CN102580791B - Preparation method for lysine-modified amphoteric macroporous ion exchange resin - Google Patents
Preparation method for lysine-modified amphoteric macroporous ion exchange resin Download PDFInfo
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- CN102580791B CN102580791B CN 201110410753 CN201110410753A CN102580791B CN 102580791 B CN102580791 B CN 102580791B CN 201110410753 CN201110410753 CN 201110410753 CN 201110410753 A CN201110410753 A CN 201110410753A CN 102580791 B CN102580791 B CN 102580791B
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Abstract
The invention provides a preparation method for a lysine-modified amphoteric macroporous ion exchange resin and relates to a preparation method for an amphoteric macroporous ion exchange resin. According to the preparation method, the commercially available lysine, dicyclohexylcarbodiimide and macroporous weakly acidic acrylic acid cation exchange resin are taken as raw materials, and the raw materials are subjected to the simple processes of solution-preparing, grafting and refining, thereby obtaining a product. The product obtained according to the preparation method has good amphoteric ionexchange performance, excellent separating and purifying effect, high efficiency and high biodegradation performance; the method is simple and the operation steps are few and simple and convenient; the producing device is conventional and simple and the investment is low; the reaction condition is mild and energy source is saved; the material resources are recyclable without 'three wastes'discharge; the environmental protection is facilitated; the raw materials are the commercially available products with wide source; the preparation method is widely applied to preparing the lysine-modified amphoteric macroporous ion exchange resin; and the product prepared according to the preparation method is widely applied to separating and purifying biocatalyst carrier, bioremediation and bio-engineering products, and treating the waste water in'three wastes'.
Description
One, technical field
The invention belongs to the ion-exchange resin technique field, be specifically related to the preparation method of both sexes macroporous ion exchange resin.
Two, background technology
Amphoteric ion-exchange resin is one to exist the parting material of two kinds of cation exchange groups of yin, yang roughly the same the time.This resinoid can carry out yin, yang ion-exchange simultaneously, be widely used in the separation and purification of Bio-engineering Products, aspect separation of biopolymer, play an important role, also be widely used in the processing of waste water in the disposal of three wastes of the industries such as electric power, oil, chemical industry, light industry, metallurgy, electronics medicine, food.
The technique of existing preparation amphoteric ion-exchange resin; for example in 5 phases of 28 volumes " SCI " May in 2007 " preparation of the hydrophilic amphoteric ion-exchange resin of single dispersion and the application in the separation of biopolymer thereof " literary composition; disclosed method is: adopt first dispersion copolymerization method to prepare monodisperse hydrophilicity seed (PGMA); again in the medium of stabilizing agent and surfactant, through swelling, pass into N
2Reaction, washing, vacuum drying obtain the crosslinked PGMA/EDMA microballoon of macropore monodisperse hydrophilicity, get macropore hydrophily reinforcing yin essence-strong positive type amphoteric ion-exchange resin with the dimethylamine chemical modification at last.The major defect of the method is: 1. preparation technology's very complicated, and step is many, and production cost is high, is unfavorable for promoting in industrial production.2. the method is used number of chemical reagent, and does not have treated and direct discharging, and contaminated environment is unfavorable for environmental protection.
Three, summary of the invention
The objective of the invention is the weak point for existing preparation both sexes macroporous ion exchange resin technique; the method that provides a kind of polylysine modification to prepare the both sexes macroporous ion exchange resin has reaction condition gentleness, reaction selectivity lysine group strong, grafting and has bioaffinity and biodegradable, simple to operate, the characteristics such as cost is lower, easy to utilize, clean and safe, protection of the environment.
Principle of the present invention is: the functional group of acroleic acid macroporous weak-acid cation-exchange resin is free carboxy, this carboxyl is at condensing agent N, under the catalysis of N-dicyclohexylcarbodiimide, amino dehydration with lysine, generate amido link, thus the both sexes macroporous ion exchange resin that synthetic lysine is modified.
Realize that purpose technical scheme of the present invention is: a kind of method for preparing polylysine modification both sexes macroporous ion exchange resin, take commercially available lysine and dicyclohexylcarbodiimide and macropore acidulous acrylic acid cationic ion-exchange resin as raw material, through obtain solution, grafting, refining simple process, prepare the both sexes macroporous ion exchange resin product of polylysine modification.Its concrete method step is as follows:
(1) preparation reaction solution
Take commercially available lysine and dicyclohexylcarbodiimide as raw material, quality (g) according to lysine: the volume of pure water (mL) is than the ratio that is 1: 19～6, lysine is joined in the pure water, be stirred to dissolving, just make the lysine mass fraction and be 5～15% lysine solution, collect for subsequent use; Again according to the quality (g) of dicyclohexylcarbodiimide: the ethanol volumetric concentration is that the volume (mL) of 70% ethanolic solution is than 1: 9～2 ratio, dicyclohexylcarbodiimide is joined in the described ethanolic solution, be stirred to dissolving, just make the dicyclohexylcarbodiimide mass fraction and be 10～30% dicyclohexylcarbodiimide ethanolic solution, collect the dicyclohexylcarbodiimide ethanolic solution of preparation, for the preparation of the lysine grafting reactant.
(2) preparation lysine grafting reactant
(1) step finish after, take commercially available macropore acidulous acrylic acid cationic ion-exchange resin (being D113 resin or D155 resin or D111 resin etc.) as raw material, quality (g) according to macropore acidulous acrylic acid cationic ion-exchange resin: the lysine solution volume (mL) that (1) step made is than the ratio that is 1: 3～6, first described resin is joined in the described lysine solution, stir, carry out stirring and adsorbing after 1～3 hour, add again the dicyclohexylcarbodiimide ethanolic solution that (1) step made, carried out graft reaction 1～2 hour, and collection grafting reactant, be the lysine grafting reactant of preparing, for subsequent use.
(3) preparation both sexes macroporous ion exchange resin
(2) step went on foot the lysine grafting reactant for preparing with (2) and pumps in the vacuum filtration machine after finishing, and carried out vacuum filtration, collected respectively suction filtration slag and suction filtration liquid.For the suction filtration liquid of collecting, because containing unreacted lysine, be used for recycling.With the suction filtration slag of collecting, quality (g) according to the suction filtration slag: the ethanol volumetric concentration is that the volume (mL) of 95% ethanolic solution is than the ratio that is 1: 4～8, suction filtration slag with the collection of ethanolic solution cyclic washing, remove the dicyclohexyl isourea of generation, until in the ethanol cleaning solution without till the dicyclohexyl isourea, collect respectively ethanol cleaning solution and ethanol washed-residue.The ethanol cleaning solution that merges at last each time collection; Ethanol washed-residue to last collection carries out cyclic washing with distilled water again, until in the cleaning solution without till the lysine, collect respectively distilled water cleaning solution and distilled water washed-residue.To the distilled water washed-residue of last collection, be and prepare polylysine modification both sexes macroporous ion exchange resin, be positioned over 4～5 ℃ of lower preservations, for subsequent use; Merge at last the distilled water cleaning solution of each time collection, pump into biochemical treatment tank, carry out biochemical treatment, rear discharging up to standard.
(4) recycling
(3) step finish after, the suction filtration liquid that (3) step was collected places vacuum concentrator, temperature be 60～80 ℃, vacuum be-0.05～-condition of 0.08MPa under, carry out Vacuum Concentration, until end when soluble solid content reaches 25～35% in the concentrate, collect concentrate, be the lysine of recovery, be used for (1) step preparation lysine solution.To (3) step the most latter incorporated ethanol cleaning solution (containing the dicyclohexyl isourea), deliver to dicyclohexylcarbodiimide factory and reclaim, for the preparation of dicyclohexylcarbodiimide.
After the present invention adopts technique scheme, mainly contain following effect:
(1) the present invention with the lysine group as " flexible arm ", the physical property that had both kept macropore acidulous acrylic acid exchanger resin, give again ion exchange functional groups certain flexibility, enlarged the scope of functional group's exchange ion, for separating the effective of anion, cation, amino acid, protein etc.Therefore, the inventive method takes full advantage of bioaffinity and the biodegradation character of lysine group, and the product of preparing has excellent amphion switching performance, and separation and purification effective, efficient is high, biodegradability is strong.
(2) the inventive method in process of production, reaction condition is gentle, energy savings; The graft reaction selectivity is strong, without side reaction, without " three wastes " discharging; Material resource is all recycled; It is the production method of a kind of environmental protection, safety non-toxic; Utilize environmental protection, further reduce production costs again, be conducive to industrial-scale production.
(3) the inventive method is simple, and operating procedure is easy again less; Conventional production device is simple and easy, and small investment is easy to utilize; Raw material is commercial product, and wide material sources are easy to get.
The inventive method can be widely used in preparation both sexes macroporous ion exchange resin, the product that adopts the inventive method to prepare can be widely used in the disposal of waste gas, water and industrial residue of the industries such as the separation and purification of living things catalysis agent carrier, biological prosthetic, Bio-engineering Products and oil, chemical industry, light industry, metallurgy, medicine, food.
Four, the specific embodiment
Below in conjunction with the specific embodiment, further specify the present invention.
Embodiment 1
A kind of method for preparing polylysine modification both sexes macroporous ion exchange resin, the concrete grammar step is as follows:
(1) preparation reaction solution
Take commercially available lysine and dicyclohexylcarbodiimide as raw material, quality (g) according to lysine: the volume of pure water (mL) is than the ratio that is 1: 19, lysine is joined in the pure water, be stirred to dissolving, just make the lysine mass fraction and be 5% lysine solution, collect for subsequent use.Again according to the quality (g) of dicyclohexylcarbodiimide: the ethanol volumetric concentration is the ratio of volume (mL) than 1: 9 of 70% ethanolic solution, dicyclohexylcarbodiimide is joined in the described ethanolic solution, be stirred to dissolving, just make the dicyclohexylcarbodiimide mass fraction and be 10% dicyclohexylcarbodiimide ethanolic solution, collect the dicyclohexylcarbodiimide ethanolic solution of preparation, for the preparation of the lysine grafting reactant.
(2) preparation lysine grafting reactant
(1) step finish after, take commercially available macropore acidulous acrylic acid cationic ion-exchange resin (being the D113 resin) as raw material, quality (g) according to macropore acidulous acrylic acid cationic ion-exchange resin: the lysine solution volume (mL) that (1) step made is than the ratio that is 1: 3, first described resin is joined in the described lysine solution, stir, and carry out stirring and adsorbing after 1 hour, add again the dicyclohexylcarbodiimide ethanolic solution that (1) step made, carried out graft reaction 1 hour, and collection grafting reactant, be the lysine grafting reactant of preparing, for subsequent use.
(3) preparation both sexes macroporous ion exchange resin
(2) step went on foot the lysine grafting reactant for preparing with (2) and pumps in the vacuum filtration machine after finishing, and carried out vacuum filtration, collected respectively suction filtration slag and suction filtration liquid.For the suction filtration liquid of collecting, because containing unreacted lysine, be used for recycling.With the suction filtration slag of collecting, quality (g) according to the suction filtration slag: the ethanol volumetric concentration is that the volume (mL) of 95% ethanolic solution is than the ratio that is 1: 4, suction filtration slag with the collection of ethanolic solution cyclic washing, remove the dicyclohexyl isourea of generation, until in the ethanol cleaning solution without till the dicyclohexyl isourea, collect respectively ethanol cleaning solution and ethanol washed-residue.The ethanol cleaning solution that merges at last each time collection; Ethanol washed-residue to last collection carries out cyclic washing with distilled water again, until in the cleaning solution without till the lysine, collect respectively distilled water cleaning solution and distilled water washed-residue.To the distilled water washed-residue of last collection, be and prepare polylysine modification both sexes macroporous ion exchange resin, be positioned under 4 ℃ and save backup; Merge at last the distilled water cleaning solution of each time collection, and pump into biochemical treatment tank, carry out biochemical treatment, rear discharging up to standard.
(4) recycling
(3) step finish after, the suction filtration liquid that (3) step was collected places vacuum concentrator, under the condition that temperature is 60 ℃, vacuum for-0.05MPa, carry out Vacuum Concentration, until end when soluble solid content reaches 25% in the concentrate, collect concentrate, be the lysine of recovery, be used for (1) step preparation lysine solution.To (3) step the most latter incorporated ethanol cleaning solution (containing the dicyclohexyl isourea), deliver to dicyclohexylcarbodiimide factory and reclaim, for the preparation of dicyclohexylcarbodiimide.
Embodiment 2
A kind of method for preparing polylysine modification both sexes macroporous ion exchange resin, with embodiment 1, wherein:
In (1) step, the quality of lysine: the volume ratio of pure water is 1g: 11mL, the mass fraction of the lysine solution of making is 10%, the quality of dicyclohexylcarbodiimide: the ethanol volumetric concentration is the volume ratio 1g of 70% ethanolic solution: 5mL, the mass fraction of the dicyclohexylcarbodiimide solution of making is 20%.
In (2) step, commercially available macropore acidulous acrylic acid cationic ion-exchange resin, raw material is the D155 resin, the quality of macropore acidulous acrylic acid cationic ion-exchange resin: the lysine solution volume ratio that (1) step made is 1g: 4.5mL, after the stirring and adsorbing 2 hours, carried out again graft reaction 1.5 hours.
In (3) step, the quality of suction filtration slag: the ethanol volumetric concentration is that the volume ratio of 95% ethanolic solution is 1g: 6mL, and the distilled water washed-residue of collecting at last is positioned over 4.5 ℃ of lower preservations.
In (4) step, to be 70 ℃, vacuum be-0.07MPa to the temperature of vacuum concentrator, until end when soluble solid content reaches 30% in the concentrate.
Embodiment 3
A kind of method for preparing polylysine modification both sexes macroporous ion exchange resin, with embodiment 1, wherein:
In (1) step, the quality of lysine: the volume ratio of pure water is 1g: 6mL, the mass fraction of the lysine solution of making is 15%, the quality of dicyclohexylcarbodiimide: the ethanol volumetric concentration is the volume ratio 1g of 70% ethanolic solution: 2mL, the mass fraction of the dicyclohexylcarbodiimide solution that makes is 30%.
In (2) step, commercially available macropore acidulous acrylic acid cationic ion-exchange resin, raw material is the D111 resin, the quality of macropore acidulous acrylic acid cationic ion-exchange resin: the lysine solution volume ratio that (1) step made is 1g: 6mL, after the stirring and adsorbing 3 hours, carried out again graft reaction 2 hours.
In (3) step, the quality of suction filtration slag: the ethanol volumetric concentration is that the volume ratio of 95% ethanolic solution is 1g: 8mL, and the distilled water washed-residue of collecting at last is positioned over 5 ℃ of lower preservations.
In (4) step, under the condition that the temperature of vacuum concentrator is 80 ℃, vacuum for-0.08MPa, until end when soluble solid content reaches 35% in the concentrate.
Claims (1)
1. method for preparing polylysine modification both sexes macroporous ion exchange resin is characterized in that the concrete grammar step of described method is as follows:
(1) preparation reaction solution
Take commercially available lysine and dicyclohexylcarbodiimide as raw material, quality according to lysine: the volume ratio of pure water is the ratio of 1g: 19～6mL, lysine is joined in the pure water, be stirred to dissolving, just make the lysine mass fraction and be 5～15% lysine solution, again according to the quality of dicyclohexylcarbodiimide: the ethanol volumetric concentration is the volume ratio 1g of 70% ethanolic solution: the ratio of 9～2mL, dicyclohexylcarbodiimide is joined in described 70% ethanolic solution, just make the dicyclohexylcarbodiimide mass fraction and be 10～30% dicyclohexylcarbodiimide ethanolic solution;
(2) preparation lysine grafting reactant
(1) step finish after, with commercially available macropore acidulous acrylic acid cationic ion-exchange resin, be that D113 resin or D155 resin or D111 resin are raw material, quality according to macropore acidulous acrylic acid cationic ion-exchange resin: the lysine solution volume ratio that (1) step made is the ratio of 1g: 3～6mL, first described resin is joined in the described lysine solution, mix, and carry out stirring and adsorbing after 1～3 hour, add again the dicyclohexylcarbodiimide ethanolic solution that (1) step made, carry out graft reaction 1～2 hour, and collected grafting reactant;
(3) preparation both sexes macroporous ion exchange resin
(2) step finish after, the lysine grafting reactant of (2) step preparation is pumped in the vacuum filtration machine, carry out vacuum filtration, collect respectively suction filtration slag and suction filtration liquid, with the suction filtration slag of collecting, quality according to the suction filtration slag: the ethanol volumetric concentration is that the volume ratio of 95% ethanolic solution is the ratio of 1g: 4～8mL, the suction filtration slag of collecting with the ethanolic solution cyclic washing again, until in the ethanol cleaning solution without till the dicyclohexyl isourea, collect respectively ethanol cleaning solution and ethanol washed-residue, merge at last the ethanol cleaning solution of each time collection; Ethanol washed-residue to last collection carries out cyclic washing with distilled water again, until in the cleaning solution without till the lysine, collect respectively distilled water cleaning solution and distilled water washed-residue, the distilled water washed-residue of collecting at last, be the polylysine modification both sexes macroporous ion exchange resin product of preparing, be positioned over 4～5 ℃ of lower preservations;
(4) recycling
(3) step finish after, the suction filtration liquid of first (3) step being collected places vacuum concentrator, temperature be 60～80 ℃, vacuum be-0.05～-condition of 0.08MPa under, carry out Vacuum Concentration, until end when soluble solid content reaches 25～35% in the concentrate, collect concentrate, the most latter incorporated ethanol cleaning solution of (3) step is delivered to dicyclohexylcarbodiimide factory reclaim.
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| CN 201110410753 CN102580791B (en) | 2011-12-12 | 2011-12-12 | Preparation method for lysine-modified amphoteric macroporous ion exchange resin |
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| CN 201110410753 CN102580791B (en) | 2011-12-12 | 2011-12-12 | Preparation method for lysine-modified amphoteric macroporous ion exchange resin |
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| CN102580791B true CN102580791B (en) | 2013-10-16 |
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| CN110590977A (en) * | 2019-09-27 | 2019-12-20 | 凯瑞环保科技股份有限公司 | Amphoteric ion exchange resin and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3821126A (en) * | 1971-06-26 | 1974-06-28 | Kyowa Hakko Kogyo Kk | Process for producing amphoteric resin |
| US4139499A (en) * | 1975-07-01 | 1979-02-13 | Ici Australia Limited | Thermally reversible amphoteric ion exchange resins of improved demineralization capacity |
| US4554376A (en) * | 1981-05-07 | 1985-11-19 | Toyo Soda Manufacturing Co., Ltd. | Method for separating and purifying amino acid |
| CN1927892A (en) * | 2006-09-07 | 2007-03-14 | 重庆大学 | Lysine-chitosan resin and preparation method thereof |
-
2011
- 2011-12-12 CN CN 201110410753 patent/CN102580791B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3821126A (en) * | 1971-06-26 | 1974-06-28 | Kyowa Hakko Kogyo Kk | Process for producing amphoteric resin |
| US4139499A (en) * | 1975-07-01 | 1979-02-13 | Ici Australia Limited | Thermally reversible amphoteric ion exchange resins of improved demineralization capacity |
| US4554376A (en) * | 1981-05-07 | 1985-11-19 | Toyo Soda Manufacturing Co., Ltd. | Method for separating and purifying amino acid |
| CN1927892A (en) * | 2006-09-07 | 2007-03-14 | 重庆大学 | Lysine-chitosan resin and preparation method thereof |
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