CN102311332A - Method for producing succinic acid - Google Patents
Method for producing succinic acid Download PDFInfo
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- CN102311332A CN102311332A CN2010102212196A CN201010221219A CN102311332A CN 102311332 A CN102311332 A CN 102311332A CN 2010102212196 A CN2010102212196 A CN 2010102212196A CN 201010221219 A CN201010221219 A CN 201010221219A CN 102311332 A CN102311332 A CN 102311332A
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- butenedioic anhydride
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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 the method that Succinic Acid is produced in a kind of maleic anhydride hydrogenation hydrolysis.
Background technology
Succsinic acid is claimed Succinic Acid again, is a kind of common natural organic acids, extensively is present in human body, animal, plant and the mikrobe.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 are 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 working 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 be the electrolytic oxidation of raw material with ethene and carbon monoxide.
Prepare in the technology of Succinic Acid in the maleic anhydride hydrogenation hydrolysis, it is first workshop section that maleic anhydride hydrogenation prepares Succinic anhydried, and it is second workshop section that Succinic anhydried is hydrolyzed to Succinic Acid.
The maleic anhydride hydrogenation reaction is divided into two kinds in 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 catalystsystem 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 the catalystsystem that solvent that solvent method hydrogen addition technology key is to select and catalyzer form; Solvent method production adopts aceticanhydride to make solvent usually, and also available THF, glycol dimethyl ether, aromatic hydrocarbons, four-carbon dicarboxylic acid ester, ETHYLE ACETATE, propyl propionate, ethyl propionate etc. are as solvent.The effect of solvent is to be used for dissolving cis-butenedioic anhydride on the one hand; Be to have guaranteed that cis-butenedioic anhydride after hydrogenation generates succinyl oxide, leaves the activity of such catalysts center immediately on the other hand, improve the selectivity that hydrogenation generates succinyl oxide; The adding of solvent has also relaxed the reaction conditions of maleic anhydride hydrogenation greatly.
Chinese patent CN03122336.2 " a kind of catalyzer of maleic anhydride hydrogenation produce succinic acid acid anhydride and preparation and application " has set forth the technology for preparing succinyl oxide with nickel 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 produced succinyl oxide carry out catalysis having under solvent and the 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 active ingredient with Ni, SiO
2, Al
2O
3Be carrier, catalyzer contains acid sites, and temperature of reaction was high when cis-butenedioic anhydride carried out hydrogenation reaction, in the maleic anhydride hydrogenation reaction process cis-butenedioic anhydride polyreaction can take place, and make product colourity high, and life of catalyst reduces greatly under the strong acidic environment.
Chinese patent CN200510012808.2 " Succinic anhydried and preparation method thereof " has set forth a kind of technology of cis-butenedioic anhydride being carried out a step hydrogenation preparing succinyl oxide with alloy catalyst.This technology is solvent with the purified petroleum benzin, and alloy powder is a catalyzer, and hydrogen pressure is 0.2MPa-0.8MPa, and temperature of reaction is 30 ℃～100 ℃.Reaction process is a waterless operation.This reaction process uses purified petroleum benzin to be solvent; Only be applicable to still formula rhythmic reaction; And need the strict maleic anhydride hydrogenation of controlling to react heating curve, to guarantee the selectivity of Succinic anhydried, the inevitable cis-butenedioic anhydride deep hydrogenation that takes place reacts the selectivity reduction that causes the purpose product in the reaction process; Because purified petroleum benzin is lower to the solubleness of Succinic anhydried, be 80 ℃～85 ℃ dischargings.Rectification under vacuum to be carried out after the product discharging, nitrogen will be led in the rectifying.This process method complicated operation has waste residue to produce during rectifying, need clean with pure water when catalyzer is reused, and it is poisonous to produce waste water and purified petroleum benzin.
Chinese patent 95109162.X " method of manufacture of succinyl oxide " set forth a kind of with I family and VIII family element as the hydrogenation activity component, and have the method that a step hydrogenation cis-butenedioic anhydride is produced Succinic anhydried with the form of metal-powder or carried catalyst.Temperature of reaction is 120 ℃～150 ℃, and hydrogen pressure is 10bar～150bar, and this method only is applicable to periodical operation.
U.S. Pat 5952514 " technology of preparation succinyl oxide " has been described the method that the direct liquid-phase hydrogenatin of a kind of cis-butenedioic anhydride prepares succinyl oxide.It is the activity of such catalysts component that this method adopts the VIII metallic element, and mixes with IV family, group 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 this method is to contain one or more of element among the Ni/Zr/Al/V/Si, owing to contain Zr/Al/Si in the catalyzer, so work-ing life of catalyzer and can not be guaranteed to the pollution of environment.Temperature of reaction is 120 ℃ among the embodiment, and product also will pass through rectification under vacuum, so the colourity of product is high, production energy consumption is big, and in the treating process of Succinic anhydried, has the strongly-acid waste discharge, can cause disadvantageous effect to environment.
U.S. Pat 5616730 " is produced the technology 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 the 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 technology is solvent with the Succinic anhydried, only is applicable to still formula rhythmic reaction, and needs strict control maleic anhydride hydrogenation reaction heating curve, and to guarantee the selectivity of Succinic anhydried, product is in the molten state bottom discharge.The product colourity that this method is produced Succinic anhydried is high, because product is in the molten state bottom discharge, so the dangerous property of the operation of reaction process, product needed is through decolouring, purification processes, and energy consumption is high.
Mostly there is temperature of reaction in the prior art and pressure is higher, temperature of reaction is restive, be easy to generate that waste liquor contamination is big, processing condition are inappropriate for a kind of or several the kinds deficiencies in continuous production, complex process, the poor product quality etc. in product and the separated from solvent difficulty, production process.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of maleic anhydride hydrogenation hydrolysis to produce the method for Succinic Acid, and 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: with weight percentage is that the cis-butenedioic anhydride gamma-butyrolactone solution of 5%～90% (wt) is raw material; Temperature of reaction be 50-100 ℃, pressure be 0.2-2MPa and hydrogenation catalyst in the presence of carry out hydrogenation reaction, hydrogenation products makes Succinic Acid after hydrolysis and Crystallization Separation.
In the inventive method in the cis-butenedioic anhydride gamma-butyrolactone solution 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.The condition of operate continuously is following on the fixed-bed reactor: temperature of reaction is 50-100 ℃, and preferred 60-90 ℃, reaction pressure is 0.2-2.0MPa, preferred 0.5-1.5MPa, and volume space velocity is 0.5h during reaction solution
-1～3.0h
-1, the mol ratio of hydrogen and cis-butenedioic anhydride is 30～500.The condition of tank reactor discontinuous operation is following: temperature of reaction is 50-100 ℃, and preferred 60-90 ℃, reaction pressure is 0.2-2.0MPa, preferred 0.5-1.5MPa, and the weight percent of hydrogenation catalyst and cis-butenedioic anhydride is 1%～5%.
The described hydrogenation catalyst of the inventive method is active ingredient with the palladium, 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 among Co, Mo, Ni, Wu, Cu, Fe, the Zn; Hydrogenation catalyst can adopt commercially available commercial catalyst, also can make by oneself by prior art, and be carrier preferably with gac after the modification, the hydrogenation catalyst of load active component palladium and metal promoter iron or copper.
The method of above-mentioned modified activated carbon is handled for adopting the organic compounds containing nitrogen solution impregnation; Organic compounds containing nitrogen can be to be selected from diethylamine, thanomin, diethylolamine, trolamine and the pyridine etc. one or more; 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 used nitrogenous compound, like ethanol, acetone etc.The weight concentration of organic compounds containing nitrogen is 1%-35% in the organic compounds containing nitrogen solution.Dipping can adopt saturated dipping or supersaturation dipping, carries out drying behind the 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 was at 280-600 ℃ of following vacuum baking 2-15 hour.
Hydrogenation catalyst described in the inventive method can adopt method well known to those skilled in the art to prepare.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 behind the dipping.Drying step descended dry 8-24 hour at 50-150 ℃, and calcination steps was at 280-600 ℃ of following roasting 2-10 hour.The weight percentage of Pd is 1%-10% in the catalyzer of preparation, and the weight percentage of metal promoter is 1%-4%.
The hydrogenation products hydrolysis temperature is 60 ℃～80 ℃ in the inventive method, 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 is merely 0.2-2MPa; Can under the condition of low-temp low-pressure, produce Succinic anhydried; Succinic anhydried makes highly purified Succinic Acid after hydrolysis and Crystallization Separation, the cis-butenedioic anhydride conversion of raw material can reach 100%, and the purpose product selectivity is high;
2, the inventive method employing gamma-butyrolactone is a solvent; Utilize gamma-butyrolactone to cis-butenedioic anhydride and Succinic anhydried solvency action preferably; Increase the content of dissolved hydrogen in the reaction soln; Utilize its solvency action to Succinic anhydried simultaneously, the Succinic anhydried that promotes reaction to generate dissociates from catalyst surface, is beneficial to RM and carries out external diffusion and internal diffusion on the surface of catalyzer.Because gamma-butyrolactone is a non-polar solvent, and Succinic anhydried is had solvency action preferably, greatly reduces 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, guaranteed not have in the maleic anhydride hydrogenation reaction process cis-butenedioic anhydride polyreaction to take place, made product colourity low; And the work-ing life that has effectively strengthened catalyzer, reduced the requirement of maleic anhydride hydrogenation reaction pair reactor material;
3, the inventive method is not only applicable in the operation of tank reactor discontinuous, more is applicable to that operate continuously on fixed-bed reactor, the waste heat of product capable of using during the hydrogenation products hydrolysis, solvent are gamma-butyrolactone with byproduct of reaction and are convenient to separating of product; Gamma-butyrolactone is to Succinic anhydried dissolving power preferably; Make reaction product be liquid phase, can avoid pipeline is heated continuously, therefore; The inventive method has flexible operation, technical process is simple, energy consumption is low, pollutes advantages such as few;
4, the inventive method is under the suitable reaction conditions and under the synergy of catalyzer and solvent, and the yield of Succinic Acid can reach more than 95%.
Embodiment
Further specify the inventive method and effect through embodiment below; Wherein the support of the catalyst gac of embodiment 4,5 respectively through weight concentration 15% and 25% diethylamine aqueous solution and the diethylolamine aqueous solution 60 ℃, 80 ℃ supersaturation dippings 20 hours and 100 hours, after the drying respectively 350 ℃ and 450 ℃ of vacuum bakings 8 hours and 3 hours.
Embodiment 1
At internal diameter is 25mm, and high for adorning 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 silica sand dilutions.Prepare MA/GBL (cis-butenedioic anhydride/gamma-butyrolactone) solution of 15% mass concentration, squeeze in the reactor drum with pump.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 is 100% through analyzing the MA transformation efficiency, SA (Succinic anhydried) selectivity 96.6%, GBL selectivity 3.4%.Product adds 30g water 80 ℃ of following hydrolysis, after-10 ℃ of Crystallization Separation, obtains white crystals Succinic Acid product then, and the Succinic Acid yield is 96.8%, purity 97.8%, and GBL recycles after separating water outlet.
Embodiment 2
At internal diameter is 25mm, and high for adorning 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 silica sand dilutions.Prepare the MA/GBL solution of 75% mass concentration, squeeze in the reactor drum with pump.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 is 100% through analyzing the MA transformation efficiency, SA selectivity 97.6%, GBL selectivity 2.4%.Product adds 30g water 80 ℃ of following hydrolysis, after-10 ℃ of Crystallization Separation, obtains white crystals Succinic Acid product then, and the Succinic Acid yield is 96.2%, purity 97.6%, and GBL recycles after separating water outlet.
Embodiment 3
At internal diameter is 25mm, and high for adorning 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 silica sand dilutions.Prepare the MA/GBL solution of 50% mass concentration, squeeze in the reactor drum with pump.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 is 100% through analyzing the MA transformation efficiency, SA selectivity 98.1%, GBL selectivity 1.9%.Product adds 30g water 80 ℃ of following hydrolysis, after-10 ℃ of Crystallization Separation, obtains white crystals Succinic Acid product then, and the Succinic Acid yield is 97.6%, purity 98.8%, and GBL recycles after separating water outlet.
Embodiment 4
At internal diameter is 25mm, and high for adorning 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 silica sand dilutions.Prepare the MA/GBL solution of 40% mass concentration, squeeze in the reactor drum with pump.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 is 100% through analyzing the MA transformation efficiency, SA selectivity 99.2%, GBL selectivity 0.8%.Product adds 30g water 80 ℃ of following hydrolysis, 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, and hydrogen pressure 1.0MPa is decided with 3.0MPa hydrogen exchange air 3 times in the sealing back.Begin reaction after autoclave is warming up to 70 ℃, hydrogen pressure is lower than 0.3MPa and promptly mends hydrogen pressure to 1.0MPa in the reaction process, and discharging behind the reaction 120min is 100% through analyzing the MA transformation efficiency, SA selectivity 99.4%, GBL selectivity 0.6%.Product adds 30g water 80 ℃ of following hydrolysis, after-10 ℃ of Crystallization Separation, obtains white crystals Succinic Acid product then, 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, and hydrogen pressure 1.0MPa is decided with 3.0MPa hydrogen exchange air 3 times in sealing back.Begin reaction after autoclave is warming up to 70 ℃, hydrogen pressure is lower than 0.3MPa and promptly mends hydrogen pressure to 1.0MPa in the reaction process, and discharging behind the reaction 120min is 100% through analyzing the cis-butenedioic anhydride transformation efficiency, SA (Succinic anhydried) selectivity 91.2%, GBL selectivity 8.8%.Product adds 30g water 80 ℃ of following hydrolysis, after-10 ℃ of Crystallization Separation, obtains white crystals Succinic Acid product then, and the Succinic Acid yield is 87.9%, purity 97.5%, and GBL recycles after separating water outlet.
Claims (10)
1. method of producing Succinic Acid; It is characterized in that comprising following content: with weight percentage is that 5%～90% cis-butenedioic anhydride gamma-butyrolactone solution is raw material; Temperature of reaction be 50-100 ℃, pressure be 0.2-2MPa and hydrogenation catalyst in the presence of carry out hydrogenation reaction, hydrogenation products makes Succinic Acid after hydrolysis and Crystallization Separation.
2. according to the described method of claim 1, it is characterized in that: the weight percentage of cis-butenedioic anhydride is 10%-80% in the described cis-butenedioic anhydride gamma-butyrolactone solution, and temperature of reaction is 60-90 ℃, and reaction pressure is 0.5-1.5MPa.
3. according to the described method of claim 1, it is characterized in that: hydrogenation reaction is in operation of tank reactor discontinuous or operate continuously on fixed-bed reactor.
4. according to claim 1 or 3 described methods, it is characterized in that: the condition of tank reactor discontinuous operation is following: temperature of reaction is 50-100 ℃, and reaction pressure is 0.2-2.0MPa, and the weight percent of cis-butenedioic anhydride is 1%～5% in hydrogenation catalyst and the raw material.
5. according to the described method of claim 4, it is characterized in that: the condition of tank reactor discontinuous operation is following: temperature of reaction is 60-90 ℃, and reaction pressure is 0.5-1.5MPa.
6. according to claim 1 or 3 described methods, it is characterized in that: the condition of operate continuously is following on the fixed-bed reactor: temperature of reaction is 50-100 ℃, and reaction pressure is 0.2-2.0MPa, and volume space velocity is 0.5h during reaction solution
-1～3.0h
-1, the mol ratio of hydrogen and cis-butenedioic anhydride is 30～500.
7. according to the described method of claim 6, it is characterized in that: the condition of operate continuously is following on the fixed-bed reactor: temperature of reaction is 60-90 ℃, and reaction pressure is 0.5-1.5MPa.
8. according to the described method of claim 1, it is characterized in that: described hydrogenation catalyst is with gac, SiO
2, TiO
2Or BaSO
4Being carrier, is active ingredient with Pd, is auxiliary agent with among Co, Mo, Ni, Wu, Cu, Fe, the Zn one or more, and by the weight of catalyzer, the weight percentage of Pd is 1%-10%, and the weight percentage of metal promoter is 1%-4%.
9. according to the described method of claim 8, it is characterized in that: described hydrogenation catalyst is carrier with the gac, is auxiliary agent with iron or copper, and described absorbent charcoal carrier is through the organic compounds containing nitrogen dip treating.
10. according to the described method of 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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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007929A (en) * | 2012-12-07 | 2013-04-03 | 上海华谊（集团）公司 | Pd-based catalyst prepared through colloid deposition, preparation method and application |
| CN104368358A (en) * | 2014-10-11 | 2015-02-25 | 中国科学院青岛生物能源与过程研究所 | Catalyst applicable to succinic acid hydrogenation reaction, and preparation method and hydrogenation reaction method thereof |
| 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 |
| CN106669730A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Catalyst for maleic anhydride liquid phase hydrogenation and preparation method thereof |
| CN111689845A (en) * | 2020-03-18 | 2020-09-22 | 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 |
| CN112479862A (en) * | 2019-09-11 | 2021-03-12 | 王宏涛 | Low-cost method for synthesizing succinic acid by continuous aqueous phase catalytic 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 |
| CN112717940A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone and preparation method and application thereof |
| 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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