CN108017514B - Method for separating 1, 3-propylene glycol, acetic acid and butyric acid in fermentation liquor by two-step salting-out extraction - Google Patents
Method for separating 1, 3-propylene glycol, acetic acid and butyric acid in fermentation liquor by two-step salting-out extraction Download PDFInfo
- Publication number
- CN108017514B CN108017514B CN201711342422.7A CN201711342422A CN108017514B CN 108017514 B CN108017514 B CN 108017514B CN 201711342422 A CN201711342422 A CN 201711342422A CN 108017514 B CN108017514 B CN 108017514B
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- Prior art keywords
- phase
- salting
- inorganic salt
- propanediol
- acetic acid
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- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 title claims abstract description 203
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000000605 extraction Methods 0.000 title claims abstract description 111
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000005185 salting out Methods 0.000 title claims abstract description 72
- 238000000855 fermentation Methods 0.000 title claims abstract description 70
- 230000004151 fermentation Effects 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000012071 phase Substances 0.000 claims abstract description 70
- 239000003960 organic solvent Substances 0.000 claims abstract description 51
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 49
- 229940035437 1,3-propanediol Drugs 0.000 claims abstract description 49
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 49
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 38
- 239000012074 organic phase Substances 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 19
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012670 alkaline solution Substances 0.000 claims abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 38
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 31
- 235000017550 sodium carbonate Nutrition 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 29
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 28
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 19
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 11
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 9
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 9
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 7
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011736 potassium bicarbonate Substances 0.000 claims description 6
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 6
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 6
- 235000011181 potassium carbonates Nutrition 0.000 claims description 6
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 6
- 238000005191 phase separation Methods 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
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- 230000008901 benefit Effects 0.000 abstract description 5
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- 235000011054 acetic acid Nutrition 0.000 description 37
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- 102000004169 proteins and genes Human genes 0.000 description 15
- 229910000162 sodium phosphate Inorganic materials 0.000 description 15
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 14
- 235000010633 broth Nutrition 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
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- 210000004027 cell Anatomy 0.000 description 7
- 235000019439 ethyl acetate Nutrition 0.000 description 7
- 239000004310 lactic acid Substances 0.000 description 7
- 235000014655 lactic acid Nutrition 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- 241001052560 Thallis Species 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
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- 241000193171 Clostridium butyricum Species 0.000 description 5
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- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000909 electrodialysis Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
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- 239000011734 sodium Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
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- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of bioengineering, and provides a method for separating 1, 3-propylene glycol, acetic acid and butyric acid from fermentation liquor by two-step salting-out extraction. The method comprises the following steps: dissolving soluble acidic inorganic salt in 1, 3-propylene glycol fermentation liquor, adding a hydrophobic organic solvent, oscillating and mixing, standing at room temperature for phase splitting, and performing first-step salting-out extraction, wherein the upper phase is an organic phase rich in butyric acid, and the lower phase is a salt phase rich in 1, 3-propylene glycol and acetic acid; back extracting butyric acid in the upper phase with an alkaline solution or an alkaline inorganic salt solution; adding hydrophilic organic solvent into the lower phase, performing second salting-out extraction, and extracting 1, 3-propylene glycol and acetic acid. The invention solves the problems of difficult separation of 1, 3-propanediol and byproducts, high cost and the like in the prior separation process for producing 1, 3-propanediol by a fermentation method. The method has the advantages of simple process, short separation time, high recovery rate and low separation cost, and is a separation method with great industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of bioengineering, relates to a separation technology of microbial fermentation liquor, and particularly relates to a method for separating 1, 3-propylene glycol, acetic acid and butyric acid in fermentation liquor by using a salting-out extraction technology.
Background
1, 3-propylene glycol, acetic acid and butyric acid are used as chemical raw materials and intermediates with wide production prospect, and have wide application in many fields. The 1, 3-propylene glycol can be used as a solvent, an adhesive, cosmetics, a preservative and a monomer for synthesizing polyester and polyurethane, wherein the polytrimethylene terephthalate (PTT) synthesized with terephthalic acid has huge application prospect in the industries of carpets, textiles, engineering plastics and the like due to the advantages of difficult generation of static electricity, ultraviolet resistance, good rebound resilience, pollution resistance, biodegradability and the like. The acetic acid is mainly used for producing vinyl acetate, acetic ester, acetic anhydride, diketene, chloroacetic acid, acetate fiber and the like, or is used as a solvent or a raw material in industrial production processes of terephthalic acid, pesticides, medicines, fuels and the like. The butyric acid can be used for preparing butyrate esters and cellulose butyrate ester, also can be used as an emulsifier, a bactericide and an extractant, and the butyric acid and derivatives thereof can also be applied to the fields of food, medicine, feed and the like.
Conventionally, 1, 3-propanediol is mainly produced by a chemical method, and with the gradual depletion of fossil energy and the resulting environmental and safety problems, people are concerned more and more, so the production of 1, 3-propanediol by fermentation through a biotransformation method becomes a hot point for research. At present, the method for converting glycerol into 1, 3-propylene glycol by using Klebsiella pneumoniae is mostly adopted in China, bacteria used in the method are conditional pathogenic bacteria, byproducts comprise 2, 3-butanediol, acetic acid, ethanol, lactic acid, succinic acid, citric acid, formic acid and the like, and the separation of products is difficult. Clostridium butyricum in nature also converts glycerol to 1, 3-propanediol, a probiotic bacterium with only acetic acid and butyric acid as by-products. If the 1, 3-propylene glycol in the fermentation liquor is separated and the organic acid is recovered, the separation cost can be reduced and the economic benefit can be improved.
At present, the method for separating 1, 3-propanediol from fermentation liquor mainly comprises the steps of removing thalli and part of biomacromolecules from the fermentation liquor through centrifugation, flocculation treatment or membrane filtration, then carrying out coarse separation through organic solvent precipitation, organic solvent extraction, reactive extraction or electrodialysis desalination and the like, removing part of impurities, and finally obtaining the 1, 3-propanediol through rectification. Adding ethanol into the concentrated fermentation liquor can separate out a large amount of precipitate, washing the precipitate, and rectifying the washing liquid and the supernatant to obtain the 1, 3-propylene glycol, but the step needs to consume a large amount of organic solvent, and the solvent is easy to volatilize and lose. 1, 3-propanediol can be extracted by ethyl acetate, the partition coefficient is 0.22, the partition coefficient can be improved to 0.33 by adding a small amount of ethanol as a cosolvent, but the recovery rate is still low. The reason is that 1, 3-propanediol is too hydrophilic to find a suitable solvent for efficient extraction. The reaction extraction can convert 1, 3-propanediol into a hydrophobic product, so that the hydrophobic product is extracted by an organic solvent, but the components in the fermentation liquor are complex, a plurality of side reactions are accompanied, and simultaneously the catalyst is easy to inactivate, so that the catalytic efficiency is reduced. If the fermentation liquor is ultrafiltered to remove partial impurities and then electrodialysis is used to remove small molecular salts, the method is favorable for reactive extraction, but the electrodialysis has high energy consumption, the membrane is easy to pollute, and the cost is high. The salting-out extraction system consisting of the hydrophilic organic solvent and the inorganic salt can efficiently extract the 1, 3-propanediol from the fermentation liquor in one step, but organic acids (such as acetic acid and lactic acid) are also extracted into an upper phase at the same time, so that the subsequent separation is still difficult.
Common organic acid separation methods mainly include a salt formation method, an adsorption method, a membrane separation method, an esterification method, a liquid-liquid extraction method and the like. The salt formation method is to add a large amount of alkali or inorganic salt into an organic acid solution to form a precipitate or a salt with thermal stability, and then to obtain a pure product through filtration, heating dehydration, acidification and distillation, and the salt formation method has a mature process but needs to consume a large amount of acid and alkali, so that secondary pollution is easily caused. The fermentation liquor contains a large amount of impurities and has complex components, so that the problems that the ion exchange and membrane separation process is easy to pollute resin and a membrane, the regeneration is frequent and a large amount of waste liquid is generated are solved, and the industrial production is difficult at present. Immobilized lipase (such as Novozym 435) is used for catalyzing to convert butyric acid in fermentation liquor into ethyl butyrate, and then Trioctylamine (TOA) -cyclohexane is used as an extracting agent to extract the ethyl butyrate, but the problems of low esterification rate and complex process exist. Acetic acid in the aqueous solution is extracted by medium-chain fatty acid, then the acetic acid is obtained by fractionation, and meanwhile, the fatty acid can be recycled, but the distribution coefficient of the acetic acid is not high, the recovery rate is too low, and a large amount of fatty acid is consumed by adopting multi-stage extraction. Salting-out is applied to the separation of butyric acid, but the system requires a lower pH and a higher concentration of butyric acid, thus usually requiring the concentration of the fermentation broth; salting-out extraction can be used for separating lactic acid, succinic acid and the like, wherein the salting-out extraction can be carried out under alkaline conditions, and the salting-out extraction requires acidic conditions.
The salting-out extraction technology is characterized in that an organic solvent is used as an extracting agent, an inorganic salt is used as a salting-out agent, and one of hydrophilic target products is extracted from an aqueous solution under the combined action of the organic solvent and the inorganic saltA separation method. Hydrophilic short-chain alcohols, ketones, and the like are often used as organic solvents, and thus such salting-out extraction systems are often referred to as aqueous two-phase systems. The salting-out extraction technology has the advantages of large distribution coefficient, high recovery rate, small organic solvent dosage, mild conditions, low corrosion to equipment and the like, is used for separating various bio-based chemicals such as butyric acid, lactic acid, succinic acid, 1, 3-propanediol, 2, 3-butanediol, acetone, butanol and the like, and also has reports of two-step salting-out extraction separation of 1, 3-propanediol and lactic acid. Since the organic solvents used for the two salting-out extractions are hydrophilic, the total yield of lactic acid is only 73.8%, and the second step requires adjusting the pH from 10.0 to 6.5, resulting in K2CO3And (4) loss. There is currently no report of the isolation of 1, 3-propanediol, acetic acid and butyric acid from clostridium butyricum fermentation broths.
Disclosure of Invention
The invention aims to provide a novel method for extracting and separating 1, 3-propanediol, acetic acid and butyric acid from fermentation liquor by using a two-step salting-out extraction technology, aiming at the problems of difficult recycling of byproducts, high separation cost, difficult recovery of thalli and protein and the like in the existing process of extracting 1, 3-propanediol from the fermentation liquor.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
a method for separating 1, 3-propanediol, acetic acid and butyric acid from a fermentation broth by two-step salting-out extraction, the method comprising the steps of:
1) first-step salting-out extraction: dissolving soluble acidic inorganic salt in 1, 3-propylene glycol fermentation liquor, adding a hydrophobic organic solvent, oscillating and mixing, standing at room temperature for phase separation, wherein the upper phase is an organic phase rich in butyric acid, and the lower phase is a salt phase rich in 1, 3-propylene glycol and acetic acid;
2) adding an alkali solution or an alkaline inorganic salt solution into the organic phase obtained in the step 1) to back extract butyric acid;
3) the second step of salting out extraction: adding a hydrophilic organic solvent into the salt phase obtained in the step 1), and extracting the 1, 3-propylene glycol and the acetic acid.
Further, in the technical scheme, the 1, 3-propanediol fermentation liquor is a 1, 3-propanediol fermentation stock solution containing bacteria or a 1, 3-propanediol fermentation clear solution from which the bacteria are removed, and in the 1, 3-propanediol fermentation liquor, the concentration of 1, 3-propanediol is 50-100 g/L, the concentration of acetic acid is 6-15 g/L, and the concentration of butyric acid is 10-20 g/L.
Further, in the above technical solution, the soluble acidic inorganic salt in step 1) is one of ammonium sulfate, sodium dihydrogen phosphate and potassium dihydrogen phosphate, and is preferably sodium dihydrogen phosphate.
Further, in the above technical solution, the hydrophobic organic solvent in step 1) is one of ethyl acetate, butyl acetate, methyl tert-butyl ether or methyl isobutyl ketone, preferably butyl acetate.
Further, in the above technical solution, the amount of the soluble acidic inorganic salt added in step 1) is 15% to 27.5% of the mass of the extraction system, and is preferably 25%.
Further, in the above technical solution, the amount of the hydrophobic organic solvent added in step 1) is 15% to 35% of the mass of the extraction system, and preferably 30%.
Further, in the above technical solution, the alkali in the alkali solution in step 2) is one of sodium hydroxide and potassium hydroxide, and the basic inorganic alkali in the basic inorganic salt solution is one of sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate.
Further, in the above technical solution, when the hydrophobic organic solvent used in step 1) is ethyl acetate or butyl acetate, in step 2), a basic inorganic salt solution is added to the organic phase, wherein the basic inorganic salt is one of sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate; when the hydrophobic organic solvent used in step 1) is one of methyl tert-butyl ether or methyl isobutyl ketone, in step 2), an alkali solution or an alkaline inorganic salt solution is added into the organic phase, wherein the alkali is one of sodium hydroxide and potassium hydroxide, and the alkaline inorganic salt is one of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, preferably sodium carbonate.
Further, in the technical scheme, the molar ratio of the organic acid to the alkali or the alkaline inorganic salt in the organic phase in the step 2) is 5: 1-8; the volume ratio of the organic phase to the alkali solution or the alkaline inorganic salt solution is 1-5: 1, preferably 2: 1. Wherein the organic acid refers to the sum of acetic acid and butyric acid.
Further, in the above technical solution, the hydrophilic organic solvent in step 3) is one of acetone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, dimethyl carbonate, and tetrahydrofuran, and preferably ethanol.
Further, in the above technical solution, the amount of the hydrophilic organic solvent added in step 3) is 20% to 52% of the volume of the extraction system, preferably 50%.
In the present invention, the 1, 3-propanediol fermentation broth refers to a fermentation broth containing 1, 3-propanediol during the production of 1, 3-propanediol by fermentation using a conventional biotransformation method, and mainly contains 1, 3-propanediol, acetic acid and butyric acid, and may also contain a small amount of formic acid, lactic acid, succinic acid and ethanol. Preferably, the fermentation broth when glycerol is converted to 1, 3-propanediol using Clostridium butyricum contains 1, 3-propanediol, acetic acid and butyric acid.
In the invention, the extraction operation mode of the 1, 3-propanediol, the acetic acid and the butyric acid can be intermittent or continuous; for a system with a smaller distribution coefficient, a multi-stage extraction mode can be adopted.
In the invention, the 1, 3-propylene glycol fermentation liquor can be pretreated by flocculation, microfiltration or centrifugation to remove thalli and partial protein; if the extraction operation is directly carried out without pretreatment, the thalli and the protein are distributed in the middle.
The invention has the beneficial effects that:
the method solves the problem that the byproduct organic acid is difficult to recover when 1, 3-propanediol is separated from fermentation liquor at present through two-step salting-out extraction. Compared with an inorganic salt/hydrophilic organic solvent system, the inorganic salt/hydrophobic organic solvent system used in the first-step salting-out extraction directly treats the fermentation liquor, and has better removal effect on thalli and protein while extracting butyric acid. The butyric acid and the acetic acid in the organic phase are back extracted by alkali (or alkaline inorganic salt solution), the recovery rate is high, the organic solvent is almost free from loss, the organic solvent can be directly recycled, and the butyrate value is higher than that of the butyric acid. In the second salting-out extraction, 1, 3-propanediol and acetic acid partition into the upper phase (organic phase), which can be separated by a conventional separation method such as distillation. The method has simple process, recovers the organic acid while separating the 1, 3-propylene glycol, achieves the aims of reducing the cost and improving the economic benefit, and is a separation method with industrial prospect.
Drawings
FIG. 1 shows the effect of the salting-out extraction system formed by different organic solvents and sodium dihydrogen phosphate on the separation degree of butyric acid from acetic acid and 1, 3-propanediol.
FIG. 2 is a graph showing the effect of salt concentration on the separation of butyric acid, acetic acid and 1, 3-propanediol in a fermentation supernatant from a sodium dihydrogen phosphate/butyl acetate salting-out extraction system, wherein FIG. 2A is a graph showing the effect on the partition coefficient and recovery rate of butyric acid; FIG. 2B is a graph of the effect on acetic acid partition coefficient and recovery; FIG. 2C is a graph of the effect on 1, 3-propanediol partition coefficient and recovery.
FIG. 3 is a graph showing the effect of organic solvent concentration on the separation of butyric acid, acetic acid and 1, 3-propanediol in a fermentation supernatant from a sodium dihydrogen phosphate/butyl acetate salting-out extraction system, wherein FIG. 3A is a graph showing the effect on the partition coefficient and recovery rate of butyric acid; FIG. 3B is a graph of the effect on acetic acid partition coefficient and recovery; FIG. 3C is a graph of the effect on 1, 3-propanediol partition coefficient and recovery.
FIG. 4 is a graph showing the effect of sodium carbonate concentration on the back-extraction yields of butyric acid, acetic acid and 1, 3-propanediol.
FIG. 5 is a graph of the effect of ethanol volume fraction on partition coefficient and recovery of acetic acid and 1, 3-propanediol in simulated fermentation broths.
FIG. 6 is a graph of the effect of ethanol volume fraction on partition coefficient and recovery of acetic acid and 1, 3-propanediol in fermentation supernatants.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. In the following examples, unless otherwise specified, the experimental methods used were all conventional methods, and the reagents used were all available from chemical or biological reagents companies.
The following describes the embodiments of the present invention in detail with reference to the technical solutions.
1.1 preparation of 1, 3-propanediol fermentation broth
The 1, 3-propanediol fermentation liquor is prepared by a conventional method and contains 1, 3-propanediol, acetic acid and butyric acid.
The following examples are obtained by batch-wise crude glycerol fermentation of mixed bacteria mainly including Clostridium butyricum (Clostridium butyricum), and the mixed bacteria composition and fermentation mode are shown in CN106399204A, wherein the concentrations of 1, 3-propanediol (1,3-PD), acetic acid (HAc) and Butyric Acid (BA) are respectively 50-100 g/L, 6-15 g/L and 10-20 g/L, and the 1,3-PD fermentation broth is filtered through a hollow fiber membrane to remove bacteria and partial protein, so as to obtain a fermentation clear solution.
2. A process for the isolation of 1,3-PD from a 1,3-PD fermentation broth or fermentation supernatant comprising the steps of:
1) dissolving soluble acidic inorganic salt in 1,3-PD fermentation liquor, adding a hydrophobic organic solvent, oscillating and mixing, standing at room temperature for phase splitting, and performing first-step salting-out extraction to obtain an upper phase which is an organic phase rich in BA and a lower phase which is a salt phase rich in 1,3-PD and HAc;
2) adding an alkali solution or an alkaline inorganic salt solution into the organic phase obtained in the step 1) to back extract BA;
3) adding a hydrophilic organic solvent into the salt phase obtained in the step 1), performing second salting-out extraction, shaking and mixing, standing at room temperature for phase separation, wherein the upper phase is an organic phase containing 1,3-PD and HAc, and the lower phase is a salt phase.
In the step 2), the back extraction liquid (salt phase) obtained by back extraction is rich in butyrate, a small amount of acetate and 1,3-PD, and the back extraction liquid is subjected to distillation, water removal and drying to obtain butyrate (sodium butyrate or potassium butyrate).
For the organic phase obtained in step 3), 1,3-PD and HAc can be separated by a conventional separation method such as distillation, depending on the boiling point of the substance. Preferably, the pH of the organic phase is adjusted to 7.0 by using sodium hydroxide or potassium hydroxide, precipitated phosphate is removed by filtration, the filtrate is distilled, 110 ℃ overhead fraction 1,3-PD is collected under the condition that the vacuum degree is 0.094-0.096MPa, and almost all acetic acid is retained in the tower kettle in the form of acetate (sodium salt or potassium salt).
In the method, the acidic inorganic salt in the step 1) is one of ammonium sulfate, sodium dihydrogen phosphate or potassium dihydrogen phosphate, and the addition amount of the inorganic salt is 15-27.5% of the mass of the extraction system; the hydrophobic organic solvent is one of ethyl acetate, butyl acetate, methyl tert-butyl ether or methyl isobutyl ketone, and the addition amount of the organic solvent is 15-35% of the mass of the extraction system.
In the method, the alkali in the step 2) is one of sodium hydroxide and potassium hydroxide, and the alkaline inorganic salt is one of sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate.
In the method, the hydrophilic organic solvent in the step 3) is one of acetone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, dimethyl carbonate or tetrahydrofuran, and the addition amount of the hydrophilic organic solvent is 20-52% of the volume of the extraction system.
Samples were taken from each step and the concentrations of 1,3-PD, HAc and BA in the upper and lower phases were determined. The partition coefficient (K), recovery rate (Y) and removal rate (R) were calculated.
The distribution coefficient (K), the recovery (Y) and the removal (R) are calculated as follows:
Ri＝100％-Yi(formula 4)
In the formulae (1) to (4), i represents 1,3-PD, HAc or BA, CtAnd CbThe mass concentration of the upper and lower phases after the equilibrium (g/L), VtAnd VbThe upper and lower phase volumes (m L) after equilibration the degree of separation is the ratio of the partition coefficients of the two species.
The final recovery rate (Y) of 1,3-PD, HAc and BA after the whole separation processf) The calculation formula of (a) is as follows:
Yf，1，3-PD＝RIYIII(formula 5)
Yf，HAc＝YIYII+RIYIII(formula 6)
Yf，BA＝YIYII(formula 7)
In the formulae (5) to (7), I, II and III respectively represent the first salting-out extraction, the back-extraction and the second salting-out extraction.
The removal rate (R) of cells and proteins in each salting-out extraction step is defined as follows:
first-step salting-out extraction:
the second step of salting out extraction:
in the formulae (8) to (9), s represents a cell or protein, MmRepresenting the mass of cells or proteins at the interface between the upper and lower phases, MtRepresenting the mass of the cell or protein in the upper phase, M1、M2Represents the total mass of cells or proteins in the salting-out extraction system.
3. Analytical method
In the salt phase, the content of 1,3-PD, HAc and BA is detected by adopting liquid chromatography, an AminexHPX-87H chromatographic column with the thickness of 300mM and the thickness of 7.8mM, a mobile phase of 5mM sulfuric acid, the flow rate of 0.6m L/min, a differential detector for detection at the position of 410nm, the sample introduction amount of 20 mu L, the column temperature of 65 ℃ and the detection time of 23 min.
In a hydrophobic organic solvent, the content of 1,3-PD, HAc and BA is detected by adopting a gas chromatography under the conditions of BGB-174 capillary column (30m × 0.25mm I.D.0.25 mu m df), FID detector with the detector temperature of 220 ℃, the injection port temperature of 210 ℃, the split ratio of 1:8, high-purity nitrogen as carrier gas, an external standard method and the sample injection amount of 2 mu L.
The cell body was measured by spectrophotometry, and the turbidity was measured at 650 nm. The protein assay was performed by Coomassie Brilliant blue.
Example 1 selection of inorganic salts and organic solvents in the first salting-out extraction step
The concentrations of 1,3-PD, HAc and BA in the clear fermentation liquid of 1,3-PD are 67.76 g/L, 7.07 g/L and 11.94 g/L respectively, firstly, inorganic salt is dissolved in the clear fermentation liquid of 1,3-PD, then NaCl, (NH) is added4)2SO4、NaH2PO4Adjusting pH of the fermented clear liquid to 4.5, adding Na respectively2CO3And K3PO4The natural pH value of the fermentation clear liquid is kept; additional organic solvent (inorganic salts and organic solvent species, as in table 1) was added. Shaking, mixing, standing at room temperature, and separating phase to obtain an upper phase as organic phase and a lower phase as salt phase. The aim was to extract the BA into the upper phase, leaving the 1,3-PD and HAc in the lower phase. The concentrations of the respective substances in the upper phase and the lower phase were sampled and measured to calculate the partition coefficient (K) and the recovery rate (Y), and the results are shown in Table 1. The mass percentage of the inorganic salt, the 1,3-PD fermentation clear liquid and the organic solvent in the extraction system are respectively 10 percent, 60 percent and 30 percent.
TABLE 1 partitioning behavior of 1,3-PD, HAc and BA in different salting-out extraction systems
From the results in Table 1, it is clear that Na is present2CO3And K3PO4In the salting-out extraction system composed of alkaline salts, BA is distributed in the lower phase except for the hydrophilic n-propanol system (recovery rate)<30%). This is because when the pH is < 4.82 (pKa value of BA),BA mainly exists in a molecular form and is easier to extract into an organic phase; at pH > 4.82, BA exists primarily in ionic form and tends to partition more readily into the aqueous phase. In the alkaline salt/n-propanol system, the separation degree of BA and 1,3-PD is about 1, the separation effect is poor, so Na2CO3And K3PO4The formed alkaline salting-out extraction system is not suitable for separating BA from 1,3-PD and HAc.
In NaCl, (NH)4)2SO4And NaH2PO4In the acid salting-out extraction system, BA is mainly distributed in the upper phase (the recovery rate is 65.30-94.10%). Wherein, NaCl has poor phase forming ability, and is difficult to form a salting-out extraction system with ethanol, thereby influencing the second salting-out extraction. NaH2PO4When used as salting-out agent, the extraction effect on BA is better than that of (NH)4)2SO4Meanwhile, the extraction effects of the 1,3-PD and the HAc are close. The fermentation liquor is a large buffer system containing various inorganic salts, organic salts, proteins, nucleic acids and the like, and the pH adjustment requires the addition of a large amount of acid, while NaH2PO4Is a relatively strong acid salt (50 g/L NaH)2PO4The pH of the solution is between 4.2 and 4.6) and a lower pH can be achieved without the addition of acid during the extraction of BA.
Then, with NaH2PO4As a salting-out agent, in a salting-out extraction system consisting of the salting-out agent and five organic solvents, the extraction effect of the system on BA is observed, and according to the extraction effect of the organic solvent of the system, the salting-out agent has the following effects: n-propanol > isobutanol > n-butanol > methyl isobutyl ketone > methyl tert-butyl ether > ethyl acetate > butyl acetate, which is almost in accordance with the hydrophilic order of the solvents. When the organic solvent is selected from alcohols with stronger hydrophilicity, the partition coefficient and the recovery rate of BA are higher, but at the same time, at least 29 percent of 1,3-PD and HAc are extracted into the organic phase, and the separation of BA and 1,3-PD is not suitable. When the organic solvent is selected to be a hydrophobic solvent, the partition coefficient and recovery rate of BA are somewhat decreased, but the partition coefficient and recovery rate of 1,3-PD are drastically decreased. FIG. 1 shows NaH2PO4Salting-out extraction system formed with different organic solvents for BA in fermentation clear liquidEffect of degree of separation from HAc, 1,3-PD, Ethyl acetate, butyl acetate, methyl tert-butyl ether and methyl isobutyl Ketone with NaH2PO4The separation degree of the formed salting-out system to BA and 1,3-PD is superior to that of a salting-out system of polar organic solvents of n-propanol, isobutanol and n-butanol, wherein the boiling point of the methyl tert-butyl ether is too low (55 ℃ under normal pressure), and the volatility is stronger. Also, with NaH2PO4Ethyl acetate and NaH2PO4Compared with salting-out extraction system of methyl isobutyl ketone (MIBK), NaH2PO4The butyl acetate system separated BA from 1,3-PD to a higher degree and BA separated from HAc to a slightly higher degree.
EXAMPLE 2 salting-out extraction of butyric acid (first step salting-out extraction)
1. Prepared according to the method described in example 1 from butyl acetate and NaH at different concentrations2PO4And an extraction system consisting of 1, 3-propylene glycol fermentation clear liquid, wherein the mass percentage of butyl acetate is respectively 25%, 30% and 35%, and NaH2PO4The mass percentage of the extraction solution is between 15 and 27.5 percent, the concentrations of 1,3-PD, HAc and BA in 1,3-PD fermentation clear liquid are 79.36 g/L, 9.30 g/L and 14.22 g/L respectively, the extraction system is stirred uniformly, the standing phase separation is carried out, and NaH is inspected2PO4The results of the effect of concentration changes on partition coefficient and recovery of the three substances are shown in fig. 2, where fig. 2A is the effect on partition coefficient and recovery of BA, fig. 2B is the effect on partition coefficient and recovery of HAc, and fig. 2C is the effect on partition coefficient and recovery of 1, 3-PD. It can be seen in fig. 2 that the partition coefficients and recovery rates for BA, HAc and 1,3-PD all improved as the mass fraction of salt increased. BA is mainly distributed in the upper phase, and the maximum recovery rate can reach 96.89%; HAc and 1,3-PD are mainly distributed in the lower phase, the maximum recovery rate of HAc is 40.12%, and the recovery rate of 1,3-PD is below 6%.
2. Prepared according to the method described in example 1 from NaH at different concentrations2PO4And the extraction system consisting of butyl acetate and 1, 3-propylene glycol fermentation clear liquid, NaH2PO4The mass percentage of the butyl acetate is respectively 20 percent and 25 percent, the mass percentage of the butyl acetate is between 15 and 35 percent, and 1,3-The concentrations of PD, HAc and BA were 79.36 g/L, 9.30 g/L and 14.22 g/L respectively, and the results of examining the influence of the change in the concentration of butyl acetate on the partition coefficient and recovery rate of the three substances are shown in FIG. 3, in which FIG. 3A shows the influence on the partition coefficient and recovery rate of BA, FIG. 3B shows the influence on the partition coefficient and recovery rate of HAc, and FIG. 3C shows the influence on the partition coefficient and recovery rate of 1, 3-PD. in FIG. 3, it can be seen that, as a whole, the partition coefficient and recovery rate of the three substances are improved as the mass fraction of the organic solvent is increased, and only for the partition coefficient of 1,3-PD, a phenomenon of decrease occurs when the concentration of butyl acetate is increased, because an excessively high ester concentration causes the concentration of 1,3-PD in the upper phase to decrease the partition coefficient.
When 25% (w/w) NaH is used2PO4The maximum BA recovery was 97.48% for a 35% (w/w) butyl acetate system; the recovery rates of HAc and 1,3-PD were 42.11%, 5.13%, respectively.
When 25% (w/w) NaH is used2PO4In the case of a 30% (w/w) butyl acetate salting-out extraction system, the partition coefficient and recovery rate of BA are 42.21 and 96.42 percent, and the recovery rates of HAc and 1,3-PD are 33.21 percent and 3.71 percent respectively.
Example 3 stripping of butyric and acetic acids
1. The procedure is as described in example 2, at 25% (w/w) NaH2PO4Carrying out first-step salting-out extraction on 1,3-PD fermentation clear liquid (the concentrations of 1,3-PD, HAc and BA are 79.36 g/L, 9.30 g/L and 14.22 g/L respectively) under the condition of a 30% (w/w) butyl acetate salting-out extraction system to extract BA, wherein the BA is enriched in an organic phase, the concentrations of the BA, HAc and 1,3-PD are 16.24 g/L, 3.96 g/L and 3.64 g/L respectively, carrying out back extraction on organic acid in an organic phase by using an alkaline solution or an alkaline inorganic salt solution, selecting a sodium carbonate solution as a back extraction agent because alkali can cause ester hydrolysis as a catalyst and a reactant, temporarily setting the back extraction ratio (the volume ratio of the organic phase to the alkali (or the alkaline inorganic salt) solution to be 2:1 and the sodium carbonate concentration range to be 0-0.8 mol/L due to the concentration effect, and examining the concentrated sodium carbonateAs shown in FIG. 4, the recovery rates of the three substances are gradually increased along with the increase of the concentration of sodium carbonate, wherein BA is the most affected by the concentration of the sodium carbonate, HAc is the second most affected by the concentration of the sodium carbonate, and 1,3-PD is the least affected by the concentration of the sodium carbonate, when the concentration of the sodium carbonate is increased from 0 to 0.3 mol/L, the recovery rate of the BA is increased from 9.98% to 91.28%, at the moment, the concentration of the sodium carbonate is continuously increased, the recovery rate of the BA is not changed greatly, the change rule of the HAc is similar to that of the BA, the 0.3 mol/L sodium carbonate solution can obtain 93.96% of HAc recovery rate, the 1,3-PD is the strongest in hydrophilicity, the existing state of the HAc is hardly affected by the pH value, the recovery rate is not obvious along with the change of the concentration of the sodium carbonate and is maintained at about 90%, therefore, the better back-extraction effect can be obtained by adopting the 0.3 mol/L sodium carbonate solution, and the molar ratio of.
2. The procedure is as described in example 2, at 25% (w/w) NaH2PO4A first salting-out extraction of 1,3-PD fermentation supernatant (1,3-PD, HAc and BA concentrations 79.36 g/L, 9.30 g/L, 14.22 g/L, respectively) under a 30% (w/w) butyl acetate salting-out extraction system conditions to extract BA enriched in the organic phase, wherein the concentrations of BA, HAc and 1,3-PD are 16.12 g/L, 3.22 g/L, 4.96 g/L, respectively, according to a molar ratio of 3:5 of sodium carbonate to organic acid in the butyl acetate solution, the butyl acetate solution is examined for its effect on stripping compared to the initial phase of sodium carbonate solution, since the stripping of BA has a concentrating effect, the initial phases selected as 2:1, 2.4:1, 3:1 and 4:1, as shown in Table 2, the concentrations of the three substances in the lower phase are increased with increasing phase, showing a good concentrating effect, but also reducing the effect of the inter-contact between the two phases, and increasing the residual mass transfer effect of the sodium carbonate in the lower phase, but not increasing the residual mass transfer effect of the sodium carbonate solution, and the residual mass transfer effect of the sodium carbonate in the lower phase, but increasing the residual mass transfer effect of the sodium carbonate solution, and the higher than that of the initial phase, the residual recovery of the initial phase, and the residual mass transfer effect of the residual salt of the sodium carbonate solution, which the residual recovery of the sodium carbonate in the sodium carbonate solution are increased, which is increased, and the residual recovery of the higher than the sodium carbonate, which is increased, and the residual recovery of the residualThe purpose of good separation cannot be achieved. And concentrating the lower phase solution after back extraction, and drying to obtain a mixture of sodium butyrate and a small amount of sodium acetate, wherein BA and HAc are important short-chain fatty acids in intestinal tracts and play a plurality of physiological roles, so the sodium butyrate and the sodium acetate can be used as feed additives and applied to animal feeds.
TABLE 2 Effect of strip comparison on BA, HAc and 1,3-PD partitioning behavior
Example 41 extraction of 3-propanediol and acetic acid (second salting-out extraction)
1. HAc and 1.3-PD standards were dissolved in deionized water to prepare HAc and 1,3-PD simulants, the concentrations of HAc and 1.3-PD were 8.05 g/L and 61.60 g/L, respectively, in example 2, the first salting-out extraction used a hydrophobic organic solvent, and almost all water and inorganic salts remained in the lower phase after extraction, so 25% (w/w) NaH was used2PO4Extracting 1,3-PD fermentation clear liquid by a salting-out extraction system of butyl acetate of 30% (w/w), and adding water and NaH into the lower phase2PO4In a mass ratio of about 9:5, adding NaH to the simulant in this ratio2PO4After dissolving, adding ethanol with the purity of 95 percent to form a salting-out extraction system. In an extraction system, the volume fraction change range of ethanol is 20-50%, and the influence of the volume fraction change range on 1,3-PD and HAc distribution in a simulated liquid is examined. As shown in fig. 5, overall, the partition coefficient and recovery rate of HAc and 1,3-PD increased with the increase in the volume fraction of ethanol, and the recovery rate of HAc and 1,3-PD reached 89.59%, 92.32% when the volume fraction of ethanol was 40%.
2. The procedure is as described in example 2, at 25% (w/w) NaH2PO4Performing first-step salt on 1,3-PD fermentation clear liquid (the concentrations of 1,3-PD, HAc and BA are 78.62 g/L, 6.41 g/L and 12.93 g/L respectively) under the condition of a 30% (w/w) butyl acetate salting-out extraction systemAnd (2) performing analytical extraction, namely distributing 1,3-PD and HAc to the lower phase, wherein the concentrations of the 1,3-PD and the HAc are respectively 6.41 g/L g/78.62 g/L. adding 95% ethanol to the lower phase, wherein the volume fraction of the ethanol is within 40-52%, and investigating the influence of the ethanol on the extraction of the 1,3-PD and HAc in the fermented clear liquid.
EXAMPLE 5 two-step salting-out extraction of fermentation broth
The concentrations of 1,3-PD, HAc and BA in the fermentation broth were 87.21 g/L, 6.66 g/L and 17.64 g/L, respectively, 125g NaH was added to 225g of the fermentation broth2PO4After dissolving, adding 150g of butyl acetate, uniformly mixing, standing at room temperature, performing first-step salting-out extraction, and dividing into three phases, wherein the upper phase is an organic phase rich in BA, the lower phase is a salt phase rich in 1,3-PD and HAc, and the intermediate phase mainly comprises thalli and protein. The partition coefficient and recovery rate of BA are 23.34 percent and 93.78 percent respectively; 95.20% of 1,3-PD and 69.04% of HAc partition in the salt phase; the removal rates of the bacteria and the protein were 99.63% and 95.78%, respectively.
The back extraction yields of BA and HAc were 87.33% and 181.44% by adding 79m L0.76.76 mol/L mol sodium hydroxide solution to the organic phase, and the recovery of HAc was far more than theoretical because the strongly basic sodium hydroxide solution caused hydrolysis of butyl acetate and generation of a large amount of acetic acid, so that the back extraction solution could not be sodium hydroxide or potassium hydroxide solution when the hydrophobic organic solvent used in the first salting-out extraction was an ester, and the back extraction yields of BA and HAc were 88.72% and 82.70% by adding 79m L0.38.38 mol/L mol sodium carbonate solution to the organic phase.
The salt phase was subjected to a second salting-out extraction by adding 251m L95% ethanol, the yield of 1,3-PD in the upper phase was 96.29%, the yield of HAc was 97.26%, and all the cells and 77.89% of the protein were removed, the recovery rates of 1,3-PD, HAc and BA in the whole process were 91.67%, 92.75% and 83.20%, respectively, and all the cells and 97.16% of the protein were removed, and the recovery rates of the three substances in each step are shown in Table 3.
TABLE 3 partitioning of 1,3-PD, HAc and BA in the fermentation broth in different unit operations
In Table 3, I, II and III represent the first salting-out extraction, the back extraction and the second salting-out extraction, respectively.
The BA in the back extraction liquid is evaporated, dewatered and dried to obtain the recovery rate of over 94 percent, and finally the mixture of the sodium butyrate and a small amount of sodium acetate is obtained.
The 1,3-PD and HAc of the ethanol phase can be separated by distillation. Adjusting the pH value of the organic phase to 7.0 by using sodium hydroxide, filtering to remove precipitated phosphate, distilling the filtrate, collecting 110 ℃ overhead fraction 1,3-PD under the condition of vacuum degree of 0.094-0.096MPa, recovering more than 92% of 1,3-PD, and retaining almost all acetic acid in the tower kettle in the form of sodium acetate.
Claims (6)
1. A method for separating 1, 3-propanediol, acetic acid and butyric acid in a fermentation broth by two-step salting-out extraction, which is characterized by comprising the following steps:
1) first-step salting-out extraction: dissolving soluble acidic inorganic salt in 1, 3-propylene glycol fermentation liquor, adding a hydrophobic organic solvent, oscillating and mixing, standing at room temperature for phase separation, wherein the upper phase is an organic phase rich in butyric acid, and the lower phase is a salt phase rich in 1, 3-propylene glycol and acetic acid;
2) adding an alkali solution or an alkaline inorganic salt solution into the organic phase obtained in the step 1) to back extract butyric acid;
3) the second step of salting out extraction: adding a hydrophilic organic solvent into the salt phase obtained in the step 1), and extracting 1, 3-propylene glycol and acetic acid;
the soluble acidic inorganic salt in the step 1) is one of ammonium sulfate, sodium dihydrogen phosphate or potassium dihydrogen phosphate, and the addition amount is 15-27.5% of the mass of the extraction system.
2. The method according to claim 1, wherein the 1, 3-propanediol fermentation liquor is a thallus-containing 1, 3-propanediol fermentation stock solution or a thallus-removed 1, 3-propanediol fermentation clear solution, and the 1, 3-propanediol fermentation liquor contains 50-100 g/L of 1, 3-propanediol, 6-15 g/L of acetic acid and 10-20 g/L of butyric acid.
3. The method as claimed in claim 1, wherein the hydrophobic organic solvent in step 1) is one of ethyl acetate, butyl acetate, methyl tert-butyl ether or methyl isobutyl ketone, and the amount added is 15-35% of the mass of the extraction system.
4. The method according to claim 3, wherein when the hydrophobic organic solvent used in step 1) is ethyl acetate or butyl acetate, a basic inorganic salt is added to the organic phase in step 2), and the basic inorganic salt is one of sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate; when the hydrophobic organic solvent used in step 1) is one of methyl tert-butyl ether or methyl isobutyl ketone, in step 2), an alkali solution or an alkaline inorganic salt solution is added into the organic phase, wherein the alkali is one of sodium hydroxide and potassium hydroxide, and the alkaline inorganic salt is one of sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate.
5. The method according to claim 1, wherein the molar ratio of the organic acid in the organic phase to the alkali or the alkaline inorganic salt in the alkaline solution or the alkaline inorganic salt solution in step 2) is 5:1 to 8, and the volume ratio of the organic phase to the alkaline solution or the alkaline inorganic salt solution is 1 to 5: 1.
6. The method as claimed in claim 1, wherein the hydrophilic organic solvent in step 3) is one of acetone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, dimethyl carbonate or tetrahydrofuran, and is added in an amount of 20-52% by volume of the extraction system.
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