CN102617326A - Preparation method for 2-methylsuccnic acid through Ni catalysis - Google Patents
Preparation method for 2-methylsuccnic acid through Ni catalysis Download PDFInfo
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- CN102617326A CN102617326A CN2012100583877A CN201210058387A CN102617326A CN 102617326 A CN102617326 A CN 102617326A CN 2012100583877 A CN2012100583877 A CN 2012100583877A CN 201210058387 A CN201210058387 A CN 201210058387A CN 102617326 A CN102617326 A CN 102617326A
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- 239000002253 acid Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 239000000706 filtrate Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract 1
- 230000006872 improvement Effects 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 201000007094 prostatitis Diseases 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method for 2-methylsuccnic acid through Ni catalysis. According to the method, taconic acid which is used as a raw material is dissolved in solvent, wherein the solvent is one or two of methanol, ethanol or tetrahydrofuran, and 2-methylsuccnic acid is prepared by using a Ni catalyst through solvent liquid phase hydrogenation; the using amount of Ni catalyst is 5 to 25 percent based on the using amount of taconic acid, reaction temperature is 10 to 100 DEG C, reaction pressure is 1.0 to 10 MPa, and reaction time is 0.5 to 1.5 hours; and the 2-methylsuccnic acid is obtained by the steps of performing reduced pressure distillation on filtrate, purifying and drying. The reaction conditions of the preparation method are mild, the preparation method is practical and is easy to operate, and low in time consumption and cost; and conversion rate and selectivity of one-step reaction both reach more than 99 percent; the used catalyst can be used repeatedly for 5 to 9 times, and reaction cost is reduced; and the Ni catalyst is high in stability, the conversion rate and selectivity of a product which is continuously used for more than 5 time are both more than 99 percent, and the product is low in price.
Description
Technical field
The present invention relates to chemical field, be specifically related to a kind of Ni catalytic preparation method of 2-pyrovinic acid.
Background technology
Methylene-succinic acid (being methylene-succinic acid) molecular formula is C
5H
6O
4, English by name itaconic acid, molecular weight 130.1, pure methylene-succinic acid are white powdery crystallization or clear crystal, stable upon storage, crystalline product is nonhygroscopic, even under hot conditions, do not lump yet, soluble in water, methyl alcohol, ethanol and acetone.Methylene-succinic acid is a kind of important intermediate in the polymer production, and purposes is very widely arranged.At present; The carbohydrate, fiber or the base of leaf waste that produce with plant change into living matter oil product and plasticizing intermediate feed; Can reduce dependence to oil; Alleviating energy crisis and Greenhouse effect, and methylene-succinic acid is one of quite potential living material wherein, and China's methylene-succinic acid turnout occupies prostatitis, the world.
The pyrovinic acid molecular formula is C
5H
8O
4, English by name methylsuccnic acid, molecular weight 132.12, pure pyrovinic acid are white or little yellow crystals, soluble in water, ethanol and THF.Pyrovinic acid is of many uses, generally is used for the waste paper bleaching, etching reagent, and esterification, photochemical reaction, and be the synthetic macromolecular indispensable reagent of high amount of drug.But it is low that its traditional compound method faces productive rate, the problem that preparation, sepn process complicacy and waste liquid are many.
The compound method of the hydrogenation products pyrovinic acid of methylene-succinic acid in existing document is many, and Saito is arranged, and (JP 08 81 for people's such as Hidekazu oxidation style; 410 [96 81,410], CA12533177r); The oxidation style productive rate is not higher than 59%; Reaction conditions need HTHP (130 ℃, 5atm), and length consuming time (60h).Mateoli is arranged, and Tefort, people such as Dawson are raw material with the methylene-succinic acid; At VIII family element is in the presence of the special title complex of central atom, uses Rh, Ru; Metal complexs such as Pd are catalyzer, hydrogenation synthesis method (Journal of Mol Catalyst A:Chem.1996,109 (1); CA 12516684r), but the polymer-metal complex catalyst metal is prone to loss, and the active site structure is indeterminate.Shi Huancong is arranged, people's such as Shen Wei palladium carbon catalytic hydrogenation method (CN1609089A), but palladium-carbon catalyst costs an arm and a leg the production cost height.Xu Xiyan is arranged, and the methylene-succinic acid elder generation esterification of Zhao Yushan is hydrogenant method (CN10171169A) again, but operation steps is complicated, and reaction conditions need HTHP (130-280 ℃, 1-100bar).
Summary of the invention
The productive rate that exists to methylene-succinic acid hydrogenation preparing 2-pyrovinic acid method in the prior art is low, reaction requirement condition height or the high defective of production cost, and main purpose of the present invention has provided a kind of Ni catalytic preparation method of 2-pyrovinic acid.The present invention is a catalyzer with Ni, is raw material with the methylene-succinic acid, stirring reaction under dissolution with solvents; Liquid-phase hydrogenatin Synthetic 2-pyrovinic acid; Expeditiously from raw material one-step synthesis product, be a kind of simple operating steps really, reaction conditions is gentle; Yield is high, the process for catalytic synthesis of lower-cost 2-pyrovinic acid.
For realizing the foregoing invention purpose, the present invention adopts following technical proposals to be achieved:
A kind of Ni catalytic preparation method of 2-pyrovinic acid is that raw material is dissolved in the solvent with the methylene-succinic acid, solvent adopt methyl alcohol, ethanol or THF wherein one or both; Adopt nickel catalyzator; Through solvent liquid-phase hydrogenatin stirring reaction Synthetic 2-pyrovinic acid, reacting the mass ratio that feeds intake is nickel catalyzator: methylene-succinic acid=5%～25%, 10～100 ℃ of said temperature of reaction; Reaction pressure 1.0～10MPa, 0.5～15 hour reaction times; Filtrating after reaction is accomplished obtains the 2-pyrovinic acid through underpressure distillation, purification, oven dry.
Further improvement to technical scheme: said solvent is preferentially selected the combination of ethanol and THF for use, and both volume ratios are 0.1～10: 1.
Further improvement to technical scheme: said catalysis synthetic temperature of reaction is 10～80 ℃.
Further improvement to technical scheme: said catalysis synthetic reaction pressure is 1.0～5.0MPa.
Further improvement to technical scheme: the said catalysis synthetic reaction times is 1～10 hour.
Further improvement to technical scheme: the functional quality mark is 5～30% Na
2The S aqueous solution is removed the nickel ion in the filtrating.
Further improvement to technical scheme: reusable 5～9 times of nickel catalyzator.
Compared with prior art, advantage of the present invention and positively effect are:
Compare with traditional method, the gentle row that is prone to of preparing method's reaction conditions of the present invention, employed solvent is common solvent, and is simple to operate, and consuming time few, cost is low, and the transformation efficiency of single step reaction, selectivity are all very high, and the both reaches more than 99%.In addition, reusable 5～9 times of catalyst system therefor of the present invention has reduced reaction cost; And nickel catalyzator stability is stronger, and transformation efficiency and the selectivity of using product more than 5 times continuously are all greater than 99%, and price is more cheap.The present invention comes purified product with underpressure distillation, and is simple to operate, and step is few, and product purity is high.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is done further detailed explanation.
Embodiment 1
Be reflected in the intermittent type tank reactor and carry out, 50g raw material methylene-succinic acid is added in the 450ml methyl alcohol, the dissolving back adds in the reactor drum, adds the 10g nickel catalyzator again, leak detection, and ventilation, logical hydrogen stirs, 50 ℃ of constant temperature, constant voltage 3MPa reacted 8 hours, the basic completion.Sedimentation is filtered; Obtain solid catalyst, can be recycled, in filtrating, add an amount of Na
2The S aqueous solution stirs to remove nickel ion in the thick product, and sedimentation is filtered again, and gained filtrating water white transparency with the distillation of gained filtrate decompression, purifies crude product, oven dry.Obtain the transformation efficiency 99.75% of pyrovinic acid, selectivity is 99.85%.
Said Na
2Na in the S aqueous solution
2The S consumption is: Na
2The excess coefficient of S is 2～7 (4 for best); Churning time 10～60min (30min is best) in removing the nickel process, stirs sedimentation, with Na
2Solution is transparent after S add-on to the filtration is as the criterion.
The reaction formula of methylene-succinic acid hydrogenation generation 2-pyrovinic acid of the present invention is following:
Embodiment 2
Reaction unit is the same, and methylene-succinic acid 50g, solvent select THF 450ml for use, nickel catalyzator 12.5g, and 30 ℃, 3MPa reacted 9 hours, and operation steps is the same, obtains product yield 99.78%, and selectivity is 99.90%.
Embodiment 3
Reaction unit is the same, and methylene-succinic acid 50g, solvent select ethanol 150ml/ THF 300ml for use, nickel catalyzator 8g, and 70 ℃, 4MPa reacted 6 hours, and operation steps is the same, obtains product yield 99.76%, and selectivity is 99.92%.
Embodiment 4
Reaction unit is the same, and methylene-succinic acid 50g, solvent select methyl alcohol 150ml/ THF 300ml for use, nickel catalyzator 2.5g, and 50 ℃, 2MPa reacted 10 hours, and operation steps is the same, obtains product yield 99.72%, and selectivity is 99.89%.
Embodiment 5
Reaction unit is the same, and methylene-succinic acid 50g, solvent select ethanol 450ml for use, nickel catalyzator 12g, and 60 ℃, 3MPa reacted 10 hours, reused catalyst reaction 5 times, and the 5th obtains product yield 99.43%, and selectivity is 99.33%.Experimental result has shown that the activity of nickel catalyzator is very strong and stability is high.
Embodiment 6
Reaction unit is the same, and methylene-succinic acid 50g, solvent select ethanol 150ml/ THF 300ml for use, nickel catalyzator 8g, and 50 ℃, 4MPa reacted 7 hours, obtained product yield 99.83%, and selectivity is 99.88%.
Temperature of reaction of the present invention is 10～100 ℃, reaction pressure 1.0～10MPa, 0.5～15 hour reaction times; Under this reaction conditions, when temperature of reaction is low, but augmenting response pressure or prolongation reaction times, otherwise, can reduce the reaction times or reduce reaction pressure, can suitably select according to concrete experiment condition.
Choosing of solvent of the present invention is very important, can adopt methyl alcohol, ethanol, THF wherein one or both, but from high conversion and highly selective, mixed solvent is more better.Mixed solvent is methyl alcohol, ethanol, any two kinds mixed solution of THF, under blending ratio of the present invention, satisfied transformation efficiency and selectivity is arranged.Wherein the combination of ethanol and THF is optimum, and both volume ratios are 0.1～10, makes up as solvent with ethanol in this volume ratio scope and THF, and the transformation efficiency and the selectivity of the product 2-pyrovinic acid that obtains all reach more than 99.8%.
The transformation efficiency of product and selectivity from the foregoing description, the better reaction conditions of the present invention is following: temperature of reaction 10-80 ℃; Reaction pressure 1.0-5.0MPa; The catalysis synthetic reaction times is 1～10 hour; Na
2The massfraction 5～30% of the S aqueous solution.The temperature of underpressure distillation is 50～90 ℃, and oven dry obtains better quality fractional pyrovinic acid then.
Above embodiment is only in order to explaining technical scheme of the present invention, but not limits it; Although the present invention has been carried out detailed explanation with reference to previous embodiment, for the person of ordinary skill of the art, still can make amendment to the technical scheme that previous embodiment is put down in writing, perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of relevant art scheme break away from the spirit and the scope of the present invention's technical scheme required for protection.
Claims (7)
1. the Ni catalytic preparation method of a 2-pyrovinic acid is characterized in that with the methylene-succinic acid being that raw material is dissolved in the solvent, solvent adopt methyl alcohol, ethanol or THF wherein one or both; Adopt nickel catalyzator; Through solvent liquid-phase hydrogenatin stirring reaction Synthetic 2-pyrovinic acid, reacting the mass ratio that feeds intake is nickel catalyzator: methylene-succinic acid=5%～25%, 10～100 ℃ of said temperature of reaction; Reaction pressure 1.0～10MPa, 0.5～15 hour reaction times; Filtrating after reaction is accomplished obtains the 2-pyrovinic acid through underpressure distillation, purification, oven dry.
2. the Ni catalytic preparation method of a kind of 2-pyrovinic acid according to claim 1 is characterized in that said solvent preferentially selects the combination of ethanol and THF for use, and both volume ratios are 0.1～10:1.
3. the Ni catalytic preparation method of a kind of 2-pyrovinic acid according to claim 1 is characterized in that said catalysis synthetic temperature of reaction is 10～80 ℃.
4. the Ni catalytic preparation method of a kind of 2-pyrovinic acid according to claim 1 is characterized in that said catalysis synthetic reaction pressure is 1.0～5.0MPa.
5. the Ni catalytic preparation method of a kind of 2-pyrovinic acid according to claim 1 is characterized in that the said catalysis synthetic reaction times is 1～10 hour.
6. the Ni catalytic preparation method of a kind of 2-pyrovinic acid according to claim 1 is characterized in that the functional quality mark is 5～30% Na
2The S aqueous solution is removed the nickel ion in the filtrating.
7. the Ni catalytic preparation method of a kind of 2-pyrovinic acid according to claim 1 is characterized in that nickel catalyzator reusable 5～9 times.
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| CN2012100583877A CN102617326A (en) | 2012-03-07 | 2012-03-07 | Preparation method for 2-methylsuccnic acid through Ni catalysis |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718778A (en) * | 2017-10-31 | 2019-05-07 | 中国科学院大连化学物理研究所 | A kind of method that Ni base catalyst itaconic acid adds hydrogen to prepare dimethyl succinic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS277263B6 (en) * | 1990-10-22 | 1992-12-16 | Vyzk Ustav Farm Biochem Sp | Process for preparing methylsuccinic acid anhydride |
| US5334758A (en) * | 1989-07-05 | 1994-08-02 | Takasago International Corporation | Process for preparing optically active carboxylic acid |
| CN1609089A (en) * | 2004-06-24 | 2005-04-27 | 复旦大学 | Catalytic synthesis process of methyl succinic acid |
-
2012
- 2012-03-07 CN CN2012100583877A patent/CN102617326A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5334758A (en) * | 1989-07-05 | 1994-08-02 | Takasago International Corporation | Process for preparing optically active carboxylic acid |
| CS277263B6 (en) * | 1990-10-22 | 1992-12-16 | Vyzk Ustav Farm Biochem Sp | Process for preparing methylsuccinic acid anhydride |
| CN1609089A (en) * | 2004-06-24 | 2005-04-27 | 复旦大学 | Catalytic synthesis process of methyl succinic acid |
Non-Patent Citations (1)
| Title |
|---|
| SMIGIELSKI, KRZYSZTOF ET AL.: "Electrocatalytic reduction of itaconic acid to methylsuccinic acid", 《CHEM. STOSOW.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718778A (en) * | 2017-10-31 | 2019-05-07 | 中国科学院大连化学物理研究所 | A kind of method that Ni base catalyst itaconic acid adds hydrogen to prepare dimethyl succinic acid |
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Application publication date: 20120801 |