and HTS be 5: 1, Si/ heteroatoms mol ratio is 50: 1, method for preparing catalyst is except zinc compound kind and amount difference thereof, other condition is with preparation example 1) be 3: 8 according to the mol ratio of hexalin and hydrogen peroxide, the mass ratio of solvent methanol and catalyzer is 10: 1, the mass ratio of hexalin and catalyzer is 0.5: 1, reacts under be 40 DEG C of pressure being 2.5MPa in temperature.The result of reacting 2 hours is as follows: hexalin transformation efficiency is 66%, and pimelinketone selectivity is 73%.
Embodiment 5
By hexalin, Peracetic Acid, solvent and catalyzer, (mass ratio 0.5: 1, the Zn/ heteroatoms mol ratio of zinc taurine and HTS be 15: 1, Si/ heteroatoms mol ratio is 150: 1; method for preparing catalyst is except zinc compound kind and amount difference thereof; other condition is with preparation example 1) be 3: 13 according to the mol ratio of hexalin and Peracetic Acid; the mass ratio of solvent methanol and catalyzer is 180: 1; the mass ratio of hexalin and catalyzer is 0.2: 1, reacts under be 70 DEG C of pressure being 1.5MPa in temperature.The result of reacting 2 hours is as follows: hexalin transformation efficiency is 68%, and pimelinketone selectivity is 68%.
Embodiment 6
By hexalin, Perpropionic Acid, solvent and catalyzer, (mass ratio 0.3: 1, the Zn/ heteroatoms mol ratio of zinc pyrophosphate and HTS be 10: 1, Si/ heteroatoms mol ratio is 160: 1, method for preparing catalyst is except zinc compound kind and amount difference thereof, other condition is with preparation example 1) be 1: 8 according to the mol ratio of hexalin and Perpropionic Acid, the mass ratio of hexalin and catalyzer is 100: 1, the mass ratio of solvent methanol and catalyzer is 0: 1, reacts under be 30 DEG C of pressure being 1.0MPa in temperature.The result of reacting 2 hours is as follows: hexalin transformation efficiency is 81%, and pimelinketone selectivity is 73%.
Embodiment 7
Pimelinketone is prepared according to the method oxidation hexalin of embodiment 1.Replaced by acetone unlike solvent methanol.After reaction 2h, hexalin transformation efficiency is 65%; Pimelinketone selectivity is 84%.
Embodiment 8
Pimelinketone is prepared according to the method oxidation hexalin of embodiment 2.Replaced by equimolar zinc chloride unlike zinc nitrate in catalyst preparation process.After reaction 2h, hexalin transformation efficiency is 71%; Pimelinketone selectivity is 87%.
Embodiment 9
Pimelinketone is prepared according to the method oxidation hexalin of embodiment 3.Replaced by hydrogen peroxide unlike oxygenant tertbutyl peroxide.After reaction 2h, hexalin transformation efficiency is 68%; Pimelinketone selectivity is 82%.
The method for preparing catalyst that following embodiment is used is except zinc compound is different with hetero-atom molecular-sieve kind and amount thereof, other condition is with preparation example 2, and wherein the mass ratio of hetero-atom molecular-sieve and zinc compound, Zn/ heteroatoms mol ratio, Si/ heteroatoms mol ratio refer to each embodiment.
Embodiment 10
Be 3: 7 by hexalin, tertbutyl peroxide, solvent and catalyzer (mass ratio 0.1: 1, the Zn/ heteroatoms mol ratio of zinc chloride and the V-Si molecular sieve prepared according to the method described in Chinese patent CN1840477A embodiment 1 are 2: 1, Si/ heteroatoms mol ratio be 80: 1) according to the mol ratio of hexalin and tertbutyl peroxide, the mass ratio of solvent methanol and catalyzer is 5: 1, the mass ratio of hexalin and catalyzer is 0.5: 1, reacts under be 40 DEG C of pressure being 2.5MPa in temperature.The result of reacting 2 hours is as follows: hexalin transformation efficiency is 75%, and pimelinketone selectivity is 87%.
Embodiment 11
By hexalin, Peracetic Acid, solvent and catalyzer (zinc taurine and according to J.Mol.Cata1.A:Chem.; 1996; mass ratio 0.2: 1, the Zn/ heteroatoms mol ratio of the tin si molecular sieves prepared of method described in 105:149 ~ 158 are 10: 1, Si/ heteroatoms mol ratio is 50: 1) be 3: 11 according to the mol ratio of hexalin and Peracetic Acid; the mass ratio of solvent methanol and catalyzer is 80: 1; the mass ratio of hexalin and catalyzer is 0.1: 1, reacts under be 70 DEG C of pressure being 1.5MPa in temperature.The result of reacting 2 hours is as follows: hexalin transformation efficiency is 56%, and pimelinketone selectivity is 78%.
Embodiment 12
By hexalin, Perpropionic Acid, solvent and catalyzer (zinc pyrophosphate and according to Chem.Commun., 1994, mass ratio 0.8: 1, the Zn/ heteroatoms mol ratio of HTS Ti-MCM-41 prepared by the method described in 147 ~ 148 are 1: 1, Si/ heteroatoms mol ratio is 60: 1) be 1: 8 according to the mol ratio of hexalin and Perpropionic Acid, the mass ratio of hexalin and catalyzer is 100: 1, the mass ratio of solvent methanol and catalyzer is 0: 1, reacts under be 30 DEG C of pressure being 1.0MPa in temperature.The result of reacting 2 hours is as follows: hexalin transformation efficiency is 63%, and pimelinketone selectivity is 96%.
Embodiment 13
By hexalin, Perpropionic Acid, solvent and catalyzer (zinc nitrate and according to J.Chem.Soc.Chem.Commun., 1997, mass ratio 0.4: 1, the Zn/ heteroatoms mol ratio of HTS Ti-Beta prepared by the method described in 677 ~ 678 are 0.5: 1, Si/ heteroatoms mol ratio is 40: 1) be 1: 8 according to the mol ratio of hexalin and Perpropionic Acid, the mass ratio of hexalin and catalyzer is 100: 1, the mass ratio of solvent methanol and catalyzer is 0: 1, reacts under be 30 DEG C of pressure being 1.0MPa in temperature.The result of reacting 2 hours is as follows: hexalin transformation efficiency is 58%, and pimelinketone selectivity is 74%.
Result as can be seen from embodiment 1 ~ 13 and comparative example 1 ~ 3: production method of the present invention adopts zinc compound and hetero-atom molecular-sieve composition to be catalyzer, and activity and selectivity is all apparently higher than comparative sample such as the independent HTS of tradition and zinc compounds.
Claims (16)
1. the method by cyclohexanol production pimelinketone, under oxidation reaction condition, hexalin, oxygenant and catalyst exposure are reacted, it is characterized in that described catalyzer is the product of roasting of the composition of zn cpds and hetero-atom molecular-sieve, in described composition, the mass ratio of zn cpds and hetero-atom molecular-sieve is 0.01 ~ 20: 1, in zn cpds, in element, whole heteroatomic mol ratio in zinc atom and described hetero-atom molecular-sieve is 0.05 ~ 50: 1, and in described hetero-atom molecular-sieve, silicon and whole heteroatomic mol ratio are 5 ~ 250: 1.
2. according to the method for claim 1, wherein, in described composition, the mass ratio of zn cpds and hetero-atom molecular-sieve is 0.05 ~ 10: 1, in zn cpds, in element, whole heteroatomic mol ratio in zinc atom and hetero-atom molecular-sieve is 0.1 ~ 20: 1, and in described hetero-atom molecular-sieve, silicon and whole heteroatomic mol ratio are 25 ~ 150: 1.
3. according to the method for claim 1 or 2, wherein, described zn cpds be selected from the oxyhydroxide of the oxide compound of zinc, the oxysalt of zinc, the anaerobic hydrochlorate of zinc and zinc one or more.
4. according to the method for claim 1 or 2, wherein, described zn cpds is selected from one or more in the oxysalt of zinc and the anaerobic hydrochlorate of zinc.
5. according to the method for claim 1 or 2; wherein, described zn cpds is selected from one or more the mixture in zinc oxide, zinc nitrate, zinc carbonate, zinc phosphate, zinc taurine, zinc hydroxide, zinc uranyl acetate, zinc potassium cyanide, zine fluosilicate, zinc hydride, zinc cyanide, zinc sulphide, zinc thiocyanide, Zinic stearas, zinc iodide, zinc phosphide, zinc peroxide, zinc dithionite, zinc molybdate, zinc chlorate, zinc chromate, zinc chloride, zinc sulfate, Zinc Gluconate, zinc acetate, zinc bromide, zinc fluoride, zinc hydrogen phosphate and zinc pyrophosphate.
6. according to the method for claim 1 or 2, wherein, the heteroatoms in described hetero-atom molecular-sieve is the atom of one or more metals be selected from IVB race metal, VB race metal, group VIII metal, IVA race metal and lanthanide series metal.
7. according to the method for claim 1 or 2, wherein, the heteroatoms in described hetero-atom molecular-sieve is one or more in titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, iron atom, cobalt atom, nickle atom, tin atom, lanthanum atom and cerium atom.
8., according to the process of claim 1 wherein, described hetero-atom molecular-sieve is HTS.
9. according to the method for claim 8, wherein, described HTS is selected from least one in TS-1, TS-2, Ti-β, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, Ti-ZSM-48, Ti-MOR, Ti-TUN molecular sieve.
10. according to the method for claim 1 or 2, wherein, described hetero-atom molecular-sieve is the HTS of the MFI structure of hollow structure crystal grain, and the radical length of the chamber portion of its hollow structure is 5 ~ 300 nanometers, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.
11. according to the process of claim 1 wherein, the method is carried out in the presence of solvent, and described solvent is water, benzene, hexanaphthene, C
1~ C
10alcohol, C
3~ C
10ketone and C
2~ C
10nitrile in one or more.
12. according to the method for claim 11, and wherein, described solvent is C
1~ C
5fatty alcohol, C
3~ C
5aliphatic ketone, C
2~ C
5aliphatic nitrile and C
7~ C
10aromatic nitriles in one or more.
13. according to the method for claim 1, it is characterized in that described oxygenant is selected from hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid one or more.
14. according to the process of claim 1 wherein, the mol ratio of hexalin and oxygenant is 1: 0.5 ~ 15, and the mass ratio of solvent and catalyzer is 0 ~ 500: 1.
15. according to the method for claim 14, and wherein, hexalin and oxygenant mol ratio are 1: 1 ~ 10, and solvent is 0 ~ 200: 1 with catalyst quality ratio, and hexalin is 0.1 ~ 150: 1 with catalyst quality ratio.
16. according to the method for claim 1, it is characterized in that the method temperature be 20 ~ 160 DEG C, pressure carries out under being 0.1 ~ 3.0MPa.
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