CN103204769A - 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, further say so about a kind of be the method for catalyst oxidation cyclohexanol production pimelinketone with zinc compound and hetero-atom molecular-sieve composition.
Background technology
Pimelinketone is a kind of important chemical material, is widely used in the industry of fiber, synthetic rubber, industrial coating, medicine, agricultural chemicals, organic solvent.Particularly because the developing rapidly of polymeric amide industry, as the demand of the pimelinketone of preparation nylon 6 and nylon 66 intermediates whole world every year all more than 1,000,000 tons.Now, the cyclohexanone production process route mainly contains three kinds: cyclohexane liquid-phase oxidation method, phenol hydrogenation method and benzene partial hydrogenation method, and cyclohexane oxidation process is the main process of industrial production pimelinketone, accounts for more than 90%.But this production process also is considered to minimum one of efficient in all chemical industry processes.Cyclohexane oxidation synthesizing cyclohexanone process is one of the restriction key of caprolactam production and bottleneck.The industrial cyclohexane oxidation production pimelinketone that utilizes generally has three kinds of methods: a kind of is that the employing cobalt salt is the catalyzed oxidation of catalyzer, and this method cyclohexane conversion is higher, but the easy fouling of reactor now is eliminated substantially owing to formation hexanodioic acid cobalt makes.The 2nd, boric acid class catalytic oxidation, this method initial cost height, the energy consumption height, the ratio of hexalin is too high in the product, increases the burden of postorder cyclohexanol dehydrogenation.And technology is very complicated, and operation easier is big, is easy to cause equipment and pipeline seriously to stop up.The 3rd, with the non-catalyst oxidation of air direct oxidation, this method has effectively been avoided the problem of reactor fouling, in industrial extensive application, but this complex process, intermediate steps is many, cyclohexane conversion is low, and the hexanaphthene internal circulating load is big, the energy consumption height, pollute also bigger, particularly in the cyclohexyl hydroperoxide decomposition course, the pimelinketone selectivity is relatively poor, and yield is low.In addition, a large amount of waste lyes that the air oxidation of cyclohexane process produces, difficult treatment is still a global environmental protection difficult problem so far.
In the above-mentioned pimelinketone preparation process, all the companion produces hexalin, and hexalin is converted into pimelinketone through the oxidative dehydrogenation process process more then, and this process employing zinc oxide etc. is made oxygenant, reacts energy consumption height, process complexity under about 300 ℃.
Therefore, can be at the deficiency of existing technology, work out a kind of environmentally friendly and technology and simply prepare the pimelinketone novel process by the hexalin environmental friendliness and be of great practical significance.
Italy Taramasso etc. disclose a kind of new catalytic oxidation material that is called as HTS (TS-1) first in USP4410501, it has good selective oxidation to hydrocarbon, alcohol, phenol etc.
(J Catal, 1995,157:631～635) such as Ulf Schuchardt have carried out a series of research to the titanium molecular sieve catalysis oxidizing ethyle alkyl.Draw from research: hexanaphthene initial oxidation on TS-1 is hexalin, reoxidizes to be pimelinketone.Because selecting optionally reason of shape, hexalin will be oxidized to pimelinketone further in the TS-1 zeolite cages.(Applied Catal A:Gen 2001,211:1～17) such as Tao Jialin etc. (J Natural Gas Chem 2001,10:295～307) and Ulf Schuchardt are also all studied the titanium molecular sieve catalysis oxidizing ethyle alkyl.
Summary of the invention
The objective of the invention is on the basis of existing technology, provide a kind of under high hexalin transformation efficiency situation, the pimelinketone selectivity is produced the method for pimelinketone preferably.
The present inventor carries out deep research, be surprised to find that: the mixture of hetero-atom molecular-sieve (as HTS) and zn cpds is carried out roasting, and in element, in the product of roasting that obtains, whole heteroatomic mol ratio in zinc atom and the described hetero-atom molecular-sieve is 0.05～50: 1 o'clock, under this product of roasting existence and oxidation reaction condition, by the cyclohexanol production pimelinketone, can obtain under high hexalin transformation efficiency situation, the pimelinketone selectivity is reaction effect preferably.Finished the present invention thus.
Therefore, method by the cyclohexanol production pimelinketone provided by the invention, be under oxidation reaction condition, with hexalin, oxygenant and catalyzer contact reacts, it is characterized in that described catalyzer is the product of roasting of the composition of zn cpds and hetero-atom molecular-sieve.
In the method provided by the invention, described catalyzer is the product of roasting of the composition of zn cpds and hetero-atom molecular-sieve.In the described composition, the mass ratio of zn cpds and hetero-atom molecular-sieve is 0.01～20: 1, preferred 0.05～10: 1; In the described zn cpds, in element, whole heteroatomic mol ratio in zinc atom and the described hetero-atom molecular-sieve is 0.05～50: 1, preferred 0.1～20: 1, and silicon and whole heteroatomic mol ratio are 5～250 in the described hetero-atom molecular-sieve: 1, preferred 25～150: 1.
In the method provided by the invention, described zn cpds can be the various zinc compounds that zinc element can be provided for catalyzer after roasting.
For example, described zn cpds can be selected from one or more in the oxyhydroxide of the anaerobic hydrochlorate of oxysalt, zinc of oxide compound, the zinc of zinc and zinc.Among 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 for example can be C
2～C
20The zinc salt of organic carboxyl acid.Among the present invention, the inorganic oxysalt of described zinc for example can be 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 that are made of the acid group that contains metallic element and hydrogen, as: isopoly-acid and heteropolyacid.Among the present invention, the example of described isopoly-acid can for 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 for but be not limited to: phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid, silicomolybdic acid, P-Mo-Wo acid and silicon molybdenum wolframic acid.Among the present invention, the example of zn cpds includes but not limited to be selected from one or more the mixture in 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 the zinc hydrogen phosphate; Preferably, described zn cpds is one or more in the inorganic oxysalt of the organic oxygen-containing hydrochlorate of zinc and 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 the zinc hydrogen phosphate.
In method provided by the invention, described hetero-atom molecular-sieve refers to the molecular sieve that the skeletal atom (for example: Siliciumatom and/or aluminium atom) of molecular sieve is formed by the heteroatoms isomorphous substitution.The present invention is not particularly limited for the heteroatomic kind in the 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 the described hetero-atom molecular-sieve is the atom of metallic element.Further preferably, the heteroatoms in the described hetero-atom molecular-sieve is the atom that is selected from one or more metals in IVB family metal, VB family metal, group VIII metal, IVA family metal and the lanthanide series metal.Among the present invention, the heteroatomic example in the described hetero-atom molecular-sieve can for 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 the described hetero-atom molecular-sieve is one or more in titanium atom, vanadium atom, iron atom, tin atom and the cerium atom.Further preferably, the heteroatoms in the described hetero-atom molecular-sieve is titanium atom and/or vanadium atom.Most preferably, the heteroatoms in the described hetero-atom molecular-sieve is titanium atom.Heteroatomic content in the described hetero-atom molecular-sieve can change within wide in range scope.Preferably, in element, the whole heteroatomic mol ratio in the Siliciumatom in the described hetero-atom molecular-sieve and the described hetero-atom molecular-sieve is 5～250: 1.Further preferably, in element, the whole heteroatomic mol ratio in the Siliciumatom in the described hetero-atom molecular-sieve and the described hetero-atom molecular-sieve is 25～150: 1.
Of the present invention a kind of preferred embodiment in, described hetero-atom molecular-sieve is HTS (that is, the heteroatoms in the 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 for but be not limited to: the HTS of MFI structure (as TS-1), the HTS of MEL structure (as TS-2), the HTS of BEA structure (as Ti-Beta), the HTS of MWW structure (as Ti-MCM-22), the HTS of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS of MOR structure (as Ti-MOR), at least a in the HTS (as Ti-ZSM-48) of the HTS of TUN structure (as Ti-TUN) and other structure.
Of the present invention a kind of 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 cavity part of its hollow structure is 5～300 nanometers, and described HTS is at 25 ℃, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity that records under 1 hour the condition is at least 70 milligrams/gram, has hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this HTS and the desorption isotherm.Hereinafter, the HTS that will have a said structure is called hollow HTS.The method according to this invention adopts hollow HTS can obtain higher pimelinketone selectivity on the one hand, can also further improve the transformation efficiency of hexalin on the other hand.
In another preferred embodiment of the present invention, described hetero-atom molecular-sieve is V-Si molecular sieve (that is, the heteroatoms in the described hetero-atom molecular-sieve is vanadium atom), and described zn cpds is in zinc fluoride, zinc chloride and the zinc bromide one or more.
Catalyzer described in the method for the present invention, its preparation is not particularly limited, as long as described catalyzer is the product that carries out roasting by the raw material that will contain zn cpds and hetero-atom molecular-sieve.
According to one embodiment of the present invention, described Preparation of catalysts method can comprise: described hetero-atom molecular-sieve is contacted with the solution that contains described zn cpds, carry out drying after loading on described solution on the described hetero-atom molecular-sieve, to obtain containing the raw material of described zn cpds and hetero-atom molecular-sieve, and described raw material carried out roasting, thereby the catalyzer that obtains using in the method according to this invention.The described solution that contains zn cpds, its solvent can be the various solvents 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 that contains the solution of zn cpds can be selected for the routine of this area, no particular requirement, for example: can under 15～40 ℃ temperature, flood described hetero-atom molecular-sieve with the described solution that contains zn cpds; Also can be under 15～40 ℃ temperature, with the described solution spraying of zn cpds that contains to described hetero-atom molecular-sieve.According to the present invention, the described number of times that contains the concentration of the solution of zn cpds, described contact was not particularly limited with the described time that contacts, as long as in the feasible catalyzer that finally obtains of the charge capacity of described zn cpds on described hetero-atom molecular-sieve, the whole heteroatomic mol ratio on zinc atom and the described hetero-atom molecular-sieve satisfies previously described requirement and gets final product.According to the present invention, the condition of described drying is not particularly limited, and can carry out appropriate selection according to described solvent types.For example, the temperature of described drying can be 25～200 ℃, and the time can be 1～8 hour.Described drying can be carried out under air conditions; also can under protection of inert gas, carry out; chemically interactive gas can not take place with described hetero-atom molecular-sieve and zn cpds for various in described rare gas element, for example: neutral element gas (as argon gas), nitrogen.Described drying can be carried out under normal pressure, also can carry out under the condition of decompression or vacuum.
According to another embodiment of the invention, described Preparation of catalysts method can comprise: described hetero-atom molecular-sieve is mixed (namely with described zn cpds, will for the described hetero-atom molecular-sieve of solid with mix for the described zn cpds of solid), to obtain containing the raw material of described hetero-atom molecular-sieve and described zn cpds, and described raw material carried out roasting, with the catalyzer that obtains using in the method according to this invention.
Among the present invention, the condition that the described raw material that contains hetero-atom molecular-sieve and zn cpds is carried out roasting is not particularly limited, and described roasting can be carried out under the normal condition of this area.Usually, the temperature of described roasting can be 200～800 ℃, 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, can regulate the severe degree of reaction more easily so on the one hand, thereby make the method according to this invention have higher security, can also make reactant more abundant with contacting of catalyzer on the other hand.The present invention is not particularly limited for described solvent types, can be this area all kinds of SOLVENTS commonly used.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
10Fragrant nitrile in one or more.For example: described solvent can be in water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone, acetonitrile, propionitrile and the benzyl cyanide one or more.
Among 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, the raw material optimum ratio is as follows: the mol ratio of hexalin and oxygenant is preferably 1: 1～and 10, 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 the catalyzer does not have clear and definite restriction, can realize that the present invention gets final product, 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 ℃, and reaction pressure is preferably 0.1～2.5MPa.
In method provided by the invention, reinforced order does not have special requirement, can add hexalin earlier, can add oxygenant or solvent earlier yet.
The method of cyclohexanol production pimelinketone provided by the invention has following advantage:
1, catalyst composition preparation is simple, can be with zinc compound and the roasting of hetero-atom molecular-sieve mechanical mixture namely, and good reproducibility;
2, under high hexalin transformation efficiency situation, the pimelinketone selectivity is better;
3, this preparation method is green synthesis process, no special producing equipment requirements, and 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 the Comparative Examples, agents useful for same is commercially available chemically pure reagent, and wherein oxygenant is 30% the aqueous solution.Used HTS (TS-1) is by prior art Zeolites, (TS-1) sieve sample that the method described in the 943rd～950 page of 1992, the Vol.12 is prepared.Used hollow HTS HTS is according to disclosed method preparation among the Chinese patent CN1132699C, this HTS is the MFI structure, have hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this HTS and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is 15～180 nanometers; This HTS sample is at 25 ℃, P/PO=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 milligrams/gram).Composition catalyzer compositional analysis adopts fluorescence analysis method, records at Rigaku 3271E type Xray fluorescence spectrometer.
In Comparative Examples and embodiment:
Comparative Examples 1
This Comparative Examples illustrates under the situation that does not have catalyzer to exist, the reaction conditions of hexalin and hydrogen peroxide and result.
Be 1: 2 with hexalin, hydrogen peroxide and solvent according to the mol ratio of hexalin and hydrogen peroxide, wherein the solvent methanol quality is 20g, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.React after 4 hours, the transformation efficiency of hexalin is 7.6%, and the pimelinketone selectivity is 16%.
Comparative Examples 2
This Comparative Examples illustrates under the situation of catalyst Ti-si molecular sieves TS-1 Individual existence, the reaction conditions of hexalin and hydrogen peroxide and result.
Be 2: 1 with 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, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 33%, and the pimelinketone selectivity is 35%.
Comparative Examples 3
This Comparative Examples illustrates under the situation of catalyst oxidation zinc Individual existence, the reaction conditions of hexalin and hydrogen peroxide and result.
Be 1: 1 with 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, is that 60 ℃ of pressure are to react under the 2.5MPa in temperature.The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 7%, and the pimelinketone selectivity is 28%.
Preparation example 1
The preparation process of catalyst system therefor among this preparation example explanation the present invention.
With zinc oxide and 10g titanium-silicon molecular sieve TS-1 mechanically mixing at normal temperatures and pressures, roasting 5h under 550 ℃ of air atmospheres.Characterize through compositional analysis, wherein the mass ratio of zinc compound and hetero-atom molecular-sieve is 0.2: 1, and Zn/ heteroatoms mol ratio is 5: 1, and Si/ heteroatoms mol ratio is 56: 1.
Preparation example 2
The preparation process of catalyst system therefor among this preparation example explanation the present invention.
Zinc nitrate is soluble in water, add 10g HTS HTS then, mix at normal temperatures and pressures, after the drying at room temperature, roasting 2h under 650 ℃ of air atmospheres.Characterize through compositional analysis, wherein the mass ratio of zinc compound and hetero-atom molecular-sieve is 1: 1, and Zn/ heteroatoms mol ratio is 2: 1, and Si/ heteroatoms mol ratio is 37: 1.
Preparation example 3
The preparation process of catalyst system therefor among this preparation example explanation the present invention.
With zinc hydroxide and 10g titanium-silicon molecular sieve TS-1 mechanically mixing at normal temperatures and pressures, roasting 5h under 550 ℃ of air atmospheres.Characterize through compositional analysis, wherein the mass ratio of zinc compound and hetero-atom molecular-sieve is 5: 1, and Zn/ heteroatoms mol ratio is 18: 1, and Si/ heteroatoms mol ratio is 49: 1.
Embodiment 1
Be 1: 2 with 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, is that 30 ℃ of pressure are to react under the 1.2MPa in temperature.The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 46%, and the pimelinketone selectivity is 78%.
Embodiment 2
Be 1: 1 with 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, is that 60 ℃ of pressure are to react under the 2.0MPa in temperature.The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 83%, and the pimelinketone selectivity is 89%.
Embodiment 3
Be 2: 5 with 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, is that 50 ℃ of pressure are to react under the 0.5MPa in temperature.The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 64%, and the pimelinketone selectivity is 76%.
The method for preparing catalyst that following embodiment uses 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 see each embodiment for details.
Embodiment 4
(mass ratio of zinc iodide and HTS 0.2: 1, Zn/ heteroatoms mol ratio are that 5: 1, Si/ heteroatoms mol ratio are 50: 1 with hexalin, hydrogen peroxide, solvent and catalyzer, 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, is that 40 ℃ of pressure are to react under the 2.5MPa in temperature.The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 66%, and the pimelinketone selectivity is 73%.
Embodiment 5
(mass ratio of zinc taurine and HTS 0.5: 1, Zn/ heteroatoms mol ratio are that 15: 1, Si/ heteroatoms mol ratio are 150: 1 with hexalin, Peracetic Acid, solvent and catalyzer; 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, is that 70 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 68%, and the pimelinketone selectivity is 68%.
Embodiment 6
(mass ratio of zinc pyrophosphate and HTS 0.3: 1, Zn/ heteroatoms mol ratio are that 10: 1, Si/ heteroatoms mol ratio are 160: 1 with hexalin, Perpropionic Acid, solvent and catalyzer, 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, is that 30 ℃ of pressure are to react under the 1.0MPa in temperature.The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 81%, and the pimelinketone selectivity is 73%.
Embodiment 7
Method oxidation hexalin according to embodiment 1 prepares pimelinketone.Different is that solvent methanol is replaced by acetone.Behind the reaction 2h, the hexalin transformation efficiency is 65%; The pimelinketone selectivity is 84%.
Embodiment 8
Method oxidation hexalin according to embodiment 2 prepares pimelinketone.Different is that zinc nitrate is replaced by equimolar zinc chloride in the catalyst preparation process.Behind the reaction 2h, the hexalin transformation efficiency is 71%; The pimelinketone selectivity is 87%.
Embodiment 9
Method oxidation hexalin according to embodiment 3 prepares pimelinketone.Different is that the oxygenant tertbutyl peroxide is replaced by hydrogen peroxide.Behind the reaction 2h, the hexalin transformation efficiency is 68%; The pimelinketone selectivity is 82%.
The method for preparing catalyst that following embodiment uses 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 see each embodiment for details.
Embodiment 10
Be 3: 7 with hexalin, tertbutyl peroxide, solvent and catalyzer (zinc chloride and be that 2: 1, Si/ heteroatoms mol ratio be 80: 1 according to mass ratio 0.1: 1, the Zn/ heteroatoms mol ratio of the V-Si molecular sieve of the method preparation of describing among the Chinese patent CN1840477A embodiment 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, is that 40 ℃ of pressure are to react under the 2.5MPa in temperature.The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 75%, and the pimelinketone selectivity is 87%.
Embodiment 11
With 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 of the method preparation of describing in 105:149～158 is that 10: 1, Si/ heteroatoms mol ratio are 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, is that 70 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 56%, and the pimelinketone selectivity is 78%.
Embodiment 12
With 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 the HTS Ti-MCM-41 of method described in 147～148 preparation is that 1: 1, Si/ heteroatoms mol ratio are 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, is that 30 ℃ of pressure are to react under the 1.0MPa in temperature.The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 63%, and the pimelinketone selectivity is 96%.
Embodiment 13
With 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 the HTS Ti-Beta of method described in 677～678 preparation is that 0.5: 1, Si/ heteroatoms mol ratio are 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, is that 30 ℃ of pressure are to react under the 1.0MPa in temperature.The result who reacts 2 hours is as follows: the hexalin transformation efficiency is 58%, and the pimelinketone selectivity is 74%.
From the result of embodiment 1～13 and Comparative Examples 1～3 as can be seen: it is catalyzer that production method of the present invention adopts zinc compound and hetero-atom molecular-sieve composition, and activity and selectivity are all apparently higher than comparative sample such as the independent HTS of tradition and zinc compounds.
Claims (17)
1. the method by the cyclohexanol production pimelinketone is under oxidation reaction condition, with hexalin, oxygenant and catalyzer contact reacts, it is characterized in that described catalyzer is the product of roasting of the composition of zn cpds and hetero-atom molecular-sieve.
2. according to the method for claim 1, wherein, the mass ratio of zn cpds and hetero-atom molecular-sieve is 0.01～20: 1 in the described composition, in the zn cpds, in element, whole heteroatomic mol ratio in zinc atom and the described hetero-atom molecular-sieve is 0.05～50: 1, and silicon and whole heteroatomic mol ratio are 5～250: 1 in the described hetero-atom molecular-sieve.
3. according to the method for claim 2, wherein, the mass ratio of zn cpds and hetero-atom molecular-sieve is 0.05～10: 1 in the described composition, in the zn cpds, in element, whole heteroatomic mol ratio in zinc atom and the hetero-atom molecular-sieve is 0.1～20: 1, and silicon and whole heteroatomic mol ratio are 25～150: 1 in the described hetero-atom molecular-sieve.
4. according to the method for one of claim 1～3, wherein, described zn cpds is selected from one or more in the oxyhydroxide of the anaerobic hydrochlorate of oxysalt, zinc of oxide compound, the zinc of zinc and zinc.
5. according to the method for one of claim 1～3, wherein, described zn cpds is selected from one or more in the anaerobic hydrochlorate of the oxysalt of zinc and zinc.
6. according to the method for one of claim 1～3; 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 the zinc pyrophosphate.
7. according to the method for one of claim 1～3, wherein, the heteroatoms in the described hetero-atom molecular-sieve is for being the atom that is selected from one or more metals in IVB family metal, VB family metal, group VIII metal, IVA family metal and the lanthanide series metal.
8. according to the method for one of claim 1～3, wherein, the heteroatoms in the 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 the cerium atom.
9. according to the process of claim 1 wherein, described hetero-atom molecular-sieve is HTS.
10. according to the method for claim 9, wherein, described HTS is selected from least a in TS-1, TS-2, Ti-β, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, Ti-ZSM-48, Ti-MOR, the Ti-TUN molecular sieve.
11. according to the method for one of claim 1～3, wherein, described hetero-atom molecular-sieve is the HTS of the MFI structure of hollow structure crystal grain, the radical length of the cavity part of its hollow structure is 5～300 nanometers, and described HTS is at 25 ℃, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity that records under 1 hour the condition is at least 70 milligrams/gram, has hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this HTS and the desorption isotherm.
12. according to the process of claim 1 wherein, this method is carried out in the presence of solvent, described solvent is water, benzene, hexanaphthene, C
1～C
10Alcohol, C
3～C
10Ketone and C
2～C
10Nitrile in one or more.
13. according to the method for claim 12, wherein, described solvent is C
1～C
5Fatty alcohol, C
3～C
5Aliphatic ketone, C
2～C
5Aliphatic nitrile and C
7～C
10Fragrant nitrile in one or more.
14. according to the method for claim 1, it is characterized in that described oxygenant is selected from one or more in hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and the Perpropionic Acid.
15. according to the process of claim 1 wherein, the mol ratio of hexalin and oxygenant is 1: 0.5～15, the mass ratio of solvent and catalyzer is 0～500: 1.
16. according to the method for claim 15, wherein, hexalin and oxygenant mol ratio are 1: 1～10, solvent is 0～200: 1 with the catalyst quality ratio, and hexalin is 0.1～150: 1 with the catalyst quality ratio.
17. according to the method for claim 1, it is characterized in that this method is that 20～160 ℃, pressure are to carry out under 0.1～3.0MPa in temperature.
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