CN102452923B - Method for catalytically oxidizing lactone - Google Patents
Method for catalytically oxidizing lactone Download PDFInfo
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- CN102452923B CN102452923B CN201010523703.4A CN201010523703A CN102452923B CN 102452923 B CN102452923 B CN 102452923B CN 201010523703 A CN201010523703 A CN 201010523703A CN 102452923 B CN102452923 B CN 102452923B
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Abstract
The invention provides a method for catalytically oxidizing lactone. The method is characterized in that reaction is carried out in the presence of a catalyst under the conditions that molar ratio of lactone to solvent to hydrogen peroxide is 1: (0-80): (0.2-20), temperature is 10-200 DEG C and reaction pressure is 0.1-3.0MPa, so as to prepare corresponding hydroxyl acid and binary acid, wherein the mass ratio of the catalyst to the lactone is 1: (5-300) and the catalyst is a tin-titanium-silicon molecular sieve.
Description
Technical field
The invention relates to the method for lactone catalyzed oxidation, is more particularly about the method for lactone through hydrogen peroxide oxidation.
Background technology
Alcohol acid is important Organic Chemicals.For 6 hydroxycaproic acid, its fusing point is 38 ~ 40 DEG C, and boiling point is 113 ~ 116 DEG C, and density is 0.981g/ml, and specific refractory power is 1.044, flash-point > 110 DEG C.It is a kind of important Organic Chemicals, and it has a wide range of applications in organic synthesis and polymeric material field.Such as prepare 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.US Patent No. P2008306153 describes a kind of at CH
2cl
2in solvent, with PCC (pyridinium chlorochromate Pyridinium Chlorochromate) for oxygenant is under 37 DEG C of conditions, 6 hydroxycaproic acid is oxidized to 6-aldehyde radical caproic acid.
At present, in the world main with pimelinketone, 6-caprolactone and hexanodioic acid for 6 hydroxycaproic acid prepared by raw material.Wherein, pimelinketone due to the advantage such as relative low price, raw material sources are extensive, and causes the concern of people.(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.Find that molecular sieve has impact by the change of physico-chemical property after pre-treatment and structure to the selectivity of 6 hydroxycaproic acid and yield.Document (Polish Journal of Chemistry, 78 (5), 687-697; 2004), under reporting several catalyst action, with water and propyl carbinol for solvent, hydrogen peroxide oxidation pimelinketone is the reaction of 6 hydroxycaproic acid.Research display, under different catalyzer, different condition the yield of 6 hydroxycaproic acid and selectivity difference all larger.Document (Angewandte Chemie, International Edition, 41 (23), 4481-4484; 2002) describe at water and (CF
3)
2in CHOH solution, with p-MeC
6h
4sO
3h is catalyzer, and at 55 DEG C, 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 suitability for industrialized production be dropped into.
People are to being that raw material is prepared 6 hydroxycaproic acid and carried out large quantifier elimination, document (Organic & Biomolecular Chemistry, 7 (4), 725-732 with 6-caprolactone; 2009) report a kind of method being prepared 6 hydroxycaproic acid by 6-caprolactone, the first step is in 0 DEG C of water and dioxane solvent, and 6-caprolactone first reacts 2.5 hours with NaOH, is raised to room temperature subsequently and HCl reacts and obtains 6 hydroxycaproic acid.Document (Journal of theAmerican Chemical Society, 130 (5), 1718-1726; 2008) a kind of pimelinketone is described equally through reacting with highly basic (NaOH) and strong acid (HCl) process obtaining 6 hydroxycaproic acid.Document (Applied andEnvironmental Microbiology, 65 (5), 2232-2234; 1999) describe a kind of at 30 DEG C close in neutral water surrounding, enzyme catalysis 6-caprolactone is hydrolyzed to the reaction of 6 hydroxycaproic acid.Owing to have employed strong acid in above-mentioned various method and highly basic is reactant, serious to equipment corrosion, produce a large amount of waste, to environmental effects, therefore do not meet the green and chemical principle of Sustainable development.
In addition, BASF AG patent CN1211969 discloses and a kind ofly prepares 1 by hexanodioic acid, adipate monoester or di adipate or containing hexanodioic acid or its ester 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 with the tower kettle product obtained after remove hexylene glycol and hydroxycaproic acid or its ester, and tower kettle product mainly contains the oligomer ester of 6 hydroxycaproic acid; Make the mixture of starting material and recycle stream cling at 100-300 DEG C and 10-300, react in the liquid phase, on described hydrogenation catalyst, in reactor, the carboxyl of hydrogenation and the molar ratio of hydrogen to be 1: 5-1: 100.
Di-carboxylic acid is also important Organic Chemicals, for hexanodioic acid, it is industrial significant di-carboxylic acid, is mainly used in adiponitrile processed, and then production hexanediamine, and produce nylon66 fiber (polymeric amide) and engineering plastics etc. together with hexanediamine.In addition also for the production of various esters product, as softening agent and quality lubricant, make the raw material of polyurethane elastomer, produce unsaturated polyester, hexylene glycol and adipic acid ester class, the raw material of the souring agent of various food and drink, medicine, yeast purificant, sterilant, tackiness agent, synthetic leather, synthetic dyestuff and spices etc.
Nineteen thirty-seven, du pont company's nitric acid oxidation hexalin, first achieves the suitability for industrialized production of hexanodioic acid.Enter the sixties, industrially progressively use cyclohexane oxidation process instead, namely first by hexanaphthene intermediate product pimelinketone and cyclohexanol mixture (namely keto-alcohol is oily, oily also known as KA), and then carry out nitric acid or the atmospheric oxidation of KA oil.Nitric acid oxidation KA oil process is generally the nitric acid of 50% ~ 60% by excessive concentration, carries out through two-stage reactor series connection.The catalyzer that reaction uses is copper-vanadium system (copper 0.1% ~ 0.5%, vanadium 0.1% ~ 0.2%), temperature 60 ~ 80 DEG C, pressure 0.1 ~ 0.4MPa.Yield is 92% ~ 96% of theoretical value.After KA oil oxidation products distills out nitric acid, then through two-stage crystal refining, just high-purity adipic acid can be obtained.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 this reaction exists deep-etching problem to equipment, environmental pollution is serious, complex process, and energy consumption is higher, do not meet Green Chemistry principle.
Air oxidation process is that acetic acid is solvent with neutralized verdigris and manganese acetate for catalyzer, with air direct oxidation KA oil.General employing two-stage reactor series connection: first step temperature of reaction 160 ~ 175 DEG C, pressure 0.7MPa (gauge pressure), the reaction times is about 3h; Second stage temperature of reaction 80 DEG C, pressure 0.7MPa (gauge pressure), the reaction times is about 3h.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 adopts still few.
Japanese Scientists Ryoji Noyori etc. develops with heteropolyacid Na
2wO
42H
2o is catalyzer, [CH
3n (n-C
8h
17)
3] HSO
4for phase-transfer catalyst, hexanodioic acid prepared by hydrogen peroxide direct oxidation tetrahydrobenzene.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 DEG C of condition, react 8h, the yield of hexanodioic acid reaches 93%.But heteropolyacid catalyst character is unstable, specific surface is little, easy in inactivation, difficult to reclaim and the shortcoming such as work-ing life is short, thus could not reaches at present and extensively promote.
Other production methods of hexanodioic acid also have chlorocyclohexane method, are reclaim hexanodioic acid from Utilize Cyclohexane Oxidation By-Product, by acrylate obtaining adipic acid etc.Asahi Kasei Corporation of Japan has also carried out the research of hexanaphthene one step atmospheric oxidation hexanodioic acid.Chinese patent CN101337879 disclose a kind of in hexanaphthene, be dissolved with 1-500ppm catalyzer monometallic porphyrin or the mixed catalyst that forms of μ-oxygen bimetallic porphyrin or they and transition metal salt or oxide compound, the technology and equipment of hexanodioic acid prepared by catalytic air oxidation hexanaphthene.
Summary of the invention
The serious shortcomings existed in method in view of above-mentioned various lactone oxidation, the object of the invention is for the deficiencies in the prior art, there is provided a kind of clean and effective, eco-friendly lactone to be oxidized the method for the corresponding alcohol acid of preparation and di-carboxylic acid, be conducive to realizing industrialization scale operation
Therefore, method provided by the invention, lactone catalyzed oxidation provided by the invention prepares the novel method of corresponding alcohol acid, it is characterized in that according to lactone: solvent: hydrogen peroxide=1: (0 ~ 80): the mol ratio of (0.2 ~ 20), temperature is 10 ~ 200 DEG C, reaction pressure is under the condition of 0.1 ~ 3.0MPa, carry out the reaction corresponding alcohol acid of preparation and diprotic acid in the presence of a catalyst, the mass ratio of catalyzer and cyclic ketones is 1: (5 ~ 300), and described catalyzer is tin HTS.
In method provided by the invention, described lactone is the lactone comprising 2 ~ 18 carbon atoms, band side chain.Can be β-, γ-, δ-or ε-lactone, such as 6-caprolactone and δ-ring valerolactone etc.
In method provided by the invention, said tin HTS, be labeled as Sn-TS-1, Sn-TS-2, Sn-Ti-BETA, Sn-Ti-MCM-22, Sn-Ti-MCM-41 and Sn-Ti-MCM-48, by the compound with stanniferous source on HTS basis, template, alkali and water at 100 ~ 160 DEG C through intermediate water thermal synthesis, again through filtering separation, dry and roasting etc. operates and obtains, in molecular sieve Theil indices with oxide basis for 1 ~ 5wt.%, stronger Lewis acid site is formed at frame position, thus in organic reaction, strengthen its activation to substrate.Said HTS can be selected from one or more the mixture in TS-1, TS-2, Ti-BETA, Ti-MCM-22, Ti-MCM-41 and Ti-MCM-48, wherein preferred TS-1, in US Patent No. P4410501, disclose the synthetic method of titanium-silicon molecular sieve TS-1 first.As preferred embodiment, adopt the TS-1 HTS with hollow structure in the present invention, this molecular sieve has the HTS of MFI crystalline structure, and crystal grain is hollow structure, and the radical length of the chamber portion of this hollow crystal grain is 5 ~ 300 nanometers; This sieve sample at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm.The said TS-1 HTS with hollow structure, has larger mesopore volume, is generally more than 0.16mL/g, and the TS-1 HTS of routine, mesopore volume is generally at about 0.084mL/g.The TS-1 HTS of said hollow structure, can buy commercially available product, also can with reference to the method preparation disclosed in the Chinese patent of ZL99126289.1.Contriver is surprised to find that, by above-mentioned hollow HTS after secondary hydro-thermal introduces tin element in MFI structure, uses it in lactone oxidizing reaction, under the same reaction conditions, effectively can improve the transformation efficiency of lactone and the selectivity of optimized product.
In method provided by the invention, taking hydrogen peroxide as oxygenant, because its reduzate is only water, environmental friendliness, is Green Oxidant, and high concentration hydrogen peroxide is due to its character instability, there is potential safety hazard, and cost is higher in production, accumulating, use procedure.Be normally that the form of the aqueous hydrogen peroxide solution of 10 ~ 60% adds in reaction system with mass percentage concentration, the aqueous hydrogen peroxide solution of such as technical grade has 27.5%, 30% and 35% etc., usually select massfraction be 30% hydrogen peroxide.In proportioning raw materials, said hydrogen peroxide is in hydrogen peroxide.
In method provided by the invention, temperature of reaction is 5 ~ 200 DEG C is suitable, all effectively can carry out catalytic oxidation.But for different temperature of reaction, we find that the distribution trend of generated reaction product is not identical, and such as, lesser temps below 100 DEG C is interval, preferably 80 ~ 95 DEG C time, favourable to the highly selective of alcohol acid, and the selectivity of di-carboxylic acid is just relatively lower; Improve the higher temperature range of temperature of reaction to 100 ~ 200 DEG C again, preferably the selectivity of 100 ~ 160 DEG C of di-carboxylic acid can improve gradually, and its selectivity is higher than the selectivity of alcohol acid.
In method provided by the invention, the change of reaction pressure is not obvious on the impact of reaction product, and consider from the economy 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 polarity is large, specific inductivity is high compound.Wherein, the said compound close with boiling point of reactant can be lower aliphatic alcohols, ketone, acid, ester, be generally the alcohol, ketone, acid, ester etc. with 1 ~ 6 carbon number, 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 such as acetonitrile, chloroform, tetramethylene sulfone etc.
Contriver is surprised to find that, when adopting ethanol or ethyl acetate to be solvent, particularly lactone: the mol ratio of hydrogen peroxide is 1: (0.2 ~ 2) and the mass ratio of catalyzer and lactone is 1: 5 ~ 100, the mol ratio proportioning of solvent and lactone is (0.2 ~ 10): 1, when temperature is 80 ~ 95 DEG C, pressure is under the condition of 0.1 ~ 0.5MPa, reaction times is between 3 to 6 hours, the selectivity ratios of corresponding alcohol acid uses to have during other solvents and improves significantly, and the selectivity of corresponding alcohol acid at least improves more than 20%; When adopting acetic acid or propionic acid as solvent, temperature brings up to more than 100 DEG C, the molar ratio of hydrogen peroxide and lactone higher than 3 when, the reaction times, then the selectivity of corresponding di-carboxylic acid comparatively used other solvents to be significantly improved again more than 5 hours.Therefore, method provided by the invention, according to the difference of target product, can control the operating parameterss such as reactant mol ratio, temperature and solvent species flexibly.Such as, when target product is alcohol acid, preferably at the temperature of 80 ~ 95 DEG C, using ethanol and/or ethyl acetate as reaction solvent; When target product is di-carboxylic acid, temperature of reaction can be improved, preferably at the temperature of 100 ~ 160 DEG C, using acetic acid and/or propionic acid as reaction solvent.
The method of lactone catalyzed oxidation provided by the invention can adopt periodical operation or continuous print operating method.Such as, when adopting intermittent mode, after lactone, solvent, catalyzer are encased in reactor, once add or add hydrogen peroxide continuously; When continuous mode carries out, adopt fixed bed or slurry bed reactor, add lactone, hydrogen peroxide continuously by after catalyzer, solvent making beating, simultaneously continuous separated product.Method provided by the invention also can adopt closed still reaction, adds rear reaction by catalyzer, solvent, lactone, hydrogen peroxide simultaneously.
In method provided by the invention, the distillation of the routine that the process of said recovery product is familiar with by people, the separation means such as crystallization and extraction.Specifically, first adopt the di-carboxylic acid that relatively-high temperature condition Crystallization Separation is more easily separated out, then adopt relatively lower condition crystallization monohydroxylic carboxylic acid, raw material and other by products then adopt the means of distillation or extraction to obtain and are separated.
The method of catalyzed oxidation lactone provided by the invention, under the effect of tin HTS, be oxygenant with hydrogen peroxide, tool has the following advantages:
1. be compared to traditional method, instant invention overcomes conventional oxidation method complex manufacturing, equipment corrosion, there is potential safety hazard and the drawback such as environmental pollution is serious
2. using tin HTS as catalyzer, the introducing of tin atom adds catalytic activity, wherein hollow structure adds the mass transfer velocity of diffusion of reactant and product, decrease the generation of the side reaction such as open loop, over oxidation, make it under the oxidation of hydrogen peroxide, when selectivity is higher, its catalytic oxidation activity and stability of catalytic activity are also better, can obtain higher interior ester conversion rate and corresponding alcohol acid and di-carboxylic acid yield under relatively mild reaction conditions.
3. control the operating parameterss such as reactant mol ratio, temperature and solvent species flexibly, different target products can be obtained.
Embodiment
Following is that the present invention is further illustrated for embodiment.
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 uses 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 transformation efficiency of lactone, corresponding alcohol acid, di-carboxylic acid selectivity calculate respectively according to the following equation:
Catalyst preparation example 1
The present embodiment illustrates according to Zeolites, 1992, Vol.12, the process of method synthesis TS-1 molecular sieve of 943rd ~ 950 pages and the building-up process of tin HTS.
22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of TPAOH, and add 59.8 grams of distilled water, at normal pressure and 60 DEG C, 1.0 hours are hydrolyzed after mixing, obtain the hydrating solution of tetraethyl orthosilicate, add the solution be made up of 1.1 grams of tetrabutyl titanates and 5.0 grams of anhydrous isopropyl alcohols with vigorous stirring lentamente, gained mixture is stirred 3 hours at 75 DEG C, by the time clear colloid.This colloid is put into stainless steel sealed reactor, and at the temperature of 170 DEG C and autogenous pressure, constant temperature places 6 days, obtains the mixture of crystallization product; Being filtered, be washed with water to PH by this mixture is 6 ~ 8, and in 110 DEG C of dryings 60 minutes, obtains the former powder of TS-1 of non-roasting.By the roasting 4 hours in air atmosphere at 550 DEG C of former for this TS-1 powder, obtain TS-1 molecular sieve.Again by TS-1 TPAOH be template, anhydrous stannic chloride is in the system of Xi Yuan, according to molecular sieve (gram): anhydrous stannic chloride (mole): TPAOH (mole): the ratio of water (mole)=100: 0.06x: 0.15: 180 mixes, wherein the value of x is the mass percent of stannic oxide in molecular sieve, by mixture through enclosed high pressure still, introduce with the tin element of oxide basis, 1 ~ 5wt% in its MFI skeleton through intermediate water thermal synthesis method for 140 DEG C, catalyzer is designated as Sn-TS-1.
Catalyst preparation example 2
Get the TS-1 molecular sieve of Catalyst Preparation Example 1 gained according to molecular sieve (gram): sulfuric acid (mole): the ratio uniform mixing of water (mole)=100: 0.15: 15, react 5.0 hours at 90 DEG C, then conventionally filter, wash and drying, obtain acid-treated TS-1 molecular sieve.
By above-mentioned acid-treated TS-1 molecular sieve according to molecular sieve (gram): trolamine (mole): TPAOH (mole): the ratio of water (mole)=100: 0.20: 0.15: 180 mixes, put into stainless steel sealed reactor, under 190 DEG C and autogenous pressure, constant temperature places 0.5 day time, after cooling release, conventionally filter, wash, dry, and air atmosphere roasting 3 hours at 550 DEG C, hollow structure molecular sieve.
Be the HTS of MFI structure through X-ray diffraction analysis, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, crystal grain is hollow crystal grain and the radical length of chamber portion is 15 ~ 180 nanometers; This sieve sample at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is 78 milligrams/gram
Again by hollow structure molecular sieve 140 DEG C, TPAOH is template, anhydrous stannic chloride is in the system of Xi Yuan, according to molecular sieve (gram): anhydrous stannic chloride (mole): TPAOH (mole): the ratio of water (mole)=100: 0.06x: 0.15: 180 mixes, the value of x is the mass percent of stannic oxide in molecular sieve, by mixture through enclosed high pressure still, Hydrothermal Synthesis 72 hours at 140 DEG C, introduce with the tin element of oxide basis, 1 ~ 5wt% in its MFI skeleton, catalyzer is designated as Sn-HTS.
Embodiment 1
Take 2.3 grams of stanniferous hollow HTS Sn-HTS (SnO
2mass percent be 2.6wt%, TiO
2mass percent be 3.2wt%) catalyzer is loaded in 100ml three-necked flask, add magnetic stir bar more successively, 22.81 grams of 6-caprolactones, 18 grams of water and 23ml concentration are the hydrogen peroxide of 30%, now the mol ratio of 6-caprolactone and hydrogen peroxide is 1: 1.Be put in by three-necked flask on temperature control magnetic stirring apparatus, three-necked flask top condensing tube condensation refluxes, and starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction controls at about 50 DEG C, reacts after 5 hours, and the transformation efficiency of 6-caprolactone is 75.72%, and the selectivity generating 6 hydroxycaproic acid is 54.27%, and the selectivity of hexanodioic acid is 39.61%.
Embodiment 2
Take 2.44 grams of stanniferous HTS Sn-TS-1 (SnO
2mass percent be 2.7wt%, TiO
2mass percent be 3.3wt%) catalyzer is loaded in 100ml three-necked flask, add magnetic stir bar more successively, 22.81 grams of 6-caprolactones, 6.4 grams of acetonitriles and 23ml concentration are the hydrogen peroxide of 30%, now the mol ratio of 6-caprolactone and hydrogen peroxide is 1: 1.Be put in by three-necked flask on temperature control magnetic stirring apparatus, three-necked flask top condensing tube condensation refluxes, and starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction controls at about 70 DEG C, reacts after 1.5 hours, and the transformation efficiency of 6-caprolactone is 62.45%, and the selectivity generating 6 hydroxycaproic acid is 73.64%.The selectivity of hexanodioic acid is 19.61%.
Embodiment 3
Take 2.65 grams of stanniferous hollow HTS Sn-HTS (SnO
2mass percent be 2.1wt%, TiO
2mass percent be 4.3wt%) catalyzer is loaded in 100ml three-necked flask, add magnetic stir bar more successively, 22.81 grams of 6-caprolactones, 18 grams of ethanol and 46ml concentration are the hydrogen peroxide of 30%, now the mol ratio of 6-caprolactone and hydrogen peroxide is 1: 2.Be put in by three-necked flask on temperature control magnetic stirring apparatus, three-necked flask top condensing tube condensation refluxes, and starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction controls at about 80 DEG C, reacts after 5 hours, and the transformation efficiency of 6-caprolactone is 50.16%, and the selectivity generating 6 hydroxycaproic acid is 88.05%.The selectivity of hexanodioic acid is 9.31%.
Embodiment 4
Take 5.30 grams of stanniferous hollow HTS Sn-HTS (SnO
2mass percent be 2.4wt%, TiO
2mass percent be 3.8wt%) catalyzer is loaded in 100ml three-necked flask, add magnetic stir bar more successively, 11.41 grams of 6-caprolactones, 10.6 grams of ethyl acetate and 23ml concentration are the hydrogen peroxide of 30%, now the mol ratio of 6-caprolactone and hydrogen peroxide is 1: 2.Be put in by three-necked flask on temperature control magnetic stirring apparatus, three-necked flask top condensing tube condensation refluxes, and starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction controls at about 85 DEG C, reacts after 6 hours, and the transformation efficiency of 6-caprolactone is 57.38%, and the selectivity generating 6 hydroxycaproic acid is 92.76%, and the selectivity of hexanodioic acid is 3.23%.
Embodiment 5
Take 4.43 grams of stanniferous hollow HTS (SnO
2mass percent be 2.6wt%, TiO
2mass percent be 3.7wt%) Sn-HTS catalyzer is loaded in 100ml three-necked flask, add magnetic stir bar more successively, 11.41 grams of δ-valerolactones, 29 grams of acetic acid and 46ml concentration are the hydrogen peroxide of 30%, now the mol ratio of δ-valerolactone and hydrogen peroxide is 1: 4.Be put in by three-necked flask on temperature control magnetic stirring apparatus, three-necked flask top condensing tube condensation refluxes, and starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction controls at about 104 DEG C, reacts after 8 hours, and the transformation efficiency of δ-valerolactone is 99.27%, and the selectivity generating 5-hydroxypentanoic acid is 5.01%, and the selectivity of pentanedioic acid is 92.65%.
Embodiment 6
Take 3.75 grams of stanniferous hollow HTS Sn-HTS (SnO
2mass percent be 2.9wt%, TiO
2mass percent be 4.0wt%) catalyzer is loaded on 100ml and is with in manometric closed reactor, add magnetic stir bar more successively, 11.41 grams of δ-valerolactones, 32 grams of propionic acid and 46ml concentration are the hydrogen peroxide of 30%, now the mol ratio of δ-valerolactone and hydrogen peroxide is 1: 4.Be put in by closed reactor on temperature control magnetic stirring apparatus, three-necked flask top condensing tube condensation refluxes, and starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction controls at about 110 DEG C, reacts after 18 hours, and the transformation efficiency of δ-valerolactone is 99.41%, and the selectivity generating 5-hydroxypentanoic acid is 1.08%, and the selectivity of pentanedioic acid is 97.23%.
Embodiment 7
Take 2.3 grams of stanniferous HTS Sn-TS-1 (SnO
2mass percent be 2.5wt%, TiO
2mass percent be 3.5wt%) catalyzer is loaded in 100ml three-necked flask, add magnetic stir bar more successively, 11.41 grams of δ-valerolactones, 9 grams of acetic acid, 19 grams of propionic acid and 46ml concentration are the hydrogen peroxide of 30%, now the mol ratio of δ-valerolactone and hydrogen peroxide is 1: 1.Be put in by three-necked flask on temperature control magnetic stirring apparatus, three-necked flask top condensing tube condensation refluxes, and starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction controls at about 116 DEG C, reacts after 9 hours, and the transformation efficiency of δ-valerolactone is 99.37%, and the selectivity generating 5-hydroxypentanoic acid is 0.36%, and pentanedioic acid selectivity is 98.99%.
Claims (12)
1. the method for a catalyzed oxidation lactone, it is characterized in that according to lactone: the mol ratio of hydrogen peroxide is 1: (0.2 ~ 10), the mass ratio of catalyzer and lactone is 1: 5 ~ 100, the mol ratio proportioning of solvent and lactone is (0.2 ~ 10): 1, it is 10 ~ 200 DEG C in temperature, pressure is under the condition of 0 ~ 3.0MPa and carries out reacting and reclaiming product under the existence of a kind of catalyzer, the mass ratio of catalyzer and lactone is 1: (5 ~ 300), described catalyzer is tin HTS, by the compound with stanniferous source on HTS basis, template, alkali and water at 100 ~ 160 DEG C through intermediate water thermal synthesis, again through filtering separation, dry and baking operation and obtaining, in molecular sieve Theil indices with oxide basis for 1 ~ 5wt.%.
2., according to the process of claim 1 wherein, said tin HTS is one or more the mixture in Sn-TS-1, Sn-TS-2, Sn-Ti-BETA, Sn-Ti-MCM-22, Sn-Ti-MCM-41 and Sn-Ti-MCM-48.
3. according to the process of claim 1 wherein, said HTS has the HTS of MFI crystalline structure, and crystal grain is hollow structure, and the radical length of the chamber portion of this hollow crystal grain is 5 ~ 300 nanometers; This sieve sample at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm.
4., according to the process of claim 1 wherein, described lactone is the lactone comprising 2 ~ 18 carbon atoms, band side chain.
5. according to the method for claim 1 or 4, wherein, described lactone be β-, γ-, δ-or ε-lactone.
6., according to the process of claim 1 wherein, described lactone is 6-caprolactone and δ-ring valerolactone.
7., according to the method for claim 1, it is characterized in that selecting inertia organism and/or water as solvent.
8. according to the method for claim 7, wherein, said inertia organism is the compound close with boiling point of reactant or polarity is large, specific inductivity is high compound.
9. according to the method for claim 8, wherein, the said compound close with boiling point of reactant is the fatty alcohol of 1 ~ 6 carbon, ketone, acid, ester.
10. according to the method for claim 9, wherein, the said compound close with boiling point of reactant is selected from methyl alcohol, ethanol, the trimethyl carbinol, acetone, acetic acid or ethyl acetate; The inert organic solvents that said polarity is large, specific inductivity is high is acetonitrile, chloroform or tetramethylene sulfone.
11. according to the process of claim 1 wherein, said temperature is 80 ~ 95 DEG C, and ethanol or ethyl acetate are solvent, and the reaction times is between 3 to 6 hours.
12. according to the process of claim 1 wherein, said temperature is 100 ~ 160 DEG C, and acetic acid or propionic acid are solvent, and the molar ratio of hydrogen peroxide and lactone is for being greater than 3 to being less than or equal to 10, and the reaction times was more than 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010523703.4A CN102452923B (en) | 2010-10-29 | 2010-10-29 | Method for catalytically oxidizing lactone |
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| CN111253259B (en) * | 2018-11-30 | 2023-04-07 | 中国石油化工股份有限公司 | Method for preparing lactate by catalyzing dihydroxyacetone and/or glyceraldehyde |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003534251A (en) * | 2000-04-25 | 2003-11-18 | ユーオーピー エルエルシー | Oxidation of ketones to esters using tin-substituted zeolite beta |
| CN1651390A (en) * | 2004-11-26 | 2005-08-10 | 天津大学 | Method of preparing adipic acid by cyclohexane oxidation liquid pickling water HzO2 catalytic oxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003534251A (en) * | 2000-04-25 | 2003-11-18 | ユーオーピー エルエルシー | Oxidation of ketones to esters using tin-substituted zeolite beta |
| CN1651390A (en) * | 2004-11-26 | 2005-08-10 | 天津大学 | Method of preparing adipic acid by cyclohexane oxidation liquid pickling water HzO2 catalytic oxidation |
Non-Patent Citations (1)
| Title |
|---|
| "钛硅分子筛失活与再生的研究进展";王梅正等;《化工进展》;20070925;第26卷(第9期);第1258～1262页 * |
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