CN105017003A - Process for purifying organic acids - Google Patents
Process for purifying organic acids Download PDFInfo
- Publication number
- CN105017003A CN105017003A CN201410270337.4A CN201410270337A CN105017003A CN 105017003 A CN105017003 A CN 105017003A CN 201410270337 A CN201410270337 A CN 201410270337A CN 105017003 A CN105017003 A CN 105017003A
- Authority
- CN
- China
- Prior art keywords
- organic acid
- purifying
- extraction
- purifying organic
- methods
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 184
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 120
- 235000005985 organic acids Nutrition 0.000 title description 2
- 238000000605 extraction Methods 0.000 claims abstract description 105
- 238000002425 crystallisation Methods 0.000 claims abstract description 71
- 230000008025 crystallization Effects 0.000 claims abstract description 71
- 239000006228 supernatant Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000000284 extract Substances 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 157
- 239000007788 liquid Substances 0.000 claims description 76
- 239000003921 oil Substances 0.000 claims description 42
- 235000019198 oils Nutrition 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 38
- 238000001704 evaporation Methods 0.000 claims description 27
- 230000008020 evaporation Effects 0.000 claims description 27
- 239000003607 modifier Substances 0.000 claims description 24
- -1 polypropylene, tetrafluoroethylene Polymers 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000004743 Polypropylene Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 229920001155 polypropylene Polymers 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008394 flocculating agent Substances 0.000 claims description 10
- 238000011033 desalting Methods 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000005189 flocculation Methods 0.000 claims description 8
- 230000016615 flocculation Effects 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000003637 basic solution Substances 0.000 claims description 4
- 239000003225 biodiesel Substances 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims 2
- 239000001530 fumaric acid Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 14
- 238000000855 fermentation Methods 0.000 abstract description 10
- 230000004151 fermentation Effects 0.000 abstract description 10
- 238000000409 membrane extraction Methods 0.000 abstract 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 49
- 238000011084 recovery Methods 0.000 description 28
- 238000012360 testing method Methods 0.000 description 18
- 238000005265 energy consumption Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000007600 charging Methods 0.000 description 15
- 238000002203 pretreatment Methods 0.000 description 13
- 238000000926 separation method Methods 0.000 description 12
- 238000000108 ultra-filtration Methods 0.000 description 12
- 238000000746 purification Methods 0.000 description 11
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 10
- 239000012510 hollow fiber Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 238000004088 simulation Methods 0.000 description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000010612 desalination reaction Methods 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- 101100184147 Caenorhabditis elegans mix-1 gene Proteins 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004283 Sodium sorbate Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004302 potassium sorbate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- STGNLGBPLOVYMA-MAZDBSFSSA-N (E)-but-2-enedioic acid Chemical compound OC(=O)\C=C\C(O)=O.OC(=O)\C=C\C(O)=O STGNLGBPLOVYMA-MAZDBSFSSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- GIEGKXINITVUOO-UHFFFAOYSA-N 2-methylidenebutanedioic acid Chemical compound OC(=O)CC(=C)C(O)=O.OC(=O)CC(=C)C(O)=O GIEGKXINITVUOO-UHFFFAOYSA-N 0.000 description 1
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004303 calcium sorbate Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 1
- UPPOTMKEODYYFG-UHFFFAOYSA-N n,n-dioctylnonan-2-amine Chemical compound CCCCCCCCN(CCCCCCCC)C(C)CCCCCCC UPPOTMKEODYYFG-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- ATKIGFUAOXHQMV-UHFFFAOYSA-N octan-1-ol Chemical compound CCCCCCCCO.CCCCCCCCO ATKIGFUAOXHQMV-UHFFFAOYSA-N 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 229920003208 poly(ethylene sulfide) Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004326 stimulated echo acquisition mode for imaging Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Extraction Or Liquid Replacement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides a method for purifying an organic acid, comprising: adding an inorganic flocculant to a fermentation broth comprising an organic acid to form a mixture; (b) subjecting the mixture to a centrifugation procedure to obtain a supernatant and a precipitate, wherein the organic acid is located in the supernatant; (c) subjecting the supernatant to a membrane extraction procedure to obtain an extract, wherein the membrane extraction procedure comprises: (i) subjecting the supernatant to oil phase extraction with an oil phase to form an oil phase extraction product; and (ii) back-extracting the oil-phase extract product in a back-extracted phase to form the extract, wherein during the back-extracting, the pH of the back-extracted phase is adjusted such that at least one carboxyl moiety of the organic acid in the formed extract is in a carboxyl salt state; and (d) subjecting the extract to a crystallization procedure to obtain crystals of the organic acid.
Description
Technical field
The present invention relates to a kind of organic acid purification process, and in particular to a kind of organic acid method that purifying is produced by fermenting process.
Background technology
Organic acid synthesis mode mainly contains two kinds, is respectively chemical method and biotechnology.And biotechnology synthesis method mainly utilizes microorganism, by fermentation, carbon source is changed into organic acid.But ferment the organic acid produced, and concentration is low, and impurity is many and complicated, and comprises the by products such as organic acid of all kinds, therefore set up the purifying procedure of a simple low cost again quite not easily.
Again; containing microorganism, the carbon source do not used, suspended substance, protein miscellaneous, alcohols and other various organic acids etc. in organic acid fermentation liquid; so usually first solid-liquid separation can be carried out via a series of filter; to remove most suspended solid; then concentrate via vaporizer; and then carry out the crystallization procedure of twice, to obtain thick methylene-succinic acid.After thick methylene-succinic acid is utilized decolorizing with activated carbon, then refine organic acid via recrystallize program.
Because the selectivity of crystallization procedure is low, therefore, to obtain highly purified organic acid, then need to carry out a pair of crystallization procedure.But the concentration process in two crystallization procedure quite consumes energy, separation and purification cost is made to account for most of organic acid production cost.
Therefore, need one can the organic acid method that produces of effectively energy-conservation purification of fermentation process current pole.
Summary of the invention
The selectivity that purifying organic acid method of the present invention can solve known crystallization procedure used is low, can obtain highly purified organic acid.
The invention provides a kind of purifying organic acid method, comprising: (a) inorganic flocculating agent is added containing in organic acid fermented liquid to form mixture; B this mixture is carried out centrifuging process to obtain supernatant liquor and throw out by (), wherein this organic acid is arranged in this supernatant liquor; C this supernatant liquor is carried out film extraction program to obtain extraction liquid by (), wherein this film extraction program comprises: this supernatant liquor is carried out oil phase extraction to form oil phase extraction product with oil phase by (i); And this oil phase extraction product carries out stripping to form this extraction liquid to strip by (ii) mutually, wherein during this reextraction, adjust the pH value of this reextraction phase, become carboxyl salt state to make at least one carboxy moiety of this organic acid in this formed extraction liquid; And this extraction liquid is carried out crystallization procedure to obtain this organic acid crystallization by (d).
Accompanying drawing explanation
Fig. 1 shows the film extraction device used in one embodiment of the invention.
Fig. 2 shows the methylene-succinic acid purifying schema of one embodiment of the invention.
The inorganic salt flocculation agent that Fig. 3 A shows one embodiment of the invention amplifies the flow process of testing.
Fig. 3 B shows the ultra-filtration flow process of one embodiment of the invention.
Fig. 3 C shows the film extraction flow process of one embodiment of the invention.
Fig. 3 D shows the decoloring process flow process of one embodiment of the invention.
Fig. 3 E shows the first time crystallization flow process of one embodiment of the invention.
Fig. 3 F show one embodiment of the invention evaporation, filter desalination and second time crystallization flow process.
Fig. 3 G shows the flow process of the crystal refining of one embodiment of the invention.
Fig. 4 shows the methylene-succinic acid of one embodiment of the invention and the succsinic acid recovery benefit at film extraction.
Fig. 5 A shows the simulation contact surface of a traditional double crystallization procedure.
Fig. 5 B shows the modeling process chart of method of the present invention.
Embodiment
The invention provides a kind of purifying organic acid method.Compared to the organic acid method that known purifying is produced by fermenting process, except can obtaining highly purified organic acid, purifying organic acid method of the present invention also has excellent energy-saving effect.
In one embodiment, purifying organic acid method of the present invention, can include, but are not limited to what follows step.
First, inorganic flocculating agent is added by fermenting process produce containing in organic acid fermented liquid, to form mixture.This step can be considered pre-treatment step, wherein, makes an addition in fermented liquid by by inorganic flocculating agent, can make the solid suspension contamination precipitation in fermented liquid, to make organic acid in fermented liquid and the initial gross separation of solid suspension impurity.
Above-mentioned organic acid example, can comprise, but be not limited to, methylene-succinic acid (itaconic acid), succsinic acid (succinic acid), oxysuccinic acid (maleic acid), citric acid (citric acid), fumaric acid (fumaric acid), hexanodioic acid (adipic acid) and above-mentioned combination etc.In one embodiment, above-mentioned organic acid can be methylene-succinic acid.
And above-mentioned inorganic flocculating agent can be inorganic salts, but be not limited thereto.The example of above-mentioned inorganic salts, can include, but are not limited to calcium chloride (CaCl
2), aluminum chloride (AlCl
3), iron(ic) chloride (FeCl
3), Tai-Ace S 150 (Al
2(SO
4)
318H
2o) with above-mentioned combination.In one embodiment, the inorganic flocculating agent used in the organic acid method produced by fermenting process in purifying of the present invention is iron(ic) chloride.
Then, said mixture is carried out centrifuging process, to obtain supernatant liquor and throw out, wherein organic acid is arranged in supernatant liquor.The centrifugal speed of above-mentioned centrifuging process is about 4000-6000rpm, but is not limited thereto.In one embodiment, centrifugal speed is about 4000-6000rpm.In one embodiment, centrifugal speed is about 6000rpm.
Then, above-mentioned supernatant liquor is carried out film extraction program, to obtain extraction liquid, wherein obtained extraction liquid contains the organic acid through concentrated gained.
The aperture of the filtering material used in above-mentioned film extraction program can be about 0.08-0.45 μm, but is not limited thereto.The aperture of the filtering material used in above-mentioned film extraction program is in one embodiment about 0.2 μm.
And, the filtering material used in above-mentioned film extraction program can comprise, but be not limited to hydrophobic filter material or hollow filter material etc., and the example of above-mentioned hydrophobic filter material, polypropylene (polypropylene, PP) can be comprised, tetrafluoroethylene (polytetrafluoroethene, PTFE) fluoridizes divinyl (polyvinylidene difluoride with poly-, etc., but be not limited thereto PVDF).
Moreover above-mentioned film extraction program can comprise two steps, but is not limited thereto.
Step 1: first above-mentioned supernatant liquor is carried out oil phase extraction to form oil phase extraction product with oil phase.The weight ratio of above-mentioned supernatant liquor and above-mentioned oil phase can be about 1-10:1, but is not limited thereto.
Again, be above set forth in the oil phase used in oil phase extraction and can comprise thinner, modifier and extraction agent.The weight ratio of above-mentioned thinner, modifier and extraction agent can be about 70-90:5-15:5-15, but is not limited thereto.In one embodiment, the weight ratio of thinner, modifier and extraction agent can be about 70:15:15.In another embodiment, the weight ratio of thinner, modifier and extraction agent can be about 80:10:10.Again, in another embodiment, the weight ratio of thinner, modifier and extraction agent can be about 85:5:10.In another embodiment, the weight ratio of thinner, modifier and extraction agent can be about 85:7.5:7.5.In another embodiment again, the weight ratio of thinner, modifier and extraction agent can be about 85:10:5.
Thinner in above-mentioned oil phase can be immiscible organic solvent with water, but is not limited thereto.And example that is above-mentioned and the immiscible organic solvent of water, kerosene, diesel oil, biodiesel, Trisun Oil R 80, soybean oil, mibk (methyl isobutyl ketone), methylene dichloride (dichloromethane) and 1-octanol (1-octanol) etc. can be included, but are not limited to.
Separately, the modifier in above-mentioned oil phase can be the organic solvent containing phosphorus, but is not limited thereto.And the example of the above-mentioned organic solvent containing phosphorus, di-(2-ethylhexyl)phosphoric acid (di-2-ethylhexylphosphoric acid can be comprised, D2EHPA), tributyl phosphate (tri-n-butylphosphate, TBP) with trioctyl-phosphine oxide (Tri-n-octyl phosphine oxide, etc., but be not limited thereto TOPO).
Extraction agent in above-mentioned oil phase can be aliphatics amine, but is not limited thereto.Above-mentioned aliphatics amine can comprise, but be not limited to, methyl tricapryl ammonium chloride (trioctylmethylammonium chloride, Aliquat336), lauryl-trialkyl methyl amine (lauryl-trialkylmethylamine, AmberliteLA-2), three pungent decyl amine (tri-n-(octyl-decyl)-amine, or methyl trioctylphosphine amine (methyltrioctylamine, MTOA) etc. TOA).
After the step 1 of above-mentioned film extraction program completes, can then carry out step 2.Step 2: the oil phase extraction product obtained in step 1 is carried out stripping to form extraction liquid to strip mutually, wherein during reextraction, adjust the pH value of above-mentioned reextraction phase, become carboxyl salt state to make at least one carboxy moiety of organic acid in formed extraction liquid.That is, before film extraction program, be all carboxylic acid state for the organic acid carboxy moiety of purifying, and after film extraction program, at least one carboxy moiety of organic acid of institute's wish purifying becomes carboxyl salt state.
In the step 2 of above-mentioned film extraction program, oil phase extraction product can be about 1-4:4-1 with the weight ratio of reextraction phase.In one embodiment, oil phase extraction product can be about 2:1 with the weight ratio of reextraction phase.
The reextraction used in above-mentioned reextraction program can comprise water or basic solution mutually, but is not limited thereto.And the example of above-mentioned basic solution can comprise the NaOH aqueous solution, the NaCl aqueous solution, Na
2cO
3the aqueous solution, NH
3the aqueous solution and above-mentioned combination etc., but be not limited thereto.
Again, in the step 2 of above-mentioned film extraction program, the pH value of reextraction phase can be adjusted to about pH3.5-11.In one embodiment, be methylene-succinic acid for the organic acid of purifying, and in the step 2 of above-mentioned film extraction program, adjust the pH value of this oil phase extraction product to about pH4-7.
In the organic acid method that purifying of the present invention is produced by fermenting process, by film extraction program, can Simultaneous purification and concentrated organic acid, and reduce the treatment capacity in follow-up evaporation step, and then reduce the energy consumption of evaporation.In addition, in film extraction program, extraction agent must do not used in a large number, and extraction agent is also reusable, to reclaim product (organic acid) continuously.
Finally, in purifying organic acid method of the present invention, after aforementioned film extraction procedures completes, the extraction liquid obtained in film extraction program is carried out crystallization procedure, with obtain the organic acid crystallization of wish purifying.Above-mentioned crystallization procedure can be carried out in about 5-15 DEG C.In one embodiment, above-mentioned crystallization procedure can be carried out in about 10 DEG C.
Depend on the needs, the purifying organic acid method of the invention described above, adds inorganic flocculating agent before containing the step in organic acid fermented liquid aforementioned, also more can comprise adjustment fermented liquid to certain ph, and this certain ph can be about pH3-7.In one embodiment, be methylene-succinic acid for the organic acid of purifying, and above-mentioned certain ph is about pH3-6.
Again, in another embodiment of purifying organic acid method of the present invention, depend on the needs, between above-mentioned centrifuging process and above-mentioned film extraction program, also can more comprise, the throw out obtained by above-mentioned centrifuging process cleans with cleaning solvent and mixes to form the second mixture, then, described second mixture is filtered to form filtrate and filter residue, then, this filtrate is added in the supernatant liquor that above-mentioned centrifuging process obtains.By this, sediment undergoes washing is reclaimed the step of eluant, can improve for the organic acid rate of recovery of purifying.
In this embodiment, the weight ratio of above-mentioned throw out and cleaning solvent can be about 1-10:1.And the example of cleaning solvent can comprise that water, alcohols, second are fine, acetone and above-mentioned combination etc., but be not limited thereto.
Separately, in another embodiment of the organic acid method that purifying of the present invention is produced by fermenting process, depend on the needs, between above-mentioned centrifuging process and above-mentioned film extraction program, also more can comprise, the supernatant liquor that above-mentioned centrifuging process obtains is performed for more than filter fly sequence.
Nominal molecular weight restriction (nominalmolecular weight limit, NMWL) of the filtering material used in above-mentioned ultra-filtration program can be about 3-30kDa, but is not limited thereto.In one embodiment, the nominal molecular weight restriction of the filtering material used in above-mentioned ultra-filtration program can be about 10kDa.
Moreover, the filtering material used in above-mentioned ultra-filtration program can comprise, but be not limited to, polystyrene (polystyrene, PS), polysulfones (polysulfone), polypropylene (polypropylene, PP), polyethersulfone (polyethersulfone, PES), poly-fluoridize divinyl (polyvinylidene difluoride, PVDF) or hollow filter material etc.
In addition, in purifying organic acid method of the present invention, between aforementioned film extraction procedures and crystallization procedure, depend on the needs, more comprise, the extraction liquid obtained in above-mentioned film extraction program is carried out micro-filtration program.The aperture of the filtering material used in micro-filtration program can be about 0.2-1 μm, but is not limited thereto.
In purifying organic acid method of the present invention, between aforementioned film extraction procedures and crystallization procedure, depend on the needs, also can more comprise, adjust extraction liquid that above-mentioned film extraction program obtains to certain ph, and this certain ph can be about pH2.5-4.In one embodiment, be methylene-succinic acid for the organic acid of purifying, and above-mentioned certain ph is about pH2.5-3.
In another embodiment again of the organic acid method produced by fermenting process at purifying of the present invention, between aforementioned film extraction procedures and crystallization procedure, depend on the needs, also can more comprise, the extraction liquid that above-mentioned film extraction program obtains is carried out decoloring process.In decoloring process, soluble impurity can be removed.
Above-mentioned decoloring process can be heated to about 60-90 DEG C afterwards to carry out by interpolation activated carbon in above-mentioned extract, but is not limited thereto.In one embodiment, the temperature of the heating of decoloring process can be about 70-80 DEG C.
The inventive method containing decoloring process embodiment in, above-mentioned crystallization procedure, can by by through decolouring extraction liquid two-part be cooled to about 5-15 DEG C to carry out.
Again, in purifying organic acid method of the present invention, depend on the needs, after above-mentioned crystallization procedure, also can more comprise, extraction liquid remaining after above-mentioned crystallization procedure being completed carries out evaporation procedure to obtain concentrated extract, then by concentrated extract in not yet lowering the temperature state (namely, the condition of high temperature) under carry out filter to obtain solution through desalting, and afterwards the solution through desalting is carried out the second crystallization procedure to obtain organic acid crystallization.Above-mentioned evaporation procedure can promote organic acid concentration, and then increases the organic efficiency of later crystallization.In addition, utilize salt solubleness at high temperature far below organic acid characteristic, to perform the program of filtration under above-mentioned not yet cooling state, the effect effectively desalted can be reached.
Above-mentioned state of not yet lowering the temperature, is the condition of high temperature, and it can be about 60-90 DEG C.In one embodiment, above-mentioned state of not yet lowering the temperature can be about 70-80 DEG C.
And above-mentioned second crystallization procedure, by the solution two-part through desalting is cooled to about 5-15 DEG C to carry out, but can be not limited thereto.In one embodiment.About 10 DEG C can be cooled to carry out by by the solution two-part through desalting.
In addition, depend on the needs equally, after above-mentioned second crystallization procedure, also can more comprise, after above-mentioned second crystallization procedure being completed, the remaining solution through desalting carries out evaporation procedure to obtain the concentrated solution that desalts, then, the concentrated solution that desalts to be carried out the 3rd crystallization procedure to obtain containing this organic acid solid, then cleaned to wash out organic acid with cleaning solvent by solid, with finally, this organic acid is carried out evaporation procedure to remove this cleaning solvent and to obtain this organic acid crystallization.
Above-mentioned 3rd crystallization procedure can be carried out in about 5-15 DEG C, but is not limited thereto.In one embodiment, the 3rd crystallization procedure can be carried out in about 15 DEG C.
Again, above-mentioned solid can be about 1-1:1-4 with the weight ratio of the cleaning solvent in order to clean this solid, but is not limited thereto.In one embodiment, above-mentioned solid can be about 1:3 with the weight ratio of the cleaning solvent in order to clean this solid.And the example in order to clean the cleaning solvent of this solid can include, but are not limited to that water, alcohols, second are fine, acetone and above-mentioned combination etc.
Compared to known method, carry out by method of the present invention the organic acid that purifying produces by fermenting process, the energy expenditure of at least 60% can be saved.Carry out by method of the present invention the organic acid that purifying produces by fermenting process again, the organic efficiency of at least 85% can be reached.
Embodiment
Embodiment 1
Condition test
A. the precipitation test of inorganic salt flocculation agent
In this test, itaconic acid fermentation liquid is carried out precipitation test with various different inorganic flocculating agent.
Because itaconic acid fermentation liquid composition is quite complicated, not only there are multiple micromolecular salt and organic acid, the solid impurity that film much can be caused to block in addition, if so only carry out initial gross separation with micro-filtration program, the easy serious scale of micro-filtration film, and cause filtering velocity deep fades, and film can be made to decline work-ing life.Therefore, from fermented liquid purifying methylene-succinic acid time, need to carry out pre-treatment to reduce solid impurity.In this test, with four kinds of common inorganic salts CaCl
2,
alCl
3with FeCl
3as flocculation agent.
After fermented liquid is adjusted to suitable pH value, get the flocculant solution of proper concn 1 milliliter in the fermented liquid of 20ml, at room temperature, stir 1 hour to form mixture (in Glass Containers).Then, get said mixture 8 or 10g and leave standstill 1 hour in centrifuge tube, with 6000rpm centrifugal 5 minutes afterwards, remove complicated solid impurity in the mode centrifugal by sedimentation.Then, get supernatant liquid body, carry out particle diameter and concentration analysis.The result of the fermented liquid of pH6 and the fermented liquid of pH3 is respectively as shown in table 1 Yu table 2.
Table 1: various flocculant concentration is the impact of the fermented liquid of 6 on pH value
Table 2: various flocculant concentration is the impact of the fermented liquid of 3 on pH value
In this test, the situation of losing with the centrifugal weight of rear subnatant of sedimentation, the particle size analysis of upper liquid and methylene-succinic acid, judges the effect of flocculation agent to the pre-treatment of different pH value fermented liquid.
Known according to table 1, when fermented liquid pH value is 6, carry out pre-treatment with the condition of A3, A7 and A8, flocculation agent all effectively can play a role and increase the particle diameter of molecule, make much impurity can centrifugal settling out, but its cause IA loss be respectively 24.4%, 40.0% and 27.7%.
And known according to table 2, when fermented liquid pH value is 3, carry out pre-treatment with the condition of B5 and B9, good separation efficiency can be obtained and lose with lower methylene-succinic acid.
B. film extraction
1. the device of film extraction and operational condition
Polypropylene (polypropylene, the PP) hollow fiber module of Liqui-cel is utilized to reclaim methylene-succinic acid as tool dispersion reextraction phase support type liquid film.Fig. 1 is shown in the film extraction device used in the present invention's experiment.
See Fig. 1, the left side of polypropylene (polypropylene, PP) hollow fiber module 101 is shell-side (shell side) 103, and the right side of polypropylene hollow fiber module 101 is pipe side (tube side) 107.During film extraction, introduce shell-side 103 via pipeline from top to bottom by containing organic acid oil phase and the mixed solution 105 of reextraction phase, and via pipeline, charging supernatant liquor 109 is introduced tubing string side 107 from lower to upper.Relatively, during cleaning polypropylene hollow fiber module 101, via pipeline, scavenging solution is introduced shell-side 103 from lower to upper to clean shell-side 103, and via pipeline by scavenging solution from top to bottom inlet tube side 107 with wash tube side 107.
According to Fig. 1, carry out connection line.After confirming that pipeline flow process is errorless, open the magnetite agitator of charging and the peristaltic pump being connected charging supernatant liquor, and adjust peristaltic pump rotating speed, charging supernatant liquor to be delivered into the pipe side 104 of hollow fiber module 101 with the flow velocity of 0.5 ~ 1L/ minute.Hollow fiber module 101 is vertical type in operation, and the flow direction of charging supernatant liquor is bottom in and top out.Due to the polypropylene material that hollow fiber conduit is hydrophobic, therefore fill up pipe side until feedstock solution and after flowing out, adjust under meter valve, applying the pressure of about 4psi in pipe side, infiltrating into mutually in feedstock solution with reextraction to prevent oil phase.Appropriate extraction agent (oil phase) and strippant (reextraction phase) mixing are inserted same container, and when the agitating vane of adjustment agitator launches between two-phase liquid level, turn on agitator, speed setting, in 300rpm, makes two-phase dispersed.
Open the peristaltic pump power supply connecting oil phase, rotating speed on adjustment peristaltic pump, the dispersion liquid of oil phase and reextraction phase is delivered to the shell-side 103 of module 101 with the flow velocity of 0.5L/ minute, flows to as upper entering and lower leaving and contrary with feedstock solution (counter-current flow).Until charging supernatant liquor with oil phase/reextraction phase mixing solutions when the interracial contact of film, the time of module is flow to from oil phase, start timing in regular hour point (every 30 minutes), draw quantitative charging supernatant liquor and fluid, so that follow-up measurement step.
After experiment terminates, separate collection oil phase, with the liquid of reextraction phase, after using the 2wt%NaOH aqueous solution, Virahol and pure water to clean film group respectively, inputs high-pressure air from the pipeline feed end of tube layer and shell simultaneously, makes its dry 4 hours.
2. the test of film extraction
The test of (a) oil phase extraction
The oil phase of film extraction comprises thinner, modifier and extraction agent.Secondly the selection of modifier focuses on its compound dissolution that extraction agent and organic acid can be helped to be formed in thinner, is then to consider its price and water-soluble; And, the selection of extraction agent focus on its can effectively catch get for the organic acid of purifying, and easily can be stripped into aqueous phase again, be secondly then consider its bio-toxicity and price.
In this test, use di-(2-ethylhexyl)phosphoric acid (di-2-ethylhexyl phosphoric acid, or tributyl phosphate (tri-n-butylphosphate D2EHPA), TBP) as modifier, and use methyl tricapryl ammonium chloride (trioctylmethylammonium chloride, Aliquat336) or three pungent decyl amine (tri-n-(octyl-decyl)-amine, TOA) be extraction agent, and inquire into its usability when multicomponent extracts and selectivity.The modifier used and the characteristic of extraction agent as shown in table 3.
Table 3: the essential property of modifier and extraction agent
And modifier, di-(2-ethylhexyl)phosphoric acid (di-2-ethylhexyl phosphoric acid, D2EHPA) is as follows respectively with the structure of tributyl phosphate (tri-n-butylphosphate TBP):
Di-(2-ethylhexyl)phosphoric acid (D2EHPA)
Tributyl phosphate (TBP)
Separately, extraction agent, the structure of methyl tricapryl ammonium chloride (trioctylmethylammonium chloride, Aliquat336) or three pungent decyl amine (tri-n-(octyl-decyl)-amine, TOA) is as follows respectively:
Methyl tricapryl ammonium chloride (Aliquat336)
Three pungent decyl amine (TOA)
In this test, extract with shake flat experiment.Charging is the mixed organic acid aqueous solution of 20g, feed composition is the methylene-succinic acid of 20mg/ml, citric acid (the citric acid of 3.7mg/ml, CA), oxysuccinic acid (the malic acid of 2.9mg/ml, MA), succsinic acid (the succinic acid of 0.87mg/ml, and (glycerine glycerol, the Gly) of 4.7mg/ml SA).The methylene-succinic acid purity of charging is 61.7%.Oil phase is then the mixing solutions of the thinner of 20g, modifier and extraction agent.
Shaking flask 2 hours under the condition of 30 DEG C and 100rpm, anti-stripping agent is then the NaCl aqueous solution of the 0.34M of 20g.First must adjust the pH value of charging supernatant liquor on pretreatment, because the extraction agent selected by this, need methylene-succinic acid just can form compound with extraction agent under non-condition of dissociating, the pka of methylene-succinic acid is 3.65 and 5.13 respectively, thus when this by pH value fixed adjustment at pH3 extract.Experimental result is as shown in table 4.
Table 4: modifier and extraction agent are on the impact of extraction efficiency
Known according to table 4, from experiment A, B and C, if be modifier with TBP, the compound that methylene-succinic acid and extraction agent are formed is not dissolved in oil phase with aqueous phase, therefore there is the generation of third phase, the system of film extraction may be unfavorable for, therefore select D2EHPA better as modifier.
Can be found by experiment A, D, E and F, the methylene-succinic acid rate of recovery can't increase along with the concentration of modifier and extraction agent and rise, that to add being combined in of extraction agent at thinner and modifier 85 to 15 best on the contrary, wherein the ratio of modifier and extraction agent on the rate of recovery without too large impact, only to solution viscosity difference to some extent, and the highest to test the methylene-succinic acid purity that F reclaims, therefore inquire into different extraction agents and the impact of thinner with the ratio of testing F again.
Learnt by the result of experiment F, G, H and I, various combination does not have too big-difference for the methylene-succinic acid purity be finally recovered to, but use biodiesel can obtain the higher rate of recovery, only the viscosity of biodiesel when extracting is higher, solution change need be noticed during use, avoid viscosity increase to cause the problem of fouling.
B test that () is stripped
In reextraction, in this test, extract with shake flat experiment.Charging is the mixed organic acid aqueous solution of 20g, and feed composition is the MeOH of the methylene-succinic acid of 23.4mg/ml, the citric acid of 2.2mg/ml, the oxysuccinic acid of 2.65mg/ml, the succsinic acid of 0.85mg/ml, the glycerine of 4.2mg/ml and 13.9mg/ml.The IA purity of charging is 49.5%.The mixing solutions of the Aliquat336 of the kerosene of the 85wt% that 20g oil phase includes, D2EHPA and 5wt% of 10wt%, shaking flask 2 hours under the condition of 30 DEG C and 100rpm, strippant is then NaCl, NaOH or Na of 20g
2cO
3the aqueous solution.
Table 5: strippant is on the impact of extraction efficiency
Known according to table 5, under no matter using which kind of salt or different salt densities, the methylene-succinic acid purity after its recovery, all more than 70%, wherein uses Na
2cO
3or the effect of the NaCl of high density is best, but use NaOH or Na
2cO
3organic efficiency as strippant is the highest, but has the formation of third phase when stripping and solution viscosity increases.Therefore in order to avoid the generation of fouling causes membrane life time to decline, whether fouling produces becomes most important selection consideration.
Embodiment 2
From itaconic acid fermentation liquid purifying methylene-succinic acid
A. flow process general introduction
Methylene-succinic acid purifying schema as shown in Figure 2.See Fig. 2.Script pH value is about the fermented liquid 1 liter of 6-7, utilizes the H of 6M
2sO
4adjust its pH value to 3 (step 201).Then the FeCl of 2M is added
3solution is to carry out pre-treatment (step 203) and after at room temperature stirring, after leaving standstill a few hours, centrifugal supernatant liquid (step 205), bottom aqueous precipitation is again with air exhaust filtering (step 207) and wash in right amount, the stripping methylene-succinic acid aqueous solution, reduces the loss of methylene-succinic acid.Then, methylene-succinic acid solution continues to remove micromolecular solid impurity (step 209) with ultra-filtration again.The pH value of filtrate is adjusted to after being less than 5.2 (steps 211) and carries out purifying and concentrated (step 213) with film extraction.Afterwards, concentrated methylene-succinic acid solution (inessential) of purifying, then after the pH value (step 215) adjusting solution, carry out decolorizing with activated carbon (step 217).Be cooled to 10 degree and carry out crystallization (step 219), collect appropriate highly purified methylene-succinic acid crystal, remaining liquid recycling evaporation mode is concentrated into a certain degree after (step 221), at high temperature carry out filtration desalination (step 223) at once, crystallization (step 225) is carried out in cooling afterwards, obtains methylene-succinic acid crystal.
B. the test of each step and result
The amplification test of 1.Fe series flocculants pre-treatment
Inorganic salt flocculation agent amplifies the flow process of test as shown in Figure 3A.See Fig. 3 A.Utilize the H of 6M
2sO
4adjustment, by after the fermented liquid pH value to 3 (step 201) of charging, adds the FeCl of appropriate 2M
3solution (step 203) also, after at room temperature stirring, leaves standstill a few hours to carry out pre-treatment.Afterwards, obtain supernatant liquid (step 205) by centrifugal for the fermented liquid after pre-treatment, and filter (step 207) after lower floor being rinsed with appropriate clear water.The weight percent of cleaning liquid and fermented liquid is about 0:1 to 1:1.Result is as shown in table 6.
It is noted that below respectively show shown in the identical sample of sample names numerical portion, be the sample with coherent previous step.
The pre-treatment of table 6:Fe series flocculants
Known according to table 6, make the rate of recovery of methylene-succinic acid be increased to 90-100% by this treatment step.
2. ultra-filtration
Fig. 3 B display utilizes the flow process of ultra-filtration, and the filtered liquid that the supernatant liquid after flocculation treatment then rinses with lower floor clear water is mixed into the flow process of ultra-filtration.Be performed for more than filter (step 209) with polysulfones (polysulfon) hollow-fibre membrane of 10kDa, by the pressure-controlling of ultra-filtration at 5-10psi, sweep Flow Velocity and control at 5L/ minute, result is as shown in table 7.
Table 7: the efficiency of ultra-filtration
Known according to table 7, in ultrafiltration steps, the methylene-succinic acid rate of recovery is about 96.7-100%, and reclaims filtering velocity and be about 2.33-15ml/m
2minute.
3. film extraction
Fig. 3 C shows the flow process of sharp film extraction.Utilize the PP hollow fiber module of Liqui-cel as tool dispersion reextraction phase support type liquid film to carry out film extraction (step 213), to reclaim methylene-succinic acid after ultra-filtration.
Consist of kerosene/D2EHPA/Aliquat336 at extraction agent and in reusable situation, after ultra-filtration, reclaim methylene-succinic acid, result is as shown in table 8.
Known according to table 8, in film extraction program, in operating time 2-4 hour, utilize the NaOH of 0.5-5.5M, can concentrate methylene-succinic acid 2-4 doubly, the rate of recovery is 63.8-112.5%, and it is 1.6-9.3gIA/m that methylene-succinic acid reclaims filtering velocity
2hr.
3. decolour
Fig. 3 D shows the flow process of decoloring process.See Fig. 3 C.To purify via film extraction concentrated after methylene-succinic acid solution, the activated carbon (step 217A) adding 1wt% between pH3-5.66 is to carry out decolour (step 217B) when 70-80 DEG C.Result is as shown in table 9.
Table 9: desolventing technology
Can learn according to table 9, after desolventing technology, the rate of recovery of methylene-succinic acid, between 70.7-100%, wherein can obtain the good rate of recovery with pH3 or below pH3 decolouring.
4. first time crystallization
Fig. 3 E figure shows first subcrystalline flow process.See Fig. 3 E.By solution adjustment when pH is 3, two-part is cooled to 10 degree and carries out crystallization (step 219).It is as shown in table 10 that methylene-succinic acid reclaims result.
Table 10: first time crystallization
Known according to table 10, first time crystallization gained crystal purity is 94.5-99.4%, and the crystal rate of recovery is 14.6-50.3%.
Follow-up methylene-succinic acid solution (D
out) then can continue evaporation again and dewater and carry out second time crystallization.
5. evaporate, filter desalination, second time crystallization
Fig. 3 F shows evaporation, filters desalination and second subcrystalline flow process.See Fig. 3 F.First by methylene-succinic acid soln using evaporation concentration (step 221) extremely to a certain degree.Then, due to the NaCl also containing high density in solution, therefore utilize salt solubleness at high temperature far below organic acid characteristic, remove salt (step 223) in the mode of filtering.Then be cooled to 10 DEG C with two-part, carry out crystallization (step 225).Second subcrystalline recovery result is as shown in table 11.
Table 11: evaporation, filtration and second time crystallization
Known according to table 11, after evaporation, filtration desalination and second subcrystalline flow process, gained crystal purity is 71.7-99.5%, and second subcrystalline crystal rate of recovery is 16.8-47.5%.
Follow-up methylene-succinic acid solution (C
out2) then can get back between step 219 in Fig. 2 and step 221, or continue crystallization in the following manner.
6. crystal refining
Fig. 3 G shows the flow process of crystal refining.See Fig. 3 G.By from the C in Fig. 3 F
out2methylene-succinic acid solution, continue evaporation and remove (step 227), at low temperatures crystallization (step 229) after most water, solid crystal is produced.And then take weight ratio as washed with methanol (step 231) solid crystal of 1:3-4.After washing out the solution containing methylene-succinic acid, recycling evaporation methanol removal (step 233).The methylene-succinic acid recovery result of the flow process of crystal refining is as shown in table 12.
Table 12: crystallization and solvent cleaning
Known according to table 12, in the process of crystal refining, the methylene-succinic acid rate of recovery can reach 97.1-100%, and the purity before non-drying is 55-87% (containing methyl alcohol), and the dried purity of vacuum drying oven can reach more than 98%.
7. recycled in its entirety rate
See Fig. 2.The output of each flow process indicated in Fig. 2, the methylene-succinic acid rate of recovery of output (OP) 1-9, and the recycled in its entirety rate of purification process of the present invention is shown in the table 13 of below.
Table 13: the methylene-succinic acid rate of recovery
Table 13 shows, to date through the flow process of pre-treatment, ultra-filtration and film extraction the methylene-succinic acid of loss 0 to 9.6%, and can be recycled to the methylene-succinic acid of 91.1 to 92.3% altogether by purification process of the present invention in output 7, output 8 with output 9, methylene-succinic acid can be made to have the rate of recovery of more than 85%.
Embodiment 3
The recovery of succsinic acid in membrane system
Be combined as extraction agent with kerosene/D2EHPA/Aliquat336, with the mixing solutions of the NaCl of NaOH and the 5M of 2M for reextraction phase, film extraction carried out to the charging of the succinic acid fermentation broth containing 58.7g/L.The results are shown in table 14.
Table 14: the film extraction of succsinic acid
Result shows, the succsinic acid of film extraction recyclable 90.4%.Again, methylene-succinic acid and succsinic acid film extraction recovery benefit comparison as shown in Figure 4.As shown in Figure 4, in film extraction flow process, if arrange in pairs or groups suitable condition, then can reclaim the target organic acid of more than 90% within the operating time of four hours.
Again, to take purifying succinic acid fermented liquid with the identical purifying flow process shown in embodiment 2.According to the output of each flow process indicated in Fig. 2, the succsinic acid rate of recovery of output (OP) 1-9, and the recycled in its entirety rate of purification process of the present invention is shown in the table 15 of below.
Table 15: the rate of recovery of succsinic acid
Result shows, and in purifying flow process, the main-process stream rate of recovery of succsinic acid is about 70.3%, lower than methylene-succinic acid, does not need through decolouring, and only need once concentration and crystallization procedure in simplification process.
Embodiment 4
The present invention compares with the rate of recovery with the energy consumption assessment of prior art
1. the energy consumption analysis of traditional double crystallization mode
Business-like methylene-succinic acid processing procedure is with continuous evaporation and concentration and binode crystalline substance (2-stagecrystallization) mode purifying methylene-succinic acid.The separation and purification programflow chart of simulate commercial binode crystalline substance in this experiment.The separation and purification programflow chart of commercialization binode crystalline substance as shown in Figure 5A.
Fermented liquid after filtering is entered first paragraph vapo(u)rization system (EVAP-1) by storage tank, is concentrated into 37wt% to make fermented liquid by 10wt% methylene-succinic acid.First paragraph vapo(u)rization system adopts double-effect evaporation (Double-effectevaporation) system (EVAP-1), and (EVAP-1 is double-effect evaporation tank, therefore the energy consumption needing calculating 2 to evaporate on calculating, energy consumption is E-201 & E-202).Concentrated fermented liquid enters the first crystallizer (CRYST-1) again, and Tc operates in 15 DEG C, and the methylene-succinic acid of about 90% can crystallize out in this.Remaining liq enters the first whizzer (CFG-1) again by solid-liquid separation.Centrifugal liquid enters the second vaporizer (EVAP-2) (energy consumption E-203) and continues thickening, enter the second crystallizer (CRYST-2) again, Tc operates in 15 DEG C, enter the second whizzer (CFG-2) again by solid-liquid separation, can reclaim the methylene-succinic acid of about 5% again, centrifugal remaining liq is used as waste.The isolated crystallization methylene-succinic acid of whizzer CFG-1 and CFG-2 need enter active carbon tank (A-CARBON) again, include the activated carbon of the 1wt% of methylene-succinic acid, and with 80 DEG C of hot water dissolving's methylene-succinic acids to carry out methylene-succinic acid decolouring, then again with strainer (FILTER) filtering activated carbon and solid impurity.Filtrate after decolouring enters the 3rd crystallizer (CRYST-3) again, Tc operates in 15 DEG C, enter the 3rd whizzer (CFG-3) again by solid-liquid separation, crystallization methylene-succinic acid is separated in this, enter rotary drier (DRYER) again to continue to dehydrate, final methylene-succinic acid purity can reach 99.5wt%.Whizzer CFG-3 centrifugal go out liquid still containing a small amount of methylene-succinic acid, recirculation can enter first paragraph vapo(u)rization system (EVAP-1), continue to reclaim methylene-succinic acid, to improve the rate of recovery.
Show the simulation contact surface of traditional double crystallization procedure according to Fig. 5 A, analyze the simulation energy consumption of Escherichia coli fermentation (Titer=8%)+traditional double crystallization processing procedure.
The design basis of above-mentioned simulation is as follows:
Fermented liquid methylene-succinic acid concentration=8wt%, the methylene-succinic acid rate of recovery=95%.
Methylene-succinic acid output=20,000ton/.
Hours run=8,000hr/.
And result is shown in table 16.
Table 16: the result of the energy consumption of emulation traditional double crystallization procedure
Note: K-101 and K-102 is the energy consumption of compressor in fermenting process, is not therefore shown in the separation and purification programflow chart shown in Fig. 5 A, but needs to be listed in energy consumption calculation.
2. the energy consumption analysis of method of the present invention
Fig. 5 B shows the modeling process chart of method of the present invention.From Fig. 5 B, the inventive method need through, inorganic salt pre-treatment, centrifugal (CFG-1), filter (FILT-1), filter (UF), film extraction (ME), first time crystallization and centrifugal (CRYST-1, CFG-1), decolouring (A-CARBON), filter (FILT-2), (EVAP is double-effect evaporation tank to the double-effect evaporator (EVAP) that can contract, therefore the energy consumption needing calculating 2 to evaporate on calculating, energy consumption is E-201 & E-202), second time crystallization and centrifugal (CRYST-2, CFG-2), drying machine (DRYER) and pump (Pumps) supervisor and device, wherein Fig. 5 B schemes the devices that shown MIX-1 and MIX-2 is two mixing, 2 bursts of chargings.
Show the simulation contact surface of the inventive method according to Fig. 5 B, analyze the simulation energy consumption of Escherichia coli fermentation (Titer=8%)+the inventive method.
The design basis of above-mentioned simulation is as follows:
Fermented liquid methylene-succinic acid concentration=8wt%, the methylene-succinic acid rate of recovery=95%.
Methylene-succinic acid output=20,000ton/.
Hours run=8,000hr/.
And result is shown in table 17.
Table 17: the result of the energy consumption of simulation the inventive method
Note: K-101 and K-102 is the energy consumption of compressor in fermenting process, is not therefore shown in the separation and purification programflow chart shown in Fig. 5 B, but needs to be listed in energy consumption calculation.
3. traditional double crystallization reclaims comparing of methylene-succinic acid with the inventive method
Result according to table 16 Yu table 17, integrates out the characteristic that traditional double crystallization procedure and the inventive method reclaim methylene-succinic acid in table 18.
Table 18, traditional double crystallization procedure and the inventive method reclaim the characteristic of methylene-succinic acid
Nomenclature
P ~ pressure warning unit;
F ~ velocimeter;
101 ~ polypropylene (polypropylene, PP) hollow fiber module;
102 ~ pump;
103 ~ shell-side (shell side);
104 ~ agitator;
105 ~ oil phase;
107 ~ pipe side (tube side);
109 ~ reextraction phase;
201 ~ adjusted to ph is to pH<7;
203 ~ pre-treatment;
205 ~ centrifugal;
207 ~ filter;
209 ~ ultra-filtration;
211 ~ adjusted to ph is to pH<5.2;
213 ~ film extraction;
215 ~ adjusted to ph is to pH<6.5;
217 ~ decolouring and filtration;
219 ~ crystallization;
221 ~ evaporation;
223 ~ filter;
225 ~ crystallization;
225 ' ~ evaporation and washed with methanol;
227 ~ evaporation;
OP1-OP9 ~ output 1-output 9;
229 ~ crystallization is in 15 DEG C;
231 ~ cleaning;
233 ~ evaporation;
STEAM ~ steam;
EVAP-1, EVAP ~ double-effect evaporation tank;
CRYST-1 ~ the first crystallizer;
CFG-1 ~ the first whizzer;
EVAP-2 ~ the second vaporizer;
CRYST-2 ~ the second crystallizer;
CFG-2 ~ the second whizzer;
A-CARBON ~ active carbon tank;
FILTER, FILT-1, FILT-2 ~ strainer;
CRYST-3 ~ the 3rd crystallizer;
CFG-3 ~ the 3rd whizzer;
DRYER ~ drying machine;
UF ~ filtration;
ME ~ film extraction;
MIX-1, MIX-2 ~ mixing device;
P-101, P-102, P-103 ~ pump.
Claims (33)
1. a purifying organic acid method, comprising:
(a) inorganic flocculating agent is added containing in organic acid fermented liquid to form mixture;
B this mixture is carried out centrifuging process to obtain supernatant liquor and throw out by (), wherein this organic acid is arranged in this supernatant liquor;
C this supernatant liquor is carried out film extraction program to obtain extraction liquid by (), wherein this extraction liquid contains through concentrated organic acid,
Wherein this film extraction program comprises:
I this supernatant liquor is carried out oil phase extraction to form oil phase extraction product with oil phase by (); And
(ii) this oil phase extraction product is carried out stripping to form extraction liquid to strip mutually, wherein during this reextraction, adjust the pH value of this reextraction phase, become carboxyl salt state to make at least one carboxy moiety of organic acid in formed extraction liquid; And
D this extraction liquid is carried out crystallization procedure to obtain this organic acid crystallization by ().
2. purifying organic acid method as claimed in claim 1, wherein this organic acid comprises methylene-succinic acid, succsinic acid, oxysuccinic acid, citric acid, fumaric acid, hexanodioic acid or above-mentioned combination.
3. purifying organic acid method as claimed in claim 1, wherein this flocculation agent comprises inorganic salts.
4. purifying organic acid method as claimed in claim 3, wherein this inorganic salts comprises calcium chloride (CaCl
2), aluminum chloride (AlCl
3), iron(ic) chloride (FeCl
3), Tai-Ace S 150 (Al
2(SO
4)
318H
2or above-mentioned combination O).
5. purifying organic acid method as claimed in claim 1, the filtering material wherein used in this film extraction program comprises hydrophobic filter material or hollow filter material.
6. purifying organic acid method as claimed in claim 1, wherein this hydrophobic filter material can comprise polypropylene, tetrafluoroethylene or poly-ly fluoridize divinyl.
7. purifying organic acid method as claimed in claim 1, wherein the weight ratio of this supernatant liquor and this oil phase is about 1-10:1.
8. purifying organic acid method as claimed in claim 1, wherein this oil phase comprises thinner, modifier and extraction agent.
9. purifying organic acid method as claimed in claim 8, wherein the weight ratio of this thinner, this modifier and this extraction agent is about 70-90:5-15:5-15.
10. purifying organic acid method as claimed in claim 8, wherein this thinner is immiscible organic solvent with water, wherein should comprise kerosene, diesel oil, biodiesel, Trisun Oil R 80, soybean oil, mibk, methylene dichloride or 1-octanol with the immiscible organic solvent of water.
11. purifying organic acid methods as claimed in claim 8, wherein this modifier is the organic solvent containing phosphorus, wherein should comprise di-(2-ethylhexyl)phosphoric acid, tributyl phosphate or trioctyl-phosphine oxide by the organic solvent containing phosphorus.
12. purifying organic acid methods as claimed in claim 8, wherein this extraction agent is aliphatics amine, and wherein this aliphatics amine comprises methyl tricapryl ammonium chloride, lauryl-trialkyl methyl amine, three pungent decyl amine or methyl trioctylphosphine amine.
13. purifying organic acid methods as claimed in claim 1, wherein this oil phase extraction product is about 1-4:4-1 with the weight ratio of this reextraction phase.
14. purifying organic acid methods as claimed in claim 1, the wherein pH value of this oil phase extraction product of adjustment extremely about pH3.5-11 in step (ii).
15. purifying organic acid methods as claimed in claim 1, wherein this organic acid is methylene-succinic acid, and in step (ii), adjusts the pH value of this oil phase extraction product to about pH4-7.
16. purifying organic acid methods as claimed in claim 1, wherein this reextraction comprises water or basic solution mutually, and wherein this basic solution comprises the NaOH aqueous solution, the NaCl aqueous solution, Na
2cO
3the aqueous solution, NH
3the aqueous solution or above-mentioned combination.
17. purifying organic acid methods as claimed in claim 1, wherein this crystallization procedure is carried out in about 5-15 DEG C.
18. purifying organic acid methods as claimed in claim 1, before this step (a), more comprise this fermented liquid of adjustment to certain ph, wherein this certain ph is about pH3-7.
19. purifying organic acid methods as claimed in claim 1, between this step (b) and this step (c), more comprise:
This throw out is cleaned with cleaning solvent and mixes to form the second mixture;
This second mixture is filtered to form filtrate and filter residue; And
This filtrate is added in this supernatant liquor.
20. purifying organic acid methods as claimed in claim 19, wherein the weight ratio of this throw out and this cleaning solvent is about 1-10:1.
21. purifying organic acid methods as claimed in claim 1, between this step (b) and this step (c), more comprise and this supernatant liquor are performed for more than filter fly sequence.
22. purifying organic acid methods as claimed in claim 21, the filtering material wherein used in this ultra-filtration program comprises polystyrene, polysulfones, polypropylene, polyethersulfone, gathers and fluoridize divinyl or hollow filter material.
23. purifying organic acid methods as claimed in claim 1, between this step (c) and (d), more comprise and this extraction liquid are carried out micro-filtration program.
24. purifying organic acid methods as claimed in claim 1, between this step (c) and (d), more comprise this extraction liquid of adjustment to certain ph, wherein this certain ph is about pH2.5-4.
25. purifying organic acid methods as claimed in claim 24, wherein this organic acid is methylene-succinic acid, and this certain ph is about pH2.5-3.
26. purifying organic acid methods as claimed in claim 1, between this step (c) and (d), more comprise and this extraction liquid are carried out decoloring process.
27. purifying organic acid methods as claimed in claim 26, wherein this decoloring process is heated to about 60-90 DEG C carry out in this extract by interpolation activated carbon afterwards.
28. purifying organic acid methods as claimed in claim 27, wherein this crystallization procedure is cooled to about 5-15 DEG C to carry out by by this extraction liquid two-part.
29. purifying organic acid methods as claimed in claim 1, after this step (d), more comprise:
E this extraction liquid that () is remaining after this crystallization procedure being completed carries out evaporation procedure to obtain concentrated extract;
F this concentrated extract is carried out filter to obtain the solution through desalting by () under not yet cooling state; And
G this solution through desalting is carried out the second crystallization procedure to obtain this organic acid crystallization by ().
30. purifying organic acid methods as claimed in claim 29, wherein this second crystallization procedure is cooled to about 5-15 DEG C to carry out by by this solution two-part through desalting.
31. purifying organic acid methods as claimed in claim 29, after this step (g), more comprise:
(h) after this second crystallization procedure is completed remaining this solution through desalting carry out evaporation procedure to obtain the concentrated solution that desalts;
I this concentrated solution that desalts is carried out the 3rd crystallization procedure to obtain containing this organic acid solid by ();
J this solid cleans with cleaning solvent to wash out this organic acid by ();
K this organic acid is carried out evaporation procedure to remove this cleaning solvent and to obtain this organic acid crystallization by ().
32. purifying organic acid methods as claimed in claim 31, wherein the 3rd crystallization procedure is carried out in about 5-15 DEG C.
33. purifying organic acid methods as claimed in claim 31, wherein the weight ratio of this solid and this cleaning solvent is about 1-1:1-4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW103115487A TWI525074B (en) | 2014-04-30 | 2014-04-30 | Method for purifying an organic acid |
| TW103115487 | 2014-04-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105017003A true CN105017003A (en) | 2015-11-04 |
| CN105017003B CN105017003B (en) | 2017-10-20 |
Family
ID=54407366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410270337.4A Active CN105017003B (en) | 2014-04-30 | 2014-06-17 | Process for purifying organic acids |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN105017003B (en) |
| TW (1) | TWI525074B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186147A (en) * | 2016-07-26 | 2016-12-07 | 北京惠宇乐邦环保科技有限公司 | A kind of recovery and treatment method of high concentration waste organic acid |
| CN115417763A (en) * | 2022-09-22 | 2022-12-02 | 盛虹控股集团有限公司 | Preparation method of bio-based succinic acid |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2345264Y (en) * | 1998-11-16 | 1999-10-27 | 复旦大学 | Membrane extraction-reextraction integral equipment |
| CN1086376C (en) * | 1999-04-27 | 2002-06-19 | 复旦大学 | Purifying technology for aromatic carboxylic acid |
| CN1088055C (en) * | 1999-09-29 | 2002-07-24 | 中国石油化工集团公司 | Process for extracting alpha-or omege-alkadicarboxylic acid from fermented liquid and refining it |
| CN1215034C (en) * | 2003-03-03 | 2005-08-17 | 清华大学 | Process for on-line extracting and concentrating organic acid in organic acid fermentation |
| CN101665428B (en) * | 2009-10-09 | 2013-08-07 | 安徽丰原发酵技术工程研究有限公司 | Method for extracting succinic acid from succinic acid fermentation liquor |
-
2014
- 2014-04-30 TW TW103115487A patent/TWI525074B/en active
- 2014-06-17 CN CN201410270337.4A patent/CN105017003B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186147A (en) * | 2016-07-26 | 2016-12-07 | 北京惠宇乐邦环保科技有限公司 | A kind of recovery and treatment method of high concentration waste organic acid |
| CN106186147B (en) * | 2016-07-26 | 2020-05-19 | 北京惠宇乐邦环保科技有限公司 | Recovery treatment method of high-concentration organic acid wastewater |
| CN115417763A (en) * | 2022-09-22 | 2022-12-02 | 盛虹控股集团有限公司 | Preparation method of bio-based succinic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201540700A (en) | 2015-11-01 |
| CN105017003B (en) | 2017-10-20 |
| TWI525074B (en) | 2016-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Grima et al. | Downstream processing of cell mass and products | |
| Zhao et al. | A uniform shearing vibration membrane system reducing membrane fouling in algae harvesting | |
| Yenkie et al. | A roadmap for the synthesis of separation networks for the recovery of bio-based chemicals: matching biological and process feasibility | |
| CN102030698B (en) | Method for separating and extracting L-tryptophan in fermentation liquor by utilizing organic film | |
| Zhao et al. | Effects of different pore sizes on membrane fouling and their performance in algae harvesting | |
| CN103073652A (en) | Method for extracting polysaccharide of spirulina platensis | |
| CN106749743A (en) | A kind of celestial grass Polyose extraction system and extraction process | |
| CN108017535A (en) | A kind of method that long-chain biatomic acid is extracted from zymotic fluid | |
| CN102476987A (en) | Method for refining long chain binary acid by combining ultrafiltration and liquid-liquid extraction | |
| Ma et al. | Microalgae dewatering using a hybrid dead-end/cross-flow forward osmosis system: Influence of microalgae properties, draw solution properties, and hydraulic conditions | |
| CN105017003A (en) | Process for purifying organic acids | |
| CN102924321A (en) | Method for extracting glutamine from fermentation liquor | |
| CN105363417A (en) | Preparation method for cross-linked carboxymethylated agarose-base gel microsphere | |
| CN103804172A (en) | Method for improving organic acid product quality | |
| CN102019192A (en) | Process method for oil-free cerium carbonate serving as cleaning catalyst for automobile tail gas | |
| CN103804173A (en) | Fermentation organic acid refining method | |
| CN101012151A (en) | Double aqueous phase extraction method for separating 1,3-dihydroxypropane from fermentation liquor | |
| CN102603814A (en) | Method for increasing crystalizing efficiency of xylose in xylose mother solution | |
| CN104591999A (en) | Long chain organic acid purifying method | |
| CN104592004A (en) | Long chain organic acid refining method | |
| CN103724457B (en) | A kind of ceramic membrane removes the method for impurity in crude heparin sodium | |
| CN103539688B (en) | A kind of method of separation and Extraction Serine from Corynebacterium glutamicum fermented liquid | |
| CN100345814C (en) | Long chain diprotic acid refining method | |
| CN104431358A (en) | System and method for treating liquid phase obtained in process course of extracting camellia oleosa seed oil by adopting aqueous enzymatic method | |
| CN104152508A (en) | Method for direct extraction of genipin from waste liquid in gardenia yellow pigment production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |