CN102452893A - Method for oxidizing cyclic ketone by utilizing zinc-supported Beta molecular sieve - Google Patents
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Abstract
The invention provides a method for oxidizing cyclic ketone by utilizing a zinc-supported Beta molecular sieve. The method is characterized in that reaction is carried out in the presence of a catalyst under the conditions that molar ratio of cyclic ketone to solvent to hydrogen peroxide is 1: (0-50): (0.2-20), temperature is 5-200 DEG C and reaction pressure is 0.1-3.0MPa, wherein the mass ratio of the catalyst to the cyclic ketone is 1: (5-300) and the catalyst is a zinc-supported pickled aluminum nano Beta-molecular sieve ZnO2/HBeta.
Description
Technical field
The present invention is a kind of method of catalyzed oxidation cyclic ketones, more specifically says so about a kind of cyclic ketones method through hydrogen peroxide oxidation in the presence of catalyzer.
Background technology
6-caprolactone have viscosity low, be prone to advantages such as processing, VOC content is low; In producing technological processs such as polycaprolactone, ε-Ji Neixianan, modifier, aqueous polyurethane coating, cast elastomers, hot melt adhesive, elastomerics, be used as oligopolymer and denaturing agent, it is functional to improve toughness, cold property and reactivity etc.; Aspect coating, the properties-correcting agent of solvent of using as vehicle paint base, top coat and various building materials and latex coating etc. can improve the toughness of filming, improve cold property, reactivity, raising cross-linking density; Aspect tackiness agent, can be used for improveing the adhesion characteristic of hot melt adhesive and Solvent Adhesive; Aspect resin modified, can be used for improving flexibility, flowability, low temperature shock-resistance, formability etc.In addition; It is as a kind of raw materials for production of important degradable plastics; Have excellent biological compatibility, nontoxicity, biodegradable and the good performances such as the property of medicine of oozing, thus biomedical engineering, disposable degradable plastic tableware, obtain widespread use in mould material, the high added value wrapping material.The enhancing of Along with people's environmental consciousness, 6-caprolactone will receive both at home and abroad more extensive concern, have vast market prospect more.
6-caprolactone is just under lab successfully synthetic as far back as the thirties in 20th century.The compound method of 6-caprolactone mainly contains Baeyer-Villiger oxidation style, 1,6-pinakon catalytic dehydrogenation method and 6 hydroxycaproic acid intramolecular condensation method etc.Take all factors into consideration from aspects such as raw material, device and reaction conditionss, the Baeyer-Villiger oxidation style is efficient ways.But peroxide acids oxygenant also has bigger shortcoming: can produce a large amount of organic carboxyl acid (salt) refuses after has reacted (1), have greater environmental impacts, recovery or intractability are bigger; (2) reactor product separates, purification ratio is difficult, selectivity is low, and Atom economy is relatively poor, does not meet the Green Chemistry fundamental principle; (3) organic peroxide acid need use the ydrogen peroxide 50 of high density in process of production, and character is unstable, production cost is higher, and danger is bigger in transportation, storage and operating process, thereby has limited its application in industrial production.
Compare H with peroxy acid
2O
2Application prospect the most wide, heavy industrialization is used and environmental friendliness because of it is easy to, and meets the development trend of Green Chemistry.(Catal.Lett.40 (1996) pp.4750.) has studied the Baeyer-Villiger oxidation three-phase reaction system (ketone+H of the pimelinketone that with TS-1 is catalyzer to Bhaumik etc. for Bhaumik, P.Kumar and R.Kumar
2O
2/ H
2And investigated and have or not of the influence of second cyanogen the O+ catalyzer), as solvent.If Bhaumik etc. find in three-phase reaction system, to add small amount of H
2SO
4Can obtain higher transformation efficiency.
Corma etc. (Corma, L.T.Nemeth, M.Renz, et al.Nature 412 (2001), pp.421-423) reported under 56 ℃ with Sn-beta-molecular sieve catalyst oxidation pimelinketone and 35%H
2O
2The aqueous solution obtains corresponding lactone, and the selectivity of lactone is very high, and catalyzer is reusable, and through the circulation of four secondary responses, catalytic activity does not obviously reduce.
A kind of method that is prepared 6-caprolactone by cyclohexanone by catalytic oxidation is disclosed among the CN101307045A; In this method; Said catalyzer is the mixture of 50～100% zinc oxide and other MOX of 0～50% by weight, and solvent is a nitrile, and oxygenant is hydrogen oxide or Peracetic Acid.This method can obtain higher caprolactone productive rate and selectivity, catalyzer is cheap and easy to get, preparation simply, not halogen-containing element, stability is high and can be repeatedly used.
Alcohol acid also is an important chemical material.With the 6 hydroxycaproic acid is example, and it has application widely in organic synthesis and polymeric material field, for example, preparation 6-aldehyde radical caproic acid, 6-caprolactone, hexanodioic acid etc., its verivate 6 hydroxycaproic acid ethyl ester etc. is organic chemical industry's midbody of using always.U.S. Pat P2008306153 has introduced a kind of at CH
2Cl
2In the solvent, with PCC (PCC PyridiniumChlorochromate) be oxygenant under 37 ℃ of conditions, 6 hydroxycaproic acid is oxidized to 6-aldehyde radical caproic acid.
At present, be the feedstock production 6 hydroxycaproic acid mainly in the world with pimelinketone, caprolactone and hexanodioic acid.Wherein, pimelinketone is because advantage such as relative low price, raw material sources be extensive, and causes people's attention.(Inorganica Chimica Acta, 349,195-202 such as LENARDA Maurizio; 2003) use HBEA type molecular sieve H β to be catalyzer, the oxidizing reaction of having carried out pimelinketone obtains 6 hydroxycaproic acid.Document (Polish Journal of Chemistry, 78 (5), 687-697; 2004) having reported under several kinds of catalyst actions, is solvent with water and propyl carbinol, and the hydrogen peroxide oxidation pimelinketone is the reaction of 6 hydroxycaproic acid.Document (Angewandte Chemie, International Edition, 41 (23), 4481-4484; 2002) introduced at water and (CF
3)
2In the CHOH solution, with p-MeC
6H
4SO
3H is a catalyzer, is 6 hydroxycaproic acid at 55 ℃ of following pimelinketone by hydrogen peroxide oxidation.But used catalyzer is a homogeneous catalyst, has not easily separated, environmentally hazardous drawback and can't drop into suitability for industrialized production.
Document (Organic&Biomolecular Chemistry, 7 (4), 725-732; 2009) reported a kind of method for preparing 6 hydroxycaproic acid by caprolactone.Document (Journal of the American Chemical Society, 130 (5), 1718-1726; 2008) introduced a kind of pimelinketone warp equally and reacted the process that makes 6 hydroxycaproic acid with highly basic (NaOH) and strong acid (HCl).Document (Applied and Environmental Microbiology, 65 (5), 2232-2234; 1999) introduced a kind of 30 ℃ near the neutral water surrounding in, the enzyme catalysis caprolactone is hydrolyzed to the reaction of 6 hydroxycaproic acid.Because it is having adopted strong acid and highly basic in the above-mentioned the whole bag of tricks is reactant, serious to equipment corrosion, produce a large amount of wastes, environment exerted an influence, so do not meet green and the chemical principle of Sustainable development.
CN1211969A disclose a kind of through hexanodioic acid, adipate monoester or di adipate contain hexanodioic acid or its ester as the starting material shortening of main ingredient preparation 1; The method of 6-pinakon and 6 hydroxycaproic acid or its ester; Wherein, The distillation hydrogenation products is recycled to hydrogenation step to remove the tower kettle product that obtains behind pinakon and hydroxycaproic acid or its ester, and tower kettle product mainly contains the oligomer ester of 6 hydroxycaproic acid; The mixture that makes starting material and recycle stream 100-300 ℃ with the 10-300 crust, in liquid phase, on said hydrogenation catalyst, react, in the reactor drum, the carboxyl of hydrogenation and the molar ratio of hydrogen is 1: 5-1: 100.
Di-carboxylic acid also is important Organic Chemicals, is example with the hexanodioic acid, and it is that significant di-carboxylic acid is gone up in industry, is mainly used in the system adiponitrile, and then produces hexanediamine, and produce nylon 66 (polymeric amide) and engineering plastics etc. with hexanediamine.Also be used to produce various esters products in addition; As softening agent and quality lubricant, do polyurethane elastomer raw material, produce the raw material or the like of souring agent, medicine, yeast purificant, sterilant, tackiness agent, synthetic leather, synthetic dyestuff and the spices of unsaturated polyester, pinakon and adipic acid ester class, various food and drink.
Nineteen thirty-seven, du pont company is used the nitric acid oxidation hexalin, has at first realized the suitability for industrialized production of hexanodioic acid.Get into the sixties, progressively use cyclohexane oxidation process in the industry instead,, and then carry out the nitric acid or the atmospheric oxidation of KA oil promptly earlier by hexanaphthene system intermediate product pimelinketone and hexalin mixture (be keto-alcohol oil, claim KA oil again).But there is the deep-etching problem in this reaction pair equipment, and environmental pollution is serious, complex process, and energy consumption is higher, do not meet the Green Chemistry principle.
Air oxidation process is to be catalyzer with neutralized verdigris and manganese acetate, and acetic acid is solvent, with air direct oxidation KA oil.Oxidation products is through the two-stage crystal refining, and recovered solvent can be recycled after treatment.This method reaction times is very long, reaction efficiency is lower, the product separation difficulty, so adopt still few.
The Japan scientist is wild to have developed with heteropolyacid Na according to very controlling etc.
2WO
42H
2O is a catalyzer, [CH
3N (n-C
8H
17)
3] HSO
4Be phase-transfer catalyst, hydrogen peroxide direct oxidation tetrahydrobenzene prepares hexanodioic acid.But shortcomings such as heteropolyacid catalyst character is unstable, specific surface is little, be prone to inactivation, difficulty reclaims and lack work-ing life, thereby can extensively not promote at present.
Other working methods of hexanodioic acid also have the chlorocyclohexane method, are from the cyclohexane oxidation by product, to reclaim hexanodioic acid, produce hexanodioic acid etc. by propenoate.Japan company of Asahi Chemical Industry has also carried out the research of one step of hexanaphthene atmospheric oxidation system hexanodioic acid.Chinese patent CN101337879 discloses the mixed catalyst that a kind of catalyzer monometallic porphyrin that in hexanaphthene, is dissolved with 1-500ppm or μ-oxygen bimetallic porphyrin or they and transition metal salt or oxide compound constitute, and the catalytic air oxidation hexanaphthene prepares the technology and the equipment of hexanodioic acid.
Summary of the invention
The objective of the invention is the deficiency to prior art, and a kind of method of the pickling dealuminzation nanometer β-molecular sieve catalytic oxidation cyclic ketones with zinc supported is provided on the basis of existing technology.
The method of the beta-molecular sieve oxidation cyclic ketones of zinc supported provided by the invention; It is characterized in that according to cyclic ketones: solvent: ydrogen peroxide 50=1: (0～50): the mole proportioning of (0.2～20); Temperature is 5～200 ℃, and reaction pressure is under the condition of 0.1～3.0MPa, in the presence of a kind of catalyzer, reacts; The mass ratio of catalyzer and cyclic ketones is 1: (5～300), described catalyzer are the pickling dealuminzation nano-beta molecular sieve of zinc supported.
In the method provided by the invention, said cyclic ketones can be selected from the cyclic ketones of various monocycle ketone, many cyclic ketones and band side chain R, and wherein to be preferably carbon number be 1～6 alkyl functional group to R.Of the present invention preferred embodiment in, it is the catalytic oxidation of raw material that the production of said lactone especially is fit to pimelinketone, ketopentamethylene or methylcyclohexanone.
In the method provided by the invention, said catalyzer is the nano-beta molecular sieve of the pickling of zinc supported.Beta-molecular sieve has the BEA crystalline structure, is the macropore supersiliceous zeolite with three-dimensional ten binary pore passage structures, is at first disclosed in 1967 in U.S. Pat P3308069 by U.S. Mobil oil company.Corma etc. (Corma, L.T.Nemeth, M.Renz, et al.Nature 412 (2001) adopts direct synthesis technique to obtain the Sn-beta-molecular sieve, and wherein tin replaces the framework silicon atom with the form of four-coordination skeleton tin, has stronger Lewi s acidity.Nanoparticle is meant the particle of yardstick between 1～100nm; Research Institute of Petro-Chemical Engineering adopts the moistened surface method to synthesize nano-beta molecular sieve (CN1108213A and CN1154342A); Further can be through pickling, for example high density (>=70wt%) sulfuric acid contacts with nano-beta molecular sieve, significantly removes the aluminium in the framework of molecular sieve; Make that the content of aluminium reduces to 1～5wt% in oxide compound by 6.5～9.0wt% in the molecular sieve, increase the framework of molecular sieve stability of structure.On the basis of above-mentioned nanometer β-molecular sieve through pickling; Introduce approximately the high dispersing of counting 1～5wt.% with zinc oxide on pickling nano-beta molecular sieve surface through the incipient impregnation load method and contain zinc species; Through high-temperature roasting, promptly obtain the pickling dealuminzation nano-beta molecular sieve of zinc supported again.The contriver finds, adopts the pickling dealuminzation nano-beta molecular sieve of zinc supported, and is helpful to macromolecular catalysis, and can prolong reaction running period.
In the method provided by the invention, being oxygenant with the hydrogen peroxide, because of its reduzate is merely water, environmental friendliness, is the green oxidation agent.The high density ydrogen peroxide 50 in production, accumulating, use, have potential safety hazard, and cost is higher because its character is unstable.Among the present invention, be that the form of 10～60% aqueous hydrogen peroxide solution adds in the reaction system with mass concentration normally, for example the aqueous hydrogen peroxide solution of technical grade has 27.5%, 30% and 35% etc., and selecting massfraction usually for use is 30% ydrogen peroxide 50.In proportioning raw materials, said ydrogen peroxide 50 is in hydrogen peroxide.
In the method provided by the invention, temperature of reaction is 5～200 ℃ and suits, and all can carry out catalytic oxidation effectively.But to different temperature of reaction; The distribution trend of the reaction product that we find to be generated is also inequality, and is for example interval at the lesser temps below 75 ℃, during preferred 20～75 ℃ of reactions; Highly selective to lactone is favourable, and the selectivity of alcohol acid and di-carboxylic acid is just low relatively; The temperature of reaction that improves temperature of reaction to 100 ℃ again is interval, and in the time of preferred 80～95 ℃, the selectivity of alcohol acid can improve gradually, and its selectivity will be higher than the selectivity of lactone and di-carboxylic acid.And 100～200 ℃ higher temperature range, preferred 100～160 ℃, the rising that we find temperature is more favourable for the generation of di-carboxylic acid.
In the method provided by the invention, the change of reaction pressure is also not obvious to the influence of reaction product, considers that from the economy of operation reaction pressure is preferably 0.1～0.5MPa.
In the method that present method provides, select for use the organic mixture of one or more inertia as solvent.Said inertia organism is compound close with boiling point of reactant or the compound that polarity is big, specific inductivity is high.Wherein, The said compound close with boiling point of reactant can be lower aliphatic alcohols, ketone, acid, ester; Be generally alcohol with 1～6 carbon number, ketone, acid, ester etc., for example methyl alcohol, ethanol, the trimethyl carbinol, acetone, acetic acid, propionic acid, ETHYLE ACETATE or dioxane etc.; The inert organic solvents that said polarity is big, specific inductivity is high is acetonitrile, chloroform, tetramethylene sulfone etc. for example.
The contriver is surprised to find that; When adopting acetone or dioxane to be solvent; Cyclic ketones particularly: the mole proportioning of ydrogen peroxide 50 is 1: the mass ratio of (0.2～10) and catalyzer and cyclic ketones is 1: 5～100, with the mol ratio proportioning of cyclic ketones be (0.2～10): 1, temperature is that 20～75 ℃, pressure are the following time of condition of 0.1～3.0MPa; With other organism such as other organic solvents such as acetonitrile, methyl alcohol, the selectivity of corresponding lactone improves more than 20% at least; And when adopting ethanol or ETHYLE ACETATE to be solvent, when temperature was brought up to 80～95 ℃, the selectivity of corresponding alcohol acid also had when using other solvents and improved significantly between 3 to 6 hours the reaction times; When adopting under acetate or the situation of propionic acid as solvent; Temperature is brought up to more than 100 ℃; The molar ratio of ydrogen peroxide 50 and cyclic ketones is higher than under 5 the situation, and the reaction times surpasses 5 hours, and then the selectivity of corresponding di-carboxylic acid uses other solvents to be significantly improved again.Therefore, method provided by the invention can be controlled operating parameterss such as reactant mole proportioning, temperature and solvent species flexibly according to the difference of title product.For example, when title product is lactone, preferably under 20～75 ℃ temperature, with dioxane and/or acetone as reaction solvent; When title product is alcohol acid, preferably under 80～95 ℃ temperature, with ethanol and/or ETHYLE ACETATE as reaction solvent; When title product is di-carboxylic acid, can improve temperature of reaction, preferably under 100～160 ℃ temperature, with acetate and/or propionic acid as reaction solvent.
In the method provided by the invention, being oxygenant with the ydrogen peroxide 50, because of its reduzate is merely water, environmental friendliness, is the green oxidation agent, and the high density ydrogen peroxide 50 in production, accumulating, use, have potential safety hazard, and cost is higher because its character is unstable.Be that the form of 10～60% aqueous hydrogen peroxide solution adds in the reaction system with mass percentage concentration normally, for example the aqueous hydrogen peroxide solution of technical grade has 27.5%, 30% and 35% etc.Usually selecting massfraction for use is 30% ydrogen peroxide 50, and the inventor finds that the lower concentration ydrogen peroxide 50 has catalytic oxidation activity more efficiently under the appropriate reaction condition.
The method of cyclic ketones catalyzed oxidation provided by the invention can adopt periodical operation or successive operating method.For example, when adopting intermittent mode to carry out, after cyclic ketones, solvent, catalyzer are encased in reactor drum, once add or add continuously ydrogen peroxide 50; When the employing continuous mode carries out, with fixed bed or slurry bed reactor, catalyzer, solvent making beating back are added cyclic ketones, ydrogen peroxide 50 continuously, the while is separated product constantly.
Method provided by the invention can adopt the closed still reaction, and soon catalyzer, solvent, cyclic ketones, ydrogen peroxide 50 add afterreaction simultaneously.
In the method provided by the invention, the employing of the process of said recovery product is at present that distillation, crystallization and the extraction etc. of the routine that people were familiar with separate means.Specifically, at first adopt relatively-high temperature condition Crystallization Separation to be prone to the di-carboxylic acid of separating out, adopt lower condition crystallization relatively to separate out the monohydroxylic carboxylic acid again, raw material, lactone and other by products then adopt the means of distillation or extraction to obtain to separate.
The method of the pickling dealuminzation nanometer β-sieve catalyst catalysis cyclic ketones of zinc supported provided by the invention has following advantage:
1. be compared to traditional method, the present invention overcome conventional oxidation method complex manufacturing, equipment corrosion, have drawbacks such as potential safety hazard and environmental pollution be serious.
2. the introducing of zinc has improved catalyst performance, and acid cleaning process has increased the mass transfer velocity of diffusion of reactant and product, has reduced the generation of side reactions such as open loop, over oxidation, and because framework aluminum content obviously reduces, its catalytic oxidation activity and activity stability are high.Make it under the oxidation of ydrogen peroxide 50, under the selectivity condition with higher, its catalytic oxidation activity and stability of catalytic activity are also better.
3. control operating parameterss such as reactant mole proportioning, temperature and solvent species flexibly, can obtain different title products.
Embodiment
Following is that embodiment will be further described the present invention.
In each embodiment, used reagent is commercially available chemically pure reagent.
Among the embodiment, used zinc load pickling nano-beta molecular sieve is that the sulphuric acid soln of nano-beta molecular sieve (Hunan is built feldspathization company and produced) usefulness >=70wt% soaks after 3 hours at least, obtains through the incipient impregnation load method with solder(ing)acid again.
The concentration of each material of reaction back uses vapor-phase chromatography to carry out quantitative analysis among Comparative Examples and the embodiment.The 6890 type gas chromatographs that used Agilent company produces; Used analysis chromatographic column is the FFAP post.
The selectivity of the transformation efficiency of cyclic ketones, corresponding lactone, alcohol acid and di-carboxylic acid is respectively to calculate according to the following equation among the embodiment:
Embodiment 1
Take by weighing pickling dealuminzation nanometer β-sieve catalyst (zinc oxide content 2.5wt% of 2.3 gram zinc supported; Alumina content is 2.3wt%) be loaded in the 100ml three-necked flask; Add magnetic agitation, 19.63 gram ketopentamethylene, 36 gram dioxane and 23ml concentration more successively and be 30% ydrogen peroxide 50, this moment, the mol ratio of ketopentamethylene and hydrogen peroxide was 1: 1.Three-necked flask is put on the temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, begins reaction.Temperature of reaction is controlled at about 64 ℃, reacts after 3 hours, and the transformation efficiency of ketopentamethylene is 20.65%, and the selectivity that generates δ-Wu Neizhi is 96.45%, and the selectivity of 5-hydroxypentanoic acid is 1.08%, and the selectivity of pentanedioic acid is 0.17%.
Embodiment 2
Take by weighing pickling dealuminzation nanometer β-sieve catalyst (zinc oxide content 3.1wtwt% of 2.44 gram zinc supported; Alumina content is 1.8wt%) be loaded in the 100ml three-necked flask; Add magnetic agitation, 19.63 gram ketopentamethylene, 6.4 gram methyl alcohol and 23ml concentration more successively and be 30% ydrogen peroxide 50, this moment, the mol ratio of ketopentamethylene and hydrogen peroxide was 1: 1.Three-necked flask is put on the temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, begins reaction.Temperature of reaction is controlled at about 70 ℃, reacts after 5 hours, and the transformation efficiency of ketopentamethylene is 37.82%, and the selectivity that generates δ-Wu Neizhi is 28.65%, and the selectivity of 5-hydroxypentanoic acid is 21.78%, and the selectivity of pentanedioic acid is 28.37%.
Embodiment 3
Take by weighing pickling dealuminzation nanometer β-sieve catalyst (zinc oxide content 2.6wt% of 2.65 gram zinc supported; Alumina content is 2.2wt%) be loaded in the 100ml three-necked flask; Add magnetic agitation, 19.63 gram ketopentamethylene, 18 gram acetone and 46ml concentration more successively and be 30% ydrogen peroxide 50, this moment, the mol ratio of ketopentamethylene and hydrogen peroxide was 1: 2.Three-necked flask is put on the temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, begins reaction.Temperature of reaction is controlled at about 70 ℃, reacts after 6 hours, and the transformation efficiency of ketopentamethylene is 68.57%, and the selectivity that generates δ-Wu Neizhi is 93.98%, and the selectivity of 5-hydroxypentanoic acid is 3.28%, and the selectivity of pentanedioic acid is 1.57%.
Embodiment 4
Take by weighing pickling dealuminzation nanometer β-sieve catalyst (zinc oxide content 3.4wt% of 2.65 gram zinc supported; Alumina content is 1.2wt%) be loaded in the 100ml three-necked flask; Add magnetic agitation, 19.63 gram pimelinketone, 16 gram ethanol and 46ml concentration more successively and be 30% ydrogen peroxide 50, this moment, the mol ratio of pimelinketone and hydrogen peroxide was 1: 2.Three-necked flask is put on the temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, begins reaction.Temperature of reaction is controlled at about 90 ℃, reacts after 6 hours, and the transformation efficiency of pimelinketone is 41.69%, and the selectivity that generates 6-caprolactone is 1.42%, and the selectivity of 6 hydroxycaproic acid is 92.98%, and the selectivity of hexanodioic acid is 4.19%.
Embodiment 5
Take by weighing pickling dealuminzation nanometer β-molecular sieve (zinc oxide content 1.6wt% of 3.31 gram zinc supported; Alumina content is 2.0wt%) catalyzer is loaded in the 100ml three-necked flask; Add magnetic agitation, 19.63 gram pimelinketone, 23 gram ETHYLE ACETATE and 23ml concentration more successively and be 30% ydrogen peroxide 50, this moment, the mol ratio of pimelinketone and hydrogen peroxide was 1: 1.Three-necked flask is put on the temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, begins reaction.Temperature of reaction is controlled at about 97 ℃, reacts after 6 hours, and the transformation efficiency of pimelinketone is 86.31%, and the selectivity that generates 6-caprolactone is 2.08%, and the selectivity of 6 hydroxycaproic acid is 95.68%, and the selectivity of hexanodioic acid is 1.28%.
Embodiment 6
Take by weighing pickling dealuminzation nanometer β-molecular sieve (zinc oxide content 2.3wt% of 2.53 gram zinc supported; Alumina content is 1.8wt%) catalyzer is loaded in the 100ml three-necked flask; Add magnetic agitation, 9.81 gram pimelinketone, 32 gram acetate and 46ml concentration more successively and be 30% ydrogen peroxide 50, this moment, the mol ratio of pimelinketone and hydrogen peroxide was 1: 4.Three-necked flask is put on the temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, begins reaction.Temperature of reaction is controlled at about 100 ℃, reacts after 8 hours, and the transformation efficiency of pimelinketone is 99.24%, and the selectivity that generates 6-caprolactone is 0.43%, and the selectivity of 6 hydroxycaproic acid is 0.62%, and the selectivity of hexanodioic acid is 98.19%.
Embodiment 7
Take by weighing pickling dealuminzation nanometer β-molecular sieve (zinc oxide content 1.4wt% of 2.3 gram zinc supported; Alumina content is 3.8wt%) be loaded in the 100ml three-necked flask; Add magnetic agitation, 9.81 gram pimelinketone, 3.6 gram water and 46ml concentration more successively and be 30% ydrogen peroxide 50, this moment, the mol ratio of pimelinketone and hydrogen peroxide was 1: 4.Three-necked flask is put on the temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, begins reaction.Temperature of reaction is controlled at about 107 ℃, reacts after 12 hours, and the transformation efficiency of pimelinketone is 99.87%, and the selectivity that generates 6-caprolactone is 0.33%, and the selectivity of 6 hydroxycaproic acid is 0.92%, and the selectivity of hexanodioic acid is 98.47%.
Claims (12)
1. the method for the beta-molecular sieve oxidation cyclic ketones of a zinc supported; It is characterized in that according to cyclic ketones: solvent: ydrogen peroxide 50=1: (0～50): the mole proportioning of (0.2～20); Temperature is 5～200 ℃, and pressure is under the condition of 0.1～3.0MPa, in the presence of a kind of catalyzer, reacts; The mass ratio of catalyzer and cyclic ketones is 1: (5～300), described catalyzer are the pickling dealuminzation nano-beta molecular sieve of zinc supported.
2. according to the process of claim 1 wherein, the pickling dealuminzation nanometer β-molecular sieve of said zinc supported, be usefulness >=70wt.% sulfuric acid at room temperature with nano-beta molecular sieve mix contact after, aluminium content is 1～5wt% in the beta-molecular sieve.Obtain through the incipient impregnation load through soluble zinc salt, the charge capacity of zinc is counted 1～5wt.% with zinc oxide again.。
3. according to the process of claim 1 wherein, said cyclic ketones is selected from monocycle ketone, many cyclic ketones or the band side chain alkyl functional R of group cyclic ketones.
4. according to the method for claim 1, said cyclic ketones is pimelinketone, ketopentamethylene or methylcyclohexanone.
5. according to the method for claim 1, said ydrogen peroxide 50 is the aqueous hydrogen peroxide solution of mass concentration 10～60%.
6. according to the method for claim 1, it is characterized in that selecting for use inertia organism and/or water as solvent.
7. according to the process of claim 1 wherein, said inertia organism is compound close with boiling point of reactant or the compound that polarity is big, specific inductivity is high.
8. according to the method for claim 7, wherein, the said compound close with boiling point of reactant is Fatty Alcohol(C12-C14 and C12-C18), ketone, acid, the ester of 1～6 carbon.
9. according to the process of claim 1 wherein cyclic ketones: the mole proportioning of ydrogen peroxide 50 is 1: (0.2～10), the mass ratio of catalyzer and cyclic ketones are 1: 5～100, and the mol ratio proportioning of solvent and cyclic ketones is (0.2～10): 1, and pressure is 0.1～0.5MPa.
10. according to the method for claim 9, wherein, be solvent with acetone or dioxane, temperature is 20～75 ℃.
11. according to the method for claim 9, wherein, be solvent with ethanol or ETHYLE ACETATE, temperature is 80～95 ℃, the reaction times is between 3 to 6 hours.
12. according to the method for claim 9, wherein, as solvent, temperature is 100～160 ℃ with acetate or propionic acid, the molar ratio of ydrogen peroxide 50 and cyclic ketones is higher than 3, and the reaction times was above 5 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016167698A1 (en) * | 2015-04-17 | 2016-10-20 | Perstorp Ab | Catalysed baeyer-villiger oxidation of cyclic ketones |
| CN114210362A (en) * | 2021-11-30 | 2022-03-22 | 大连理工大学 | Preparation method and application of zinc ion modified Sn-Beta zeolite |
| CN115108883A (en) * | 2021-03-17 | 2022-09-27 | 山东泰和水处理科技股份有限公司 | Preparation method of benzyl chloride |
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| US4870192A (en) * | 1985-08-12 | 1989-09-26 | Mobil Oil Corporation | Production of lactones and omega-hydroxycarboxylic acids |
| CN101307045A (en) * | 2008-07-11 | 2008-11-19 | 湖南大学 | Method for preparing caprolactone from cyclohexanone by catalytic oxidation |
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| US4870192A (en) * | 1985-08-12 | 1989-09-26 | Mobil Oil Corporation | Production of lactones and omega-hydroxycarboxylic acids |
| CN101307045A (en) * | 2008-07-11 | 2008-11-19 | 湖南大学 | Method for preparing caprolactone from cyclohexanone by catalytic oxidation |
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| AVELINO CORMA ET AL: "Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer-Villiger oxidations", 《NATURE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016167698A1 (en) * | 2015-04-17 | 2016-10-20 | Perstorp Ab | Catalysed baeyer-villiger oxidation of cyclic ketones |
| CN115108883A (en) * | 2021-03-17 | 2022-09-27 | 山东泰和水处理科技股份有限公司 | Preparation method of benzyl chloride |
| CN114210362A (en) * | 2021-11-30 | 2022-03-22 | 大连理工大学 | Preparation method and application of zinc ion modified Sn-Beta zeolite |
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