CN102311332B - Method for producing succinic acid - Google Patents
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- CN102311332B CN102311332B CN2010102212196A CN201010221219A CN102311332B CN 102311332 B CN102311332 B CN 102311332B CN 2010102212196 A CN2010102212196 A CN 2010102212196A CN 201010221219 A CN201010221219 A CN 201010221219A CN 102311332 B CN102311332 B CN 102311332B
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Abstract
The invention discloses a method for producing succinic acid. The method comprises the following steps of: performing hydrogenation reaction by taking 5 to 90 weight percent of a maleic anhydride gamma-butyrolactone solution as a raw material at the reaction temperature of between 50 and 100 DEG C under the pressure of between 0.2 and 2 MPa in the presence of a hydrogenation catalyst, hydrolyzing a hydrogenation product, crystallizing and separating to obtain succinic acid. The method is can be operated flexibly; reaction conditions are mild and controllable; and products are easy to separate and have good quality.
Description
Technical field
The present invention relates to a kind of method of producing succinic acid, specifically relate to a kind of method that succinic acid is produced in maleic anhydride hydrogenation hydrolysis.
Background technology
Succsinic acid, claim again succinic acid, is a kind of common natural organic acids, extensively is present in human body, animal, plant and microorganism.Molecular formula is C
4H
6O
4, molecular weight is 118.09, is shaped as colourless anorthic crystal or monoclinic crystal, and is flammable, density is 1.572g/cm
3(25 ℃), 188 ℃ of fusing points, 235 ℃ of boiling points, water-soluble, ethanol and ether, be insoluble to dithiocarbonic anhydride and tetracol phenixin.The natural origin of succinic acid is that the resin of pine genus plant is embedded in the underground amber that forms etc. for a long time.
The production method of succinic acid is mainly biological fermentation process, cis-butenedioic anhydride electroreduction method and chemical process.Chemical method mainly contains the maleic anhydride hydrogenation hydrolysis method; Paraffin oxidation style; The light oil oxidation style; The butane oxidation method; The succinonitrile hydrolysis method; Ethene bromination, cyaniding, hydrolysis method; Butadiene oxidation, hydrogenation, hydrolysis method; Benzene oxidation, hydrogenation, hydrolysis method; The hydrocarbon oxidation method; Toxilic acid shortening method and the electrolytic oxidation take ethene and carbon monoxide as raw material.
In the maleic anhydride hydrogenation hydrolysis prepared the technique of succinic acid, it was the first workshop section that maleic anhydride hydrogenation prepares Succinic anhydried, and it is the second workshop section that Succinic anhydried is hydrolyzed to succinic acid.
The maleic anhydride hydrogenation reaction is divided into two kinds in the first workshop section, and a kind of is the scorification shortening, and a kind of is to use the dissolution with solvents cis-butenedioic anhydride, and catalyst system carries out liquid-phase hydrogenatin to cis-butenedioic anhydride solution.Scorification hydrogen addition technology key is in the control of catalyst performance and reaction conditions.And solvent method hydrogen addition technology key is the catalyst system that the solvent of selecting and catalyzer form, solvent method production adopts aceticanhydride to make solvent usually, and also available tetrahydrofuran (THF), glycol dimethyl ether, aromatic hydrocarbons, four-carbon dicarboxylic acid ester, ethyl acetate, propyl propionate, ethyl propionate etc. are as solvent.The effect of solvent is to dissolve cis-butenedioic anhydride on the one hand; Be to have guaranteed that cis-butenedioic anhydride after hydrogenation generates succinyl oxide, leaves the active centre of catalyzer immediately on the other hand, improve hydrogenation and generate the selectivity of succinyl oxide; Solvent add the reaction conditions that has also greatly relaxed maleic anhydride hydrogenation.
Chinese patent CN03122336.2 " a kind of catalyzer of maleic anhydride hydrogenation produce succinic acid acid anhydride and preparation and application " has set forth uses nickel and prepares the technique of succinyl oxide as the active ingredient heterogeneous catalytic hydrogenation.The mol ratio of its catalyst activity component nickel and carrier is Ni: SiO
2: Al
2O
3=1: (1.47-5.98): (0-3.3), can maleic anhydride hydrogenation be produced succinyl oxide carry out catalysis having under solvent and solvent-free condition.The reduction temperature of catalyzer is 400 ℃-580 ℃, and reaction conditions is that temperature of reaction is 120 ℃-180 ℃, and the reaction times is 1h-3h, and the mol ratio of nickel, cis-butenedioic anhydride is 0.30-1.6: 100, and hydrogen pressure is 0.5MPa-3MPa.This catalyzer is take Ni as active ingredient, SiO
2, Al
2O
3For carrier, catalyzer contains acid sites, and when cis-butenedioic anhydride carries out hydrogenation reaction, temperature of reaction is high, in the maleic anhydride hydrogenation reaction process, the cis-butenedioic anhydride polyreaction can occur, and makes product colourity high, and under strong acidic environment the life-span of catalyzer greatly reduce.
Chinese patent CN200510012808.2 " Succinic anhydried and preparation method thereof " has set forth a kind of technique of a standby succinyl oxide of step Hydrogenation of cis-butenedioic anhydride being carried out with alloy catalyst.This technique is take purified petroleum benzin as solvent, and alloy powder is catalyzer, and hydrogen pressure is 0.2MPa-0.8MPa, and temperature of reaction is 30 ℃～100 ℃.Reaction process is waterless operation.This reaction process uses purified petroleum benzin to be solvent, be only applicable to the autoclave rhythmic reaction, and need the strict maleic anhydride hydrogenation reaction heating curve of controlling, to guarantee the selectivity of Succinic anhydried, in reaction process, the inevitable cis-butenedioic anhydride deep hydrogenation that occurs reacts the elective reduction that causes the purpose product, because purified petroleum benzin is lower to the solubleness of Succinic anhydried, be 80 ℃～85 ℃ dischargings.Rectification under vacuum to be carried out after product discharge, nitrogen will be led in rectifying.This processing method complicated operation, have waste residue to produce during rectifying, need to clean with pure water when catalyzer is reused, and produces waste water and purified petroleum benzin poisonous.
Chinese patent 95109162.X " manufacture method of succinyl oxide " has set forth a kind ofly uses I family and VIII family element as the hydrogenation activity component, and has the method for a step hydrogenation maleic anhydride production Succinic anhydried with the form of metal-powder or carried catalyst.Temperature of reaction is 120 ℃～150 ℃, and hydrogen pressure is 10bar～150bar, and the method is only applicable to periodical operation.
US Patent No. 5952514 " technique for preparing succinyl oxide " has been described the direct liquid-phase hydrogenatin of a kind of cis-butenedioic anhydride and has been prepared the method for succinyl oxide.It is the active ingredient of catalyzer that the method adopts the VIII metallic element, and mixes with IV family, group Ⅴ element or form alloy to strengthen the physical strength of catalyzer.Specific surface area is 20～100m
2/ g, physical strength is 20～220N.At fixing bed reaction, temperature of reaction is 60 ℃～180 ℃, and reaction pressure is 10bar～400bar.The catalyzer of mentioning in the method is to contain one or more of element in Ni/Zr/Al/V/Si, owing to containing Zr/Al/Si in catalyzer, so work-ing life of catalyzer and to the pollution of environment, can not being guaranteed.In embodiment, temperature of reaction is 120 ℃, and product also will pass through rectification under vacuum, so the colourity of product is high, production energy consumption is large, and has the strongly-acid waste discharge in the treating process of Succinic anhydried, to environment, can cause disadvantageous effect.
US Patent No. 5616730 " is produced the technique of succinyl oxide " and has been set forth the method that succinyl oxide is produced in the direct liquid-phase hydrogenatin of a kind of cis-butenedioic anhydride.The cis-butenedioic anhydride that contains 5%～100% weight fraction in raw material, 95%～0% Succinic anhydried.Adopt Raney's nickel or platinum group metal catalysts, temperature of reaction is at 120 ℃～150 ℃, and hydrogen pressure is at 10bar～150bar.This technique, take Succinic anhydried as solvent, is only applicable to the autoclave rhythmic reaction, and needs the strict maleic anhydride hydrogenation reaction heating curve of controlling, and to guarantee the selectivity of Succinic anhydried, product is in the molten state bottom discharge.The product colourity that the method is produced Succinic anhydried is high, and in the molten state bottom discharge, so the dangerous property of the operation of reaction process, product needed is through decolouring, purification processes due to product, and energy consumption is high.
Mostly there is temperature of reaction in prior art and pressure is higher, temperature of reaction is restive, easily produce that waste liquor contamination is large, processing condition are unsuitable for one or more deficiencies in continuous production, complex process, poor product quality etc. in product and separated from solvent difficulty, production process.
Summary of the invention
For the deficiencies in the prior art, the invention provides the method that succinic acid is produced in the hydrolysis of a kind of maleic anhydride hydrogenation, the inventive method reaction conditions gentleness is controlled, flexible operation, product is easy to separate and quality is good.
The method that succinic acid is produced in a kind of maleic anhydride hydrogenation hydrolysis of the present invention, comprise following content: the cis-butenedioic anhydride gamma-butyrolactone solution take weight percentage as 5%～90% (wt) is as raw material, be that 50-100 ℃, pressure are to carry out hydrogenation reaction under the existence of 0.2-2MPa and hydrogenation catalyst in temperature of reaction, hydrogenation products makes succinic acid after hydrolysis and Crystallization Separation.
In the inventive method in cis-butenedioic anhydride gamma-butyrolactone solution the weight percentage of cis-butenedioic anhydride be 10%-80%, temperature of reaction is 60-90 ℃, reaction pressure is 0.5-1.5MPa.
The inventive method can tank reactor discontinuous operation, also can operate continuously on fixed-bed reactor, preferably operate continuously on fixed-bed reactor.On fixed-bed reactor, the condition of operate continuously is as follows: temperature of reaction is 50-100 ℃, preferred 60-90 ℃, and reaction pressure is 0.2-2.0MPa, preferred 0.5-1.5MPa, during reaction solution, volume space velocity is 0.5h
-1～3.0h
-1, the mol ratio of hydrogen and cis-butenedioic anhydride is 30～500.The condition of tank reactor discontinuous operation is as follows: temperature of reaction is 50-100 ℃, preferred 60-90 ℃, and reaction pressure is 0.2-2.0MPa, preferred 0.5-1.5MPa, the weight percent of hydrogenation catalyst and cis-butenedioic anhydride is 1%～5%.
The described hydrogenation catalyst of the inventive method is take palladium as active ingredient, with gac, SiO
2, TiO
2Or BaSO
4Load hydrogenation catalyst for carrier; This hydrogenation catalyst can also contain metal promoter, and described metal promoter is one or more in Co, Mo, Ni, Wu, Cu, Fe, Zn; Hydrogenation catalyst can adopt commercially available commercial catalyst, also can make by oneself by prior art, and preferably take gac after modification as carrier, the hydrogenation catalyst of load active component palladium and metal promoter iron or copper.
The method of above-mentioned modified activated carbon is for adopting the organic compounds containing nitrogen solution impregnation to process, organic compounds containing nitrogen can be one or more that are selected from diethylamine, thanomin, diethanolamine, trolamine and pyridine etc., organic compounds containing nitrogen solution generally can adopt the aqueous solution or organic solution, preferred aqueous solutions, organic solution adopts the organic solvent that can dissolve nitrogenous compound used, as ethanol, acetone etc.In organic compounds containing nitrogen solution, the weight concentration of organic compounds containing nitrogen is 1%-35%.Dipping can adopt saturated dipping or supersaturation dipping, carries out drying after dipping, also can proceed calcination process.The dip treating temperature is 50-95 ℃, and the dip treating time is 2-150h.Drying temperature is 50-150 ℃, and be 0.5-36h time of drying, and roasting is at 280-600 ℃ of lower vacuum baking 2-15 hour.
Hydrogenation catalyst described in the inventive method can adopt method well known to those skilled in the art to be prepared.As adopt following process: adopt the absorbent charcoal carrier after the salt solution impregnation modification that contains active metal component Pd and metal promoter, can comprise drying step and calcination steps after dipping.Drying step is dry 8-24 hour under 50-150 ℃, and calcination steps is at 280-600 ℃ of lower roasting 2-10 hour.In the catalyzer of preparation, the weight percentage of Pd is 1%-10%, and the weight percentage of metal promoter is 1%-4%.
In the inventive method, the hydrogenation products hydrolysis temperature is 60 ℃～80 ℃, and the Crystallization Separation temperature is-30 ℃～10 ℃.
The method that succinic acid is produced in maleic anhydride hydrogenation hydrolysis of the present invention compared with prior art has following advantage:
1, the inventive method reaction conditions is gentle, the hydrogenation reaction temperature is no more than 100 ℃, reaction pressure and only is 0.2-2MPa, can produce Succinic anhydried under the condition of low-temp low-pressure, Succinic anhydried makes highly purified succinic acid after hydrolysis and Crystallization Separation, the transformation efficiency of cis-butenedioic anhydride raw material can reach 100%, and the selectivity of purpose product is high;
2, the inventive method employing gamma-butyrolactone is solvent, utilize gamma-butyrolactone to cis-butenedioic anhydride and Succinic anhydried solvency action preferably, increase the content of dissolved hydrogen in reaction soln, utilize simultaneously its solvency action to Succinic anhydried, the Succinic anhydried that promotes reaction to generate dissociates from catalyst surface, is beneficial to reactive material and carries out external diffusion and internal diffusion on the surface of catalyzer.Because gamma-butyrolactone is non-polar solvent, and Succinic anhydried there is solvency action preferably, greatly reduce the acidity of maleic anhydride hydrogenation environment, make catalyst surface not have the Succinic anhydried crystallization to generate, guaranteed the cis-butenedioic anhydride transformation efficiency of catalyzer and the selectivity of Succinic anhydried, guaranteeing in the maleic anhydride hydrogenation reaction process does not have the cis-butenedioic anhydride polyreaction to occur, and makes product colourity low, and the work-ing life that has effectively strengthened catalyzer, reduced the requirement of maleic anhydride hydrogenation reaction to reactor material;
3, the inventive method is not only applicable in the operation of tank reactor discontinuous, is more suitable for operate continuously on fixed-bed reactor, can utilize the waste heat of product during the hydrogenation products hydrolysis, solvent is gamma-butyrolactone with byproduct of reaction and is convenient to separating of product, gamma-butyrolactone is to Succinic anhydried dissolving power preferably, make reaction product be liquid phase, can avoid pipeline is carried out laser heating, therefore, the inventive method has flexible operation, technical process is simple, energy consumption is low, pollutes the advantages such as few;
4, the inventive method is under suitable reaction conditions and under the synergy of catalysts and solvents, and the yield of succinic acid can reach more than 95%.
Embodiment
Further illustrate the inventive method and effect below by embodiment, wherein embodiment 4,5 support of the catalyst gac respectively through the diethylamine aqueous solution of weight concentration 15% and 25% and the diethanolamine aqueous solution 60 ℃, 80 ℃ supersaturation dippings 20 hours and 100 hours, after drying respectively 350 ℃ and 450 ℃ of vacuum bakings 8 hours and 3 hours.
Embodiment 1
Be 25mm at internal diameter, high for filling 20mlPd/Cu/C (weight content of Pd in catalyzer is 5%, the weight content of Cu be 3%) catalyzer on the continuous fixed-bed reactor of 1.2m, catalyzer is with 3 times of quartz sand dilutions.Prepare MA/GBL (cis-butenedioic anhydride/gamma-butyrolactone) solution of 15% mass concentration, with pump, squeeze in reactor.Reaction conditions is: 75 ℃ of temperature of reaction, hydrogen dividing potential drop 1.0MPa, hydrogen/cis-butenedioic anhydride mol ratio 100, LHSV2.0h
-1(in the liquid of cis-butenedioic anhydride gamma-butyrolactone solution time volume space velocity), successive reaction 300h, the MA transformation efficiency is 100%, SA (Succinic anhydried) selectivity 96.6% by analysis, GBL selectivity 3.4%.Product adds 30g water to be hydrolyzed under 80 ℃, then obtains white crystals succinic acid product after-10 ℃ of Crystallization Separation, and the succinic acid yield is 96.8%, purity 97.8%, and GBL recycles after separating water outlet.
Embodiment 2
Be 25mm at internal diameter, high for filling 20mlPd/Cu/C (the Pd weight content is 10%, the weight content of Cu be 1%) catalyzer on the continuous fixed-bed reactor of 1.2m, catalyzer is with 3 times of quartz sand dilutions.Prepare the MA/GBL solution of 75% mass concentration, with pump, squeeze in reactor.Reaction conditions is: 90 ℃ of temperature of reaction, hydrogen dividing potential drop 1.0MPa, hydrogen/cis-butenedioic anhydride mol ratio 300, LHSV1.0h
-1, successive reaction 300h, the MA transformation efficiency is 100%, SA selectivity 97.6% by analysis, GBL selectivity 2.4%.Product adds 30g water to be hydrolyzed under 80 ℃, then obtains white crystals succinic acid product after-10 ℃ of Crystallization Separation, and the succinic acid yield is 96.2%, purity 97.6%, and GBL recycles after separating water outlet.
Embodiment 3
Be 25mm at internal diameter, high for filling 20mlPd/Fe/C (the Pd weight content is 4%, the weight content of Fe be 3%) catalyzer on the continuous fixed-bed reactor of 1.2m, catalyzer is with 3 times of quartz sand dilutions.Prepare the MA/GBL solution of 50% mass concentration, with pump, squeeze in reactor.Reaction conditions is: 65 ℃ of temperature of reaction, hydrogen dividing potential drop 1.5MPa, hydrogen/cis-butenedioic anhydride mol ratio 400, LHSV1.0h
-1, successive reaction 300h, the MA transformation efficiency is 100%, SA selectivity 98.1% by analysis, GBL selectivity 1.9%.Product adds 30g water to be hydrolyzed under 80 ℃, then obtains white crystals succinic acid product after-10 ℃ of Crystallization Separation, and the succinic acid yield is 97.6%, purity 98.8%, and GBL recycles after separating water outlet.
Embodiment 4
Be 25mm at internal diameter, high for filling 20mlPd/Fe/C (the Pd weight content is 5%, the weight content of Fe be 2%) catalyzer on the continuous fixed-bed reactor of 1.2m, catalyzer is with 3 times of quartz sand dilutions.Prepare the MA/GBL solution of 40% mass concentration, with pump, squeeze in reactor.Reaction conditions is: 70 ℃ of temperature of reaction, hydrogen dividing potential drop 1.5MPa, hydrogen/cis-butenedioic anhydride mol ratio 400, LHSV1.0h
-1, successive reaction 300h, the MA transformation efficiency is 100%, SA selectivity 99.2% by analysis, GBL selectivity 0.8%.Product adds 30g water to be hydrolyzed under 80 ℃, and then obtains white crystals succinic acid product after-10 ℃ of Crystallization Separation, and the succinic acid yield is 97.8%, purity 98.6%, and GBL recycles after separating water outlet.
Embodiment 5
The catalyzer room temperature of 100gMA, 200gGBL, 4gPd/Fe/C (the Pd weight content is 8%, the weight content of Fe be 4%) is transferred in the 2L autoclave,, with 3.0MPa hydrogen exchange air 3 times, determined hydrogen pressure 1.0MPa after sealing.Start reaction after autoclave is warming up to 70 ℃, in reaction process, hydrogen pressure is namely mended hydrogen pressure to 1.0MPa lower than 0.3MPa, discharging after reaction 120min, and the MA transformation efficiency is 100%, SA selectivity 99.4% by analysis, GBL selectivity 0.6%.Product adds 30g water to be hydrolyzed under 80 ℃, then obtains white crystals succinic acid product after-10 ℃ of Crystallization Separation, and the succinic acid yield is 97.9%, purity 99.2%, and GBL recycles after separating water outlet.
Embodiment 6
The commercial catalyst of 100gMA (cis-butenedioic anhydride), 200gGBL (gamma-butyrolactone), 4gPd/C (the Pd weight content is 5%) is at room temperature put into the 2L autoclave, use 3.0MPa hydrogen exchange air 3 times after sealing, determine hydrogen pressure 1.0MPa.Start reaction after autoclave is warming up to 70 ℃, in reaction process, hydrogen pressure is namely mended hydrogen pressure to 1.0MPa lower than 0.3MPa, discharging after reaction 120min, and the cis-butenedioic anhydride transformation efficiency is 100%, SA (Succinic anhydried) selectivity 91.2% by analysis, GBL selectivity 8.8%.Product adds 30g water to be hydrolyzed under 80 ℃, then obtains white crystals succinic acid product after-10 ℃ of Crystallization Separation, and the succinic acid yield is 87.9%, purity 97.5%, and GBL recycles after separating water outlet.
Claims (9)
1. method of producing succinic acid, it is characterized in that comprising following content: the cis-butenedioic anhydride gamma-butyrolactone solution take weight percentage as 5%～90% is as raw material, be 50-100 ℃ in temperature of reaction, pressure is to carry out hydrogenation reaction under the existence of 0.2-2MPa and hydrogenation catalyst, hydrogenation products makes succinic acid after hydrolysis and Crystallization Separation, described hydrogenation catalyst is take gac as carrier, take Pd as active ingredient, with Cu, one or more in Fe are auxiliary agent, press the weighing scale of catalyzer, the weight percentage of Pd is 1%-10%, the weight percentage of metal promoter is 1%-4%.
2. in accordance with the method for claim 1, it is characterized in that: in described cis-butenedioic anhydride gamma-butyrolactone solution, the weight percentage of cis-butenedioic anhydride is 10%-80%, and temperature of reaction is 60-90 ℃, and reaction pressure is 0.5-1.5MPa.
3. it is characterized in that in accordance with the method for claim 1: hydrogenation reaction is in the operation of tank reactor discontinuous or operate continuously on fixed-bed reactor.
4., according to the described method of claim 1 or 3, it is characterized in that: the condition of tank reactor discontinuous operation is as follows: temperature of reaction is 50-100 ℃, and reaction pressure is 0.2-2.0MPa, and in hydrogenation catalyst and raw material, the weight percent of cis-butenedioic anhydride is 1%～5%.
5. in accordance with the method for claim 4, it is characterized in that: the condition of tank reactor discontinuous operation is as follows: temperature of reaction is 60-90 ℃, and reaction pressure is 0.5-1.5MPa.
6., according to the described method of claim 1 or 3, it is characterized in that: on fixed-bed reactor, the condition of operate continuously is as follows: temperature of reaction is 50-100 ℃, and reaction pressure is 0.2-2.0MPa, and during reaction solution, volume space velocity is 0.5h
-1～3.0h
-1, the mol ratio of hydrogen and cis-butenedioic anhydride is 30～500.
7. in accordance with the method for claim 6, it is characterized in that: on fixed-bed reactor, the condition of operate continuously is as follows: temperature of reaction is 60-90 ℃, and reaction pressure is 0.5-1.5MPa.
8. in accordance with the method for claim 1, it is characterized in that: described hydrogenation catalyst is take gac as carrier, and take iron or copper as auxiliary agent, described absorbent charcoal carrier is through the organic compounds containing nitrogen dip treating.
9. in accordance with the method for claim 1, it is characterized in that: the hydrogenation products hydrolysis temperature is 60 ℃～80 ℃, and the Crystallization Separation temperature is-30 ℃～10 ℃.
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| CN103007929B (en) * | 2012-12-07 | 2018-01-12 | 上海华谊（集团）公司 | The Pd bases catalyst of colloidal deposition method preparation, preparation method and application |
| CN104368358B (en) * | 2014-10-11 | 2017-06-06 | 中国科学院青岛生物能源与过程研究所 | It is a kind of suitable for the catalyst of butanedioic acid hydrogenation reaction and its preparation and process for selective hydrogenation |
| CN106669730B (en) * | 2015-11-09 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method thereof for cis-butenedioic anhydride liquid-phase hydrogenatin |
| CN105597742A (en) * | 2016-01-07 | 2016-05-25 | 上海华谊（集团）公司 | Catalyst and method of reaction for preparing butanedioic anhydride from maleic anhydride through liquid phase hydrogenation |
| CN112473709A (en) * | 2019-09-11 | 2021-03-12 | 王宏涛 | Catalyst for synthesizing succinic acid by aqueous phase catalytic hydrogenation and application thereof |
| CN112479862A (en) * | 2019-09-11 | 2021-03-12 | 王宏涛 | Low-cost method for synthesizing succinic acid by continuous aqueous phase catalytic hydrogenation |
| CN112717940B (en) * | 2019-10-28 | 2023-07-21 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone, and preparation method and application thereof |
| CN111689845B (en) * | 2020-03-18 | 2021-07-30 | 中国科学院山西煤炭化学研究所 | Process for producing succinic acid by maleic anhydride aqueous phase hydrogenation |
| CN115745772A (en) * | 2022-09-30 | 2023-03-07 | 云南大为恒远化工有限公司 | Method for producing succinic acid by esterification and hydrogenation of maleic anhydride |
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