CN102476975A - Method for catalytic oxidation of cycloketone in the presence of magnesium and aluminum modified titanosilicate molecular sieve - Google Patents
Method for catalytic oxidation of cycloketone in the presence of magnesium and aluminum modified titanosilicate molecular sieve Download PDFInfo
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Abstract
The present invention relates to a method for catalytic oxidation of cycloketone in the presence of magnesium and aluminum modified titanosilicate molecular sieve. The method is characterized by allowing reaction at a temperature of 5-200 DEG C under a pressure of 0.1-3.0 MPa at a molar ratio of cycloketone to solvent to hydrogen peroxide of 1:(0-80):(0.2-20) in the presence of a catalyst, and recovering product, wherein a weight ratio of the catalyst to cycloketone is 1:(5-300). The catalyst is obtained by modifying titanosilicate molecular sieve with magnesium and aluminum, wherein a weight ratio of magnesium (based on magnesia) to titanosilicate molecular sieve is x, and x=0.001-0.99; and a weight ratio of aluminum (based on alumina) to titanosilicate molecular sieve is y, and y=0.001-0.99.
Description
Technical field
The invention relates to a kind of catalysed oxidation processes of cyclic ketones, further say so about the method for a kind of cyclic ketones through hydrogen peroxide oxidation.
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.
Worldwide; Because the security that the synthetic existence of 6-caprolactone is produced and the difficult problems such as stability of product, 6-caprolactone are mainly produced by Daicel (Daicel) Co., Ltd. of the BASF AG that is positioned at the U.S., Japan and the three big caprolactone manufacturerss of Sol dimension (Solvay) company of Britain.
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.
At present; The suitability for industrialized production of 6-caprolactone mainly adopts the Baeyer-Villiger oxidizing process of pimelinketone and peroxycarboxylic acid; 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.
It is catalyzer that CN101186601A has disclosed with certain amount of nano sheet magnesio compound, and with a certain proportion of cyanobenzene and 1,4-dioxane mixed solution is a solvent, under the specific reactions temperature, and the method for catalyzing cyclone oxide to synthesizing lactone.This method makes the lactone cpd total recovery reach as high as 90% under relatively mild condition.This method has been abandoned traditional environmental issues that oxidation style produces such as peroxy acid because the employing aqueous hydrogen peroxide solution is an oxygenant.But metal oxide catalyst is used for this type of reaction and has vice proper, and, reaction conversions frequency (TON) lower like catalytic efficiency (is less etc., is difficult to solve, and can't realizes suitability for industrialized production.
Alcohol acid 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 Pyridinium Chlorochromate) 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 and a kind ofly prepared the method for 6 hydroxycaproic acid that the first step is in 0 ℃ of water and dioxane solvent by caprolactone, caprolactone earlier with NaOH reaction 2.5 hours, be raised to room temperature and HCl subsequently and react and obtain 6 hydroxycaproic acid.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).The excessive concentration of the general use of nitric acid oxidation KA oil process is 50%～60% nitric acid, carries out through the two-stage reactor series connection.The catalyzer that reaction is used is copper-vanadium system (copper 0.1%～0.5%, vanadium 0.1%～0.2%), 60～80 ℃ of temperature, pressure 0.1～0.4MPa.Yield is 92%～96% of a theoretical value.After KA oil oxidation products distills out nitric acid, pass through the two-stage crystal refining again, just can obtain high-purity adipic acid.The raw material consumption quota: hexalin (or KA oil) 740kg/t, nitric acid (100%) 908kg/t, copper 0.2kg/t, vanadium are (with V
2O
5Meter) 0.1kg/t.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.The general two-stage reactor that adopts is connected: 160～175 ℃ of first step temperature of reaction, pressure 0.7MPa (gauge pressure), about 3h of reaction times; 80 ℃ of second stage temperature of reaction, pressure 0.7MPa (gauge pressure), about 3h of reaction times.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.Reactant ratio is tetrahydrobenzene: Na
2WO
42H
2O: [CH
3N (n-C
8H
17)
3] HSO
4=100: 1: 1,30%H
2O
2Be oxygenant, under 75-90 ℃ of condition, react 8h, the yield of hexanodioic acid reaches 93%.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 purpose of this invention is to provide a kind of catalyzed oxidation cyclic ketones in order to prepare the method for corresponding lactone, alcohol acid and di-carboxylic acid.
The method of catalyzed oxidation cyclic ketones provided by the invention; It is characterized in that according to cyclic ketones: solvent: ydrogen peroxide 50=1: (0～80): the mole proportioning of (0.2～20), temperature are 5～200 ℃, and reaction pressure is under the condition of 0.1～3.0MPa; In the presence of a kind of catalyzer, react and reclaim product; The mass ratio of catalyzer and cyclic ketones is 1: (5～300), described catalyzer obtains for by magnesium and aluminium HTS being carried out modification, and magnesium is x in the quality ratio of MgO and HTS; X=0.001～0.99, aluminium is with Al
2O
3Meter is y with the quality ratio of HTS, y=0.001～0.99.
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 can carry out modification through the solid ionic transfer method to HTS by magnesium and aluminium and obtain, and magnesium is x in the quality ratio of MgO and HTS, x=0.001～0.99, and aluminium is with Al
2O
3Meter is y with the quality ratio of HTS; Y=0.001～0.99, said x is preferred 0.005～0.50, more preferably 0.005～0.15, and said y preferred 0.005～0.50, more preferably 0.005～0.15; And the ratio of x and y is preferably between 0.1～5, more preferably 0.5～2.Said HTS is selected from one or more the mixture among TS-1, TS-2, Ti-BETA and the Ti-MCM-22; Preferred HTS is TS-1; Be more preferably a kind of TS-1 HTS (referring to CN1301599A) of hollow crystal grain; The radical length of the cavity part of its hollow crystal grain is 2～300 nanometers, at 25 ℃, P/P
0=0.10 with 1 hour condition of adsorption time under the benzene adsorptive capacity that records at least 50 milligrams/gram, have hysteresis loop between adsorption isothermal line that low temperature conditioning adsorbs and the desorption isotherm.
Said magnesium and aluminium comprise according to HTS the method that HTS carries out modification through the solid ionic transfer method: the acid metallic aluminium salt of crystallization: crystallization alkalescence MAGNESIUM METAL 99 salt=100: (0.01～100): (0.01～100), preferred 100: (0.1～90): the ratio of (0.1～90); The acid metallic aluminium salt of HTS, crystallization and crystallization alkalescence MAGNESIUM METAL 99 salt joined change in the crucible after grinding mixing in the mortar; Under roasting condition, handle and reclaim product; Wherein, HTS is in gram, and the acid metallic aluminium salt of crystallization is with Al
2O
3The gram meter, crystallization alkalescence MAGNESIUM METAL 99 salt is in the MgO gram, and said crystallization acid metal salt is selected from aluminum soluble salt, like AlCl
3, Al
2(SO
4)
3And Al (NO
3)
3In one or more, said crystallization alkaline metal salt is selected from the solubility magnesium salts, like MgCl
2, MgSO
4And Al (NO
3)
2In one or more.
In the method provided by the invention; Said catalyzer can also be through the preparation of following process: according to HTS: the acid metallic aluminium salt of crystallization: crystallization alkalescence MAGNESIUM METAL 99 salt=100: (0.0001～100): the ratio of (0.0001～100); HTS, the acid metallic aluminium salt of crystallization and crystallization alkalescence MAGNESIUM METAL 99 salt and water are mixed dipping; Product is reclaimed in dry then, roasting.
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., 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 inertia organism and/or water 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 0.1～0.5MPa; 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, difference that can the based target product is controlled operating parameters such as reactant mole proportioning, temperature and solvent species flexibly.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.
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 adopting continuous mode to carry out, adopt fixed bed or slurry bed reactor, add cyclic ketones, ydrogen peroxide 50 continuously, simultaneously continuous separated product after catalyzer, solvent are pulled an oar.Method provided by the invention also 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 process of said recovery product is that distillation, crystallization and the extraction etc. of the routine be familiar with of people 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 catalyzed oxidation cyclic ketones provided by the invention, the difunctional HTS of the soda acid that obtains that adopts magnesium and aluminium modification are as catalyzer, owing in molecular sieve, introduced the soda acid center; Can be effectively collaborative with the catalytic oxidation performance of HTS; It is to specific catalytic oxidation, and reactive behavior and activity stability improve, and 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.Method provided by the invention can be controlled operating parameterss such as reactant mole proportioning, temperature and solvent species flexibly, can obtain different title products.
Embodiment
Below by embodiment the present invention is further described, but does not therefore limit content of the present invention.
In following each embodiment, used reagent is commercially available chemically pure reagent.
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, lactone, alcohol acid, di-carboxylic acid is respectively to calculate according to the following equation among the embodiment:
Embodiment 1
Catalyst preparation process: (Hunan is built feldspathization company and is produced to get the HTS of the hollow crystal grain of 10 grams; Trade mark HTS; Through the X-ray diffraction analysis is the MFI structure; Have hysteresis loop between the adsorption isothermal line of the low temperature conditioning absorption of this molecular sieve and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is 15～180 nanometers; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 a milligrams/gram), 12.75 gram crystallizations nine water aluminum nitrate Al (NO
3)
39H
2O and 7.02 gram magnesium chloride hexahydrate MgCl
26H
2O joins in the mortar to grind to change over to behind the mixing and changes in the crucible in the retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer that obtains is expressed as xMgO-yAl
2O
3-HTS (x=0.014, y=0.017).
The process of catalyzed oxidation cyclic ketones: the HTS xMgO-yAl that takes by weighing 2.3 above-mentioned magnesium of gram and aluminium modification
2O
3-HTS (x=0.014; Y=0.017) catalyzer is loaded in the 100ml three-necked flask; Add magnetic agitation, 9.81 gram pimelinketone, 3.6 gram water, 20 gram acetate, 6.4 gram methyl alcohol 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 105 ℃, reacts after 6 hours, and the transformation efficiency of pimelinketone is 89.35%, and the selectivity that generates 6-caprolactone is 4.75%, and the selectivity of 6 hydroxycaproic acid is 13.89%, and the selectivity of hexanodioic acid is 78.67%.
Embodiment 2
Catalyst preparation process: (Hunan is built feldspathization company and is produced to get the HTS of the hollow crystal grain of 10 grams; Trade mark HTS; Through the X-ray diffraction analysis is the MFI structure; Have hysteresis loop between the adsorption isothermal line of the low temperature conditioning absorption of this molecular sieve and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is 15～180 nanometers; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 a milligrams/gram), 14.87 gram crystallizations nine water aluminum nitrate Al (NO
3)
39H
2O and 11 gram magnesium chloride hexahydrate MgCl
26H
2O joins in the mortar to grind to change over to behind the mixing and changes in the crucible in the retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer that obtains is expressed as xMgO-yAl
2O
3-HTS (x=0.022, y=0.019).
The process of catalyzed oxidation cyclic ketones: the HTS xMgO-yAl that takes by weighing 2.44 gram magnesium and aluminium modification
2O
3(x=0.022 y=0.019) is loaded in the 100ml three-necked flask-HTS, adds magnetic agitation, 9.81 gram pimelinketone, 24 gram propionic acid and 46ml concentration more successively and be 30% ydrogen peroxide 50, and 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 110 ℃, reacts after 12 hours, and the transformation efficiency of pimelinketone is 99.27%, and the selectivity of 6-caprolactone is 0.01%, and the selectivity of 6 hydroxycaproic acid is 0.21%, and the selectivity of hexanodioic acid is 98.10%.
Embodiment 3
Catalyst preparation process: (Hunan is built feldspathization company and is produced to get the HTS of the hollow crystal grain of 10 grams; Trade mark HTS; Through the X-ray diffraction analysis is the MFI structure; Have hysteresis loop between the adsorption isothermal line of the low temperature conditioning absorption of this molecular sieve and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is 15～180 nanometers; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 a milligrams/gram), 12 gram crystallizations nine water aluminum nitrate Al (NO
3)
39H
2O and 16 gram magnesium chloride hexahydrate MgCl
26H
2O joins in the mortar to grind to change over to behind the mixing and changes in the crucible in the retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer that obtains is expressed as xMgO-yAl
2O
3-HTS (x=0.031, y=0.016).
The process of catalyzed oxidation cyclic ketones: the HTS xMgO-yAl that takes by weighing 2.65 gram magnesium and aluminium modification
2O
3(x=0.031 y=0.016) is loaded in the 100ml three-necked flask-HTS, adds magnetic agitation, 19.63 gram pimelinketone, 28 gram ethanol and 46ml concentration more successively and be 30% ydrogen peroxide 50, and 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 84 ℃, reacts after 6 hours, and the transformation efficiency of pimelinketone is 73.25%, and the selectivity of 6-caprolactone is 2.61%, and the selectivity of 6 hydroxycaproic acid is 86.97%, and the selectivity of hexanodioic acid is 10.08%.
Embodiment 4
Catalyst preparation process: (Hunan is built feldspathization company and is produced to get the HTS of the hollow crystal grain of 10 grams; Trade mark HTS; Through the X-ray diffraction analysis is the MFI structure; Have hysteresis loop between the adsorption isothermal line of the low temperature conditioning absorption of this molecular sieve and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is 15～180 nanometers; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 a milligrams/gram), 20 gram crystallizations nine water aluminum nitrate Al (NO
3)
39H
2O and 17 gram magnesium chloride hexahydrate MgCl
26H
2O joins in the mortar to grind to change over to behind the mixing and changes in the crucible in the retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer that obtains is expressed as xMgO-yAl
2O
3-HTS (x=0.034, y=0.026).
The process of catalyzed oxidation cyclic ketones: the HTS xMgO-yAl that takes by weighing 7.98 gram magnesium and aluminium modification
2O
3-HTS (x=0.034; Y=0.026) being loaded on 100ml is with in the manometric closed reactor; Add magnetic agitation, 19.63 gram ketopentamethylene, 5.4 gram acetone, 14 gram ETHYLE ACETATE and 46ml concentration more successively and be 30% ydrogen peroxide 50, this moment, the mol ratio of ketopentamethylene and hydrogen peroxide was 1: 2.Closed reactor is put on the temperature control magnetic stirring apparatus of band oil bath, starts magnetic stirring apparatus and heating unit, begin reaction, temperature of reaction is controlled at about 83 ℃, reacts after 7.5 hours, and this moment, autogenous pressure was 1.6MPa.The transformation efficiency of ketopentamethylene is 92.31%, and the selectivity of δ-Wu Neizhi is 3.92%, and the selectivity of 5-hydroxypentanoic acid is 89.26%, and the selectivity of pentanedioic acid is 5.61%.
Embodiment 5
Catalyst preparation process: (Hunan is built feldspathization company and is produced to get the HTS of the hollow crystal grain of 10 grams; Trade mark HTS; Through the X-ray diffraction analysis is the MFI structure; Have hysteresis loop between the adsorption isothermal line of the low temperature conditioning absorption of this molecular sieve and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is 15～180 nanometers; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 a milligrams/gram), 8.2 gram crystallizations nine water aluminum nitrate Al (NO
3)
39H
2O and 7.1 gram magnesium chloride hexahydrate MgCl
26H
2O joins in the mortar to grind to change over to behind the mixing and changes in the crucible in the retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer that obtains is expressed as xMgO-yAl
2O
3-HTS (x=0.011, y=0.014).
The process of catalyzed oxidation cyclic ketones: the HTS xMgO-yAl that takes by weighing 3.31 gram magnesium and aluminium modification
2O
3(x=0.011 y=0.014) is loaded in the 100ml three-necked flask-HTS, adds magnetic agitation, 19.63 gram ketopentamethylene, 23 gram dioxane and 23ml concentration more successively and be 30% ydrogen peroxide 50, and 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 68 ℃, reacts after 5 hours, and the transformation efficiency of ketopentamethylene is 72.45%, and the selectivity of δ-Wu Neizhi is 94.32%, and the selectivity of 5-hydroxypentanoic acid is 2.62%, and the selectivity of pentanedioic acid is 3.29%.
Embodiment 6
Catalyst preparation process: (Hunan is built feldspathization company and is produced to get the HTS of the hollow crystal grain of 10 grams; Trade mark HTS; Through the X-ray diffraction analysis is the MFI structure; Have hysteresis loop between the adsorption isothermal line of the low temperature conditioning absorption of this molecular sieve and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is 15～180 nanometers; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 a milligrams/gram), 7.7 gram crystallizations nine water aluminum nitrate Al (NO
3)
39H
2O and 3.5 gram magnesium chloride hexahydrate MgCl
26H
2O joins in the mortar to grind to change over to behind the mixing and changes in the crucible in the retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer that obtains is expressed as xMgO-yAl
2O
3-HTS (x=0.01, y=0.007).
The process of catalyzed oxidation cyclic ketones: the HTS xMgO-yAl that takes by weighing 2.53 gram magnesium and aluminium modification
2O
3(x=0.01 y=0.007) is loaded in the 100ml three-necked flask-HTS, adds magnetic agitation, 19.63 gram ketopentamethylene, 32 gram acetone and 46ml concentration more successively and be 30% ydrogen peroxide 50, and 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 72 ℃, reacts after 4 hours, and the transformation efficiency of ketopentamethylene is 65.28%, and the selectivity that generates δ-Wu Neizhi is 92.53%, and the selectivity of 5-hydroxypentanoic acid is 2.33%, and the selectivity of pentanedioic acid is 1.94%.
Embodiment 7
Catalyst preparation process: get 10 gram TS-1 HTSs (" Zeolites, 1992, the 943rd～950 page of Vol.12 "), 12 gram crystallizations, nine water aluminum nitrate Al (NO
3)
39H
2O and 4.8 gram magnesium chloride hexahydrate MgCl
26H
2O joins in the mortar to grind to change over to behind the mixing and changes in the crucible in the retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer that obtains is expressed as xMgO-yAl
2O
3-TS-1 (x=0.024, y=0.016).
The process of catalyzed oxidation cyclic ketones: the HTS xMgO-yAl that takes by weighing 2.3 gram magnesium and aluminium modification
2O
3(x=0.024 y=0.016) is loaded in the 100ml three-necked flask-TS-1, adds magnetic agitation, 19.63 gram ketopentamethylene, 3.6 gram water and 46ml concentration more successively and be 30% ydrogen peroxide 50, and 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 80 ℃, reacts after 12 hours, and the transformation efficiency of ketopentamethylene is 63.26%, and the selectivity of δ-Wu Neizhi is 11.32%, and the selectivity of 5-hydroxypentanoic acid is 46.76%, and the selectivity of pentanedioic acid is 40.51%.
Claims (18)
1. the method for the titanium molecular sieve catalysis oxidation cyclic ketones of magnesium and aluminium modification; It is characterized in that according to cyclic ketones: solvent: ydrogen peroxide 50=1: (0～80): the mole proportioning of (0.2～20), temperature are 5～200 ℃, and reaction pressure is under the condition of 0.1～3.0MPa; In the presence of a kind of catalyzer, react and reclaim product; The mass ratio of catalyzer and cyclic ketones is 1: (5～300), said catalyzer obtains for by magnesium and aluminium HTS being carried out modification, and magnesium is x in the quality ratio of MgO and HTS; X=0.001～0.99, aluminium is with Al
2O
3Meter is y with the quality ratio of HTS, y=0.001～0.99.
2. according to the process of claim 1 wherein, said x=0.005～0.5, said y=0.005～0.5, and the ratio of x and y is between 0.1～5.
3. according to the method for claim 2, wherein, said x=0.005～0.15, said y=0.005～0.15, the ratio of x and y is between 0.5～2.
4. according to the process of claim 1 wherein, said HTS is selected from one or more the mixture among TS-1, TS-2, Ti-BETA and the Ti-MCM-22.
5. according to the process of claim 1 wherein, said HTS is TS-1.
6. according to the method for claim 5, wherein said TS-1 has hollow crystal grain, and the radical length of the cavity part of hollow crystal grain is 2～300 nanometers, at 25 ℃, P/P
0=0.10 with 1 hour condition of adsorption time under the benzene adsorptive capacity that records at least 70 milligrams/gram, have hysteresis loop between adsorption isothermal line that low temperature conditioning adsorbs and the desorption isotherm.
7. according to the method for claim 1, it is characterized in that said catalyzer is that magnesium and aluminium carry out modification through the solid ionic transfer method to HTS and obtains.
8. according to the method for claim 7; Wherein, said solid ionic transfer method comprises according to HTS: the acid metallic aluminium salt of crystallization: crystallization alkalescence MAGNESIUM METAL 99 salt=100: (0.01～100): the ratio of (0.01～100) joins HTS, the acid metallic aluminium salt of crystallization and crystallization alkalescence MAGNESIUM METAL 99 salt and changes in the crucible after grinding mixing in the mortar; Under roasting condition, handle and reclaim product; Wherein, HTS is in gram, and the acid metallic aluminium salt of crystallization is with Al
2O
3The gram meter, crystallization alkalescence MAGNESIUM METAL 99 salt is in the MgO gram.
9. according to the method for claim 1; It is characterized in that said catalyzer prepares through following process: according to HTS: the acid metallic aluminium salt of crystallization: crystallization alkalescence MAGNESIUM METAL 99 salt=100: (0.0001～100): the ratio of (0.0001～100); HTS, the acid metallic aluminium salt of crystallization and crystallization alkalescence MAGNESIUM METAL 99 salt and water are mixed dipping; Product is reclaimed in dry then, roasting.
10. according to the process of claim 1 wherein, said cyclic ketones comprises the cyclic ketones of monocycle ketone, many cyclic ketones or the R of band side chain alkyl functional group.
11. according to the process of claim 1 wherein, said cyclic ketones is selected from pimelinketone, ketopentamethylene or methylcyclohexanone.
12. according to the process of claim 1 wherein, said ydrogen peroxide 50 is 10～60% in hydrogen peroxide quality concentration.
13., it is characterized in that selecting for use inertia organism and/or water as solvent according to the method for claim 1.
14. 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.
15. 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.
16. according to the method for claim 15, wherein, be solvent with acetone or dioxane, temperature is 20～75 ℃.
17. according to the method for claim 15, wherein, be solvent with ethanol or ETHYLE ACETATE, temperature is 80～95 ℃, the reaction times is between 3 to 6 hours.
18. according to the method for claim 15, 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 (5)
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| CN105622386A (en) * | 2014-10-27 | 2016-06-01 | 湖南师范大学 | Green process for synthesizing adipic acid from cyclohexanone |
| CN105622385A (en) * | 2014-10-27 | 2016-06-01 | 湖南师范大学 | Process for preparing adipic acid through cleaning catalytic oxidation of cyclohexanone, catalyst, and catalyst preparation method |
| CN106883115A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | The method that one kettle way prepares adipic acid by cyclopentanone |
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| CN107737611A (en) * | 2017-10-24 | 2018-02-27 | 万华化学集团股份有限公司 | A kind of composite catalyst and the method that 5 hexenoic acids are prepared using the composite catalyst |
| CN114426549A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene dioxide DCPDO and 2-phenyl-2-propanol |
| CN114426549B (en) * | 2020-10-15 | 2024-02-09 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene dioxide DCPDPO and 2-phenyl-2-propanol |
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