CN102452921B - Method for preparing dicarboxylic acid - Google Patents
Method for preparing dicarboxylic acid Download PDFInfo
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- CN102452921B CN102452921B CN201010521111.9A CN201010521111A CN102452921B CN 102452921 B CN102452921 B CN 102452921B CN 201010521111 A CN201010521111 A CN 201010521111A CN 102452921 B CN102452921 B CN 102452921B
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Abstract
The invention discloses a method for preparing a dicarboxylic acid. The method is characterized by comprising the following steps of: undergoing a reaction at the temperature of 100-200 DEG C under the pressure of 0.1-3.0 MPa in the presence of a catalyst in the molar ratio of 1:(0-80):(0.2-20) of cyclic ketone to a solvent to hydrogen peroxide; and recovering to obtain the dicarboxylic acid, wherein the catalyst is a titanium-silicon molecular sieve; and the mass ratio of the catalyst to cyclic ketone is 1:(5-300). Compared with the prior art, the method has the advantage that: the defects of complex production process, corrosion of equipment, potential safety hazard, severe environmental pollution and the like existing in the conventional nitric acid oxidizing method are overcome.
Description
Technical field
The invention relates to a kind of method of preparing corresponding di-carboxylic acid, more specifically say about a kind of cyclic ketones through hydrogen peroxide, to be the method for the corresponding di-carboxylic acid of oxygenant oxidation preparation.
Background technology
Di-carboxylic acid is important Organic Chemicals, take hexanodioic acid as example, and it is industrial significant di-carboxylic acid, is mainly used in adiponitrile processed, and then produces hexanediamine, and produces 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, do polyurethane elastomer raw material, produce the raw material etc. of souring agent, medicine, yeast purificant, sterilant, tackiness agent, synthetic leather, synthetic dyestuff and the spices of unsaturated polyester, hexylene glycol and adipic acid ester class, various food and drink.
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, but this reaction exists deep-etching problem to equipment, and environmental pollution is serious, complex process, and energy consumption is higher, do not meet Green Chemistry principle.
Air oxidation process is that to take neutralized verdigris and manganese acetate be catalyzer, and acetic acid is solvent, with air direct oxidation KA oil.The general two-stage reactor that adopts is connected, and 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.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 CN101337879A 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 shortcomings such as traditional catalyzed oxidation exists equipment corrosion is strong, energy consumption is higher, complex process, processing cost are higher, the present invention be directed to the deficiencies in the prior art, provide that a kind of object selectivity of product is high, good stability, technique is simple and environmentally safe, is conducive to realize that large-scale industrialization produces by lactone, prepares the method for corresponding di-carboxylic acid.
The method of preparing di-carboxylic acid 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 to react under 100～200 ℃ and the pressure condition that is 0.1～3.0MPa and a kind of catalyzer exist, and reclaim the di-carboxylic acid obtain, described catalyzer is HTS, and the mass ratio of catalyzer and cyclic ketones is 1: 5～300.
In method provided by the invention, said cyclic ketones is selected from monocycle ketone, many cyclic ketones and with the cyclic ketones of side chain R, R is alkyl functional group.For example, cyclic ketones is pimelinketone, cyclopentanone or methylcyclohexanone etc.
In method provided by the invention, said catalyzer is 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, preferred HTS is TS-1, in US Patent No. P4410501, announced first the synthetic method of titanium-silicon molecular sieve TS-1.As preferred embodiment, in the present invention, HTS used is a kind of TS-1 HTS of unique hollow structure, in the Chinese patent of ZL99126289.1, disclosed above-mentioned unique hollow structure TS-1 HTS and preparation method thereof, it has the HTS of MFI crystalline structure, crystal grain is hollow structure, and the radical length of the cavity part of this hollow crystal grain is 5～300 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 at least 70 milligrams/grams, between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, has hysteresis loop.The said TS-1 HTS with hollow structure, have and have larger mesoporous volume, more than being generally 0.16mL/g, and conventional TS-1 HTS, mesoporous volume is generally in 0.084mL/g left and right, and contriver is surprised to find that, uses it in the reaction of the corresponding di-carboxylic acid of cyclic ketones oxidation preparation, under same reaction conditions, can effectively improve the selectivity of transformation efficiency and the di-carboxylic acid of cyclic ketones.
In method provided by the invention, take hydrogen peroxide as oxygenant, hydrogen peroxide, because its reduzate is only water, environmental friendliness, is Green Oxidant.High density hydrogen peroxide is because its character is unstable, in production, accumulating, use procedure, there is potential safety hazard, and cost is higher, the form of the aqueous hydrogen peroxide solution that the mass concentration of normally take is 10～60% adds in reaction system, such as the aqueous hydrogen peroxide solution of technical grade, have 27.5%, 30% and 35% etc., conventionally selecting massfraction is 30% hydrogen peroxide.Inventor's discovery, lower concentration hydrogen peroxide has more efficient catalytic oxidation activity under appropriate reaction condition.In proportioning raw materials, hydrogen peroxide is in hydrogen peroxide.
In the method that present method provides, said solvent is selected inertia organism and/or water.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 for lower than 6 fat of carbon atom alcohol, ketone, acid, ester, such as methyl alcohol, ethanol, the trimethyl carbinol, acetone, acetic acid, dioxane or ethyl acetate etc.; The inert organic solvents that said polarity is large, specific inductivity is high such as acetonitrile, chloroform or tetramethylene sulfone etc.
Contriver is surprised to find that, in the reaction system that particularly, low temperature lower at hydrogen peroxide concentration and catalyst concn are lower, under acetic acid or propionic acid exist as solvent, the selectivity of corresponding di-carboxylic acid is higher.For example, when adopting acetic acid or propionic acid to be solvent, cyclic ketones particularly: mole proportioning of hydrogen peroxide is 1: the mass ratio of (0.5～10) and catalyzer and cyclic ketones is 1: 5～100, temperature is the lower time of condition that 105～140 ℃, pressure are 0.1～1.0MPa, with other organism such as acetone, methyl alcohol are made solvent, the selectivity of corresponding di-carboxylic acid has significantly and improves.Therefore, in method provided by the invention, said solvent is acetic acid or propionic acid more preferably, with mole proportioning of cyclic ketones be (0.2～10): 1.
Cyclic ketones catalyzed oxidation provided by the invention is prepared the method for corresponding di-carboxylic acid, 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; While adopting continuous mode to carry 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 can also adopt closed still reaction, and soon catalyzer, solvent, cyclic ketones, hydrogen peroxide add rear reaction simultaneously.
The process of the di-carboxylic acid that in the present invention, said recovery obtains is familiar with by those skilled in the art, adopts conventional separation means, and from mixture of reaction products, separation obtains corresponding di-carboxylic acid, comprises distillation, crystallization and extraction etc.For example, in this research, can adopt relatively-high temperature crystallization process to isolate the product di-carboxylic acid of this reaction.
Cyclic ketones catalyzed oxidation provided by the invention is prepared the method for corresponding di-carboxylic acid, has following feature:
1. overcome conventional oxidation method complex manufacturing, equipment corrosion, had potential safety hazard and the drawback such as environmental pollution is serious.
2. take hydrogen peroxide as oxygenant, under relatively mild reaction conditions, can obtain higher cyclic ketones transformation efficiency and corresponding di-carboxylic acid yield, especially there is good activity stability.
3., in the reaction system that particularly, low temperature lower at hydrogen peroxide concentration and catalyst concn are lower, at acetic acid or propionic acid, be that under solvent exists, the selectivity of corresponding di-carboxylic acid is higher.
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 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 transformation efficiency of cyclic ketones, corresponding di-carboxylic acid selectivity are respectively to calculate according to the following equation:
Embodiment 1
(Hunan is built feldspathization company and is produced to take 2.3 grams of hollow HTS, trade mark HTS, it through X-ray diffraction analysis, is the HTS of 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, down together) catalyzer is loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 19.63 grams of pimelinketone, 3.6 grams of water, 6.4 grams of methyl alcohol 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 110 ℃ of left and right, reacts after 6 hours, and the transformation efficiency of pimelinketone is 69.35%, and the selectivity that generates hexanodioic acid is 72.17%.
Embodiment 2
Taking 5.44 grams of hollow HTS is loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 9.81 grams of pimelinketone, 6.4 grams of water, 15 grams of acetone and 23ml 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 105 ℃ of left and right, reacts after 4 hours, and the transformation efficiency of pimelinketone is 65.27%, and the selectivity that generates hexanodioic acid is 60.35%.
Embodiment 3
Take 2.65 grams of hollow HTS and be loaded in 100ml three-necked flask, then add successively the hydrogen peroxide that magnetic stir bar, 19.63 grams of pimelinketone, 14.8 grams of trimethyl carbinols and 46ml concentration are 30%, now the mol ratio of pimelinketone 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 110 ℃ of left and right, reacts after 8 hours, and the transformation efficiency of pimelinketone is 78.25%, and the selectivity that generates hexanodioic acid is 86.31%.
Embodiment 4
Taking 7.98 grams of hollow HTS is loaded on 100ml and is with in manometric closed reactor, add successively the hydrogen peroxide that magnetic stir bar, 16.83 grams of cyclopentanone, 5.4 grams of acetone, 7.4 grams of trimethyl carbinols 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 90 ℃ of left and right, reacts after 4 hours, and now autogenous pressure is 1.6MPa.The transformation efficiency of cyclopentanone is 42.31%, and the selectivity that generates pentanedioic acid is 78.25%.
Embodiment 5
Take 3.31 grams of hollow HTS and be loaded in 100ml three-necked flask, then add successively the hydrogen peroxide that magnetic stir bar, 16.83 grams of cyclopentanone, 23.9 grams of water and 23ml concentration are 30%, now the mol ratio of cyclopentanone and hydrogen peroxide is 1: 1.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 108 ℃ of left and right, reacts after 16 hours, and the transformation efficiency of cyclopentanone is 31.54%, and the selectivity that generates pentanedioic acid is 76.32%.
Embodiment 6
Take 2.53 grams of hollow HTS and be loaded in 100ml three-necked flask, then add successively the hydrogen peroxide that magnetic stir bar, 8.42 grams of cyclopentanone, 8.2 grams of acetonitriles and 46ml concentration are 30%, now the mol ratio of cyclopentanone 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 2 hours, and the transformation efficiency of cyclopentanone is 55.28%, and the selectivity that generates pentanedioic acid is 72.54%.
Embodiment 7
Take 2.3 grams of titanium-silicon molecular sieve TS-1 (Zeolites, 1992,943rd～950 pages of Vol.12) be 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 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 12 hours, and the transformation efficiency of pimelinketone is 73.26%, and the selectivity that generates hexanodioic acid is 75.72%.
Embodiment 8
Taking 2.3 grams of conventional titanium-silicon molecular sieve TS-1 catalysts is loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 9.81 grams of pimelinketone, 26 grams of acetic acid 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 12 hours, and the transformation efficiency of pimelinketone is 93.26%, and the selectivity that generates hexanodioic acid is 99.72%.
Embodiment 9
Taking 7.98 grams of hollow HTS HTS catalyzer is loaded on 100ml and is with in manometric closed reactor, add successively the hydrogen peroxide that magnetic stir bar, 9.83 grams of cyclopentanone, 11.21 grams of propionic acid and 46ml concentration are 30%, now the mol ratio of cyclopentanone and hydrogen peroxide is 1: 4 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 120 ℃ of left and right, reacts after 10 hours, and now autogenous pressure is 1.6MPa.The transformation efficiency of cyclopentanone is 99.31%, and the selectivity that generates pentanedioic acid is 98.95%.
Claims (6)
1. a method of preparing di-carboxylic acid, it is characterized in that according to cyclic ketones: solvent: hydrogen peroxide=1:(0.5～10): mole proportioning of (0.2～10), in temperature, be to react under 105～140 ℃ and the pressure condition that is 0.1～1.0MPa and a kind of catalyzer exist, and reclaim the di-carboxylic acid obtain, described catalyzer is HTS, the mass ratio of catalyzer and cyclic ketones is 1:5～300, and said solvent is selected from acetic acid or propionic acid.
2. according to the process of claim 1 wherein, described HTS is selected from one or more the mixture in TS-1, TS-2, Ti-BETA, Ti-MCM-22, Ti-MCM-41 and Ti-MCM-48.
3. according to the method for claim 2, wherein, described TS-1, crystal grain is hollow structure, the radical length of the cavity part of crystal grain is 5～300 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 at least 70 milligrams/grams, between the adsorption isothermal line of nitrogen absorption under low temperature and desorption isotherm, has hysteresis loop.
4. according to the method for claim 1, described cyclic ketones is monocycle ketone, many cyclic ketones and with the cyclic ketones of side chain R, and R is alkyl functional group.
5. according to the method for claim 1, described cyclic ketones is selected from pimelinketone, cyclopentanone or methylcyclohexanone.
6. according to the method for claim 1, described hydrogen peroxide is the aqueous hydrogen peroxide solution of mass concentration 10～60%.
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| 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 |
| CN107266344B (en) * | 2017-07-17 | 2021-09-14 | 湘潭大学 | Preparation method of cyclohexanone peroxide |
Citations (4)
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|---|---|---|---|---|
| US3551300A (en) * | 1968-12-13 | 1970-12-29 | Witco Chemical Corp | By-water dissolution,steam distillation,activated carbon and cation exchange treatment and crystallization |
| CN1167082A (en) * | 1996-06-05 | 1997-12-10 | 中国石油化工总公司 | Method for preparing titanium-silicon molecular sieve (TS-1) |
| 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 |
| CN1946704A (en) * | 2004-03-08 | 2007-04-11 | Abb路慕斯全球股份有限公司 | Process for olefin epoxidation and c0-production of nylon precursor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54135720A (en) * | 1978-04-14 | 1979-10-22 | Yasutaka Ishii | Manufacture of adipic acid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3551300A (en) * | 1968-12-13 | 1970-12-29 | Witco Chemical Corp | By-water dissolution,steam distillation,activated carbon and cation exchange treatment and crystallization |
| CN1167082A (en) * | 1996-06-05 | 1997-12-10 | 中国石油化工总公司 | Method for preparing titanium-silicon molecular sieve (TS-1) |
| 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 |
| CN1946704A (en) * | 2004-03-08 | 2007-04-11 | Abb路慕斯全球股份有限公司 | Process for olefin epoxidation and c0-production of nylon precursor |
Non-Patent Citations (2)
| Title |
|---|
| Cyclohexane Oxidation Catalyzed by Titanium Silicalite (TS-1): Overoxidation and Comparison with Other Oxidation Systems;Estevam V. Spinacé等;《Journal of Catalysis》;19951231;第157卷(第2期);第631-635页 * |
| Estevam V. Spinacé等.Cyclohexane Oxidation Catalyzed by Titanium Silicalite (TS-1): Overoxidation and Comparison with Other Oxidation Systems.《Journal of Catalysis》.1995,第157卷(第2期),第631-635页. |
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