CN102659724A - Preparation method of succinic anhydride - Google Patents
Preparation method of succinic anhydride Download PDFInfo
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- CN102659724A CN102659724A CN2012101071289A CN201210107128A CN102659724A CN 102659724 A CN102659724 A CN 102659724A CN 2012101071289 A CN2012101071289 A CN 2012101071289A CN 201210107128 A CN201210107128 A CN 201210107128A CN 102659724 A CN102659724 A CN 102659724A
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Abstract
The invention discloses a preparation method of succinic anhydride, comprising the following step of: performing liquid-phase hydrogenation reaction between maleic anhydride and hydrogen in the presence of a hydrogenation catalyst to obtain the succinic anhydride. The hydrogenation catalyst contains a carrier and an active component loaded on the carrier. The active component contains one or more elements selected from group IB, group IIB, group VIB, group VIIB and group VIIIB in the chemical element periodic table. The carrier contains oxides of one or more elements from group IA, group IIA, group IIIA, group IVA, group VA and group IVB in the chemical element periodic table and active carbon. The invention provides a method by which the hydrogenation catalyst is simple to synthesize, reaction condition is mild, the process is continuous and succinic anhydride is prepared with high yield.
Description
Technical field
The present invention relates to a kind of preparation method of succinyl oxide.
Background technology
Pharmaceutically, succinyl oxide can be used for producing sulfa drug, vitamin A, vitamins B
6, styptic and diuretic(s) or the like, with Oxacyclotetradecane,erythromycin deriv effect synthetic antibacterial drug; On agricultural, the reaction of succinyl oxide and unsymmetrical dimethyl hydrazine makes TMSDMA N dimethylamine base succinic diamide, is a kind of low toxicity, plant growth inhibitor efficiently, regulates nutrient, increases drought resisting, disease-resistant, freezing tolerance, widespread use in cash crop such as fruit and vegetable.In addition, succinyl oxide can also be used for food to be added, the food processing aid of GB2760-90 regulation wherein, and medicine, agricultural chemicals, ester class and resin synthetic also can be used for the synthetic analytical reagent that reaches of Succinic Acid.The market of tool development prospect is promptly as the main raw material of biodegradable plastic poly butylene succinate (PBS).
Produce at present succinyl oxide and mainly contain three kinds of technological lines: be i.e. succsinic acid evaporation, biological fermentation process and maleic anhydride hydrogenation method.The succsinic acid evaporation is to prepare succsinic acid earlier, again the succsinic acid dehydration is obtained succinyl oxide (abbreviation two step method).The method for making of Succinic Acid is that paraffin oxidation gets the mixed dibasic acid oxidized petroleum waves, through the overheated steam distillation, removes unstable hydroxyl oil-soluble acid and ester, and the water Succinic Acid is through dehydration, and oven dry obtains Succinic Acid; Shortcomings such as two step method produces that Succinic anhydried ubiquity operational path is long, operation is many, equipment and initial cost height, product cost are high, quality instability.The biological fermentation process technological line, the productive rate of its Succinic Acid is about 85%, exists production cycle length, complex procedures, fermentation waste water many, is difficult to the shortcoming of industrial mass production.Shortcomings such as the maleic anhydride hydrogenation method is divided into electrochemical reducing and the direct shortening method of cis-butenedioic anhydride, and electrochemical reducing is produced succinyl oxide, and to have current consumption big, and ionic membrane cracky, anode consumption are serious.Therefore the direct shortening method of cis-butenedioic anhydride is the good method of producing succinyl oxide at present.For this reason, raw catalyst and technology that the direct hydrogenation of exploitation cis-butenedioic anhydride is produced Succinic anhydried have reduced flow process, have reduced energy consumption.
One Chinese patent application CN1078716A has set forth following method: at 160～210 ℃, the hydrogen dividing potential drop is 1.2～2.0MPa, and the reaction times is 30～120min; The catalyst quality mark is 4%～10%, is that metal is as hydrogenation catalyst, under the batch reactor condition with nickel; Do not use solvent raw material direct heating to molten state; Carry out the direct shortening process of cis-butenedioic anhydride, the cis-butenedioic anhydride transformation efficiency is greater than 99%, succinyl oxide yield about 90%.One Chinese patent application CN101805318A discloses following method: in forerunner's alloy powder nickel, aluminium, added the third component, like Fe; Mn, Sn, the mixture of one or more among Mo and the Cr; Adopt under the quenching Raney nickel mild conditions, carry out the cis-butenedioic anhydride shortening and prepare succinyl oxide; This catalyzer has carried out partially modified to traditional skeleton nickel, in the catalyzer use, need utilize caustic soda to carry out dissolution of metals aluminium, produces more waste lye and discharges a large amount of hydrogen.One Chinese patent application CN1453066A discloses at catalyst n i/SiO
2-Al
2O
3Effect is used nickelous nitrate, tetraethoxy or tetraethoxy and aluminum nitrate, ethanol down, with the pH value generation gel of acetic acid, ammoniacal liquor or urea regulator solution; Roasting 400-550 ℃, reduce under the 400-580 ℃ of preparation condition, carry out maleic anhydride hydrogenation in the reaction kettle and prepare the succinyl oxide test.Owing to use teos hydrolysis to prepare SiO
2Carrier has significantly increased the Catalyst Production cost.US5616730 report is under skeleton nickel or platinum group catalyst, 120-150 ℃, hydrogen 1-15MPa condition, carry out cis-butenedioic anhydride liquid phase catalytic hydrogenation prepared in reaction succinyl oxide.In a word, above-mentioned reaction process is carried out maleic anhydride hydrogenation and is prepared succinyl oxide in batch reactor, obviously has shortcomings such as throughput is little, powder dress catalyzer and product separation difficulty, labor strength is big, environmental pollution is bigger.
U.S. Patent application US5770744 is under VIIIB catalyzer, 60-180 ℃, hydrogen 10-30MPa condition, fixed bed carries out cis-butenedioic anhydride liquid phase catalytic hydrogenation prepared in reaction succinyl oxide continuously; This reaction process pressure is higher, increases the device fabrication difficulty.In addition, Chinese patent CN101502802A, at active component nickel content 13-20%, promotor 1-7%, loaded catalyst, carrier are SiO
2, Al
2O
3Or SiO
2-Al
2O
3Under complex body and the fixed bed condition, carry out the cis-butenedioic anhydride continuous hydrogenation and prepare Succinic anhydried, succinyl oxide reaches about 98.8% yield.But being carrier, its deficiency need increase preparation catalyzer difficulty 400-800 ℃ of calcination process; After the catalyst reduction simultaneously, need perhaps in liquid, to protect, increased catalyzer and used difficulty and security through the oxygen Passivation Treatment.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of succinyl oxide.
The preparation method of a kind of succinyl oxide provided by the invention comprises the steps: that under the condition that hydrogenation catalyst exists MALEIC ANHYDRIDE and hydrogen promptly get said succinyl oxide through the liquid-phase hydrogenatin reaction;
Said hydrogenation catalyst comprises carrier and is carried on the active ingredient on this carrier; Said active ingredient is selected from one or more elements in IB family in the periodic table of chemical element, IIB family, group vib, VIIB and the VIIIB family, and said carrier is selected from the oxide compound and the gac of one or more elements in IA family in the periodic table of chemical element, IIA family, IIIA family, IVA family, VA and the IVB family.
Among the above-mentioned preparation method, in the said hydrogenation catalyst, the quality percentage composition of said active ingredient can be 0.1%～85%.
Among the above-mentioned preparation method, in the said hydrogenation catalyst, said active ingredient specifically can be in nickel, palladium, cobalt, rhenium, rhodium, iridium and the platinum at least a; Said carrier specifically can be in gac, aluminum oxide, zinc oxide, chromic oxide, silicon oxide, zirconium white and the titanium oxide at least a.
Among the above-mentioned preparation method, said hydrogenation catalyst can be sedimentation type catalyzer or immersion type carried catalyst.The sedimentation type catalyzer can prepare as follows: at first with said active ingredient from their salts solution, especially from their solution of nitrate salt and/or acetate, through adding basic metal and/or alkaline earth metal hydroxides solution and/or carbonate solution; For example oxyhydroxide, oxide hydrate, basic salt or the carbonate deposition as indissoluble comes out, and the throw out that obtains filters subsequently, washing and dry; And calcining, usually at 250～700 ℃, especially transfer corresponding oxide compound to 300～500 ℃ of calcinings; The oxide compound of mixed oxide and/or mixed valence; They, are especially handled for 100～400 ℃ usually at 50～700 ℃ through with hydrogen or hydrogenous gas; Be reduced into corresponding metal and/or than the oxide compound of suboxide valency, and change into the form of their real catalytic activity; Can select other suitable reductive agent for this reason, as: formaldehyde, hydrazine to replace hydrogen, have economic worth or hydrogen most certainly; Usually under certain reductive condition, be reacted to not consuming hydrogen, or the generation water yield does not become principle.Supported catalyst preparation: can adopt the said active ingredient of said carrier direct impregnation, perhaps from relevant salts solution, be precipitated out then more favourable simultaneously with carrier said active ingredient.
Among the above-mentioned preparation method, said hydrogenation catalyst can be made up of said carrier, the active ingredient and the auxiliary agent that are carried on this carrier; Said auxiliary agent can be selected from copper, barium, potassium, palladium and the tin at least a, and the quality percentage composition of said auxiliary agent can be 0.05%～2.5%, specifically can be 0.08% or 0.1%.
Among the above-mentioned preparation method; Said hydrogenation catalyst is a nickel-base hydrogenation catalyst, and said nickel-base hydrogenation catalyst is nickel/palladium/gac hydrogenation catalyst, nickel/aluminum oxide hydrogenation catalyst, palladium/nickel/aluminum oxide hydrogenation catalyst, copper/nickel/aluminum oxide hydrogenation catalyst, copper/nickel/aluminium oxide-titanium oxide hydrogenation catalyst, copper/nickel/aluminium oxide-zirconium oxide hydrogenation catalyst or copper/nickel/aluminum oxide-zinc oxide hydrogenation catalyst.
Among the above-mentioned preparation method, in the said nickel-base hydrogenation catalyst, the content of nickel is in nickel oxide, and the quality percentage composition of nickel oxide can be 12%～40%, specifically can be 15%, 18%, 20% or 25%.
Among the above-mentioned preparation method; The temperature of said liquid-phase hydrogenatin reaction can be 80～160 ℃; Specifically can be 85 ℃, 90 ℃, 95 ℃, 130 ℃, 140 ℃, 148 ℃, 150 ℃ or 155 ℃, pressure can be 2.5～4MPa, specifically can be 2.5MPa, 3MPa, 3.2MPa or 3.5MPa.
Among the above-mentioned preparation method, the liquid air speed of said liquid-phase hydrogenatin reaction can be 0.05hr
-1～0.3hr
-1, specifically can be 0.1hr
-1, 0.13hr
-1, 0.15hr
-1, 0.2hr
-1Or 0.25hr
-1, hydrogen can be (10～80) with the molfraction ratio of MALEIC ANHYDRIDE: 1, specifically can be 20: 1,40: 1,60: 1,65: 1,70: 1 or 80: 1.
Among the above-mentioned preparation method, said liquid-phase hydrogenatin reaction can be carried out in fixed-bed reactor or paste state bed reactor; From the come out crude product of heat of said fixed-bed reactor or paste state bed reactor, through being cooled to thick product, get final product sampling analysis, obtain its crude product and constitute, grasp the activity and the selectivity of catalyzed reaction.Crude product can be handled by traditional mode, through fractional distillation, removes by product, obtains specification product.
The invention provides that a kind of hydrogenation catalyst is synthetic simple, reaction conditions is gentle, process is continuous and high yield prepares the method for succinyl oxide.
Embodiment
Employed experimental technique is ordinary method like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
Among the embodiment below; The transformation efficiency of cis-butenedioic anhydride and the selectivity of succinyl oxide are all measured through the gc hydrogen flame detector, and concrete measuring method is: adopt capillary column 30m * 320um * 0.5um, DB-Waxetr; Post case condition; Initial temperature stopped 9 minutes for 30 ℃, was raised to 140 ℃ with 10 ℃/minute and stopped 4 minutes, was raised to 250 ℃ with 10 ℃/minute again; 260 ℃ of detectors, sample size 0.2ul.
The transformation efficiency of cis-butenedioic anhydride=100% * (the cis-butenedioic anhydride amount/initial cis-butenedioic anhydride amount of reaction has taken place);
The total amount that the cis-butenedioic anhydride amount that the selectivity of succinyl oxide=be converted into purpose product succinyl oxide is consumed/cis-butenedioic anhydride transforms.
Embodiment 1, preparation succinyl oxide
The fixed-bed reactor that indirect heating, flow control arranged (in the Φ 14 * 1000mm), 20～40 purpose 15g nickel-palladium/activated-carbon catalysts (NiO content 15%, Pd content 0.08%, gac 84.92%) of packing into; Method for making: take by weighing needed nickelous nitrate and palladium nitrate solution, mix, use the ammonia soln neutralization precipitation then with gac, throw out through filter, washing and dry, 480 ℃ of calcinings down under nitrogen, last fragmentation moulding of sieving promptly gets nickel-palladium/activated-carbon catalyst.
At 2.5MPa, liquid air speed 0.25hr
-1Under 20: 1 conditions of hydrogen acid anhydride mol ratio, when 85 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 92.5%, succinyl oxide selectivity 99.5%; When 130 ℃ of temperature of reaction, cis-butenedioic anhydride (MALEIC ANHYDRIDE) transformation efficiency 98.7%, succinyl oxide selectivity 99.1%; When 150 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 100%, succinyl oxide selectivity 98.5%.
Embodiment 2, preparation succinyl oxide
Press the same method of embodiment 1, in fixed-bed reactor, the 15g20 that packs into～40 purpose nickel/aluminium oxide catalyst (NiO content 20%, γ-Al
2O
380%); The preparation method: nickelous nitrate carries out the acidity allotment with ammoniacal liquor earlier, then required γ-Al
2O
3Carrier is poured into, and soaked carrier is 110 ℃ of dryings, 450 ℃ of roastings, last fragmentation moulding of sieving.
At 3.5MPa, liquid air speed 0.2hr
-1Under 40: 1 conditions of hydrogen acid anhydride mol ratio, when 90 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 85.5%, succinyl oxide selectivity 99.6%; During 140 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 100%, succinyl oxide selectivity 98.8%.
Embodiment 3, preparation succinyl oxide
Press the same method of embodiment 1, in fixed-bed reactor, the 15g20 that packs into～40 purpose nickel-palladium/aluminium oxide catalyst (NiO18%, Pd0.1%, γ-Al
2O
381.9%); The preparation method: nickelous nitrate and Palladous nitrate carry out the acidity allotment with ammoniacal liquor earlier, then required γ-Al
2O
3Carrier is poured into, and soaked carrier is 110 ℃ of dryings, 450 ℃ of roastings, last fragmentation moulding of sieving.
At 3MPa, liquid air speed 0.13hr
-1Under 80: 1 conditions of hydrogen acid anhydride mol ratio, when 95 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 90.6%, succinyl oxide selectivity 99.7%; During 150 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 100%, succinyl oxide selectivity 99.1%.
Embodiment 4, preparation succinyl oxide
Press the same method of embodiment 1, in fixed-bed reactor, the 15g20 that packs into～40 purpose nickel-copper/aluminium oxide catalyst (NiO25%, CuO1.5%, γ-Al
2O
373.5%); The preparation method: nickelous nitrate and cupric nitrate carry out the acidity allotment with ammoniacal liquor earlier, then required γ-Al
2O
3Carrier is poured into, and soaked carrier is 110 ℃ of dryings, 450 ℃ of roastings, last fragmentation moulding of sieving.
At 3MPa, liquid air speed 0.13hr
-1Under 60: 1 conditions of hydrogen acid anhydride mol ratio, when 95 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 88.4%, succinyl oxide selectivity 99.3%; During 155 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 100%, succinyl oxide selectivity 98.9%.
Embodiment 5, preparation succinyl oxide
Press the same method of embodiment 1, in fixed-bed reactor, the 15g20 that packs into～40 purpose nickel-copper/aluminium oxide-titanium oxide catalyzer (NiO18%, CuO1.5%, γ-Al
2O
360.5%, TiO
220%); The preparation method: at first proportionally prepare the titanium and the aluminum salt solution of solubility, carry out in the acidity and the formation gel precipitation with ammoniacal liquor, throw out is through filtration, washing, drying; 500 ℃ of calcinings; Fragmentation is sieved and is prepared 20～40 order composite alumina-titanium dioxide carriers, then nickelous nitrate and cupric nitrate is carried out the acidity allotment with ammoniacal liquor earlier, pours required aluminum oxide-titanium dioxide carrier into; Soaked carrier is 110 ℃ of dryings, 450 ℃ of roastings.
At 3.5MPa, liquid air speed 0.15hr
-1Under 70: 1 of hydrogen acid anhydride mol ratios, when 90 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 90.5%, succinyl oxide selectivity 99.5%; During 150 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 100%, succinyl oxide selectivity 98.7%.
Embodiment 6, preparation succinyl oxide
Press the same method of embodiment 1, in fixed-bed reactor, the 15g20 that packs into～40 purpose nickel-copper/aluminium oxide-zirconium oxide catalyzer (NiO18%, CuO1.5%, γ-Al
2O
365.5%, ZrO
215%); The preparation method: at first proportionally prepare the zirconium and the aluminum salt solution of solubility, carry out in the acidity and the formation gel precipitation with ammoniacal liquor, throw out is through filtration, washing, drying, and 500 ℃ of calcinings, fragmentation is sieved and prepared 20～40 order composite alumina-Zirconia carriers; Then nickelous nitrate and cupric nitrate are carried out the acidity allotment with ammoniacal liquor earlier, pour required aluminum oxide-Zirconia carrier into, soaked carrier is 110 ℃ of dryings, 450 ℃ of roastings.
At 3.2MPa, liquid air speed 0.15hr
-1Under 65: 1 conditions of hydrogen acid anhydride mol ratio, when 86 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 88.5%, succinyl oxide selectivity 99.7%; During 140 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 100%, succinyl oxide selectivity 99.2%.
Embodiment 7, preparation succinyl oxide
Press the same method of embodiment 1, in fixed-bed reactor, the 15g20 that packs into～40 purpose nickel-copper/aluminum oxide-Zinc oxide catalytic (NiO18%, CuO1.5%, γ-Al
2O
370.5%, ZnO10%); The preparation method: at first proportionally prepare the zinc and the aluminum salt solution of solubility, neutralizing with yellow soda ash forms deposition, and throw out is through filtration, washing, drying, and 480 ℃ of calcinings, the moulding fragmentation is sieved and prepared 20～40 order composite alumina-Zirconia carriers; Then nickelous nitrate and cupric nitrate are carried out the acidity allotment with ammoniacal liquor earlier, pour required aluminum oxide-zinc oxide carrier into, soaked carrier is 110 ℃ of dryings, 450 ℃ of roastings.
At 3.5MPa, liquid air speed 0.1hr
-1Under 50: 1 conditions of hydrogen acid anhydride mol ratio, when 95 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 91.5%, succinyl oxide selectivity 99.1%; During 148 ℃ of temperature of reaction, cis-butenedioic anhydride transformation efficiency 100%, succinyl oxide selectivity 98.3%.
Claims (9)
1. the preparation method of a succinyl oxide comprises the steps: under the condition that hydrogenation catalyst exists, and MALEIC ANHYDRIDE and hydrogen promptly get said succinyl oxide through the liquid-phase hydrogenatin reaction;
Said hydrogenation catalyst comprises carrier and is carried on the active ingredient on this carrier; Said active ingredient is selected from one or more elements in IB family in the periodic table of chemical element, IIB family, group vib, VIIB and the VIIIB family, and said carrier is selected from the oxide compound and the gac of one or more elements in IA family in the periodic table of chemical element, IIA family, IIIA family, IVA family, VA and the IVB family.
2. method according to claim 1 is characterized in that: in the said hydrogenation catalyst, the quality percentage composition of said active ingredient is 0.1%～85%.
3. method according to claim 1 and 2 is characterized in that: in the said hydrogenation catalyst, said active ingredient is at least a in nickel, palladium, cobalt, rhenium, rhodium, iridium and the platinum; Said carrier is at least a in gac, aluminum oxide, zinc oxide, chromic oxide, silicon oxide, zirconium white and the titanium oxide.
4. according to arbitrary described method among the claim 1-3, it is characterized in that: said hydrogenation catalyst is made up of said carrier, the active ingredient and the auxiliary agent that are carried on this carrier; Said auxiliary agent is selected from copper, barium, potassium, palladium and the tin at least a, and the quality percentage composition of said auxiliary agent is 0.05%～2.5%.
5. according to arbitrary described method among the claim 1-4; It is characterized in that: said hydrogenation catalyst is a nickel-base hydrogenation catalyst, and said nickel-base hydrogenation catalyst is nickel/palladium/gac hydrogenation catalyst, nickel/aluminum oxide hydrogenation catalyst, palladium/nickel/aluminum oxide hydrogenation catalyst, copper/nickel/aluminum oxide hydrogenation catalyst, copper/nickel/aluminium oxide-titanium oxide hydrogenation catalyst, copper/nickel/aluminium oxide-zirconium oxide hydrogenation catalyst or copper/nickel/aluminum oxide-zinc oxide hydrogenation catalyst.
6. method according to claim 5 is characterized in that: in the said nickel-base hydrogenation catalyst, the content of nickel is in nickel oxide, and the quality percentage composition of nickel oxide is 12%～40%.
7. according to arbitrary described method among the claim 1-6, it is characterized in that: the temperature of said liquid-phase hydrogenatin reaction is 80～160 ℃, and pressure is 2.5～4MPa.
8. according to arbitrary described method among the claim 1-7, it is characterized in that: the liquid air speed of said liquid-phase hydrogenatin reaction is 0.05hr
-1～0.3hr
-1, hydrogen is (10～80) with the molfraction ratio of MALEIC ANHYDRIDE: 1.
9. according to arbitrary described method among the claim 1-8, it is characterized in that: said liquid-phase hydrogenatin is reflected in fixed-bed reactor or the paste state bed reactor to be carried out.
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| CN103769105A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for hydrogenating cis-butenedioic anhydride to prepare butanedioic anhydride and its 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 |
| CN104399469A (en) * | 2014-12-05 | 2015-03-11 | 复旦大学 | Catalyst for catalyzing maleic anhydride and hydrogenating to prepare butanedioic anhydride under low temperature and low pressure and preparation method of catalyst |
| CN104874416A (en) * | 2015-05-13 | 2015-09-02 | 山西大学 | Catalyst for hydrogenating maleic anhydride to prepare succinic anhydride and preparation method of catalyst |
| CN105833863A (en) * | 2015-01-13 | 2016-08-10 | 广东工业大学 | Catalyst for preparing succinic anhydride from maleic anhydride through low-temperature hydrogenation and preparation method and application of catalyst |
| CN106861702A (en) * | 2017-02-28 | 2017-06-20 | 山西大学 | It is a kind of that the catalyst and its preparation method and application for being directly synthesized succinic acid are mutually hydrogenated with for cis-butenedioic anhydride water |
| CN108709948A (en) * | 2018-04-27 | 2018-10-26 | 河南能源化工集团鹤壁煤化工有限公司 | A method of quickly measuring industrial succinic anhydride purity using gas chromatography |
| CN110227488A (en) * | 2019-06-25 | 2019-09-13 | 河南能源化工集团研究总院有限公司 | A kind of maleic anhydride hydrogenation prepares catalyst of succinic anhydride and preparation method thereof |
| CN112661625A (en) * | 2021-03-16 | 2021-04-16 | 中化学科学技术研究有限公司 | Preparation process of succinic acid |
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| CN103769105B (en) * | 2012-10-24 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of maleic anhydride hydrogenation prepares Catalysts and its preparation method and the application of succinic anhydride |
| CN103769117A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for hydrogenating cis-butenedioic anhydride to prepare butanedioic anhydride and its preparation method and application |
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| 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 |
| CN104399469A (en) * | 2014-12-05 | 2015-03-11 | 复旦大学 | Catalyst for catalyzing maleic anhydride and hydrogenating to prepare butanedioic anhydride under low temperature and low pressure and preparation method of catalyst |
| CN105833863A (en) * | 2015-01-13 | 2016-08-10 | 广东工业大学 | Catalyst for preparing succinic anhydride from maleic anhydride through low-temperature hydrogenation and preparation method and application of catalyst |
| CN104874416A (en) * | 2015-05-13 | 2015-09-02 | 山西大学 | Catalyst for hydrogenating maleic anhydride to prepare succinic anhydride and preparation method of catalyst |
| CN104874416B (en) * | 2015-05-13 | 2017-08-25 | 山西大学 | A kind of maleic anhydride hydrogenation prepares succinic anhydride catalyst and preparation method thereof |
| CN106861702A (en) * | 2017-02-28 | 2017-06-20 | 山西大学 | It is a kind of that the catalyst and its preparation method and application for being directly synthesized succinic acid are mutually hydrogenated with for cis-butenedioic anhydride water |
| CN108709948A (en) * | 2018-04-27 | 2018-10-26 | 河南能源化工集团鹤壁煤化工有限公司 | A method of quickly measuring industrial succinic anhydride purity using gas chromatography |
| CN110227488A (en) * | 2019-06-25 | 2019-09-13 | 河南能源化工集团研究总院有限公司 | A kind of maleic anhydride hydrogenation prepares catalyst of succinic anhydride and preparation method thereof |
| CN112661625A (en) * | 2021-03-16 | 2021-04-16 | 中化学科学技术研究有限公司 | Preparation process of succinic acid |
| CN112661625B (en) * | 2021-03-16 | 2021-06-22 | 中化学科学技术研究有限公司 | Preparation process of succinic acid |
| CN113735805A (en) * | 2021-07-06 | 2021-12-03 | 上海昶法新材料有限公司 | Process for preparing alkenyl succinic anhydride |
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