CN102476975B - 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
- Publication number
- CN102476975B CN102476975B CN201010558627.0A CN201010558627A CN102476975B CN 102476975 B CN102476975 B CN 102476975B CN 201010558627 A CN201010558627 A CN 201010558627A CN 102476975 B CN102476975 B CN 102476975B
- Authority
- CN
- China
- Prior art keywords
- hts
- acid
- crystallization
- magnesium
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 a kind of method through hydrogen peroxide oxidation about cyclic ketones.
Background technology
6-caprolactone has the advantages such as low, the easy processing of viscosity, VOC content is low, in the technological processs such as production polycaprolactone, ε-caprolactam, modifier, aqueous polyurethane coating, cast elastomers, hot melt adhesive, elastomerics, be used as oligopolymer and denaturing agent, can improve toughness, cold property and reactivity etc. functional; Aspect coating, the properties-correcting agent of the solvent of using as vehicle paint base, top coat and various building materials and latex coating etc., can improve film toughness, improve cold property, reactivity, raising cross-linking density; Aspect tackiness agent, can be used for the adhesion characteristic of improved hot melten gel and Solvent Adhesive; Aspect resin modified, can be used for improving flexibility, mobility, low temperature shock-resistance, formability etc.In addition, it is as a kind of raw materials for production of important degradable plastics, there is good biocompatibility, 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, high added value wrapping material.Along with the enhancing of people's environmental consciousness, 6-caprolactone will be subject to both at home and abroad more extensive concern, have more wide market outlook.
Worldwide, the difficult problems such as the security of producing due to the synthetic existence of 6-caprolactone and the stability of product, 6-caprolactone is mainly by the BASF AG, Daicel (Daicel) Co., Ltd. of Japan and the production of large caprolactone manufacturers of the Sol of Britain dimension (Solvay) company three that are positioned at the U.S..
6-caprolactone is just under lab successfully synthetic as far back as the thirties in 20th century.The synthetic method of 6-caprolactone mainly contains Baeyer-Villiger oxidation style, 1,6-hexylene glycol catalytic dehydrogenation method and 6 hydroxycaproic acid intramolecular condensation method etc.From aspects such as raw material, device and reaction conditionss, consider, Baeyer-Villiger oxidation style is the most effective method.
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 larger shortcoming: (1) can produce a large amount of organic carboxyl acid (salt) refuses after having reacted, have greater environmental impacts, recovery or intractability are larger; (2) reactor product separates, purification ratio is more difficult, selectivity is low, and Atom economy is poor, does not meet Green Chemistry fundamental principle; (3) organic peroxide acid needs to use the hydrogen peroxide of high density in process of production, and character is unstable, production cost is higher, and danger is larger in transportation, storage and operating process, thereby has limited its application in industrial production.
Compared with peroxy acid, H
2o
2application prospect the most wide, because it is easy to heavy industrialization application and environmental friendliness, meet the development trend of Green Chemistry.Bhaumik etc. (Bhaumik, P.Kumar and R.Kumar, Catal.Lett.40 (1996), pp.4750.) have studied the Baeyer-Villiger oxidation three-phase reaction system (ketone+H of the pimelinketone take TS-1 as catalyzer
2o
2/ H
2o+ catalyzer), and investigated and have or not the impact of second cyanogen as solvent.If the discoveries such as Bhaumik add a small amount of H in three-phase reaction system
2sO
4can obtain higher transformation efficiency.
Corma etc. (Corma, L.T.Nemeth, M.Renz, et al.Nature 412 (2001), pp.421-423) have reported at 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 four secondary response circulations, catalytic activity does not obviously reduce.
A kind of method of being prepared 6-caprolactone by cyclohexanone by catalytic oxidation is disclosed in CN101307045A, in the method, said catalyzer is the mixture of 50～100% zinc oxide and other metal oxide of 0～50% by weight, and solvent is nitrile, and oxygenant is hydrogen oxide or Peracetic Acid.The 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.
CN101186601A has disclosed take a certain amount of nano-sheet magnesio compound as catalyzer, take a certain proportion of cyanobenzene and Isosorbide-5-Nitrae-dioxane mixed solution as solvent, and under specific temperature of reaction, the method for catalyzing cyclone oxide to synthesizing lactone.The method, under relatively mild condition, makes lactone compound total recovery reach as high as 90%.The method is oxygenant owing to adopting aqueous hydrogen peroxide solution, has abandoned the environmental issues that oxidation style produces such as traditional peroxy acid.But metal oxide catalyst exists inherent defect for this type of reaction, and as lower in catalytic efficiency, reaction conversions frequency (TON) is less etc., be difficult to solve, and cannot realize suitability for industrialized production.
Alcohol acid is important industrial chemicals.Take 6 hydroxycaproic acid as example, it has a wide range of applications in organic synthesis and polymeric material field, for example, preparation 6-aldehyde radical caproic acid, 6-caprolactone, hexanodioic acid etc., its derivative 6 hydroxycaproic acid ethyl ester etc. is conventional organic chemical industry's intermediate.U.S. Pat P2008306153 has introduced a kind of at CH
2cl
2in solvent, take PCC (pyridinium chlorochromate Pyridinium Chlorochromate) as oxygenant is under 37 ℃ of conditions, 6 hydroxycaproic acid is oxidized to 6-aldehyde radical caproic acid.
At present, mainly take pimelinketone, caprolactone and hexanodioic acid as raw material, prepare 6 hydroxycaproic acid in the world.Wherein, pimelinketone is due to the advantage such as relative low price, raw material sources be extensive, and causes people's concern.(Inorganica Chimica Acta, 349, the 195-202 such as LENARDA Maurizio; 2003) using HBEA type molecular sieve H β is catalyzer, and the oxidizing reaction of having carried out pimelinketone obtains 6 hydroxycaproic acid.Document (Polish Journal of Chemistry, 78 (5), 687-697; 2004) reported under several catalyst actions, take water and propyl carbinol as solvent, the reaction that hydrogen peroxide oxidation pimelinketone is 6 hydroxycaproic acid.Document (Angewandte Chemie, International Edition, 41 (23), 4481-4484; 2002) in, introduced at water and (CF
3)
2in CHOH solution, with p-MeC
6h
4sO
3h is catalyzer, and at 55 ℃, pimelinketone is 6 hydroxycaproic acid by hydrogen peroxide oxidation.But catalyzer used is homogeneous catalyst, there is not easily separated, environmentally hazardous drawback and cannot drop into suitability for industrialized production.
Document (Organic & Biomolecular Chemistry, 7 (4), 725-732; 2009) reported a kind of method of being prepared 6 hydroxycaproic acid by caprolactone, the first step is in 0 ℃ of water and dioxane solvent, and caprolactone first reacts with NaOH 2.5 hours, is raised to subsequently room temperature and reacts with HCl and obtain 6 hydroxycaproic acid.Document (Journal of the American Chemical Society, 130 (5), 1718-1726; 2008) introduced equally a kind of pimelinketone through reacting with highly basic (NaOH) and strong acid (HCl) process that makes 6 hydroxycaproic acid.Document (Applied and Environmental Microbiology, 65 (5), 2232-2234; 1999) introduced and a kind ofly at 30 ℃, approached in neutral water surrounding, enzyme catalysis caprolactone is hydrolyzed to the reaction of 6 hydroxycaproic acid.Owing to having adopted strong acid and highly basic in above-mentioned the whole bag of tricks, be reactant, serious to equipment corrosion, produce a large amount of wastes, environment exerted an influence, therefore do not meet the green and chemical principle of Sustainable development.
CN1211969A discloses a kind of by hexanodioic acid, adipate monoester or di adipate or contain hexanodioic acid or its ester prepares 1 as the starting material shortening of main ingredient, the method of 6-hexylene glycol and 6 hydroxycaproic acid or its ester, wherein, distillation hydrogenation products is recycled to hydrogenation step to remove the tower kettle product obtaining after hexylene glycol 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 at 100-300 ℃ and 10-300 bar, in liquid phase, react on described hydrogenation catalyst, and in reactor, the carboxyl of hydrogenation and the molar ratio of hydrogen is 1: 5-1: 100.
Di-carboxylic acid is also important Organic Chemicals, take hexanodioic acid as example, it is industrial significant di-carboxylic acid, is mainly used in adiponitrile processed, and then production hexanediamine, and produce nylon 66 (polymeric amide) and engineering plastics etc. together with hexanediamine.In addition also for the production of various esters products, as softening agent and quality lubricant, make raw material of souring agent, medicine, yeast purificant, sterilant, tackiness agent, synthetic leather, synthetic dyestuff and the spices of raw material, production unsaturated polyester, hexylene glycol and the adipic acid ester class of polyurethane elastomer, various food and drink etc.
Nineteen thirty-seven, du pont company's nitric acid oxidation hexalin, has first realized the suitability for industrialized production of hexanodioic acid.Enter the sixties, the industrial cyclohexane oxidation process of progressively using instead, first by hexanaphthene intermediate product pimelinketone processed and hexalin mixture (be keto-alcohol oil, claim again KA oil), and then carries out nitric acid or the atmospheric oxidation of KA oil.The nitric acid that nitric acid oxidation KA oil process is generally 50%～60% by excessive concentration, carries out through 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 theoretical value.KA oil oxidation products distills out after nitric acid, then passes through two-stage crystal refining, just can obtain high-purity adipic acid.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 deep-etching problem to equipment in this reaction, environmental pollution is serious, complex process, energy consumption is higher, do not meet Green Chemistry principle.
Air oxidation process is that acetic acid is solvent take neutralized verdigris and manganese acetate as catalyzer, 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 two-stage crystal refining, and recovered solvent can be recycled after treatment.This method reaction times is very long, reaction efficiency is lower, product separation is difficult, therefore adopt still few.
Japan scientist Ryoji Noyori etc. has been developed with heteropolyacid Na
2wO
42H
2o is catalyzer, [CH
3n (n-C
8h
17)
3] HSO
4for phase-transfer catalyst, hydrogen peroxide direct oxidation tetrahydrobenzene is prepared 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
2for oxygenant, under 75-90 ℃ of condition, react 8h, the yield of hexanodioic acid reaches 93%.But heteropolyacid catalyst character is unstable, specific surface is little, easy inactivation, difficult recovery and the shortcoming such as work-ing life is short, thereby could not reach at present extensively popularization.
Other production methods of hexanodioic acid also have chlorocyclohexane method, are from Utilize Cyclohexane Oxidation By-Product, to reclaim hexanodioic acid, by acrylate obtaining adipic acid etc.Japan Asahi Kasei Corporation has also carried out the research of hexanaphthene one step atmospheric oxidation hexanodioic acid processed.Chinese patent CN101337879 discloses the mixed catalyst that a kind of catalyzer monometallic porphyrin that is dissolved with 1-500ppm in hexanaphthene or μ-oxygen bimetallic porphyrin or they and transition metal salt or oxide compound form, and catalytic air oxidation hexanaphthene is prepared the technology and equipment of hexanodioic acid.
Summary of the invention
The object of this invention is to provide a kind of catalytic oxidation of cyclic ketone in order to prepare the method for corresponding lactone, alcohol acid and di-carboxylic acid.
The method of catalytic oxidation of cyclic ketone provided by the invention, it is characterized in that according to cyclic ketones: solvent: hydrogen peroxide=1: (0～80): mole proportioning of (0.2～20), temperature is 5～200 ℃, reaction pressure is under the condition of 0.1～3.0MPa, under a kind of catalyzer exists, react and reclaim product, the mass ratio of catalyzer and cyclic ketones is 1: (5～300), described catalyzer obtains for HTS being carried out to modification by magnesium and aluminium, magnesium take MgO with the quality ratio of HTS as x, 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 method provided by the invention, said cyclic ketones can be selected from various monocycle ketone, many cyclic ketones and the cyclic ketones with side chain R, and to be wherein preferably carbon number be 1～6 alkyl functional group to R.Of the present invention preferred embodiment in, the production of said lactone is especially applicable to catalytic oxidation take pimelinketone, cyclopentanone or methylcyclohexanone as raw material.
In method provided by the invention, said catalyzer can carry out modification by solid ionic transfer method to HTS by magnesium and aluminium and obtain, magnesium take MgO with the quality ratio of HTS as x, x=0.001～0.99, aluminium is with Al
2o
3meter is y with the quality ratio of HTS, y=0.001～0.99, said x preferably 0.005～0.50, more preferably 0.005～0.15, said y preferably 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 in TS-1, TS-2, Ti-BETA and 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 and the adsorption time condition of 1 hour under the benzene adsorptive capacity that records be at least 50 milligrams/grams, between the adsorption isothermal line of nitrogen absorption under low temperature and desorption isotherm, there is hysteresis loop.
The method that said magnesium and aluminium carry out modification by solid ionic transfer method to HTS comprises according to HTS: the acid metallic aluminium salt of crystallization: crystallization alkalescence MAGNESIUM METAL salt=100: (0.01～100): (0.01～100), preferably 100: (0.1～90): the ratio of (0.1～90), by HTS, the acid metallic aluminium salt of crystallization and crystallization alkalescence MAGNESIUM METAL salt proceed in crucible after joining and being ground in mortar, under roasting condition, process and reclaim product, wherein, HTS in gram, the acid metallic aluminium salt of crystallization is with Al
2o
3gram meter, crystallization alkalescence MAGNESIUM METAL salt is in MgO gram, and said crystallization acid metal salt is selected from aluminum soluble salt, as AlCl
3, Al
2(SO
4)
3and Al (NO
3)
3in one or more, said crystallization alkaline metal salt is selected from solubility magnesium salts, as MgCl
2, MgSO
4and Al (NO
3)
2in one or more.
In 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 salt=100: (0.0001～100): the ratio of (0.0001～100), HTS, the acid metallic aluminium salt of crystallization and crystallization alkalescence MAGNESIUM METAL salt are mixed to dipping with water, then dry, roasting, reclaims product.
In method provided by the invention, take hydrogen peroxide as oxygenant, because its reduzate is only water, environmental friendliness, be Green Oxidant, and high density hydrogen peroxide is because its character is unstable, has potential safety hazard in production, accumulating, use procedure, and cost is higher.Normally the form of the aqueous hydrogen peroxide solution take mass percentage concentration as 10～60% adds in reaction system, and the aqueous hydrogen peroxide solution of such as technical grade has 27.5%, 30% and 35% etc., and conventionally selecting massfraction is 30% hydrogen peroxide.In proportioning raw materials, said hydrogen peroxide is in hydrogen peroxide.
In method provided by the invention, it is suitable that temperature of reaction is 5～200 ℃, all can effectively carry out catalytic oxidation.But for different temperature of reaction, we find that the distribution trend of generated reaction product is not identical, for example lesser temps interval below 75 ℃, preferably 20～75 ℃ of whens reaction, highly selective to lactone is favourable, and the selectivity of alcohol acid and di-carboxylic acid is just relative lower; Improve the temperature of reaction interval of temperature of reaction to 100 ℃, preferably 80～95 ℃ time, the selectivity of alcohol acid can improve gradually again, and its selectivity will be higher than the selectivity of lactone and di-carboxylic acid.And the higher temperature range of 100～200 ℃, preferably 100～160 ℃, we find that the rising of temperature is more favourable for the generation of di-carboxylic acid.
In method provided by the invention, the change of reaction pressure is on the impact of reaction product not obvious, and from the economy consideration of operation, reaction pressure is preferably 0.1～0.5MPa.
In the method that present method provides, select inertia organism and/or water as solvent.Said inertia organism is the compound close with boiling point of reactant or the compound that polarity is large, 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, ketone, acid, ester of having 1～6 carbon number etc., such as methyl alcohol, ethanol, the trimethyl carbinol, acetone, acetic acid, propionic acid, ethyl acetate or dioxane etc.; The inert organic solvents that said polarity is large, specific inductivity is high is acetonitrile, chloroform, tetramethylene sulfone etc. such as.
Contriver is surprised to find that, when adopting acetone or dioxane to be solvent, particularly cyclic ketones: mole proportioning of hydrogen peroxide 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 the lower time of condition that 20～75 ℃, pressure are 0.1～0.5MPa, with other organism such as other organic solvents such as acetonitrile, methyl alcohol, the selectivity of corresponding lactone at least improves more than 20%; And when adopting ethanol or ethyl acetate to be solvent, when temperature is 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 in acetic acid or the situation of propionic acid as solvent, temperature is brought up to more than 100 ℃, the molar ratio of hydrogen peroxide and cyclic ketones is higher than in 5 situation, and the reaction times exceedes 5 hours, and the selectivity of corresponding di-carboxylic acid is used other solvents to be significantly improved again.Therefore, method provided by the invention, can be according to the difference of target product, controls flexibly the operating parameterss such as reactant mole proportioning, temperature and solvent species.For example, when target product is lactone, preferably at the temperature of 20～75 ℃, using dioxane and/or acetone as reaction solvent; When target product is alcohol acid, preferably at the temperature of 80～95 ℃, using ethanol and/or ethyl acetate as reaction solvent; When target product is di-carboxylic acid, can improve temperature of reaction, preferably at the temperature of 100～160 ℃, using acetic acid and/or propionic acid as reaction solvent.
The method of cyclic ketones catalyzed oxidation provided by the invention can adopt periodical operation or continuous operating method.For example, while adopting intermittent mode to carry out, cyclic ketones, solvent, catalyzer are encased in after reactor, once add or add continuously hydrogen peroxide; Adopt continuous mode while carrying out, adopt fixed bed or slurry bed reactor, will catalyzer, add continuously cyclic ketones, hydrogen peroxide after solvent making beating, continuous separated product simultaneously.Method provided by the invention also can adopt closed still reaction, and soon catalyzer, solvent, cyclic ketones, hydrogen peroxide add rear reaction simultaneously.
In method provided by the invention, separation means such as the process of said recovery product conventional distillation, crystallization and extraction that to be people be familiar with etc.Specifically, the di-carboxylic acid that first adopts relatively-high temperature condition Crystallization Separation more easily to separate out, then adopt lower condition crystallization monohydroxylic carboxylic acid relatively, raw material, lactone and other by products to adopt the means of distillation or extraction to obtain Fen Li.
The method of catalytic oxidation of cyclic ketone provided by the invention, adopt the soda acid difunctional titanium silicon molecular sieve obtaining of magnesium and aluminium modification as catalyzer, owing to having introduced soda acid center in molecular sieve, 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 hydrogen peroxide, in the situation that selectivity is higher, its catalytic oxidation activity and stability of catalytic activity are also better.Method provided by the invention, can control the operating parameterss such as reactant mole proportioning, temperature and solvent species flexibly, can obtain different target products.
Embodiment
Below by embodiment, the present invention is further described, but content not thereby limiting the invention.
In each of the embodiments described below, reagent used is commercially available chemically pure reagent.
In comparative example and embodiment, after reaction, the concentration of each material is used vapor-phase chromatography to carry out quantitative analysis.The 6890 type gas chromatographs that Agilent company used produces; Analysis chromatographic column used is FFAP post.
In embodiment, the selectivity of the transformation efficiency of cyclic ketones, lactone, alcohol acid, di-carboxylic acid is respectively to calculate according to the following equation:
Embodiment 1
Catalyst preparation process: get 10 grams of hollow crystal grain HTS (Hunan build feldspathization company produce, trade mark HTS, through X-ray diffraction analysis, it is MFI structure, between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, have hysteresis loop, 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 recording under the adsorption time condition of 1 hour is 78 milligrams/gram), 12.75 grams of crystallization nine water aluminum nitrate Al (NO
3)
39H
2o and 7.02 grams of magnesium chloride hexahydrate MgCl
26H
2o proceeds to after joining and being ground in mortar and in crucible, proceeds in retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer obtaining is expressed as xMgO-yAl
2o
3-HTS (x=0.014, y=0.017).
The process of catalytic oxidation of cyclic ketone: the HTS xMgO-yAl that takes 2.3 grams of above-mentioned magnesium and aluminium modification
2o
3-HTS (x=0.014, y=0.017) catalyzer is loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 9.81 grams of pimelinketone, 3.6 grams of water, 20 grams of acetic acid, 6.4 grams of methyl alcohol and 46ml concentration are 30%, now the mol ratio of pimelinketone and hydrogen peroxide is 1: 4 again.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction is controlled at 105 ℃ of left and right, 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: get 10 grams of hollow crystal grain HTS (Hunan build feldspathization company produce, trade mark HTS, through X-ray diffraction analysis, it is MFI structure, between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, have hysteresis loop, 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 recording under the adsorption time condition of 1 hour is 78 milligrams/gram), 14.87 grams of crystallization nine water aluminum nitrate Al (NO
3)
39H
2o and 11 grams of magnesium chloride hexahydrate MgCl
26H
2o proceeds to after joining and being ground in mortar and in crucible, proceeds in retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer obtaining is expressed as xMgO-yAl
2o
3-HTS (x=0.022, y=0.019).
The process of catalytic oxidation of cyclic ketone: the HTS xMgO-yAl that takes 2.44 grams of magnesium and aluminium modification
2o
3-HTS (x=0.022, y=0.019) is loaded in 100ml three-necked flask, then adds successively the hydrogen peroxide that magnetic stir bar, 9.81 grams of pimelinketone, 24 grams of propionic acid and 46ml concentration are 30%, and now the mol ratio of pimelinketone and hydrogen peroxide is 1: 4.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction is controlled at 110 ℃ of left and right, 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: get 10 grams of hollow crystal grain HTS (Hunan build feldspathization company produce, trade mark HTS, through X-ray diffraction analysis, it is MFI structure, between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, have hysteresis loop, 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 recording under the adsorption time condition of 1 hour is 78 milligrams/gram), 12 grams of crystallization nine water aluminum nitrate Al (NO
3)
39H
2o and 16 grams of magnesium chloride hexahydrate MgCl
26H
2o proceeds to after joining and being ground in mortar and in crucible, proceeds in retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer obtaining is expressed as xMgO-yAl
2o
3-HTS (x=0.031, y=0.016).
The process of catalytic oxidation of cyclic ketone: the HTS xMgO-yAl that takes 2.65 grams of magnesium and aluminium modification
2o
3-HTS (x=0.031, y=0.016) be loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 19.63 grams of pimelinketone, 28 grams of ethanol and 46ml concentration are 30%, now the mol ratio of pimelinketone and hydrogen peroxide is 1: 2 again.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction is controlled at 84 ℃ of left and right, 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: get 10 grams of hollow crystal grain HTS (Hunan build feldspathization company produce, trade mark HTS, through X-ray diffraction analysis, it is MFI structure, between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, have hysteresis loop, 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 recording under the adsorption time condition of 1 hour is 78 milligrams/gram), 20 grams of crystallization nine water aluminum nitrate Al (NO
3)
39H
2o and 17 grams of magnesium chloride hexahydrate MgCl
26H
2o proceeds to after joining and being ground in mortar and in crucible, proceeds in retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer obtaining is expressed as xMgO-yAl
2o
3-HTS (x=0.034, y=0.026).
The process of catalytic oxidation of cyclic ketone: the HTS xMgO-yAl that takes 7.98 grams of magnesium and aluminium modification
2o
3-HTS (x=0.034, y=0.026) being loaded on 100ml is with in manometric closed reactor, add successively the hydrogen peroxide that magnetic stir bar, 19.63 grams of cyclopentanone, 5.4 grams of acetone, 14 grams of ethyl acetate and 46ml concentration are 30%, now the mol ratio of cyclopentanone and hydrogen peroxide is 1: 2 again.Closed reactor is put on the temperature control magnetic stirring apparatus with oil bath, starts magnetic stirring apparatus and heating unit, start reaction, temperature of reaction is controlled at 83 ℃ of left and right, reacts after 7.5 hours, and now autogenous pressure is 1.6MPa.The transformation efficiency of cyclopentanone is 92.31%, and the selectivity of δ-valerolactone is that the selectivity of 3.92%, 5-hydroxypentanoic acid is 89.26%, and the selectivity of pentanedioic acid is 5.61%.
Embodiment 5
Catalyst preparation process: get 10 grams of hollow crystal grain HTS (Hunan build feldspathization company produce, trade mark HTS, through X-ray diffraction analysis, it is MFI structure, between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, have hysteresis loop, 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 recording under the adsorption time condition of 1 hour is 78 milligrams/gram), 8.2 grams of crystallization nine water aluminum nitrate Al (NO
3)
39H
2o and 7.1 grams of magnesium chloride hexahydrate MgCl
26H
2o proceeds to after joining and being ground in mortar and in crucible, proceeds in retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer obtaining is expressed as xMgO-yAl
2o
3-HTS (x=0.011, y=0.014).
The process of catalytic oxidation of cyclic ketone: the HTS xMgO-yAl that takes 3.31 grams of magnesium and aluminium modification
2o
3-HTS (x=0.011, y=0.014) be loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 19.63 grams of cyclopentanone, 23 grams of dioxane and 23ml concentration are 30%, now the mol ratio of cyclopentanone and hydrogen peroxide is 1: 1 again.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction is controlled at 68 ℃ of left and right, reacts after 5 hours, and the transformation efficiency of cyclopentanone is 72.45%, and the selectivity of δ-valerolactone is that the selectivity of 94.32%, 5-hydroxypentanoic acid is 2.62%, and the selectivity of pentanedioic acid is 3.29%.
Embodiment 6
Catalyst preparation process: get 10 grams of hollow crystal grain HTS (Hunan build feldspathization company produce, trade mark HTS, through X-ray diffraction analysis, it is MFI structure, between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, have hysteresis loop, 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 recording under the adsorption time condition of 1 hour is 78 milligrams/gram), 7.7 grams of crystallization nine water aluminum nitrate Al (NO
3)
39H
2o and 3.5 grams of magnesium chloride hexahydrate MgCl
26H
2o proceeds to after joining and being ground in mortar and in crucible, proceeds in retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer obtaining is expressed as xMgO-yAl
2o
3-HTS (x=0.01, y=0.007).
The process of catalytic oxidation of cyclic ketone: the HTS xMgO-yAl that takes 2.53 grams of magnesium and aluminium modification
2o
3-HTS (x=0.01, y=0.007) is loaded in 100ml three-necked flask, then adds successively the hydrogen peroxide that magnetic stir bar, 19.63 grams of cyclopentanone, 32 grams of acetone and 46ml concentration are 30%, and now the mol ratio of cyclopentanone and hydrogen peroxide is 1: 2.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction is controlled at 72 ℃ of left and right, reacts after 4 hours, and the transformation efficiency of cyclopentanone is 65.28%, and the selectivity that generates δ-valerolactone is that the selectivity of 92.53%, 5-hydroxypentanoic acid is 2.33%, and the selectivity of pentanedioic acid is 1.94%.
Embodiment 7
Catalyst preparation process: get 10 grams of TS-1 HTS (" Zeolites, 943rd～950 pages of 1992, Vol.12 "), 12 grams of crystallization nine water aluminum nitrate Al (NO
3)
39H
2o and 4.8 grams of magnesium chloride hexahydrate MgCl
26H
2o proceeds to after joining and being ground in mortar and in crucible, proceeds in retort furnace still 550 ℃ of calcination process 4 hours, and reclaims product, and the catalyzer obtaining is expressed as xMgO-yAl
2o
3-TS-1 (x=0.024, y=0.016).
The process of catalytic oxidation of cyclic ketone: the HTS xMgO-yAl that takes 2.3 grams of magnesium and aluminium modification
2o
3-TS-1 (x=0.024, y=0.016) be loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 19.63 grams of cyclopentanone, 3.6 grams of water and 46ml concentration are 30%, now the mol ratio of cyclopentanone and hydrogen peroxide is 1: 2 again.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction is controlled at 80 ℃ of left and right, reacts after 12 hours, and the transformation efficiency of cyclopentanone is 63.26%, and the selectivity of δ-valerolactone is that the selectivity of 11.32%, 5-hydroxypentanoic acid is 46.76%, and the selectivity of pentanedioic acid is 40.51%.
Claims (14)
1. the method for the titanium molecular sieve catalysis oxidizing cyclic ketone of a magnesium and aluminium modification, it is characterized in that according to cyclic ketones: solvent: hydrogen peroxide=1: (0～80): mole proportioning of (0.2～20), temperature is 5～200 ℃, reaction pressure is under the condition of 0.1～3.0MPa, under a kind of catalyzer exists, react and reclaim product, the mass ratio of catalyzer and cyclic ketones is 1: (5～300), said catalyzer obtains for HTS being carried out to modification by magnesium and aluminium, magnesium take MgO with the quality ratio of HTS as x, x=0.001～0.99, aluminium is with Al
2o
3meter is y with the quality ratio of HTS, y=0.001～0.99, and said cyclic ketones is pimelinketone or cyclopentanone, said solvent is selected from one and/or the water in methyl alcohol, ethanol, acetone, acetic acid, propionic acid, ethyl acetate and dioxane.
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 in TS-1, TS-2, Ti-BETA and 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 and the adsorption time condition of 1 hour under the benzene adsorptive capacity that records be at least 70 milligrams/grams, between the adsorption isothermal line of nitrogen absorption under low temperature and desorption isotherm, there is hysteresis loop.
7. according to the method for claim 1, it is characterized in that said catalyzer is that magnesium and aluminium carry out modification by 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 salt=100: (0.01～100): the ratio of (0.01～100), acid to HTS, crystallization metallic aluminium salt and crystallization alkalescence MAGNESIUM METAL salt are joined after being ground in mortar and proceeded in crucible, under roasting condition, process and reclaim product, wherein, HTS in gram, the acid metallic aluminium salt of crystallization is with Al
2o
3gram meter, crystallization alkalescence MAGNESIUM METAL salt is in MgO gram.
9. according to the method for claim 1, it is characterized in that said catalyzer prepared through following process: according to HTS: the acid metallic aluminium salt of crystallization: crystallization alkalescence MAGNESIUM METAL salt=100: (0.0001～100): the ratio of (0.0001～100), HTS, the acid metallic aluminium salt of crystallization and crystallization alkalescence MAGNESIUM METAL salt are mixed to dipping with water, then dry, roasting, reclaims product.
10. according to the process of claim 1 wherein, said hydrogen peroxide is take hydrogen peroxide quality concentration as 10～60%.
11. according to the method for claim 1, wherein, cyclic ketones: mole proportioning of hydrogen peroxide is 1: (0.2～10), the mass ratio of catalyzer and cyclic ketones is 1: 5～100, the mol ratio proportioning of solvent and cyclic ketones is (0.2～10): 1, and pressure is 0.1～0.5MPa.
12. according to the process of claim 1 wherein, take acetone or dioxane as solvent, temperature is 20～75 ℃.
13. according to the process of claim 1 wherein, take ethanol or ethyl acetate as solvent, temperature is 80～95 ℃, and the reaction times is between 3 to 6 hours.
14. according to the process of claim 1 wherein, using acetic acid or propionic acid as solvent, temperature is 100～160 ℃, and the molar ratio of hydrogen peroxide and cyclic ketones is higher than 3, and the reaction times exceedes 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010558627.0A CN102476975B (en) | 2010-11-25 | 2010-11-25 | Method for catalytic oxidation of cycloketone in the presence of magnesium and aluminum modified titanosilicate molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010558627.0A CN102476975B (en) | 2010-11-25 | 2010-11-25 | Method for catalytic oxidation of cycloketone in the presence of magnesium and aluminum modified titanosilicate molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102476975A CN102476975A (en) | 2012-05-30 |
| CN102476975B true CN102476975B (en) | 2014-04-30 |
Family
ID=46089766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010558627.0A Active CN102476975B (en) | 2010-11-25 | 2010-11-25 | Method for catalytic oxidation of cycloketone in the presence of magnesium and aluminum modified titanosilicate molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102476975B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106883115B (en) * | 2015-12-15 | 2019-01-11 | 中国科学院大连化学物理研究所 | The method that one kettle way prepares adipic acid by cyclopentanone |
| CN107737611B (en) * | 2017-10-24 | 2020-06-16 | 万华化学集团股份有限公司 | Composite catalyst and method for preparing 5-hexenoic acid by using same |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
| CN1387496A (en) * | 1999-09-07 | 2002-12-25 | 代尔夫特科技大学 | Inorganic oxides with mesoporosity or combined neso- and microporosity and process for preparation thereof |
| CN1418876A (en) * | 2001-11-14 | 2003-05-21 | 中国石油化工股份有限公司 | Catalyst for olefine epoxidation |
| TW200406379A (en) * | 2002-05-23 | 2004-05-01 | Rhodia Polyamide Intermediates | Process for the oxidation of hydrocarbons, of alcohols and/or of ketones |
| CN1720098A (en) * | 2002-12-06 | 2006-01-11 | Abb路慕斯全球股份有限公司 | Mesoporous material with active metals |
| WO2009154783A2 (en) * | 2008-06-20 | 2009-12-23 | Exxonmobil Research And Engineering Company | Synthesis and use of mse-framework type molecular sieves |
-
2010
- 2010-11-25 CN CN201010558627.0A patent/CN102476975B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1387496A (en) * | 1999-09-07 | 2002-12-25 | 代尔夫特科技大学 | Inorganic oxides with mesoporosity or combined neso- and microporosity and process for preparation thereof |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
| CN1418876A (en) * | 2001-11-14 | 2003-05-21 | 中国石油化工股份有限公司 | Catalyst for olefine epoxidation |
| TW200406379A (en) * | 2002-05-23 | 2004-05-01 | Rhodia Polyamide Intermediates | Process for the oxidation of hydrocarbons, of alcohols and/or of ketones |
| CN1720098A (en) * | 2002-12-06 | 2006-01-11 | Abb路慕斯全球股份有限公司 | Mesoporous material with active metals |
| WO2009154783A2 (en) * | 2008-06-20 | 2009-12-23 | Exxonmobil Research And Engineering Company | Synthesis and use of mse-framework type molecular sieves |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102476975A (en) | 2012-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102452869B (en) | Method for catalytically oxidizing cyclic ketone | |
| CN102452895B (en) | Method for catalyzing cycloalkane by utilizing Sn-containing Ti-Si molecular sieve | |
| CN102476975B (en) | Method for catalytic oxidation of cycloketone in the presence of magnesium and aluminum modified titanosilicate molecular sieve | |
| CN102452894B (en) | Method for catalytic oxidation of cyclic ketone by nanometer Beta molecule sieve | |
| CN102453017B (en) | Lactone production method | |
| CN102452871B (en) | Method for catalytic oxidation of cyclic ketone | |
| EP0092867B1 (en) | Process for preparing cyclohexanol and cyclohexanone | |
| CN102452870B (en) | Method for catalytically oxidizing cyclic olefin | |
| CN102452893B (en) | Method for oxidizing cyclic ketone by utilizing zinc-supported Beta molecular sieve | |
| CN102452918B (en) | Method for preparing corresponding dicarboxylic acid by catalytic oxidation of hydroxy acid | |
| CN102451733B (en) | Method of catalytic oxidization of cyclic ketone by using tin supported molecular sieve | |
| CN102452872B (en) | Reaction method for catalyzing cyclic ketone by total silicone molecular sieve | |
| CN108144612B (en) | Cobalt-based catalyst for synthesizing carboxylic ester by one-pot method and preparation and application thereof | |
| CN102452923B (en) | Method for catalytically oxidizing lactone | |
| CN102452920B (en) | Method for preparing corresponding hydroxy acid by catalytically oxidizing cyclic ketone | |
| CN102452921B (en) | Method for preparing dicarboxylic acid | |
| CN112851496A (en) | Preparation method of p-toluic acid | |
| CN1277801C (en) | Method for preparation of propionic acid | |
| CN102452917B (en) | Method for catalytically oxidizing hydroxy acid | |
| CN102452919B (en) | Method for preparing corresponding hydroxy acid by catalytically oxidizing lactone | |
| CN102649082A (en) | Method for enhancing activity of catalyst for preparing oxalic ester from CO | |
| CN102452922B (en) | Production method of dicarboxylic acid | |
| CN100415707C (en) | Method for preparing anchoic acid by microwave reaction | |
| US3703547A (en) | Method of preparing phthalic acids | |
| WO2021153586A1 (en) | METHOD FOR PRODUCING trans, trans-MUCONIC ACID OR ALKYL ESTER THEREOF |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |