CN100999545B - Process of recovering sericine by ion exchanging - Google Patents
Process of recovering sericine by ion exchanging Download PDFInfo
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- CN100999545B CN100999545B CN2007100364366A CN200710036436A CN100999545B CN 100999545 B CN100999545 B CN 100999545B CN 2007100364366 A CN2007100364366 A CN 2007100364366A CN 200710036436 A CN200710036436 A CN 200710036436A CN 100999545 B CN100999545 B CN 100999545B
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- silk gum
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Abstract
The sericin recovering ion exchange process includes the following steps: 1. pressure filtering waste liquid containing sericin at 5-95 deg.c to eliminate mechanical impurity; 2. injecting the waste liquid into ion exchange column for adsorption; 3. leaching the ion exchange column with deionized water to eliminate alkali, salt and surfactant; 4. leaching with 0.1-3.0 M concentration acid solution and collecting outflow liquid; and 5. regulating the pH value of the collected concentrated sericin solution to neutrality and spray drying to obtain sericin powder. The present invention has lowered waste liquid treating cost, can recover sericin and is environment friendly.
Description
Technical field
The invention belongs to the light industry field, particularly relate to a kind of method that reclaims sericine with ion-exchange.
Background technology
Can produce the waste water that much contains silk gum in the nest silk of real silk and the concise course of processing of silk fabric, these waste water often mix with back arrangement waste water with follow-up dyeing and handle, so not only increased the burden of wastewater treatment, and be significant wastage to a large amount of sericins that use value is arranged, because studies show that sericin very high value is arranged, can be applied to a lot of aspects, such as medicine, food, makeup and textile industry.Recovery research to silk gum is had it long ago, and its method has: acid-precipitation method, Coagulation Method, organic solvent method, centrifuging, ultrafiltrationmembrane process and freezing method.
Acid-precipitation method is exactly to utilize protein in the minimum principle of iso-electric point place solubleness, and the pH value by regulator solution makes the sericine precipitation and reclaimed to the iso-electric point of sericine, and this method is had relatively high expectations to the erosion resistance of equipment.
Coagulation Method utilizes high salt concentration to destroy proteinic hydration layer exactly, makes the easier gathering of protein and precipitates, and reaches the recovery purpose, to contain impurity many for the sericin of Hui Shouing like this, be worth not highly, can not be applied to medicine, the industry that purity requirements such as food are high.
Organic solvent method utilizes organic solvent can reduce the specific inductivity of solution, thereby reduce proteinic solubleness and its precipitation is separated out, need a large amount of organic solvents in this method treating processes, so cost height, less economical, can only be applicable to that the silk gum after concentrating is handled.Because of using solvent to bring certain danger, also need to dispose solvent recovering system simultaneously in order to reclaim solvent to removal process.
Centrifuging is the common method of solid-liquid separation, the centrifugal force difference of utilizing the material density difference to be subjected to, separating sericine solution with its often needs in advance the sericine solution precipitation, so it generally is as the replenishing of other recovery methods, can not use separately.
Ultrafiltrationmembrane process, its principle is to utilize the size in separatory membrane aperture, the material of differing molecular size is separated, usually macromole can not small-molecule substance can by semi-permeable membranes, by this method macromolecular sericine of purifying, the used film expense of this method is very high and be easy to stop up.
Freezing method is according to the gel property difference of sericine protein to be divided into can the congeal silk gum and the silk gum that can not congeal, then according to the different qualities of silk gum, determine recovery method, usually carry out gelation and reach the purpose that reclaims silk gum with the method for cooling, it is bigger that this method reclaims the sericin energy consumption, and the technological process time is long.
This shows that the concise processing sewage of silk is handled the method that reclaims silk gum to be had multiple, wherein the utilization research with membrane separation technique is main direction, but this method exists cost height, shortcoming that processing speed is low, realize that suitability for industrialized production also needs to solve many technical barriers.
Summary of the invention
For overcoming the defective of above-mentioned various recovery methods; the invention provides a kind of method with ion-exchange recovery sericine, this method can reduce cost, and handles the concise processing sewage of real silk rationally and effectively; sericine in the sewage is for recycling and reuse, and the protection environment reduces pollution.
A kind of method with ion-exchange recovery sericine of the present invention comprises the following steps:
(1) the silk gum waste liquid is removed mechanicalness impurity by mechanical filter, temperature can be between the 5-95 degree;
(2) ion-exchange absorption: the sericine solution after will filtering weighs 1 kilogram ion exchange column with per minute 10-1000ml by resin, and the content of silk gum of silk gum waste liquid is 1.8-2.3g/l, stops to inject after handling 100-250L silk gum waste liquid;
(3) deionized water drip washing: with the speed eluent ion exchange column of 5L deionized water, until the anhydrous outflow of ion exchange column with per minute 100ml;
(4) wash-out: with 5L concentration is that the acetum of 0.1-3.0M carries out drip washing, injects ion exchange column with the speed of per minute 10-100ml, collects flowing liquid;
(5) spraying drying: with the sericin strong solution of collecting, it is neutral being adjusted to the pH value with ammoniacal liquor, carries out spraying drying then on spray-drier, obtains the silk gum powder.
Described step 1 temperature is the 15-35 degree;
Described step 1 mechanical filter adopts non-woven fabrics of synthetic fiber, also can be glass fibre, and filtering material can be that sheet material also can be a bag shaped structure; The aperture of filtering material is good with glass fibre between 0.1-100um, and 1um is good;
The preparation of described step 2 ion exchange column: fill exchange column with Zeo-karb;
Described resin cation (R.C.) can be particulate state, powder or fibrous, is good with filamentary structure;
Described resin cation (R.C.) can be that synthetic resins also can be natural macromolecular material or modified natural polymer material; Cation group in the resin cation (R.C.) can be primary amine, secondary amine, tertiary amine and quaternary ammonium, and is more suitable with quaternary ammonium;
The drip washing consumption of described step 3 deionized water is the void volume in the 1-4 ion exchange column doubly;
Described step 4 acid solution can be mineral acid or organic acid, or the mixing acid of the two; With small molecular organic acid such as acetic acid is good;
The present invention utilizes ion exchange resin that sericine is adsorbed, sericine is separated with concise sewage, then with elutriant with sericine wash-out from the ion exchange resin, obtain spissated sericine solution, obtain powder silk gum with spray-drying process again.
The present invention utilizes the electrostatic force between proteic amphoteric properties and the zwitterion to reclaim sericin.Generally under alkaline condition, carry out owing to come unstuck, so this moment, sericin had negative charge, the resin cation (R.C.) that use has positive charge utilizes the electrostatic attraction reactive force to absorb sericin, use clear water drip washing then, to remove water-soluble impurity, with acid resin cation (R.C.) is soaked or drip washing again, this moment, protein was positive charge at acidic conditions, produce the Coulomb repulsion effect with the positive charge on the fiber, thereby resolve from resin,, obtain higher concentration sericin solution with this purpose that reaches the enrichment thread glue protein, carry out spraying drying at last, obtain the sericin powder.
Method of the present invention can be handled the factory effluent in the nest silk processing, also can be the waste water that produces in the silk scouring processing or with the waste liquid that comes unstuck of pyroprocess production.
The concentration of acid solution can be between the 0.1-3.0M among the present invention, and too high or too low acid solution can make the concentration of concentrated protein solution change or the stability of resin cation (R.C.) is changed.
The resulting concentrated protein solution of the present invention through adjusting the pH value of solution value, can carry out drying treatment with most spray-drying process, obtains powder body material.
The deionized water that uses among the present invention can be the deionized water of handling with the yin, yang ion exchange resin; In this process, with the inorganic and organic impurity in the removal resin absorption system, as: basic cpd yellow soda ash, water glass, Sodium hexametaphosphate 99, tensio-active agent laurilsulfate etc.; Improve the purity that reclaims sericine; Improve the deionized water wash consumption and can improve the purity that reclaims sericin powder, but the loss that can increase silk gum, otherwise then improve the yield of sericin powder, but silk gum purity can reduce.
The filtration of silk gum waste liquid among the present invention its objective is the mechanicalness solid impurity of removing in the silk gum waste liquid, improves the purity that reclaims silk gum, and filter method can be that suction filtration also can be pressure filtration.
The present invention handles the method for silk gum waste liquid, is not suitable for containing the silk gum waste liquid of illuminating colour; The silky fibre of twisting contain usually with difference twist with the fingers to illuminating colour, the waste liquid that comes unstuck of this fibrid, fabric contains dyestuff, the color that will influence reclaims silk gum is not suitable for the use of this method.
The silk gum that the present invention handles silk gum waste liquid gained is the powder form, can be used for all many-sides such as makeup, textiles.
The present invention can high-level efficiency, and the silk gum waste liquid that produces in can a large amount of processing production process; The purity of the silk gum powder that is reclaimed can obtain by the change to manufacturing condition as required.
The present invention not with an organic solvent, solvent-free recovery and relevant security requirement; Only use simple organic acid and mineral alkali, whole wastewater treatment process energy consumption is low, and speed is fast, can carry out processing to a large amount of waste water.
Description of drawings
Sericine is reclaimed in Fig. 1 ion-exchange absorption.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Get 1 kilogram of fibrous Zeo-karb, the cation radical mass contg is 1.5-2.0mol, is assembled into ion exchange column, connects the inlet and outlet device that disposes waste liquid by accompanying drawing; To press the speed injection ion exchange column of per minute 100ml through the silk gum waste liquid of mechanical filter, the content of silk gum of silk gum waste liquid is 1.8-2.3g/l; After handling 250L silk gum waste liquid, stop to inject; Use the 5L deionized water, press the speed of per minute 100ml and inject ion exchange column, after the anhydrous outflow of ion exchange column, with 5L concentration is the acetum of 1M, injects ion exchange column with the speed of per minute 10ml, collects flowing liquid, to neutral, carry out spraying drying with the ammoniacal liquor regulator solution; Obtain 360 gram silk gum powders.
Embodiment 2
Get 1 kilogram of fibrous Zeo-karb, the cation radical mass contg is 1.5-2.0mol, is assembled into ion exchange column, connects the inlet and outlet device that disposes waste liquid by accompanying drawing; To press the speed injection ion exchange column of per minute 500ml through the silk gum waste liquid of mechanical filter, the content of silk gum of silk gum waste liquid is 1.8-2.3g/l; After handling 250L silk gum waste liquid, stop to inject; Use the 50L deionized water, press the speed of per minute 100ml and inject ion exchange column, after the anhydrous outflow of ion exchange column, with 5L concentration is the acetum of 1M, injects ion exchange column with the speed of per minute 10ml, collects flowing liquid, to neutral, carry out spraying drying with the ammoniacal liquor regulator solution; Obtain 290 gram silk gum powders.
Embodiment 3
Get 1 kilogram of fibrous Zeo-karb, the cation radical mass contg is 1.5-2.0mol, is assembled into ion exchange column, connects the inlet and outlet device that disposes waste liquid by accompanying drawing; To press the speed injection ion exchange column of per minute 10ml through the silk gum waste liquid of mechanical filter, the content of silk gum of silk gum waste liquid is 1.8-2.3g/l; After handling 250L silk gum waste liquid, stop to inject; Use the 5L deionized water, press the speed of per minute 100ml and inject ion exchange column, after the anhydrous outflow of ion exchange column, with 5L concentration is the acetum of 1M, injects ion exchange column with the speed of per minute 10ml, collects flowing liquid, to neutral, carry out spraying drying with the ammoniacal liquor regulator solution; Obtain 390 gram silk gum powders.
Claims (9)
1. the method with ion-exchange recovery sericine comprises the following steps:
(1) the silk gum waste liquid is removed mechanicalness impurity, filtration temperature 5-95 degree by mechanical filter;
(2) ion-exchange absorption: the sericine solution after will filtering weighs 1 kilogram ion exchange column with per minute 10-1000ml by resin, and the content of silk gum of silk gum waste liquid is 1.8-2.3g/l, stops to inject after handling 100-250L silk gum waste liquid;
(3) deionized water drip washing: with the speed eluent ion exchange column of 5L deionized water, until the anhydrous outflow of ion exchange column with per minute 100ml;
(4) wash-out: with 5L concentration is that the acid solution of 0.1-3.0M carries out drip washing, injects ion exchange column with the speed of per minute 10-100ml, collects flowing liquid;
(5) spraying drying: with the sericin solution of collecting, it is neutral being adjusted to the pH value with alkali, carries out spraying drying then on spray-drier, obtains the silk gum powder.
2. a kind of method with ion-exchange recovery sericine according to claim 1, it is characterized in that: described step 1 filtration temperature is the 15-35 degree.
3. a kind of method according to claim 1 with ion-exchange recovery sericine, it is characterized in that: described step 1 mechanical filter adopts non-woven fabrics of synthetic fiber or glass fibre, and filtering material is sheet material or bag shaped structure; The aperture of filtering material is between 0.1-100um.
4. according to claim 1 or 3 described a kind of methods with ion-exchange recovery sericine, it is characterized in that: described step 1 mechanical filter is to use glass fibre, and aperture 1um.
5. a kind of method with ion-exchange recovery sericine according to claim 1 is characterized in that: the preparation of described step 2 ion exchange column: fill exchange column with the filamentary structure Zeo-karb.
6. a kind of method with ion-exchange recovery sericine according to claim 5, it is characterized in that: the cation group in the described resin cation (R.C.) is primary amine, secondary amine, tertiary amine or quaternary ammonium.
7. according to claim 5 or 6 described a kind of methods with ion-exchange recovery sericine, it is characterized in that: the cation group in the described resin cation (R.C.) is a quaternary ammonium.
8. a kind of method with ion-exchange recovery sericine according to claim 1 is characterized in that: the drip washing consumption of described step 3 deionized water is the void volume in the 1-4 ion exchange column doubly.
9. a kind of method with ion-exchange recovery sericine according to claim 1, it is characterized in that: described step 4 acid solution is an acetic acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007100364366A CN100999545B (en) | 2007-01-12 | 2007-01-12 | Process of recovering sericine by ion exchanging |
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| CN2007100364366A CN100999545B (en) | 2007-01-12 | 2007-01-12 | Process of recovering sericine by ion exchanging |
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| CN100999545A CN100999545A (en) | 2007-07-18 |
| CN100999545B true CN100999545B (en) | 2010-09-08 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575371B (en) * | 2009-05-13 | 2013-09-18 | 桂林奥尼斯特节能环保科技有限责任公司 | Method for adopting tannin to process silkworm cocoon processing wastewater and recycle sericin protein |
| CN101857320B (en) * | 2010-05-25 | 2012-01-25 | 苏州大学 | Method for treatment of silk degumming wastewater and recovery of silk gum |
| CN102633872A (en) * | 2012-03-31 | 2012-08-15 | 西安交通大学 | Method for enriching and recovering sericin protein by magnetic high-polymer hydrogel |
| CN106009032B (en) * | 2016-06-30 | 2019-01-01 | 浙江汇能生物股份有限公司 | A method of sericin is recycled using anion-modified glucan |
| CN106745878A (en) * | 2016-11-30 | 2017-05-31 | 广西大学 | The recovery method of sericin in filature industrial wastewater |
| CN108164059A (en) * | 2018-01-30 | 2018-06-15 | 浙江工业大学膜分离与水处理协同创新中心湖州研究院 | A kind of embrane method processing cocoon boiling wastewater and the method for recycling sericin |
| CN110040818A (en) * | 2019-05-17 | 2019-07-23 | 浙江工业大学 | Utilize the technique of silk gum in 201 × 7 ion exchange resin recycling filature industrial wastewater |
| CN112456713A (en) * | 2020-11-24 | 2021-03-09 | 广东闻扬环境科技有限公司 | Process and equipment for recovering and treating protein in bean product wastewater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1228438A (en) * | 1998-12-01 | 1999-09-15 | 浙江丝绸工学院 | Sericin polypeptide extracted from frison, husks and waste silk and its extracting method |
| CN1343733A (en) * | 2000-09-18 | 2002-04-10 | 刘云聪 | Process for recovering sericin of cocoon silk |
| CN1477141A (en) * | 2003-07-09 | 2004-02-25 | 苏州大学 | Production method of water soluble sericin |
| CN1493722A (en) * | 2003-08-29 | 2004-05-05 | 湖州澳特丝生物化工有限公司 | Quick dissolving sericin powder and its making method |
-
2007
- 2007-01-12 CN CN2007100364366A patent/CN100999545B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1228438A (en) * | 1998-12-01 | 1999-09-15 | 浙江丝绸工学院 | Sericin polypeptide extracted from frison, husks and waste silk and its extracting method |
| CN1343733A (en) * | 2000-09-18 | 2002-04-10 | 刘云聪 | Process for recovering sericin of cocoon silk |
| CN1477141A (en) * | 2003-07-09 | 2004-02-25 | 苏州大学 | Production method of water soluble sericin |
| CN1493722A (en) * | 2003-08-29 | 2004-05-05 | 湖州澳特丝生物化工有限公司 | Quick dissolving sericin powder and its making method |
Non-Patent Citations (3)
| Title |
|---|
| 段亚峰等.丝绸废水的膜法处理与丝胶蛋白质回收技术.纺织学报26 2.2005,26(2),24-26. * |
| 段亚峰等.丝胶蛋白质浓缩液的离心喷雾干燥技术研究.丝绸 5.2004,(5),16-18. * |
| 田亚峰等.丝绸工业废水中丝胶蛋白质的回收技术.丝绸 7.2001,(7),23-25. * |
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