CN101367955B - Method for recycling polyglycol from dual-aqueous phase abstraction waste liquor - Google Patents
Method for recycling polyglycol from dual-aqueous phase abstraction waste liquor Download PDFInfo
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- CN101367955B CN101367955B CN2008100793440A CN200810079344A CN101367955B CN 101367955 B CN101367955 B CN 101367955B CN 2008100793440 A CN2008100793440 A CN 2008100793440A CN 200810079344 A CN200810079344 A CN 200810079344A CN 101367955 B CN101367955 B CN 101367955B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a method for reclaiming PEG from aqueous two-phase extraction waste liquid, including the following steps: (1) the phase containing rich PEG is taken out from the waste liquid after aqueous two-phase extraction, and oxidizing agent is added for decolorization; (2) electrolyte is added into the decolorized waste liquid for concentration, and acidifier is added into the concentrated liquid for acidification; (3) the phase containing rich PEG is separated after acidifying liquid centrifugation, and then electrolyte is added thereinto for concentration, and alkalizer is added into the concentrated solution for caustic washing; (4) regulating system pH equal to 7, the upper phase is taken after centrifugation, and dried and dehydrated until the water content becomes eligible. The invention is applicable to all double water-phase systems composed of PEG, e.g. PEG-dextran and PEG-salt systems. The maximum PEG recovery rate can exceed 97 percent, and the PEG reclaimed by the method can be recycled.
Description
Technical field
The present invention relates to the recovery technology field of the one-tenth gathering compound of aqueous two-phase extraction, particularly reclaim the method for polyoxyethylene glycol (PEG) the waste liquid that behind the double-aqueous phase system extracting substance that non-ionic polyalcohol participates in constituting, obtains.
Background technology
Aqueous two-phase system is meant between some superpolymer or can forms two immiscible water systems with suitable concentration dissolving between superpolymer and the inorganic salt in water.Carrying out method of extraction by solute in the difference of alternate partition ratio is aqueous two-phase extraction.Modal aqueous two-phase system is polyoxyethylene glycol (PEG)/dextran (DEX)/water and PEG/ phosphoric acid salt/water system.The double water-phase technology is widely used in the downstream engineering of biology, medicine and other fields as purification technique important in the liquid-liquid extraction.Aqueous two-phase extraction has tangible advantage: (1) is easy to amplify; (2) energy consumption is less, can realize sharp separation; (3) be easy to carry out continuous operation; (4) biological activity of target substance is difficult for being damaged, and can directly carry out biochemical conversion and suppress to eliminate product in aqueous two-phase system, helps carrying out the application of reaction separation coupling technology; (5) at room temperature operate mild condition.At present, aqueous two-phase extraction successfully has been applied to separating and purifying of biological products such as protein, nucleic acid and virus, the separation and the detection of Chinese herbal medicine effective ingredients extraction and rare metal/precious metal.Yet the recovery and reuse of superpolymer PEG are keys of aqueous two phase extraction technique large-scale application in the dual-aqueous phase abstraction waste liquor.The technology that disclosed relevant PEG recycles in the existing document is few, only has United States Patent (USP) (US6863828B2) report to utilize microwave method to separate from dual-aqueous phase abstraction waste liquor and reclaims polyoxyethylene glycol.Its main process is: separate the last phase that is rich in polyoxyethylene glycol (PEG) from waste liquid; Be placed in the microwave field, continue 1.5～3min, or form two-phase up to separating out moisture, thus form rich aqueous down mutually and be rich in PEG upward mutually; Separate the described also drying that goes up mutually that is rich in PEG, thereby obtain the Powdered PEG of exsiccant with 94%～95% the rate of recovery.The problem one that this method exists in the industrial application process is the bad control of microwave action time, and the time weak point causes phase-splitting not obvious, and microwave time length is splashed solution, causes solution loss; The 2nd, the PEG purity that reclaims is not enough, and color and luster is dark; The 3rd, to handle for the industrial microwave of liquid and to be difficult to realize serialization, production efficiency is low.
Summary of the invention
The purpose of this invention is to provide a kind of technology simply reclaims polyoxyethylene glycol (PEG) from dual-aqueous phase abstraction waste liquor method, make superpolymer PEG recycling, reduce production costs.
The said method that reclaims polyoxyethylene glycol (PEG) from dual-aqueous phase abstraction waste liquor of the present invention may further comprise the steps:
(1) will be rich in the taking-up mutually of polyoxyethylene glycol (PEG) in the waste liquid behind the aqueous two-phase extraction material, add the oxygenant decolouring;
(2) add ionogen in the waste liquid after decolouring and concentrate, concentrated solution adds souring agent and carries out acidifying;
(3) polyoxyethylene glycol (PEG) phase is rich in acidizing fluid centrifugal back separation, concentrates to wherein adding ionogen again, and concentrated solution adds the basifier alkali cleaning;
(4) regulation system pH=7 gets phase after centrifugal, and drying and dehydrating is qualified to moisture content.
Particularly, method of the present invention is specifically described as:
(1) behind the biochemical substances such as aqueous two-phase extraction range protein, nucleic acid, microbiotic, centrifugal or the settled process separation with the employing mutually of being rich in PEG in the double water-phase waste liquid, a kind of oxygenant that adds in clorox, ozone or the hydrogen peroxide decolours, adjust processing parameters such as temperature, time, concentration, percent of decolourization is reached more than 90%;
(2) adding ionogen in the waste liquid after decolouring concentrates, selectable ionogen comprises: ammonium sulfate, vitriolate of tartar, sodium sulfate, volatile salt, yellow soda ash, salt of wormwood, potassiumphosphate, sodium phosphate, ammonium phosphate, potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC, the mixture of one or more in dipotassium hydrogen phosphate or the Sodium phosphate dibasic, concentrated solution adds the souring agent acidifying again, said souring agent is a sulfuric acid, hydrochloric acid, nitric acid, a kind of in acetic acid or the phosphoric acid, the purpose in this step is to remove the solubility in acid impurity of polyoxyethylene glycol in mutually, and simultaneously polyglycol solution is concentrated, cycles of concentration is more than 2 times;
(3) acidizing fluid is got after centrifugal and is rich in the PEG phase, the mixture of one or more in wherein adding ionogen ammonium sulfate, vitriolate of tartar, sodium sulfate, volatile salt, yellow soda ash, salt of wormwood, potassiumphosphate, sodium phosphate, ammonium phosphate, potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate or Sodium phosphate dibasic concentrates, and concentrated solution adds one or more the mixture alkali cleaning in basifier sodium hydroxide, potassium hydroxide, ammoniacal liquor, yellow soda ash, salt of wormwood, volatile salt, saleratus, sodium bicarbonate, the ammonium bicarbonate aqueous solution again.The purpose of this operation is to remove the caustic solubility impurity of polyoxyethylene glycol in mutually in step, and simultaneously polyglycol solution is further concentrated, and the cycles of concentration in this step is more than 1.5;
(4) with sulfuric acid, hydrochloric acid, nitric acid, acetic acid or phosphoric acid regulation system pH value to neutrality, get phase after centrifugal, dehydrate the finished product PEG that can obtain reclaiming with thermostatic drying chamber or other drying methods.
Drying and dehydrating is to water content below 1% in the step (4).
Utilize BaCl
2-I
2The double reagent method is measured the polyoxyethylene glycol concentration of different relative molecular masses.Calculate the rate of recovery of PEG according to the concentration that reclaims front and back PEG, volume, quality etc.
The present invention determined waste liquid that aqueous two-phase extraction obtains through decolouring, concentrate, PEG reusable edible that acid-alkali washing, dewatering process are handled.
The double-aqueous phase system system that the present invention is suitable for comprises the double-aqueous phase system that all are made of the polyoxyethylene glycol participation, as polyoxyethylene glycol-superpolymer and polyoxyethylene glycol-salt system.
The polyoxyethylene glycol that the present invention is suitable for comprises all polyethylene glycol substances in molecular weight from 200 to 20000 scopes.
The beneficial effect that the present invention obtains is as follows:
Polyoxyethylene glycol is the derived product of refining of petroleum, and the growing tension of petroleum resources and price increase make the rising all the way of polyoxyethylene glycol price.For aqueous two-phase extraction technology, reclaim polyoxyethylene glycol and be very important for industrial application its recycle, reduced COD and the BOD in the discharge of wastewater, reduce environmental pollution, also reduced production cost simultaneously.
Embodiment
Following examples are used to illustrate the present invention.
Embodiment 1
Get 100mL and be rich in PEG mutually by in PEG1500 and the waste liquid after double-aqueous phase system that ammonium sulfate is formed has extracted Sumizyme MP, utilize the hydrogen peroxide decolouring, percent of decolourization reaches 90%; In the decolouring waste liquid, add ionogen sodium sulfate, make solution form two-phase, add hcl acidifying, control pH≤3, the cycles of concentration of PEG is 2; Get phase after centrifugal, add ionogen sodium sulfate and form two-phase, the hydro-oxidation sodaization, control pH 〉=12, the cycles of concentration of PEG is 1.5; Total cycles of concentration is that the twice spissated multiple in front and back is long-pending, and promptly total cycles of concentration is 3.Get phase after centrifugal, regulate the pH value to neutrality, centrifugal, to get and utilize thermostatic drying chamber to be dried to moisture content 0.8% mutually, the rate of recovery of PEG is 94%.
The present invention reclaims PEG and the contrast of PEG1500 standard model quality index
Embodiment 2
Get in the waste liquid after the double-aqueous phase system extraction α-Dian Fenmei that 100mL is made up of PEG4000 and sal epsom and be rich in PEG mutually, add clorox, and make its concentration reach 5%, in 35 ℃ of effect 2h decolourings down, percent of decolourization reaches 85%; Add the ionogen vitriolate of tartar in the decolouring waste liquid, mix, centrifugal or leave standstill, solution forms two-phase, adds 6mol.L
-1Hcl acidifying makes pH value=1, stirs 10min, and is centrifugal or leave standstill phase-splitting.The cycles of concentration of PEG reaches 3.16; Get phase after centrifugal, add the ionogen vitriolate of tartar and form two-phase, add potassium hydroxide solution, stir 10min, centrifugal or leave standstill phase-splitting.Twice salt in front and back is handled, and total cycles of concentration of PEG reaches about 3.5.Get phase after centrifugal, to neutral, centrifugal, getting once more is the PEG phase mutually with acid for adjusting pH value, and utilizing thermostatic drying chamber to be dried to moisture content is 0.7%, and the rate of recovery of PEG is 97%.Utilize the PEG extracting and separating α-Dian Fenmei that reclaims, two-phase volume ratio, partition ratio, effect of extracting are with commodity PEG no significant difference.
Embodiment 3
Get in the waste liquid behind the double-aqueous phase system extraction phycoerythrin that 100mL is made up of PEG6000 and dextran and be rich in PEG mutually, utilize the hydrogen peroxide method decolouring; Add ionogen sodium sulfate in the decolouring waste liquid, make solution form two-phase, add hcl acidifying, stir 10min, centrifugal or leave standstill phase-splitting, this moment, the cycles of concentration of PEG was 3.45; Get phase after centrifugal, add ionogen sodium sulfate and form two-phase, hydro-oxidation sodium is basified to pH=13, stirs 10min, and is centrifugal or leave standstill phase-splitting, and the cycles of concentration of PEG is 1.23.The cycles of concentration of twice salt processing is 4.25 times.Get phase after centrifugal, to neutral, centrifugal, getting once more is the PEG phase mutually with acid for adjusting pH value, and utilizing thermostatic drying chamber to be dried to moisture content is 0.5%, and the rate of recovery of PEG is 87%.Utilize the PEG extracting and separating ox phycoerythrin that reclaims, two-phase volume ratio, partition ratio, effect of extracting are with commodity PEG no significant difference.
Embodiment 4
Get 100mL by being rich in PEG mutually in the waste liquid behind PEG800 and the double-aqueous phase system extracting penicillin acylase that Trisodium Citrate is formed, add hydrogen peroxide, and make its concentration reach 7%, decolouring, percent of decolourization reaches 85%; In the decolouring waste liquid, add ionogen sodium sulfate, mix, centrifugal or leave standstill, make solution form two-phase, add phosphoric acid and be acidified to pH value=2; Mix once more, centrifugal or leave standstill, solution is finished phase process, on be PEG solution after concentrating mutually, the cycles of concentration of PEG reaches 3.1; Get phase after centrifugal, add ionogen sodium sulfate and form two-phase, add potassium hydroxide solution and be basified to pH=13, stir 10min, centrifugal or leave standstill phase-splitting, the cycles of concentration 1.04 of last phase PEG; Get phase after centrifugal, to neutral, centrifugal, getting once more is the PEG phase mutually, is dried to moisture content with thermostat container and reaches 0.5% with acid for adjusting pH value, and the rate of recovery of PEG reaches 90%.
Embodiment 5
Get in the waste liquid behind the double-aqueous phase system extraction oxyphorase that 100mL is made up of PEG8000 and dipotassium hydrogen phosphate and be rich in PEG mutually, add clorox, and make its concentration reach 5%, in 40 ℃ of effect 3h decolourings down, percent of decolourization reaches 95%; Add ionogen ammonium sulfate in the decolouring waste liquid, mix, centrifugal or leave standstill, solution forms two-phase, adds 6mol.L
-1Nitric acid is acidified to pH=1, stirs 10 minutes, and is centrifugal or leave standstill phase-splitting, finishes the pickling concentration process.The cycles of concentration of PEG reaches 2.5; Get phase after centrifugal, add the ionogen vitriolate of tartar and form two-phase, add potassium hydroxide solution and be basified to pH=13, stir 10h, centrifugal or leave standstill phase-splitting.Twice salt in front and back is handled, and total cycles of concentration of PEG reaches about 3.0.Get phase after centrifugal, to neutral, centrifugal, getting once more is the PEG phase mutually, is dried to water-content 0.7% with thermostatic drying chamber with acid for adjusting pH value, and the rate of recovery of PEG is 94%.Utilize the PEG extracting and separating bovine hemoglobin that reclaims, two-phase volume ratio, partition ratio, effect of extracting are with commodity PEG no significant difference.
Claims (5)
1. method that reclaims polyoxyethylene glycol (PEG) from dual-aqueous phase abstraction waste liquor is characterized in that may further comprise the steps:
(1) will be rich in the taking-up mutually of polyoxyethylene glycol (PEG) in the waste liquid behind the aqueous two-phase extraction material, add the oxygenant decolouring;
(2) add ionogen in the waste liquid after decolouring and concentrate, concentrated solution adds souring agent and carries out acidifying;
(3) polyoxyethylene glycol (PEG) phase is rich in acidizing fluid centrifugal back separation, concentrates to wherein adding ionogen again, and concentrated solution adds the basifier alkali cleaning;
(4) regulation system pH=7 gets phase, drying and dehydrating after centrifugal;
Wherein, said oxygenant is a kind of in clorox, ozone, the hydrogen peroxide in the step (1);
Said ionogen is one or more the mixture in ammonium sulfate, vitriolate of tartar, sodium sulfate, volatile salt, yellow soda ash, salt of wormwood, potassiumphosphate, sodium phosphate, ammonium phosphate, potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate or the Sodium phosphate dibasic in step (2) and the step (3);
Said souring agent is a kind of in sulfuric acid, hydrochloric acid, nitric acid, acetic acid or the phosphoric acid in the step (2);
Said basifier is one or more the mixture in sodium hydroxide, potassium hydroxide, ammoniacal liquor, yellow soda ash, salt of wormwood, volatile salt, saleratus, sodium bicarbonate, the ammonium bicarbonate aqueous solution in the step (3).
2. method according to claim 1 is characterized in that: said double-aqueous phase system is the double-aqueous phase system that is made of the polyoxyethylene glycol participation, can be polyoxyethylene glycol-superpolymer or polyoxyethylene glycol-salt system.
3. method according to claim 1 is characterized in that: the said material that is extracted is a range protein.
4. method according to claim 1 is characterized in that: said polyoxyethylene glycol (PEG) molecular weight is 200～20000.
5. method according to claim 1 is characterized in that: drying and dehydrating is to water content below 1% in the step (4).
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| CN101367955B true CN101367955B (en) | 2011-04-27 |
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| CN104640901B (en) * | 2012-09-18 | 2017-03-08 | 大荣产业株式会社 | The thermal dissociation sealer of the manufacture method of enclosed type polyisocyanate composition, prepolymer composite and these compositions and enclosed type polyisocyanate composition |
| CN103254335B (en) * | 2013-05-31 | 2014-05-14 | 晋江汇森高新材料科技有限公司 | Method for preparing polyacrylate super absorbent resin from composite alkaline liquid |
| KR101761680B1 (en) * | 2015-03-31 | 2017-08-23 | 포항공과대학교 산학협력단 | Isolation Method of Extracellular Vesicles by Aqueous Two-phase System |
| CN105237367B (en) * | 2015-09-02 | 2017-03-01 | 山东新时代药业有限公司 | A kind of method reclaiming 2,2'-ethylenedioxybis(ethanol). the synthesis mother liquid from Sevoflurane |
| CN106947108A (en) * | 2017-02-22 | 2017-07-14 | 广西科学院 | A kind of polyglycol solution recycling technology for preparing spherex |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6863828B2 (en) * | 2003-03-25 | 2005-03-08 | Council Of Scientific And Industrial Research | Process for separation and recovery of polyethylene glycol (PEG) from spent aquesous two-phase systems |
| CN1771200A (en) * | 2003-03-31 | 2006-05-10 | 科学与工业研究委员会 | Process for separation and recovery of polyethylene glycol (PEG) from spent aqueous two-phase systems |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6863828B2 (en) * | 2003-03-25 | 2005-03-08 | Council Of Scientific And Industrial Research | Process for separation and recovery of polyethylene glycol (PEG) from spent aquesous two-phase systems |
| CN1771200A (en) * | 2003-03-31 | 2006-05-10 | 科学与工业研究委员会 | Process for separation and recovery of polyethylene glycol (PEG) from spent aqueous two-phase systems |
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