CN105130783A - Preparation method of succinic acid - Google Patents
Preparation method of succinic acid Download PDFInfo
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- CN105130783A CN105130783A CN201510618176.8A CN201510618176A CN105130783A CN 105130783 A CN105130783 A CN 105130783A CN 201510618176 A CN201510618176 A CN 201510618176A CN 105130783 A CN105130783 A CN 105130783A
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- Prior art keywords
- succinic acid
- acid
- furfural
- carbon back
- preparation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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Abstract
The invention relates to the field of a succinic acid, in particular to a preparation method of the succinic acid. The method provided by the invention comprises the following steps: mixing furfural, sulfonated carbon-based solid acid, an oxidant and a solvent, and reacting to obtain the succinic acid. According to the method provided by the invention, under the catalysis condition of the sulfonated carbon-based solid acid, the furfural serves as a reaction material to prepare the succinic acid; the use of fossil-type products such as paraffin is avoided, and the sustainable development of environmental resources is facilitated; meanwhile, the method provided by the invention has higher furfural conversion rate and succinic acid yield. Experiment results show that after the succinic acid is prepared by adopting the method provided by the invention, the highest furfural conversion rate can be up to over 99 percent, and the highest succinic acid yield can be 73.8 percent.
Description
Technical field
The invention belongs to succinic acid field, particularly relate to a kind of preparation method of succinic acid.
Background technology
Succinic acid is as a kind of important industrial chemicals and intermediate, application is industrially very extensive, such as can as the tensio-active agent in chemical industry, sanitising agent, additive and pore forming material, or for the ion chelating agent of spot corrosion in electroplating industry, souring agent in food service industry, pH modifying agent and antiseptic-germicide, Material Field can be used as the raw material preparing biodegradable polyesters plastics (PBS).Therefore, how to prepare succinic acid efficiently, especially utilize renewable resources to prepare succinic acid, cause the extensive concern of various countries.
The production method of succinic acid is a lot, but the method industrially applied only has paraffin oxidation style, electrolytic process and shortening method, and wherein paraffin oxidation style uses the most extensive.Paraffin oxidation style is succinic acid production method the most traditional, the method uses paraffin as reaction raw materials, under calcium, manganese catalysis, deep oxidation obtains mixed dibasic acid oxidized petroleum wax, then the distillate containing succinic acid is obtained after the hot water and steam distillation unstable hydroxyl oil-soluble acid of removing and ester being carried out to mixed dibasic acid, finally to distillate drying crystalline, obtain succinic acid goods.The technique that paraffin oxidation style prepares succinic acid is comparatively ripe, but the method needs to use the fossil series products such as paraffin as raw materials for production, is unfavorable for the Sustainable development of environmental resources.
At present, technology that fossil series products prepares succinic acid causes both domestic and external showing great attention to use renewable carbon source to substitute, also obtain fast development, but the renewable carbon source of carrying out at present prepares feed stock conversion that in succinic acid research, ubiquity and the low problem of product yield both at home and abroad simultaneously.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of preparation method of succinic acid, method provided by the invention does not need to use fossil series products as raw materials for production, and feed stock conversion and succinic acid yield higher.
The invention provides a kind of preparation method of succinic acid, comprise the following steps:
The sulfonated solid acid of furfural, carbon back, oxygenant and solvent, react, obtain succinic acid.
Preferably, the mass ratio of described furfural and the sulfonated solid acid of carbon back is (1 ~ 2000): 1.
Preferably, the content of described oxygenant in the mixed system of furfural, the sulfonated solid acid of carbon back, oxygenant and solvent composition is 1 ~ 1000mmol/L.
Preferably, the temperature of described reaction is 30 ~ 120 DEG C; The time of described reaction is 0.5 ~ 24h.
Preferably, the pressure of described reaction is 0.1 ~ 5Mpa.
Preferably, the Surface acidity of the sulfonated solid acid of described carbon back is 1 ~ 4mmol/g.
Preferably, the specific surface area of the sulfonated solid acid of described carbon back is 50 ~ 1200m
2/ g; The aperture of the sulfonated solid acid of described carbon back is 2 ~ 10nm; The pore volume of the sulfonated solid acid of described carbon back is 0.05 ~ 4cm
3/ g.
Preferably, the sulfonated solid acid of described carbon back is prepared according to following steps:
Porous carbon materials and sulphonating agent mixing, react, obtain the sulfonated solid acid of carbon back;
Described sulphonating agent comprise in diazobenzene sulfonic acid, tosic acid, sulfuric acid, oleum and propyl sulfonic acid one or more.
Preferably, described porous carbon materials comprises one or more in Graphene, carbon nanotube and gac.
Preferably, described porous carbon materials is the carbon material made for template with micro-mesoporous material.
Compared with prior art, the invention provides a kind of preparation method of succinic acid.Method provided by the invention comprises the following steps: the sulfonated solid acid of furfural, carbon back, oxygenant and solvent, reacts, obtains succinic acid.Method provided by the invention, under the sulfonated solid acid catalysis condition of carbon back, has obtained succinic acid using furfural as reaction raw materials.This method avoid the use of fossil series products as paraffin, be beneficial to the Sustainable development of environmental resources.Meanwhile, preparation method provided by the invention has higher furfural turnover ratio and succinic acid yield.Experimental result shows, the highest furfural transformation efficiency adopting method provided by the invention to prepare succinic acid can reach more than 99%, and succinic acid yield reaches as high as 73.8%.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is GC-MS (gas chromatography-mass spectrography) spectrogram that the embodiment of the present invention 2 provides;
Fig. 2 is the high-efficient liquid phase chromatogram that the embodiment of the present invention 2 provides.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of preparation method of succinic acid, comprise the following steps:
The sulfonated solid acid of furfural, carbon back, oxygenant and solvent, react, obtain succinic acid.
In the present invention, directly furfural, the sulfonated solid acid of carbon back, oxygenant and solvent are reacted, can obtain succinic acid, this process is specially:
First by furfural, the sulfonated solid acid of carbon back, oxygenant and solvent.Wherein, described furfural, also known as 2 furan carboxyaldehyde, is same substance with alditol, and its formal name used at school is furaldehyde.The source of the present invention to described furfural is not particularly limited, and can adopt commercial goods, also can be transformed by other biological matter and obtain.
In the present invention, the effect of the sulfonated solid acid of described carbon back is the catalyzer as reaction.The Surface acidity of the sulfonated solid acid of described carbon back is preferably 1 ~ 4mmol/g, is more preferably 1 ~ 2.5mmol/g; The sulphur content of the sulfonated solid acid of described carbon back is preferably 0.1 ~ 1.5wt%, is more preferably 0.2 ~ 0.8wt%; The specific surface area of the sulfonated solid acid of described carbon back is preferably 50 ~ 1000m
2/ g, is more preferably 500 ~ 800m
2/ g; The aperture of the sulfonated solid acid of described carbon back is preferably 2 ~ 7nm; The pore volume of the sulfonated solid acid of described carbon back is preferably 0.05 ~ 2cm
3/ g, is more preferably 0.4 ~ 1.2cm
3/ g.The mass ratio of described furfural and the sulfonated solid acid of described carbon back is preferably (1 ~ 2000): 1, is more preferably (1 ~ 10): 1, most preferably is (1 ~ 4): 1.In the present invention, the source of the sulfonated solid acid of described carbon back is not particularly limited, can commercial goods be selected, also can be prepared according to the preparation method of the sulfonated solid acid of carbon back well known to those skilled in the art, can also prepare according to following steps:
Porous carbon materials and sulphonating agent mixing, react, obtain the sulfonated solid acid of carbon back;
Described sulphonating agent comprise in diazobenzene sulfonic acid, tosic acid, sulfuric acid, oleum and propyl sulfonic acid one or more.
In the preparation method of the sulfonated solid acid of above-mentioned carbon back provided by the invention, described porous carbon materials and acid are mixed in a solvent, reacts, the sulfonated solid acid of carbon back can be obtained.In an embodiment provided by the invention, described porous carbon materials comprise in Graphene, carbon nanotube and gac one or more; In another embodiment provided by the invention, described porous carbon materials is the carbon material made for template with micro-mesoporous material.The specific surface area of described porous carbon materials is preferably 300 ~ 1000m
2/ g; The aperture of described porous carbon materials is preferably 2 ~ 10nm; The pore volume of described porous carbon materials is preferably 1 ~ 3cm
3/ g.In the present invention, the described carbon material made for template with micro-mesoporous material is specifically prepared in accordance with the following methods:
First, micro-mesoporous material is mixed with carbon source.Wherein, described micro-mesoporous material is preferably γ-Al
2o
3, silicon oxide or zeolite molecular sieve.The specific surface area of described micro-mesoporous material is preferably 100 ~ 500m
2/ g; The aperture of described micro-mesoporous material is preferably 2 ~ 10nm; The pore volume of described micro-mesoporous material is preferably 1 ~ 4cm
3/ g.Described carbon source be preferably in fructose, sucrose and glucose one or more.The mass ratio of described micro-mesoporous material and carbon source is preferably 1:(0.1 ~ 3.0), be more preferably 1:(0.3 ~ 1).Carbon source and water are preferably first hybridly prepared into carbon source solution, then be immersed in carbon source solution by micro-mesoporous material by the mode that described micro-mesoporous material mixes with carbon source.
Then, after micro-mesoporous material mixes with carbon source, the mixture obtained is baked and banked up with earth.Described baking and banking up with earth preferably is carried out in shielding gas atmosphere, and described shielding gas is preferably N
2.Described temperature of baking and banking up with earth is preferably 400 ~ 800 DEG C; The described time of baking and banking up with earth is preferably 0.1 ~ 1h.After baking and banking up with earth end, obtain baking and banking up with earth product.
Finally, bake and bank up with earth the micro-mesoporous material in product described in removing, this process is specially: be impregnated into baking and banking up with earth product in the solution of micro-mesoporous material described in erodable.In an embodiment provided by the invention, the micro-mesoporous material adopted is γ-Al
2o
3, described in the erodable adopted, the solution of micro-mesoporous material is HF solution, and in described HF solution, the mass concentration of HF is preferably 5 ~ 40wt%, is more preferably 20 ~ 30wt%.Described product dipping time in the solution of mesoporous material micro-described in erodable of baking and banking up with earth is preferably 0.1 ~ 3h, is more preferably 2 ~ 3h.After baking and banking up with earth the micro-mesoporous material in product described in removing, obtain the carbon material made for template with micro-mesoporous material.In the present invention, in order to improve the purity of the carbon material made, preferably carry out aftertreatment to the described carbon material made, the mode of described aftertreatment is preferably washed successively described carbon material and dries.The temperature of described oven dry is preferably 50 ~ 110 DEG C.
In the preparation method of the sulfonated solid acid of carbon back provided by the invention, described sulphonating agent comprise in diazobenzene sulfonic acid, tosic acid, sulfuric acid, oleum and propyl sulfonic acid one or more.Described solvent is preferably water.Described porous carbon materials and sulphonating agent mass ratio are preferably 0.4:(0.01 ~ 10), be more preferably 0.4:(0.01 ~ 0.4), most preferably be 0.4:(0.2 ~ 0.3).In the present invention, it can be porous carbon materials, sulphonating agent and solvent that described porous carbon materials and sulphonating agent mix detailed process in a solvent, also can be that porous carbon materials mixes with the solution of sulphonating agent.In an embodiment provided by the invention, in order to remove the impurity salt that may contain in sulphonating agent, as diazobenzene sulfonic acid sodium, the reaction that described porous carbon materials and sulphonating agent carry out in a solvent is preferably carried out under HCl exists, and the content of described HCl in reaction system is preferably 0.01 ~ 0.1mol/L.The temperature of the reaction that described porous carbon materials and acid are carried out in a solvent is preferably-10 ~ 15 DEG C, is more preferably 0 ~ 10 DEG C; The time of described reaction is preferably 0.1 ~ 5h, is more preferably 2 ~ 4h.After reaction terminates, obtain the solution containing reaction product.Filter the described solution containing reaction product, the filtrate obtained is the sulfonated solid acid of carbon back.In the present invention, in order to improve the purity of the sulfonated solid acid of obtained carbon back, preferably aftertreatment is carried out to the obtained sulfonated solid acid of carbon back, the process of described aftertreatment is specially: the sulfonated solid acid of described carbon back is successively through water washing, N, dinethylformamide washing and washing with acetone, obtain the sulfonated solid acid of carbon back of aftertreatment.
In the present invention, in the sulfonated solid acid of described furfural, carbon back, oxygenant and solvent process, described oxygenant preferably include in hydrogen oxide, potassium permanganate, Potcrate and oxygen one or more.Described solvent is preferably water.The content of described oxygenant in the mixed system of furfural, the sulfonated solid acid of carbon back, oxygenant and solvent composition is preferably 1 ~ 1000mmol/L, is more preferably 1 ~ 100mmol/L, most preferably is 1 ~ 10mmol/L, is the most preferably 1 ~ 5mmol/L.
In the present invention, after the sulfonated solid acid of described furfural, carbon back, oxygenant and solvent, react.Wherein, the pressure of described reaction is preferably 0.1 ~ 5Mpa; The temperature of described reaction is preferably 30 ~ 120 DEG C, is more preferably 70 ~ 90 DEG C; The time of described reaction is preferably 0.5 ~ 24h, is more preferably 6 ~ 16h.In the present invention, the reaction after the sulfonated solid acid of described furfural, carbon back, oxygenant and solvent is preferably carried out under agitation, and the speed of described stirring is preferably 200 ~ 1000rpm, is more preferably 400 ~ 600rpm.After reaction terminates, obtain the solution containing reaction product.The described solution containing reaction product filters, and filtration obtains filtrate and carries out evaporation recrystallize, and obtain white solid, this white solid is succinic acid.In the present invention, the filtrate that described filtration obtains is the sulfonated solid acid of carbon back, reuses after recyclable.
Method provided by the invention is under the sulfonated solid acid catalysis condition of carbon back, in oxidizing agent solution system, furfural is converted into succinic acid and part by product (by product comprises maleic acid, FUMARIC ACID TECH GRADE and furancarboxylic acid), obtains highly purified succinic acid solid by aftertreatment means such as recrystallize evaporations afterwards.This method avoid the use of fossil series products as paraffin, be beneficial to the Sustainable development of environmental resources.Meanwhile, preparation method provided by the invention has higher furfural transformation efficiency and succinic acid yield.
In addition, method reaction conditions provided by the invention is gentle, does not need the condition of high pressure-temperature, overcome the shortcoming that traditional electrochemical synthesis and shortening method need harsh reaction conditions, and side reaction is few, green non-pollution, can effectively reduce early investment cost.
In addition, the present invention uses the sulfonated solid acid of carbon back as catalyzer, it is high that carbon-based solid acid has thermostability, catalytic selectivity is strong, the advantages such as reusability is good, avoid the product using traditional diluted acid catalyzer to cause to be difficult to be separated with catalyzer, to defects such as reaction unit corrodibility are larger.
In sum, succinic acid preparation method provided by the invention is a kind of method utilizing carbon-based solid acid catalyst catalytic oxidizing biomass base furfural to prepare succinic acid.The method has sustainable developability and environment friendly, higher selectivity and reusability.By using biomass-based furfural as reaction raw materials, alleviate the pressure of Petroleum Industry, and can promote that biomass by hydrolyzation prepares the development of furfural industry, be conducive to shifting industrial focal point, no matter from environmental angle or economic angle, all there is bright application prospect.
Experimental result shows, the highest furfural transformation efficiency adopting method provided by the invention to prepare succinic acid reaches as high as more than 99%, and succinic acid yield reaches as high as 73.8%.
For the purpose of clearer, be described in detail below by following examples.
Embodiment 1
Kaolinite Preparation of Catalyst (the sulfonated solid acid of carbon back)
Get a certain amount of γ-Al
2o
3(producer: Aladdin) and sucrose, use pickling process by γ-Al
2o
3be dipped in the aqueous solution of sucrose, the sucrose of use and γ-Al
2o
3mass ratio be 0.3:1.
By the sucrose/γ-Al flooded
2o
3at N
2protect lower 600 DEG C to cure 0.5h, then immersed 3h in the HF solution of 24wt% and remove Al
2o
3, use the black powder that distilled water flushing obtains, and dry at 110 DEG C.
The aqueous solution getting black powder prepared by 0.4g aforesaid method and 0.22g4-BDS (diazobenzene sulfonic acid) reacts in 0.05MHCl, temperature of reaction 5 DEG C, reaction times 3h.The product obtained uses water, DMF and washing with acetone after filtering successively, obtains the sulfonated solid acid of carbon back.
Characterize the sulfonated solid acid of above-mentioned obtained carbon back, result is: the Surface acidity of the sulfonated solid acid of described carbon back is 2.1mmol/g, sulphur content is 0.8wt%, specific surface area is 554m
2/ g, aperture 5.32nm, pore volume is 1.10cm
3/ g.
Embodiment 2
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 0.72g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 4mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 12h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, is succinic acid goods.
Carry out composition detection to above-mentioned obtained white solid, detailed process is:
1) qualitative detection:
Get the above-mentioned gained white solid of 0.01g, be dissolved among 100ml acetone, mix, ultrasonic 10min, use Shimadzu GCMS-QP2010S (gas chromatograph-mass spectrometer) to carry out qualitative detection analysis, obtain the collection of illustrative plates shown in Fig. 1.Fig. 1 is GC-MS (gas chromatography-mass spectrography) figure that the embodiment of the present invention 2 provides.As seen in Figure 1, succinic acid and furancarboxylic acid is comprised in above-mentioned white solid.
2) detection by quantitative:
Get the above-mentioned gained white solid of 0.5g, be dissolved in 100ml distilled water, use Waters515HPLC (high performance liquid chromatograph) to carry out quantitative detecting analysis, as shown in Figure 2, Fig. 2 is the high-efficient liquid phase chromatogram that the embodiment of the present invention 2 provides to detected result.Appearance time Fig. 2 being contrasted succinic acid and furancarboxylic acid standard model is known, and second chromatographic peak is succinic acid, and the 4th chromatographic peak is furancarboxylic acid.The content that can calculate succinic acid in white solid according to chromatographic peak area is 92.4wt%, and namely the purity of above-mentioned obtained succinic acid goods is 92.4%.
Calculate the yield of above-mentioned obtained succinic acid goods, result is: yield is 72.3%.
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is more than 99%.
Embodiment 3
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 0.72g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 1mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 12h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 91.3%, and yield is 26.2%.
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 32%.
Embodiment 4
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 0.72g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 2mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 12h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 90.5%, and yield is 43.6%.
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 76%.
Embodiment 5
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 0.72g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 3mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, stop 12h at 1.0MPa; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 91.7%, and yield is 65.2%.
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 96%.
Embodiment 6
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 0.72g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 5mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 12h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 92.6%, and yield is 53.5%.
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 99%.
Embodiment 7
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 0.72g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 4mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 6h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained a part of for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 90.6%, and yield is 24.1%.
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 43.4%.
Embodiment 8
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 0.72g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 4mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 8h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 89.8%, and yield is 38.7%.
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 67%.
Embodiment 9
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 0.72g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 4mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 10h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 94.3%, and yield is 57.1%.
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 84%.
Embodiment 10
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 0.72g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 4mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 14h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 92.5%, and yield is 68.4%
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 99%.
Embodiment 11
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 0.72g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 4mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 16h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 93.6%, and yield is 66.7%.
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 99%.
Embodiment 12
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 0.36g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 4mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 12h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 92.5%, and yield is 42.4%.
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 57.4%.
Embodiment 13
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 0.48g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 4mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 12h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 91.3%, and yield is 56.6%.
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 73.5%.
Embodiment 14
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, the sulfonated solid acid of carbon back that 1.44g embodiment 1 is obtained, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 4mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 12h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 93.6%, and yield is 73.8%.
After the described filtrate for composition detection dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 99%.
Embodiment 15
Be that succinic acid (with sulfonation ordered mesopore carbon for catalyzer) prepared by raw material with furfural
1) Kaolinite Preparation of Catalyst:
Use SBA-15 molecular sieve as template, furfuryl alcohol, as carbon source, is that 1:1 mixes according to furfuryl alcohol and the mass ratio of SBA-15 molecular sieve, reacts at 100 ~ 150 DEG C; The reaction product be obtained by reacting sinters, and obtains sintered product; Sintered product immerses 3h in the HF solution of 24wt% and removes SBA-15 molecular sieve, then uses the black powder that distilled water flushing obtains, dry, obtains ordered mesopore carbon (OMC).
Above-mentioned for 0.15g ordered mesopore carbon (OMC) and the mixing of 3g diazobenzene sulfonic acid are added in the aqueous solution (ethanol/water=1/1, v/v) of 100mL ethanol, then in the aqueous solution of ethanol, adds the H of 100mL50wt%
3pO
2the aqueous solution, keep temperature of reaction 5 DEG C, reaction times 30min, then uses distilled water and acetone cleaning down respectively by reacted filter residue, can obtain sulfonation ordered mesopore carbon after being placed in the baking oven oven dry of 100 DEG C.
Characterized by above-mentioned obtained sulfonation ordered mesopore carbon, result is: specific surface area 500 ~ 800m
2/ g, aperture 2.0 ~ 5.0nm, pore volume 0.4 ~ 0.8cm
3/ g, Surface acidity is 1 ~ 1.8mmol/g, and sulphur content is 0.2 ~ 0.6wt%.
2) succinic acid is prepared:
Get 1.44g furfural, the order mesoporous C catalyst of the above-mentioned obtained sulfonic acid of 0.72g, 45mL distilled water, is placed in high-pressure machinery stirring tank, then adds superoxol, makes H in reaction system
2o
2concentration is 4mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 12h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Reaction solution is migrated out from reactor, filters, filter filter residue (the sulfonated solid acid of the carbon back) dry for standby obtained; Filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, is succinic acid goods.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 87.4%, and yield is 56.3%.
After the described filtrate for calculating furfural transformation efficiency dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is more than 80%.
Embodiment 16
The cycle performance test of the sulfonated solid acid catalyst of carbon back
Filter residue after drying embodiment 2 characterizes, and result is that the Surface acidity of filter residue is 3.0mmol/g, sulphur content is 0.76wt%, specific surface area is 532m
2/ g, aperture are 4.92nm, pore volume is 0.76cm
3/ g.
1) loop test:
Using the sulfonated solid acid of carbon back of above-mentioned filter residue alternative embodiment 2 use as catalyzer, prepare succinic acid according to the preparation condition of embodiment 2.
Characterize preparing in succinic acid process to filter after the filter residue obtained is dried, result is that the Surface acidity of filter residue is 2.8mmol/g, sulphur content is 0.48wt%, specific surface area is 524m
2/ g, aperture are 4.43nm, pore volume is 0.71cm
3/ g.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to white solid, result is: the main component of this white solid is succinic acid; The purity of succinic acid goods is 90.6%, and yield is 68.7%.
Filtering after the filtrate obtained dilutes 100 times by preparing in succinic acid process, using Waters515HPLC (high performance liquid chromatograph) to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 97%.
2) cycle test:
The filter residue obtained with loop test replaces the catalyzer that loop test uses, and prepares succinic acid according to the preparation condition of a loop test.
Adopt the analytical procedure of embodiment 2 to carry out qualitative and quantitative analysis to the goods of cycle test, result is: the main component of goods is succinic acid; The purity of succinic acid goods is 90.3%, and yield is 67.4%.
Filtering after the filtrate obtained dilutes 100 times by preparing in succinic acid process, using Waters515HPLC (high performance liquid chromatograph) to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 95%.
By once finding out with the result of cycle test, the catalyzer that the embodiment of the present invention 1 is obtained to recycle performance good.
Comparative example
Be that succinic acid prepared by raw material with furfural
Get 1.44g furfural, 45mL distilled water, be placed in high-pressure machinery stirring tank, then add superoxol, make H in reaction system
2o
2concentration is 4mmol/L; Regulate reactor, make its rotating speed be 500rpm, after full power is warming up to 80 DEG C, under 1.0MPa, stop 12h; Reaction terminates rear powered-down, and reactor is placed in frozen water is cooled to room temperature rapidly; Migrated out from reactor by reaction solution, filter, filter the filtrate obtained and retain a part for calculating furfural transformation efficiency, another part filtrate carries out evaporation recrystallize, obtains white solid, and this white solid is succinic acid goods.
Carry out composition analysis to above-mentioned obtained succinic acid goods, result is: not containing succinic acid.
After the described filtrate for composition detection dilutes 100 times, Waters515HPLC (high performance liquid chromatograph) is used to carry out Measurement and analysis.Result shows, and in the above conditions, the transformation efficiency of furfural is 0.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a preparation method for succinic acid, comprises the following steps:
The sulfonated solid acid of furfural, carbon back, oxygenant and solvent, react, obtain succinic acid.
2. preparation method according to claim 1, is characterized in that, the mass ratio of described furfural and the sulfonated solid acid of carbon back is (1 ~ 2000): 1.
3. preparation method according to claim 1, is characterized in that, the content of described oxygenant in the mixed system of furfural, the sulfonated solid acid of carbon back, oxygenant and solvent composition is 1 ~ 1000mmol/L.
4. preparation method according to claim 1, is characterized in that, the temperature of described reaction is 30 ~ 120 DEG C; The time of described reaction is 0.5 ~ 24h.
5. preparation method according to claim 1, is characterized in that, the pressure of described reaction is 0.1 ~ 5Mpa.
6. preparation method according to claim 1, is characterized in that, the Surface acidity of the sulfonated solid acid of described carbon back is 1 ~ 4mmol/g.
7. preparation method according to claim 1, is characterized in that, the specific surface area of the sulfonated solid acid of described carbon back is 50 ~ 1200m
2/ g; The aperture of the sulfonated solid acid of described carbon back is 2 ~ 10nm; The pore volume of the sulfonated solid acid of described carbon back is 0.05 ~ 4cm
3/ g.
8. preparation method according to claim 1, is characterized in that, the sulfonated solid acid of described carbon back is prepared according to following steps:
Porous carbon materials and sulphonating agent mixing, react, obtain the sulfonated solid acid of carbon back;
Described sulphonating agent comprise in diazobenzene sulfonic acid, tosic acid, sulfuric acid, oleum and propyl sulfonic acid one or more.
9. preparation method according to claim 8, is characterized in that, described porous carbon materials comprise in Graphene, carbon nanotube and gac one or more.
10. preparation method according to claim 8, is characterized in that, described porous carbon materials is the carbon material made for template with micro-mesoporous material.
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