CN118146086B - Method for purifying succinic acid from fermentation broth - Google Patents
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 223
- 239000001384 succinic acid Substances 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000000855 fermentation Methods 0.000 title claims abstract description 44
- 230000004151 fermentation Effects 0.000 title claims abstract description 42
- 238000001179 sorption measurement Methods 0.000 claims abstract description 69
- 238000000605 extraction Methods 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000003795 desorption Methods 0.000 claims abstract description 8
- 239000003463 adsorbent Substances 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000012452 mother liquor Substances 0.000 claims description 14
- 238000004064 recycling Methods 0.000 claims description 13
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 claims description 12
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 11
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- USTXUJIHHVNDFR-UHFFFAOYSA-K tripotassium 1-dodecoxydodecane phosphate Chemical compound P(=O)([O-])([O-])[O-].[K+].C(CCCCCCCCCCC)OCCCCCCCCCCCC.[K+].[K+] USTXUJIHHVNDFR-UHFFFAOYSA-K 0.000 claims description 5
- 239000004113 Sepiolite Substances 0.000 claims description 4
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052621 halloysite Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 4
- 235000011009 potassium phosphates Nutrition 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 claims description 3
- RGKUSPKMWIGVLG-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;trimethoxy(propyl)silane Chemical compound NCCNCCN.CCC[Si](OC)(OC)OC RGKUSPKMWIGVLG-UHFFFAOYSA-N 0.000 claims description 3
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 3
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 3
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 description 18
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000909 electrodialysis Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 238000010170 biological method Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- -1 polybutylene succinate Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
A method for purifying succinic acid from fermentation broth belongs to the field of biotechnology, and comprises 5 steps of pretreatment, extraction, adsorption, high-temperature desorption and low-temperature crystallization; according to the method for purifying succinic acid from fermentation broth, the purity of the obtained succinic acid is 99.4-99.7%, and the yield of the succinic acid is 84-87%.
Description
Technical Field
The invention relates to a method for purifying succinic acid from fermentation broth, belonging to the technical field of biological fermentation.
Background
Succinic acid, also called succinic acid, is an important C4 platform compound, is widely applied to the fields of food, medicine and agriculture, can be used as raw materials for synthesizing 1, 4-butanediol, tetrahydrofuran, N-methylpyrrolidone, a degradable biological high polymer material polybutylene succinate and the like, and has wide application prospect. Since succinic acid can be obtained by anaerobic fermentation of renewable biomass and greenhouse gas carbon dioxide through some microorganisms, so that the biological method for preparing succinic acid can greatly contribute to carbon reduction, the biological method for preparing succinic acid is highly valued, and the biological method for preparing succinic acid has gradually become a hot spot for research and development. But the concentration of succinic acid in fermentation liquor prepared by a biological method is very low, belongs to a polar organic dilute solution, and also contains byproducts such as formic acid, acetic acid and the like, proteins, pigments and unconsumed substrates, so that the separation and purification cost is high, and the industrial development of the fermentation liquor is restricted. Therefore, how to efficiently separate succinic acid from fermentation broth, improve product purity and recovery rate, and reduce operation cost is an urgent need for realizing large-scale industrial production of succinic acid by biological method.
At present, the method for extracting and separating succinic acid from fermentation liquor mainly comprises a calcium salt method, an ammonium salt method, an electrodialysis method, a membrane separation method, an ion exchange method and the like. The calcium salt method has the problems that the product yield is low, the consumption of calcium hydroxide and sulfuric acid in the precipitation process is large, the reagents cannot be reused, a large amount of unavailable byproducts of calcium sulfate are generated in the separation process, and extra cost is increased. The ammonium salt method has the obvious defect that the energy consumption is large in the process of thermally cracking ammonium sulfate, and the generated byproduct ammonium bisulfate cannot be reused as alkali liquor. Electrodialysis has a relatively mature commercial application, but the cost of the electrodialysis membrane is the highest in all separation methods due to the cost of the prior equipment and maintenance costs in the use of the electrodialysis membrane. Although the membrane separation method is widely used for preparing the superior succinic acid product, the problems of membrane pollution, membrane flux attenuation, cost and the like are still main factors which restrict the cost of the method to be high and difficult to be applied on a large scale. The ion exchange method has simple process, compared with the calcium salt precipitation method, the method does not generate calcium sulfate waste residue in the production process, reduces energy consumption, improves the quality and yield of products, but has large reagent consumption in the elution process due to frequent regeneration and periodic replacement of the resin in the use process, and is difficult to avoid generating certain waste water and solid waste.
Chinese patent CN104876817a discloses a method for extracting succinic acid by using succinic acid fermentation broth, the extraction method comprises (1) preparing succinic acid fermentation broth, (2) converting succinate salt into diammonium succinate by using ammonia gas, then acidizing to treat succinic acid fermentation broth, (3) extracting succinic acid, (4) introducing magnesium salt to ammonia process and bipolar membrane electrodialysis to recover acid and alkali process, recycling evaporated water, ammonia gas, magnesium carbonate suspension and hydrochloric acid; the intermediate product of the diammonium succinate in the process realizes clean production in the process, simultaneously avoids the problem of large sewage discharge caused by converting the diammonium succinate into the succinic acid by using resin exchange in the traditional process, reduces the process difficulty, and is a closed clean production process. The patent realizes clean production, but the technology relates to electrodialysis process, has high maintenance cost, and in addition, the diammonium succinate is acidified by hydrochloric acid in the step of extracting succinic acid, and then evaporated and concentrated, in the process, because the concentration of the succinic acid obtained by fermentation liquor is very low, a large amount of water needs to be removed in the evaporation and concentration, so that the energy consumption is very high, and the concentration of the residual hydrochloric acid in the evaporation process is continuously increased, so that the corrosion problem of equipment is also caused.
Chinese patent CN109206313a discloses a method for preparing succinic acid from succinate anaerobic fermentation liquid, which starts from succinate fermentation liquid, and adopts modes of filtering, anion-cation exchange, concentration, coarse crystallization, hydrogen peroxide decolorization and recrystallization, etc. to obtain high-purity succinic acid. The purity of the recrystallized succinic acid can reach 99.5%, the nitrogen content is lower than 40 mug/g, the light transmittance is higher than 99.5%, the yield after circulation can reach more than 90%, and the yield is higher than 80% of the prior art. The method disclosed by the patent has the advantages of high succinic acid yield and high purity, but the method uses both anion exchange resin and cation resin, the operation process is complicated, waste liquid is difficult to avoid by regenerating the resin, and the cost caused by periodic replacement of the resin is not quite small.
As can be seen from the above, the existing method for extracting and purifying succinic acid from fermentation broth still has the defects of needing to periodically replace adsorption materials, high cost, complex operation, more waste solids or liquid, equipment corrosion, high energy consumption and the like, so that a method for purifying succinic acid from fermentation broth needs to be developed specifically to solve the problems.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for purifying succinic acid from fermentation broth, which realizes the following aims: the method uses fermentation liquor as raw material, and adopts the process method which is simple and efficient, low in cost, low in energy consumption, free from frequent replacement of adsorption material at regular intervals and few in waste solid or liquid to separate and purify the succinic acid with high yield and high purity.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
A method for purifying succinic acid from fermentation broth, which comprises 5 steps of pretreatment, extraction, adsorption, high-temperature desorption and low-temperature crystallization;
The following is a further improvement of the above technical scheme:
Step 1, pretreatment
Filtering succinic acid fermentation liquor to remove solid impurities, and decoloring with active carbon to obtain colorless transparent pretreatment liquor;
in the succinic acid fermentation broth, the mass concentration of succinic acid is 1.0-100.0 g/L.
Step 2, extraction
Adding the pretreatment liquid and the extractant into an extraction kettle according to the mass ratio of 1:1-7, controlling the rotating speed to be 350-700 r/min, stirring and extracting for 3-7 hours, stopping stirring, standing and layering for 6-13 hours, and separating an organic phase and a water phase, wherein the obtained organic phase is an extract liquid rich in succinic acid;
The extractant is a mixture of tetrahydroxyethyl ethylenediamine, sorbitol, D-xylose and deionized water;
the mass ratio of the tetrahydroxyethyl ethylenediamine to the sorbose to the D-xylose to the deionized water is 70-110:13-36:15-30:10-25.
Step 3, adsorption
Adding the extract into an adsorption column filled with the adsorbent at normal temperature, collecting all liquid flowing out from the bottom of the adsorption column by gravity and flowing through the adsorbent, adding the collected self-flowing liquid into the adsorption column again, repeating the cycle for adsorption for a plurality of times, continuously detecting the mass content value of succinic acid in the self-flowing liquid at the bottom of the adsorption column until the mass content value is reduced to 0.1-0.5wt% of the mass content value of succinic acid in the extract, collecting all liquid flowing out from the last time, repeatedly using as the extractant, and taking out the adsorbent for adsorbing succinic acid in the adsorption column for later use;
the mass ratio of the extract to the adsorbent is 68-117:50;
The preparation method of the adsorbent comprises the following steps: drying an inorganic microporous adsorption material at 100-130 ℃ for 10-15 hours, then placing the inorganic microporous adsorption material into a dried reaction kettle, adding absolute ethyl alcohol and lauryl ether potassium phosphate, controlling the speed to be 3000-5000 r/min, stirring at normal temperature for dispersing for 5-12 hours, reducing the stirring speed to 500-1400 r/min, heating and keeping the temperature to 50-70 ℃, adding a polyamino silane coupling agent, stirring at a constant temperature for reacting for 10-17 hours, centrifuging, and drying the obtained solid at 40-60 ℃ in vacuum for 6-13 hours to obtain an adsorbent;
The inorganic microporous adsorption material is one of sepiolite, palygorskite and halloysite;
The particle size of the inorganic microporous adsorption material is 10-1000 nm;
The inorganic microporous adsorption material, absolute ethyl alcohol, lauryl alcohol ether potassium phosphate and polyamino silane coupling agent are added in a mass ratio of 20-45:150-270:1-4:2-5;
The polyamino silane coupling agent is one of N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, N-beta (aminoethyl) -gamma-aminopropyl trimethoxy silane, N- (2-aminoethyl) -3-aminopropyl triethoxy silane, diethylenetriamine propyl trimethoxy silane and N- (2-aminoethyl) -3-aminopropyl methyl diethoxy silane.
Step 4, high-temperature desorption
Adding the adsorbent for adsorbing succinic acid obtained in the step 3 and deionized water into an elution kettle according to the mass ratio of 4-7:3, controlling the stirring speed to be 150-500 r/min, heating to 80-95 ℃, stirring at constant temperature for 3-6 hours, maintaining the temperature to be 80-95 ℃ for centrifugal separation, and recycling the solid adsorbent obtained by separation to the step 3 for continuous use, wherein the obtained liquid is the eluent rich in succinic acid.
Step 5, low temperature crystallization
And (3) cooling the eluent to 0-4 ℃, standing for 20-30 hours at the temperature of 0-4 ℃, crystallizing and separating out succinic acid, filtering and separating out crystals and mother liquor, wherein the mother liquor can be collected and then mixed into the pretreatment liquid in the step (1) for recycling, and the separated crystals are dried to obtain a high-purity succinic acid finished product.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention uses fermentation liquor as raw material, and adopts a simple and efficient process method with low cost, low energy consumption, no need of frequent regular replacement of adsorption material and little waste solid or liquid to separate and purify succinic acid with high yield and high purity;
2. The invention uses the sugar-out extractant composed of the tetrahydroxyethyl ethylenediamine, the sorbose, the D-xylose and the deionized water to carry out sugar-out extraction on the succinic acid with low concentration contained in the succinic acid fermentation liquor, the tetrahydroxyethyl ethylenediamine contains a tertiary amine structure, and the lone pair on nitrogen atoms and the succinic acid have charge effect, so that the sugar-out extractant and the succinic acid have certain complexation extraction effect besides the sugar-out extraction effect, thereby being capable of extracting the succinic acid in the fermentation liquor with high efficiency and high yield;
3. The invention uses polyamino silane coupling agent containing primary amine and secondary amine to modify the inner and outer surfaces of sepiolite, palygorskite and halloysite, after modification, the inner and outer surfaces of the inorganic micropore adsorption materials are enriched with primary amine and secondary amine functional groups, and the two functional groups and succinic acid in the extract liquor have strong hydrogen bonding effect, so that succinic acid in the extract liquor can be selectively fixed in the surface and inner micropores in a directional manner, and then high-temperature desorption is carried out to obtain succinic acid with extremely high purity;
4. in the process of extracting succinic acid, only physical adsorption, reversible chemical complexation and reversible hydrogen bonding effect exist, and the effects on the extractant and the adsorbent are not too great, so the sugar-out extractant and the adsorbent can be repeatedly and circularly used for many times without obvious attenuation of efficiency;
5. According to the method for purifying succinic acid from fermentation broth, the purity of the obtained succinic acid is 99.4-99.7%, and the yield of the succinic acid is 84-87%.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
Example 1: method for purifying succinic acid from fermentation broth
Step 1, pretreatment
Filtering succinic acid fermentation liquor to remove solid impurities, and decoloring with active carbon to obtain colorless transparent pretreatment liquor;
In the succinic acid fermentation broth, the mass concentration of succinic acid is 60g/L.
Step 2, extraction
Adding the pretreatment liquid and the extractant into an extraction kettle according to the mass ratio of 1:5, controlling the rotating speed to 600 revolutions per minute, stirring and extracting for 4 hours, stopping stirring, standing and layering for 12 hours, and separating an organic phase and a water phase, wherein the obtained organic phase is an extract liquid rich in succinic acid;
The extractant is a mixture of tetrahydroxyethyl ethylenediamine, sorbitol, D-xylose and deionized water;
the mass ratio of the tetrahydroxyethyl ethylenediamine to the sorbose to the D-xylose to the deionized water is 100:30:18:21.
Step 3, adsorption
Adding the extract into an adsorption column filled with the adsorbent at normal temperature, collecting all liquid flowing out from the bottom of the adsorption column by gravity and flowing through the adsorbent, adding the collected flowing-out liquid into the adsorption column again, repeating the cycle for adsorption for a plurality of times, continuously detecting the mass content value of succinic acid in the flowing-out liquid at the bottom of the adsorption column until the mass content value is reduced to 0.2wt% of the mass content value of succinic acid in the extract, collecting all liquid flowing out from the last time, repeatedly using as the extractant, and taking out the adsorbent for adsorbing succinic acid in the adsorption column for later use;
the mass ratio of the extract to the adsorbent is 79:50;
The preparation method of the adsorbent comprises the following steps: drying an inorganic microporous adsorption material at 125 ℃ for 14 hours, then placing the inorganic microporous adsorption material into a dried reaction kettle, adding anhydrous ethanol and lauryl ether potassium phosphate, controlling the speed to 4500 r/min, stirring at normal temperature for 8 hours, reducing the stirring speed to 1200 r/min, heating and keeping the temperature to 65 ℃, adding a polyamino silane coupling agent, stirring at the constant temperature for 15 hours, centrifuging, and drying the obtained solid at 55 ℃ for 9 hours in vacuum to obtain an adsorbent;
the inorganic microporous adsorption material is sepiolite;
the particle size of the inorganic microporous adsorption material is 600nm;
The inorganic microporous adsorption material, absolute ethyl alcohol, lauryl alcohol ether potassium phosphate and polyamino silane coupling agent are added in a mass ratio of 26:210:3:4;
The polyamino silane coupling agent is N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane.
Step 4, high-temperature desorption
Adding the adsorbent for adsorbing succinic acid obtained in the step 3 and deionized water into an elution kettle according to the mass ratio of 5:3, controlling the stirring speed to be 400 r/min, heating to 90 ℃, stirring at constant temperature for 4 hours, maintaining the temperature for centrifugal separation at 84 ℃, and recycling the solid adsorbent obtained by separation into the step 3 for continuous use, wherein the obtained liquid is the eluent rich in succinic acid.
Step 5, low temperature crystallization
Cooling the eluent to 2 ℃, standing for 26 hours at the temperature of 2 ℃, crystallizing and separating out succinic acid, filtering and separating crystal and mother liquor, collecting the mother liquor, mixing the mother liquor into the pretreatment liquid in the step 1 for recycling, and drying the separated crystal to obtain a succinic acid finished product with high purity.
Example 2: method for purifying succinic acid from fermentation broth
Step 1, pretreatment
Filtering succinic acid fermentation liquor to remove solid impurities, and decoloring with active carbon to obtain colorless transparent pretreatment liquor;
In the succinic acid fermentation broth, the mass concentration of succinic acid is 1.0g/L.
Step 2, extraction
Adding the pretreatment liquid and the extractant into an extraction kettle according to the mass ratio of 1:1, controlling the rotating speed to be 350 revolutions per minute, stirring and extracting for 3 hours, stopping stirring, standing and layering for 6 hours, and separating an organic phase and a water phase, wherein the obtained organic phase is an extract liquid rich in succinic acid;
The extractant is a mixture of tetrahydroxyethyl ethylenediamine, sorbitol, D-xylose and deionized water;
the mass ratio of the tetrahydroxyethyl ethylenediamine to the sorbose to the D-xylose to the deionized water is 70:13:15:10.
Step 3, adsorption
Adding the extract into an adsorption column filled with the adsorbent at normal temperature, collecting all liquid flowing out from the bottom of the adsorption column by gravity and flowing through the adsorbent, adding the collected flowing-out liquid into the adsorption column again, repeating the cycle for adsorption for a plurality of times, continuously detecting the mass content value of succinic acid in the flowing-out liquid at the bottom of the adsorption column until the mass content value is reduced to 0.1wt% of the mass content value of succinic acid in the extract, collecting all liquid flowing out from the last time, repeatedly using as the extractant, and taking out the adsorbent for adsorbing succinic acid in the adsorption column for later use;
the mass ratio of the extract to the adsorbent is 68:50;
The preparation method of the adsorbent comprises the following steps: drying inorganic microporous adsorption material at 100 ℃ for 10 hours, then placing the inorganic microporous adsorption material into a dried reaction kettle, adding absolute ethanol and lauryl ether potassium phosphate, controlling the rotation speed to 3000 rpm, stirring and dispersing at normal temperature for 5 hours at high speed, reducing the stirring speed to 500 rpm, heating and keeping the temperature to 50 ℃, adding polyamino silane coupling agent, stirring and reacting at constant temperature for 10 hours, centrifuging, and drying the obtained solid at 40 ℃ in vacuum for 6 hours to obtain adsorbent;
the inorganic microporous adsorption material is palygorskite;
The particle size of the inorganic microporous adsorption material is 10nm;
The inorganic microporous adsorption material, absolute ethyl alcohol, lauryl alcohol ether potassium phosphate and polyamino silane coupling agent are added in a mass ratio of 20:150:1:2;
The polyamino silane coupling agent is N-beta (aminoethyl) -gamma-aminopropyl trimethoxy silane.
Step 4, high-temperature desorption
Adding the adsorbent for adsorbing succinic acid obtained in the step 3 and deionized water into an elution kettle according to the mass ratio of 4:3, controlling the stirring speed to be 150 r/min, heating to 80 ℃, stirring at constant temperature for 3 hours, maintaining the temperature for centrifugal separation at 80 ℃, recycling the solid adsorbent obtained by separation into the step 3 for continuous use, and obtaining liquid which is eluent rich in succinic acid.
Step 5, low temperature crystallization
Cooling the eluent to 0 ℃, standing for 20 hours at the temperature of 0 ℃, crystallizing and separating out succinic acid, filtering and separating crystal and mother liquor, collecting the mother liquor, mixing the mother liquor into the pretreatment liquid in the step 1 for recycling, and drying the separated crystal to obtain a succinic acid finished product with high purity.
Example 3: method for purifying succinic acid from fermentation broth
Step 1, pretreatment
Filtering succinic acid fermentation liquor to remove solid impurities, and decoloring with active carbon to obtain colorless transparent pretreatment liquor;
in the succinic acid fermentation broth, the mass concentration of succinic acid is 100.0g/L.
Step 2, extraction
Adding the pretreatment liquid and the extractant into an extraction kettle according to the mass ratio of 1:7, controlling the rotating speed to be 700 revolutions per minute, stirring and extracting for 7 hours, stopping stirring, standing and layering for 13 hours, and separating an organic phase and a water phase, wherein the obtained organic phase is an extract liquid rich in succinic acid;
The extractant is a mixture of tetrahydroxyethyl ethylenediamine, sorbitol, D-xylose and deionized water;
The mass ratio of the tetrahydroxyethyl ethylenediamine to the sorbose to the D-xylose to the deionized water is 110:36:30:25.
Step 3, adsorption
Adding the extract into an adsorption column filled with the adsorbent at normal temperature, collecting all liquid flowing out from the bottom of the adsorption column by gravity and flowing through the adsorbent, adding the collected flowing-out liquid into the adsorption column again, repeating the cycle for adsorption for a plurality of times, continuously detecting the mass content value of succinic acid in the flowing-out liquid at the bottom of the adsorption column until the mass content value is reduced to 0.5wt% of the mass content value of succinic acid in the extract, collecting all liquid flowing out from the last time, repeatedly using as the extractant, and taking out the adsorbent for adsorbing succinic acid in the adsorption column for later use;
The mass ratio of the extract to the adsorbent is 117:50;
The preparation method of the adsorbent comprises the following steps: drying an inorganic microporous adsorption material at 130 ℃ for 15 hours, then placing the inorganic microporous adsorption material into a dried reaction kettle, adding absolute ethanol and lauryl ether potassium phosphate, controlling the speed to be 5000 r/min, stirring and dispersing at normal temperature for 12 hours at a high speed, reducing the stirring speed to 1400 r/min, heating and keeping the temperature to 70 ℃, adding a polyamino silane coupling agent, stirring and reacting at the constant temperature for 17 hours, centrifuging, and drying the obtained solid at 60 ℃ in vacuum for 13 hours to obtain an adsorbent;
the inorganic microporous adsorption material is halloysite;
the particle size of the inorganic microporous adsorption material is 1000nm;
the mass ratio of the inorganic microporous adsorption material to the anhydrous alcohol to the potassium laureth phosphate to the polyamino silane coupling agent is 45:270:4:5;
the polyamino silane coupling agent is N- (2-aminoethyl) -3-aminopropyl triethoxy silane.
Step 4, high-temperature desorption
Adding the adsorbent for adsorbing succinic acid obtained in the step 3 and deionized water into an elution kettle according to the mass ratio of 7:3, controlling the stirring speed to be 500 r/min, heating to 95 ℃, stirring at constant temperature for 6 hours, maintaining the centrifugal separation at 95 ℃, recycling the solid adsorbent obtained by separation into the step 3 for continuous use, and obtaining liquid which is eluent rich in succinic acid.
Step 5, low temperature crystallization
Cooling the eluent to 4 ℃, standing for 30 hours at the temperature of 4 ℃, crystallizing and separating out succinic acid, filtering and separating crystal and mother liquor, collecting the mother liquor, mixing the mother liquor into the pretreatment liquid in the step 1 for recycling, and drying the separated crystal to obtain a succinic acid finished product with high purity.
Example 4: method for purifying succinic acid from fermentation broth
Steps 1 and 2 are the same as in example 1;
Step 3, adsorption
The polyaminosilane coupling agent is diethylenetriamine propyl trimethoxy silane, and the other operations are the same as in example 1;
Steps 4 and 5 were performed as in example 1.
Example 5: method for purifying succinic acid from fermentation broth
Steps 1 and 2 are the same as in example 1;
Step 3, adsorption
The polyaminosilane coupling agent was N- (2-aminoethyl) -3-aminopropyl methyldiethoxysilane, and the procedure was the same as in example 1;
Steps 4 and 5 were performed as in example 1.
Succinic acid yield and purity, and recycling efficiency of extractant and adsorbent:
in examples 1,2,3, 4 and 5, the yield and purity of succinic acid are shown in Table 1 below, and the same batch of extractant and adsorbent was recycled 100 times as in example 1, and the 101 st operation was continued as in example 1 to obtain succinic acid with the yields and purity shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the succinic acid yields of the five examples were all above 84% and the purities exceeded 99.4%, and the extractant and the adsorbent maintained 81% succinic acid yields and 99.3% purities after 100 cycles, indicating very good recycling properties of the extractant and the adsorbent.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (2)
1. A method for purifying succinic acid from a fermentation broth, characterized by:
the method for purifying the succinic acid from the fermentation broth comprises 5 steps of pretreatment, extraction, adsorption, high-temperature desorption and low-temperature crystallization;
the pretreatment, the succinic acid fermentation broth is filtered to remove solid impurities, and then is decolorized by active carbon to obtain colorless and transparent pretreatment broth;
Adding the pretreatment liquid and the extractant into an extraction kettle according to the mass ratio of 1:1-7, controlling the rotating speed to be 350-700 rpm, stirring and extracting for 3-7 hours, stopping stirring, standing and layering for 6-13 hours, and separating out an organic phase and a water phase, wherein the obtained organic phase is an extract liquid rich in succinic acid;
The extractant is a mixture of tetrahydroxyethyl ethylenediamine, sorbitol, D-xylose and deionized water;
Adding the extract into an adsorption column filled with the adsorbent at normal temperature, collecting all liquid flowing out of the adsorbent from the bottom of the adsorption column by gravity, adding the collected self-flowing liquid into the adsorption column again, repeatedly adsorbing for a plurality of times, continuously detecting the mass content value of succinic acid in the self-flowing liquid at the bottom of the adsorption column until the mass content value is reduced to 0.1-0.5wt% of the mass content value of succinic acid in the extract, collecting all liquid flowing out of the adsorption column for repeated use as the adsorbent, and taking out the adsorbent for adsorbing succinic acid in the adsorption column for later use;
The preparation method of the adsorbent comprises the following steps: drying an inorganic microporous adsorption material at 100-130 ℃ for 10-15 hours, then placing the inorganic microporous adsorption material into a dried reaction kettle, adding absolute ethyl alcohol and lauryl ether potassium phosphate, controlling the speed to be 3000-5000 r/min, stirring at normal temperature for dispersing for 5-12 hours, reducing the stirring speed to 500-1400 r/min, heating and keeping the temperature to 50-70 ℃, adding a polyamino silane coupling agent, stirring at a constant temperature for reacting for 10-17 hours, centrifuging, and drying the obtained solid at 40-60 ℃ in vacuum for 6-13 hours to obtain an adsorbent;
The inorganic microporous adsorption material is one of sepiolite, palygorskite and halloysite;
The polyamino silane coupling agent is one of N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, N-beta (aminoethyl) -gamma-aminopropyl trimethoxy silane, N- (2-aminoethyl) -3-aminopropyl triethoxy silane, diethylenetriamine propyl trimethoxy silane and N- (2-aminoethyl) -3-aminopropyl methyl diethoxy silane;
Adding the adsorbent for adsorbing succinic acid obtained in the step 3 and deionized water into an elution kettle according to the mass ratio of 4-7:3, controlling the stirring speed to be 150-500 r/min, heating to 80-95 ℃ and stirring at constant temperature for 3-6 hours, maintaining the temperature of 80-95 ℃ for centrifugal separation, and recycling the solid adsorbent obtained by separation to the step 3 for continuous use, wherein the obtained liquid is the eluent rich in succinic acid;
In the succinic acid fermentation broth, the mass concentration of succinic acid is 1.0-100.0 g/L;
the mass ratio of the tetrahydroxyethyl ethylenediamine to the sorbose to the D-xylose to the deionized water is 70-110:13-36:15-30:10-25;
the mass ratio of the extract to the adsorbent is 68-117:50;
The particle size of the inorganic microporous adsorption material is 10-1000 nm;
The inorganic microporous adsorption material, the absolute ethyl alcohol, the lauryl alcohol ether potassium phosphate and the polyamino silane coupling agent are added in a mass ratio of 20-45:150-270:1-4:2-5.
2. A method of purifying succinic acid from a fermentation broth according to claim 1, wherein:
And (2) cooling the eluent to 0-4 ℃, standing for 20-30 hours at the temperature of 0-4 ℃, separating out succinic acid crystals, filtering to separate crystals and mother liquor, collecting the mother liquor, mixing the mother liquor into the pretreatment liquid in the step (1), recycling, and drying the separated crystals to obtain a high-purity succinic acid finished product.
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