CN106745878A - The recovery method of sericin in filature industrial wastewater - Google Patents
The recovery method of sericin in filature industrial wastewater Download PDFInfo
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- 108010013296 Sericins Proteins 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 83
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 27
- 238000011084 recovery Methods 0.000 title abstract description 25
- 239000002351 wastewater Substances 0.000 claims abstract description 41
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 32
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 32
- 238000001179 sorption measurement Methods 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000000926 separation method Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000010828 elution Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 15
- 238000004458 analytical method Methods 0.000 claims description 13
- 238000002386 leaching Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 235000013305 food Nutrition 0.000 abstract description 5
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 108090000623 proteins and genes Proteins 0.000 description 10
- 102000004169 proteins and genes Human genes 0.000 description 10
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- 238000003795 desorption Methods 0.000 description 7
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- 238000013375 chromatographic separation Methods 0.000 description 4
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- 239000003814 drug Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 108010022355 Fibroins Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
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- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- JVIPLYCGEZUBIO-UHFFFAOYSA-N 2-(4-fluorophenyl)-1,3-dioxoisoindole-5-carboxylic acid Chemical compound O=C1C2=CC(C(=O)O)=CC=C2C(=O)N1C1=CC=C(F)C=C1 JVIPLYCGEZUBIO-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-WFVLMXAXSA-N DEAE-cellulose Chemical compound OC1C(O)C(O)C(CO)O[C@H]1O[C@@H]1C(CO)OC(O)C(O)C1O GUBGYTABKSRVRQ-WFVLMXAXSA-N 0.000 description 1
- 206010012289 Dementia Diseases 0.000 description 1
- 229920001425 Diethylaminoethyl cellulose Polymers 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229960004543 anhydrous citric acid Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 108091005899 fibrous proteins Proteins 0.000 description 1
- 102000034240 fibrous proteins Human genes 0.000 description 1
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- 238000007602 hot air drying Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/43504—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates
- C07K14/43563—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects
- C07K14/43586—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects from silkworms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Zoology (AREA)
- Tropical Medicine & Parasitology (AREA)
- Insects & Arthropods (AREA)
- Toxicology (AREA)
- Gastroenterology & Hepatology (AREA)
- Biochemistry (AREA)
- Biophysics (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of recovery method of sericin in filature industrial wastewater, specifically by filature industrial wastewater through obtaining sericin collection liquid including the operation including filtering and impurity removing, resin adsorption, wash-out, collection；Resin employed in wherein described resin adsorption operation is the ion exchange resin of DEAE 52.The inventive method process is simple, equipment investment are few, and selected resin is repeatable to be utilized, and easily realizes that continuous processing is produced, and is adapted to industrialization promotion；The sericin purity for obtaining is returned to invention this method higher, and be not introduced into harmful substance, can be used for food and other industry.The inventive method can not only solve the discharge pressure of reeling enterprises waste water, moreover it is possible to realize making full use of for accessory substance.
Description
Technical Field
The invention relates to the field of industrial production of silk reeling, in particular to a method for recovering sericin in industrial wastewater of silk reeling.
Background
Silk is a fibrous protein, mainly composed of sericin and silk fibroin; sericin is coated on the outer layer of silk fibroin to play a role in adhesion protection. The process of dissociating cocoon filaments from the cocoon layer is called reeling. Reeling generally uses a process of immersing cocoons in hot alkaline water or hot water for boiling, dissolving sericin in the hot water, and then drawing out raw silk and winding and collecting the raw silk. The sericin content in the cocoon silk is nearly 30%, so that the waste water generated in the silk reeling process is rich in a large amount of sericin. Detection and analysis show that the concentration of protein in industrial reeling waste water is between 0.4 and 3.8 mg/mL.
Sericin is a water-soluble protein containing 18 amino acids and all essential amino acids required by the human body. Studies show that sericin or sericin peptide can improve human memory, prevent brain aging and prevent dementia. In addition, sericin has very good physicochemical properties such as oxidation resistance, ultraviolet resistance, moisture retention, antibacterial property and the like, and can be applied to various fields such as medicines, cosmetics, biomaterials, textiles, foods and the like. Therefore, as a valuable protein resource, the production mode of directly discharging the conventional sericin along with the reeling wastewater not only pollutes the water body, improves the COD value and the BOD value of the wastewater, increases the cost and the difficulty of sewage treatment, but also causes the waste of the protein resource. Through retrieval and analysis, the following schemes are mainly adopted in relevant researches to solve the problem of environmental pollution of reeling waste water and reduce sericin protein resource waste:
(1) acid precipitation method: adding HCl or dilute H into sericin protein wastewater2SO4The pH is adjusted to 3.8 to 4.5, and the sericin protein solubility is decreased under the condition of isoelectric point to gradually settle and separate. Due to the large volume of the wastewater, the method is time-consuming in treatment, a large number of sedimentation tanks are needed, the recovery rate is not high (generally not more than 50%), and the sericin obtained by recovery contains more impurities.
(2) A chemical coagulation method: generally, a large amount of concentrated or saturated salt solution is used, and the property that strong electrolyte is completely ionized into ions in water to deprive water molecules combined with proteins is utilized, so that a hydration layer around the proteins is broken, and the proteins are coagulated and precipitated. The method has simple process, but has the following disadvantages: because the flocculant is mostly ferric salt or aluminum salt, the sericin obtained by recycling contains some metal ions, and the product needs to be purified when being applied to fields with strict requirements such as food and medicine. The following steps are provided: chinese patent application (application No. 201310073594.4) entitled precipitation method of sericin in silk reeling wastewater discloses adding proper amount of anhydrous citric acid C in turn into silk reeling wastewater6H8O7And disodium hydrogen phosphate Na2HPO4Stirring with a stirrer, and adding appropriate amount of tannic acid C76H52O46Then heating and standing to precipitate sericin in the silk reeling wastewater; the method is describedSericin can be obtained, but a plurality of chemical reagents are added, and the process is complicated. And: the chinese patent application (application No. 200710093091.8) entitled "treatment method of wastewater containing sericin" synthesizes sericin metal complex by coordination reaction of sericin itself and metal, coagulates and precipitates sericin in wastewater from a silk mill as a flocculant to effectively treat the wastewater, and finally recovers sericin by a dilute acid washing method, which comprises the following specific processes: adding a sericin metal complex into the sericin-containing wastewater, oscillating for 6-10 h, extracting a precipitate, adding dilute hydrochloric acid or dilute sulfuric acid into the obtained precipitate for washing, magnetically stirring for 1-12 h, and drying the precipitate obtained by centrifugation to obtain sericin powder; although sericin can be obtained by the method, the application of the recovered sericin is limited due to the introduction of metal ions in the preparation process of the sericin complex, further purification is needed if the sericin complex is used in medicine and food, and the preparation process of the sericin metal complex used in the method is relatively complicated.
(3) Organic solvent precipitation method: the method is to use the water absorption of alcohol or acetone to destroy the hydration layer of protein micelle and precipitate protein, but the method is not suitable for waste liquid with low concentration and large treatment capacity, only suitable for sericin after concentration to separate out from the solution, and the protein is easy to be denatured in organic solvent. The safety and cost of this approach also limit its application.
(4) And (3) ultrafiltration: the method utilizes the aperture of a membrane to separate sericin in wastewater, namely a filter membrane which cannot permeate sericin and can permeate other substances is used to achieve the separation effect. Although the method has good purification effect, the filter membrane is easy to pollute and needs to be cleaned regularly, which undoubtedly increases the production cost for the reeling industry with large wastewater treatment capacity.
As can be seen from the above, although there are many methods for recovering sericin from the reeling waste water, there are limitations in the different methods due to the large treatment capacity of the reeling waste water due to the low protein content in the reeling waste water. Therefore, a new method which has low cost and good effect and can treat the reeling waste water in a large scale is urgently needed to solve the problem of recycling the sericin in the reeling waste water.
Disclosure of Invention
In order to overcome the defects of the prior method, the invention provides a novel method for recovering sericin in the reeling industrial wastewater, which adopts normal-temperature operation, has low energy consumption and simple operation and does not have secondary pollution; the continuous production of the reeling industrial wastewater with large treatment capacity is easy to realize, the recovery rate of sericin is high, and the purity of the sericin obtained by recovery is high.
The invention relates to a method for recovering sericin in silk reeling industrial wastewater, which specifically comprises the steps of filtering and impurity removal, resin adsorption, elution and collection of the silk reeling industrial wastewater to obtain sericin collection liquid; the method is characterized in that the resin adopted in the resin adsorption process is DEAE-52 ion exchange resin, and the specific processes of filtering, impurity removal, resin adsorption, elution and collection can refer to and adopt the prior art in the related field.
DEAE-52 ion exchange resin, chemical name diethylaminoethyl cellulose 52, foreign name DEAEcellulose DE-52. Experiments of the inventor show that when the DEAE-52 ion exchange resin is used for recovering sericin in the reeling industrial wastewater, the adsorption and analysis effects of the DEAE-52 ion exchange resin are obviously better than those of the DEAE-52 ion exchange resin when other resin adsorbents such as AB-8, LX-1180, D101, DA201-C, 201X 7 and the like are adopted, and the DEAE-52 ion exchange resin has better adsorption and analysis performances and high sericin recovery rate, can effectively recover the sericin in the wastewater and plays a good role in enriching the sericin in the wastewater.
Experiments of the inventor also find that when the resin adsorption and elution in the scheme of the invention adopt the following processes at the same time, the adsorption quantity, the resolution ratio, the sericin recovery rate, the concentration ratio, the comprehensive recovery cost and other parameters of the sericin simultaneously reach excellent values: the resin adsorption means that the filtered and impurity-removed silk reeling wastewater is introduced into a separation column filled with the resin at a flow rate of 3-7.5 BV/h without adjusting the pH value so that sericin in the silk reeling wastewater is adsorbed onto the resin, and the liquid feeding of the silk reeling wastewater is stopped until the concentration of the sericin in the effluent liquid of the separation column is 0.05 mg/mL; the elution is to introduce an analytic solution with the pH value of 2-5 and the concentration of 0.05-0.2 mol/L into the separation column at the flow rate of 1-3 BV/h, and simultaneously monitor the concentration change of sericin in an eluent flowing out of the separation column until the elution is complete, and stop the liquid inlet of the analytic solution; the resolving solution is preferably one or more of acidified sodium chloride and potassium chloride solution.
Before the DEAE-52 ion exchange resin is filled into the separation column, the DEAE-52 ion exchange resin is usually subjected to pretreatment such as swelling and dilute acid/dilute alkali soaking, and the preferred pretreatment process of the DEAE-52 ion exchange resin in the method comprises the following steps: soaking the substrate in deionized water for 12-24 h, washing the substrate, and then using 1-2 mol.L-1Soaking in a hydrochloric acid solution for 2-6 h; then washing the mixture to be neutral by using deionized water, and then using 1-2 mol.L-1Soaking in NaOH solution for 2-6 h; and washing the mixture to be neutral by using deionized water for later use.
In order to improve the resin adsorption efficiency, facilitate continuous industrial production and reduce the production cost, a process of regenerating DEAE-52 ion exchange resin in the separation column can be arranged after the elution and collection processes, and the preferred DEAE-52 ion exchange resin regeneration method comprises the following steps: after the separation column is used for 8-10 cycles, soaking the separation column in 3-5% hydrochloric acid for 3-5 hours, and then leaching the separation column with 2-3 times of hydrochloric acid with the same concentration; washing the mixture with deionized water until the mixture is neutral, and soaking the mixture for 3-5 hours by using 3-5% NaOH; and then, leaching with 2-3 times of volume of sodium hydroxide solution with the same concentration, and finally washing with deionized water to be neutral, so that the sodium hydroxide can be reused.
The product produced by adopting the technical scheme is sericin protein collecting liquid, and the method can also be provided with the working procedures of concentrating and drying the collected sericin protein collecting liquid after the collecting working procedure so as to obtain powdery sericin protein. One concentration process that is preferably employed is: concentrating the sericin collected liquid obtained in the collecting procedure in vacuum until the solid content reaches more than 10 percent and adjusting the pH to be neutral; the vacuum degree preferably adopted during vacuum concentration is-0.06 to-0.1 MPa, and the temperature is 55 to 65 ℃.
The method for recovering sericin in the reeling industrial wastewater has the following characteristics and advantages:
1. compared with the existing recovery methods of sericin in reeling wastewater such as an acid precipitation method, a chemical coagulation method, an organic solvent method, an ultrafiltration method and the like, the recovery method of sericin in reeling wastewater adopts normal-temperature operation, and has the advantages of less equipment investment, low energy consumption, simple operation and no secondary pollution; the DEAE-52 ion exchange resin which is selected, has stronger adsorption pertinence to sericin in the reeling waste water and excellent analytic effect is adopted, so that the high-efficiency recovery and enrichment of sericin and the high-efficiency reuse of resin are realized, and the comprehensive production cost is lower; by matching with a production mode of multi-column switching, the continuous treatment and recovery of sericin in industrial wastewater of industrial mass reeling are obviously easy to realize, so that the method has great industrial popularization potential;
2. the sericin obtained by recovery has high purity and good quality, can be used in various aspects such as food, skin care products, medicine and the like, and can greatly increase the added value of production; in addition, sericin with different purities can be obtained easily by changing the production process conditions so as to meet different application requirements;
3. the method can be used for treating the wastewater generated in the cocoon cooking and silk reeling processes, and realizes the full utilization of byproducts while solving the problem of wastewater discharge pressure of silk reeling enterprises.
Detailed Description
The method for recovering sericin from industrial waste water of silk reeling according to the present invention will be further described with reference to the following specific examples.
First, embodiment 1 of the method for recovering sericin in reeling industrial wastewater:
1. the main process comprises the following steps: filtering and removing impurities from the reeling industrial wastewater, adsorbing by resin, eluting, collecting, concentrating and drying to obtain powdery sericin; wherein,
and (3) filtering and removing impurities: removing insoluble impurities from the reeling industrial wastewater by adopting a centrifugal precipitation filtration mode, and adopting filter cloth with 150-200 meshes and a centrifugal rotation speed of 3000-8000 rpm;
resin adsorption; introducing the filtered and impurity-removed silk reeling wastewater into a chromatographic separation column at a flow rate of 5BV/h without adjusting the pH value until the concentration of sericin in the effluent of the chromatographic separation column is 0.05mg/mL, and stopping feeding the silk reeling wastewater; the adsorbent filled in the chromatographic separation column is DEAE-52 ion exchange resin which is obtained from the market and is pretreated (or regenerated); one column volume (1BV) was 212 mL;
and (3) elution and collection: using an acidic sodium chloride solution with the pH value of 2 and the concentration of 0.05mol/L as an analytic solution, flowing through a separation column at the speed of 2BV/h for leaching, and simultaneously monitoring the concentration change of sericin in an eluent until the eluent is completely eluted, and stopping the feed liquor of the analytic solution; collecting the eluent to obtain sericin collecting liquid;
concentration: concentrating the collected liquid obtained in the previous procedure in vacuum (the vacuum degree is-0.06 to-0.1 MPa, the temperature is 55 to 65 ℃) until the solid content reaches 10 percent, and adjusting the pH value to be neutral;
and (3) drying: and (3) carrying out hot air drying on the concentrated solution obtained in the previous step at the drying temperature of 55-65 ℃ to obtain powdery sericin.
2. Experimental data and analysis:
in the above embodiment, the sericin concentration in the sampling wastewater, the sericin concentration in the effluent of the separation column, the sericin concentration in the collection liquid, the liquid inlet/outlet amount of the separation column, the liquid collection amount of the sericin, and other experimental data are monitored/counted at the same time, and the purity of the obtained powdery sericin is detected after the experiment is completed. The following results are obtained through calculation and analysis: the adsorption quantity of the DEAE-52 ion exchange resin to sericin in the reeling industrial wastewater is 25.910mg/g, and the adsorption rate is 96.46%; the recovery rate of sericin obtained by elution is 95.26 percent, and the purity is 96.71 percent; the concentration of sericin in the collected liquid is 16.33 times of that in the industrial silk reeling wastewater.
Second, comparative example group a:
1. the main process comprises the following steps: the technical scheme of the comparative example group is basically the same as that of the example 1, except that the adsorbents filled in the chromatographic separation column are respectively resin adsorbents AB-8, LX-1180, D101, DA201-C and 201X 7 (all of which are obtained commercially); meanwhile, after the resin is adsorbed and saturated, corresponding analytical reagents (AB-8, LX-1180, D101 and DA201-C use 75% ethanol, 201X 7 use 0.5mol/L sodium hydroxide solution) are respectively adopted for elution.
2. Experimental data and analysis:
the adsorption amounts of AB-8, LX-1180, D101, DA201-C and 201 multiplied by 7 resin to sericin in the reeling industrial wastewater are 14.627mg/g, 8.269mg/g, 4.546mg/g, 11.118mg/g and 21.957mg/g respectively, and the adsorption rates are 54.69%, 31.53%, 17.20%, 41.99% and 82.95% respectively. As the DEAE-52 ion exchange resin has 25.910mg/g of adsorption amount and 96.46% of adsorption rate on sericin in the reeling industrial wastewater, the DEAE-52 ion exchange resin has obviously better adsorption effect on sericin.
The resolution rates of AB-8, LX-1180, D101, DA201-C and 201 x 7 resins are 89.48%, 94.65%, 81.82%, 85.91% and 98.02% respectively, and the corresponding sericin recovery rates are 48.94%, 29.84%, 14.07%, 36.07% and 81.31% respectively; the corresponding sericin concentration multiples are 8.39, 5.12, 2.41, 6.18 and 13.94 respectively; while the DEAE-52 ion exchange resin has the resolution ratio of 98.76 percent, the sericin recovery rate of 95.26 percent and the sericin concentration multiple of 16.33, and the DEAE-52 ion exchange resin has excellent resolution performance, better wastewater sericin separation performance and better enrichment recovery performance.
Third, comparative example group B:
the following results were compared with the results of the recovery of sericin from the waste water of the reeling industry using DEAE-52 resin under different adsorption and elution process parameters by using the following tables 1(a) and 1(b) (in the following tables, the same process as in example 1 above was used except for the items and parameters specifically listed):
TABLE 1(a)
The data in the table show that the method for recovering sericin by DEAE-52 ion exchange resin has higher adsorption capacity, resolution ratio, sericin recovery rate and concentration multiple under different implementation conditions, and the technical scheme of the invention can separate sericin from wastewater better and has the function of enriching and recovering sericin in wastewater.
TABLE 1(b)
The data in the table show that when the sample loading flow rate is too high, the adsorption effect is obviously poor, and similarly, the elution rate is too high, so that the analysis effect is also obviously influenced; when the pH of the desorption solution is alkaline or the salt concentration is low, the desorption effect of the DEAE-52 ion exchange resin is greatly changed.
Fourth, comparative example group C:
1. the main process comprises the following steps: the technical scheme of the group of embodiments is basically the same as that of embodiment 1, except that the adsorption and desorption process is performed for 8-10 periods by using the regenerable property of DEAE-52 ion exchange resin, wherein:
(1) DEAE-52 ion exchange resin is filled inBefore the separation column, the following pretreatment is carried out: soaking for 12-24 h by using deionized water, washing, and then using 1-2 mol.L-1Soaking in a hydrochloric acid solution for 2-6 h; then washing the mixture to be neutral by using deionized water, and then using 1-2 mol.L-1Soaking in NaOH solution for 2-6 h; and washing the mixture to be neutral by using deionized water for later use.
(2) After the elution and collection procedures, the DEAE-52 ion exchange resin in the separation column is regenerated according to the following process: after the separation column is used for 8-10 cycles, soaking the separation column in 3-5% hydrochloric acid for 3-5 hours, and then leaching the separation column with 2-3 times of hydrochloric acid with the same concentration; washing the mixture with deionized water until the mixture is neutral, and soaking the mixture for 3-5 hours by using 3-5% NaOH; and then, leaching with 2-3 times of volume of sodium hydroxide solution with the same concentration, and finally washing with deionized water to be neutral, so that the sodium hydroxide can be reused.
2. The experimental results are as follows:
in the 2 nd, 5 th, 8 th and 10 th periods of DEAE-52 ion exchange resin adsorption and analysis, the recovery rates of the sericin in the collected liquid are 93.70%, 85.79%, 81.26% and 78.02% respectively, and the purities of the sericin are 93.15%, 88.87%, 86.92% and 85.89% respectively.
3. Analysis of Experimental data
In the 2 nd period of DEAE-52 ion exchange resin adsorption and desorption, the recovery rate of the sericin in the collected liquid is 93.70 percent, and the purity of the sericin is 93.15 percent; in the 8 th period of DEAE-52 ion exchange resin adsorption and desorption, the recovery rate of the collected sericin is 81.26%, and the purity of the sericin is 86.92%; in the 10 th period of DEAE-52 ion exchange resin adsorption and desorption, the recovery rate of the collected sericin is 78.02%, and the purity of the sericin is 85.89%, which can still meet the requirement. The recovery rate and purity of sericin in the collected liquid in the adsorption and desorption period can show that DEAE-52 ion exchange resin can be repeatedly used for 8-10 periods, and can be continuously used after regeneration.
The above description is only for the purpose of illustrating some preferred embodiments of the present invention and should not be taken as limiting the invention. Equivalent changes and modifications that can be made by those skilled in the art according to the technical solutions of the present invention are within the scope of the technical solutions of the present invention.
Claims (7)
1. The method for recovering sericin in the reeling industrial wastewater is characterized by comprising the following steps: the silk reeling industrial wastewater is subjected to the procedures of filtering, impurity removal, resin adsorption, elution and collection to obtain sericin collecting liquid; wherein the resin adopted in the resin adsorption process is DEAE-52 ion exchange resin.
2. The method for recovering sericin from the silk reeling industrial wastewater according to claim 1, wherein the method comprises the following steps: the resin adsorption is to introduce the filtered and impurity-removed silk reeling wastewater into a separation column filled with the resin at a flow rate of 3-7.5 BV/h without adjusting the pH value, and stop feeding the silk reeling wastewater until the concentration of sericin in the effluent liquid of the separation column is 0.05 mg/mL;
introducing an analysis solution into the separation column at a flow rate of 1-3 BV/h, and simultaneously monitoring the change of sericin concentration of an eluent until the elution is complete, namely stopping the liquid feeding of the analysis solution; the analysis solution comprises one or more of acidified sodium chloride and potassium chloride solutions, the pH value is 2-5, and the concentration is 0.05-0.2 mol/L.
3. The method for recovering sericin from silk reeling industrial wastewater according to claim 2, wherein the DEAE-52 ion exchange resin is pretreated before being packed in the separation column as follows: soaking the substrate in deionized water for 12-24 h, washing the substrate, and then using 1-2 mol.L-1Soaking in a hydrochloric acid solution for 2-6 h; then washing the mixture to be neutral by using deionized water, and then using 1-2 mol.L-1Soaking in NaOH solution for 2-6 h; and washing the mixture to be neutral by using deionized water for later use.
4. The method for recovering sericin from silk reeling industrial wastewater according to claim 2, further comprising the step of regenerating the DEAE-52 ion exchange resin in the separation column after the elution and collection steps: after the separation column is used for 8-10 cycles, soaking the separation column in 3-5% hydrochloric acid for 3-5 hours, and then leaching the separation column with 2-3 times of hydrochloric acid with the same concentration; washing the mixture with deionized water until the mixture is neutral, and soaking the mixture for 3-5 hours by using 3-5% NaOH; and then, leaching with 2-3 times of volume of sodium hydroxide solution with the same concentration, and finally washing with deionized water to be neutral, so that the sodium hydroxide can be reused.
5. The method for recovering sericin from silk reeling industrial wastewater according to any one of claims 1 to 4, wherein: after the collecting step, the method further comprises the steps of concentrating and drying the sericin collected liquid obtained in the collecting step.
6. The method for recovering sericin from silk reeling industrial wastewater according to claim 5, wherein the method comprises the following steps: and the concentration is to concentrate the sericin collected liquid obtained in the collecting process in vacuum until the solid content reaches more than 10 percent and adjust the pH to be neutral.
7. The method for recovering sericin from the silk reeling industrial wastewater according to claim 6, wherein the method comprises the following steps: the vacuum degree of the vacuum concentration is-0.06 to-0.1 MPa, and the temperature is 55 to 65 ℃.
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| CN112456682A (en) * | 2020-11-25 | 2021-03-09 | 赛得利(九江)纤维有限公司 | Process for recovering viscose in viscose wastewater |
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