CN102452917B - Method for catalytically oxidizing hydroxy acid - Google Patents
Method for catalytically oxidizing hydroxy acid Download PDFInfo
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- CN102452917B CN102452917B CN201010521115.7A CN201010521115A CN102452917B CN 102452917 B CN102452917 B CN 102452917B CN 201010521115 A CN201010521115 A CN 201010521115A CN 102452917 B CN102452917 B CN 102452917B
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000001590 oxidative effect Effects 0.000 title abstract description 3
- 150000001261 hydroxy acids Chemical class 0.000 title abstract 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 76
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 6
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical group [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- PHOJOSOUIAQEDH-UHFFFAOYSA-N 5-hydroxypentanoic acid Chemical compound OCCCCC(O)=O PHOJOSOUIAQEDH-UHFFFAOYSA-N 0.000 claims description 17
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 14
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- 235000019260 propionic acid Nutrition 0.000 claims description 7
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 230000000274 adsorptive effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 229940061720 alpha hydroxy acid Drugs 0.000 claims description 2
- 150000001280 alpha hydroxy acids Chemical class 0.000 claims description 2
- 150000001277 beta hydroxy acids Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 238000003760 magnetic stirring Methods 0.000 description 18
- 230000009466 transformation Effects 0.000 description 12
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical class CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- -1 adipic acid ester Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- RPYFZMPJOHSVLD-UHFFFAOYSA-N copper vanadium Chemical compound [V][V][Cu] RPYFZMPJOHSVLD-UHFFFAOYSA-N 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
一种催化氧化羟基酸的方法，其特征在于按照羟基酸∶溶剂∶双氧水＝1∶(0～100)∶(0.1～20)的摩尔配比，温度为40～200℃和压力为0.1～3.0MPa的条件以及一种催化剂存在下进行反应，并回收得到的相应二元羧酸，所述的催化剂为钛硅分子筛，催化剂与羟基酸的质量比为1∶5～100。与现有技术相比，本发明克服了传统硝酸氧化法生产工艺复杂、设备腐蚀、存在安全隐患以及环境污染严重等弊端，且催化剂易回收、可再生重复利用。A method for catalytically oxidizing hydroxy acid, characterized in that according to the molar ratio of hydroxy acid:solvent:hydrogen peroxide=1:(0～100):(0.1～20), the temperature is 40～200°C and the pressure is 0.1～3.0 The reaction is carried out under the condition of MPa and the presence of a catalyst, and the obtained corresponding dicarboxylic acid is recovered. The catalyst is a titanium silicon molecular sieve, and the mass ratio of the catalyst to the hydroxy acid is 1:5-100. Compared with the prior art, the invention overcomes the disadvantages of the traditional nitric acid oxidation method, such as complex production process, equipment corrosion, potential safety hazards and serious environmental pollution, and the catalyst is easy to recycle and can be regenerated and reused.
Description
Technical field
The invention relates to a kind of green catalysis oxidation alcohol acid and prepare the method for corresponding di-carboxylic acid, more specifically say about a kind of alcohol acid to be the method for the corresponding di-carboxylic acid of oxygenant oxidation preparation through hydrogen peroxide.
Background technology
Di-carboxylic acid is important Organic Chemicals, taking 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, 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 acetic acid is solvent taking neutralized verdigris and manganese acetate as catalyzer, 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.Asahi Kasei Corporation of Japan 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 is inevitable to be existed 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, the simple and environmentally safe of good stability, technique, be conducive to realize that large-scale industrialization produces prepares the method for corresponding di-carboxylic acid by alcohol acid.
The method of being prepared corresponding di-carboxylic acid by alcohol acid provided by the invention, it is characterized in that according to alcohol acid: solvent: hydrogen peroxide=1: (0～100): mole proportioning of (0.1～20), temperature is to react under 40～200 DEG C and the pressure condition that is 0.1～3.0MPa and a kind of catalyzer exist, and reclaim the corresponding di-carboxylic acid that obtains, described catalyzer is HTS, and the mass ratio of catalyzer and alcohol acid is 1: 5～300.
In method provided by the invention, said alcohol acid is the compound that simultaneously contains hydroxyl-OH and carboxyl-COOH in molecule.Said alcohol acid is selected from alpha hydroxy acid, beta-hydroxy acid, γ-alcohol acid, δ-alcohol acid and ε and above alcohol acid, and for example, alcohol acid is 6 hydroxycaproic acid or 5-hydroxypentanoic acid.
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, announce 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, disclose 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 DEG C, 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 alcohol acid oxidation preparation, under same reaction conditions, can effectively improve the selectivity of transformation efficiency and the di-carboxylic acid of alcohol acid.
In method provided by the invention, taking 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 taking mass percentage concentration as 10～60% adds in reaction system, the aqueous hydrogen peroxide solution of such as technical grade has 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, select the organic mixture of one or more inertia 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 fatty alcohol, ketone, acid, the ester lower than 6 carbon atoms, such as methyl alcohol, ethanol, the trimethyl carbinol, acetone, acetic acid, propionic acid, dioxane or ethyl acetate 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, 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.In the time adopting acetic acid or propionic acid to be solvent, particularly alcohol acid: mole proportioning of hydrogen peroxide is 1: the mass ratio of (0.2～10) and catalyzer and alcohol acid is 1: 5～100, temperature is the lower time of condition that 70～120 DEG C, pressure are 0.1～3.0MPa, with other organism such as acetone, methyl alcohol make solvent, the selectivity of corresponding di-carboxylic acid has raising significantly, therefore, in method provided by the invention, said solvent is acetic acid or propionic acid more preferably, with mole proportioning of alcohol acid be (0.2～10): 1.
Method provided by the invention can adopt periodical operation or continuous operating method.For example, while adopting intermittent mode to carry out, alcohol acid, 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 alcohol acid, hydrogen peroxide after solvent making beating, continuous separated product simultaneously.Method provided by the invention can also adopt closed still reaction, adds rear reaction by catalyzer, solvent, alcohol acid, hydrogen peroxide simultaneously.
The process of the di-carboxylic acid that in the present invention, said recovery obtains, by those skilled in the art is familiar with, adopts conventional separation means, from mixture of reaction products, separates and 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.
Alcohol acid 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. taking hydrogen peroxide as oxygenant, under relatively mild reaction conditions, can obtain higher alcohol acid 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, under acetic acid or propionic acid equal solvent exist, the selectivity of corresponding di-carboxylic acid is higher.
Embodiment
Following is that the present invention is further illustrated for strength.
In embodiment, 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 alcohol acid, 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 is the HTS of MFI structure through X-ray diffraction analysis, 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 DEG C, P/P
0=0.10, the benzene adsorptive capacity recording under the adsorption time condition of 1 hour is 78 milligrams/gram, lower same) be loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 23.62 grams of 5-hydroxypentanoic acids, 3.6 grams of water and 46ml concentration are 30%, now the mol ratio of 5-hydroxypentanoic acid 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 70 DEG C of left and right, reacts after 1 hour, and the transformation efficiency of 5-hydroxypentanoic acid is 25.27%, and the selectivity that generates pentanedioic acid is 78.67%.
Embodiment 2
Taking 3.66 grams of hollow HTS is loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 23.62 grams of 5-hydroxypentanoic acids, 12.8 grams of methyl alcohol and 46ml concentration are 30%, now the mol ratio of 5-hydroxypentanoic acid 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 85 DEG C of left and right, reacts after 2 hours, and the transformation efficiency of 5-hydroxypentanoic acid is 56.23%, and the selectivity that generates pentanedioic acid is 80.35%.
Embodiment 3
Taking 2.65 grams of hollow HTS is loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 26.42 grams of 6 hydroxycaproic acids, 14.8 grams of trimethyl carbinols and 23ml concentration are 30%, now the mol ratio of 6 hydroxycaproic acid 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 95 DEG C of left and right, reacts after 8 hours, and the transformation efficiency of 6 hydroxycaproic acid is 43.23%, and the selectivity that generates hexanodioic acid is 78.52%.
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, 26.42 grams of 6 hydroxycaproic acids, 10.6 grams of acetone and 46ml concentration are 30%, now the mol ratio of 6 hydroxycaproic acid 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 120 DEG C of left and right, reacts after 16 hours, and now autogenous pressure is 1.6MPa.The transformation efficiency of 6 hydroxycaproic acid is 97.36%, and the selectivity that generates hexanodioic acid is 73.25%.
Embodiment 5
Taking 3.31 grams of hollow HTS is loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 13.21 grams of 6 hydroxycaproic acids, 18.4 grams of ethanol and 46ml concentration are 30%, now the mol ratio of 6 hydroxycaproic acid 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 75 DEG C of left and right, reacts after 24 hours, and the transformation efficiency of 6 hydroxycaproic acid is 81.54%, and the selectivity that generates hexanodioic acid is 76.72%.
Embodiment 6
Taking 2.53 grams of hollow HTS is loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 23.62 grams of 5-hydroxypentanoic acids, 8.2 grams of acetonitriles and 23ml concentration are 30%, now the mol ratio of 5-hydroxypentanoic acid 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 73 DEG C of left and right, reacts after 4 hours, and the transformation efficiency of 5-hydroxypentanoic acid is 28.41%, and the selectivity that generates pentanedioic acid is 75.83%.
Embodiment 7
Take 2.3 grams of conventional titanium-silicon molecular sieve TS-1 (Zeolites, 1992, Vol.12,943rd～950 pages) catalyzer is loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 26.42 grams of 6 hydroxycaproic acids, 3.6 grams of water and 46ml concentration are 30%, now the mol ratio of 6 hydroxycaproic acid 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 90 DEG C of left and right, reacts after 12 hours, and the transformation efficiency of 6 hydroxycaproic acid is 45.60%, and the selectivity that generates hexanodioic acid is 79.72%.
Embodiment 8
Taking 2.53 grams of hollow HTS is loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 23.62 grams of 5-hydroxypentanoic acids, 21 grams of acetic acid and 46ml concentration are 30%, now the mol ratio of 5-hydroxypentanoic acid 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 90 DEG C of left and right, reacts after 6 hours, and the transformation efficiency of 5-hydroxypentanoic acid is 94.57%, and the selectivity that generates pentanedioic acid is 99.54%.
Embodiment 9
Taking 2.53 grams of hollow HTS is loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 11.81 grams of 5-hydroxypentanoic acids, 8.2 grams of propionic acid and 46ml concentration are 30%, now the mol ratio of 5-hydroxypentanoic acid 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 110 DEG C of left and right, reacts after 9 hours, and the transformation efficiency of 5-hydroxypentanoic acid is 98.41%, and the selectivity that generates pentanedioic acid is 98.54%.
Claims (5)
1. the method for an acid by catalytic oxidation of hydroxy, it is characterized in that according to alcohol acid: solvent: hydrogen peroxide=1: (0.2～10): mole proportioning of (0.5～10), 70～120 DEG C of temperature, pressure 0.1～1.0MPa and a kind of catalyzer react under existing, and reclaim the corresponding di-carboxylic acid that obtains, described catalyzer is titanium-silicon molecular sieve 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 DEG C, 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, have hysteresis loop, the mass ratio of catalyzer and alcohol acid is 1: 5～100, and said solvent is selected from acetic acid or propionic acid.
2. according to the process of claim 1 wherein, said alcohol acid is the compound that simultaneously contains hydroxyl-OH and carboxyl-COOH in molecule.
3. according to the method for claim 1, said alcohol acid is selected from alpha hydroxy acid, beta-hydroxy acid, γ-alcohol acid, δ-alcohol acid or ε and above alcohol acid.
4. according to the method for claim 1, said alcohol acid is 6 hydroxycaproic acid or 5-hydroxypentanoic acid.
5. according to the method for claim 1, said hydrogen peroxide is the aqueous solution of mass concentration 10～60%.
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| A Rationale of the Baeyer–Villiger Oxidation of Cyclohexanone to ε-Caprolactone with Hydrogen Peroxide: Unprecedented Evidence for a Radical Mechanism Controlling Reactivity;Fabrizio Cavani et al.;《Chem.Eur.J.》;20100928;第16卷;第12962-12969页 * |
| Fabrizio Cavani et al..A Rationale of the Baeyer–Villiger Oxidation of Cyclohexanone to ε-Caprolactone with Hydrogen Peroxide: Unprecedented Evidence for a Radical Mechanism Controlling Reactivity.《Chem.Eur.J.》.2010,第16卷第12962-12969页. |
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