CN102580791A - 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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- CN102580791A CN102580791A CN2011104107536A CN201110410753A CN102580791A CN 102580791 A CN102580791 A CN 102580791A CN 2011104107536 A CN2011104107536 A CN 2011104107536A CN 201110410753 A CN201110410753 A CN 201110410753A CN 102580791 A CN102580791 A CN 102580791A
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- lysine
- exchange resin
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- dicyclohexylcarbodiimide
- ion exchange
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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 ion exchange 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; Playing an important role aspect the large biological molecule separation, also be widely used in the processing of waste water in the disposal of three wastes of industries such as electric power, oil, chemical industry, light industry, metallurgy, electronics medicine, food.
The technology of existing preparation amphoteric ion-exchange resin; For example in 28 5 phases of volume of " SCI " May in 2007 " single disperse the preparation of hydrophilic amphoteric ion-exchange resin and in the large biological molecule applications in separation " literary composition; Disclosed method is: adopt dispersion copolymerization method to prepare monodisperse hydrophilicity seed (PGMA) earlier; Again in the medium of stabilizing agent and surfactant, through swelling, feeding 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 this method is: 1. preparation technology's very complicated, and step is many, and production cost is high, is unfavorable in commercial production, promoting.2. this 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 weak point to existing preparation both sexes macroporous ion exchange resin technology; 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, characteristics such as cost is lower, easy to utilize, clean and safe, protection environment.
Principle of the present invention is: the functional group of acroleic acid macroporous weak-acid cation-exchange resin is a free carboxy; This carboxyl is at condensing agent N; Under the catalysis of N-dicyclohexylcarbodiimide; With the lysine amino dehydration, generate amido link, thus the both sexes macroporous ion exchange resin that synthetic lysine is modified.
Realize that the object of the invention technical scheme is: a kind of method for preparing polylysine modification both sexes macroporous ion exchange resin; With commercially available lysine and dicyclohexylcarbodiimide and macropore acidulous acrylic acid cationic ion-exchange resin is 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 following:
(1) preparing reaction solution
With commercially available lysine and dicyclohexylcarbodiimide is 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 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, be used to prepare the lysine grafting reactant.
(2) preparation lysine grafting reactant
(1) step be a raw material with commercially available macropore acidulous acrylic acid cationic ion-exchange resin (being D113 resin or D155 resin or D111 resin etc.) after accomplishing, and according to the quality (g) of macropore acidulous acrylic acid cationic ion-exchange resin: (1) goes on foot the lysine solution volume (mL) that makes than the ratio that is 1: 3～6; Earlier described resin is joined in the described lysine solution; Stir, carry out stirring and adsorbing after 1～3 hour, add the dicyclohexylcarbodiimide ethanolic solution that (1) step made again; Carried out graft reaction 1～2 hour; And the collection grafting reactant, be the lysine grafting reactant of preparing, 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 accomplishing, and carried out vacuum filtration, collected suction filtration slag and suction filtration liquid respectively.For the suction filtration liquid of collecting,, be used for recycling because of containing unreacted lysine.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, in washing with alcohol liquid, till the no dicyclohexyl isourea, collect washing with alcohol liquid and washing with alcohol slag respectively.The washing with alcohol liquid that merges each time collection at last; Washing with alcohol slag to last collection carries out cyclic washing with distilled water again, in cleaning solution, till the no lysine, collects distilled water cleaning solution and distilled water washed-residue respectively.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 ℃ and preserve down, subsequent use; Merge the distilled water cleaning solution of each time collection at last, pump into biochemical treatment tank, carry out biochemical treatment, back up to standard discharging.
(4) recycling
After the completion of (3) step; 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, it is concentrated to carry out vacuum; Soluble solid content reaches at 25～35% o'clock only in concentrate; Collect concentrate, be the lysine of recovery, be used for (1) step preparation lysine solution.To the last washing with alcohol liquid (containing the dicyclohexyl isourea) that merges of (3) step, deliver to dicyclohexylcarbodiimide factory and reclaim, be used to prepare 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 ion exchange functional groups certain flexibility again; Enlarged the scope of functional group's exchange ion, for separating the effective of anion, cation, amino acid, protein etc.Therefore, the inventive method has made full use of the bioaffinity and the biodegradation character of lysine group, and the product of preparing has excellent amphion switching performance, and effect of separating purification is good, efficient is high, and biodegradability is strong.
(2) the inventive method in process of production, reaction condition is gentle, energy savings; The graft reaction selectivity is strong, and no side reaction does not have " 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, help 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 industries such as separation and purification and oil, chemical industry, light industry, metallurgy, medicine, food of living things catalysis agent carrier, biological restoration, Bio-engineering Products.
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 following:
(1) preparing reaction solution
With commercially available lysine and dicyclohexylcarbodiimide is raw material; Quality (g) according to lysine: the volume of pure water (mL) joins lysine in the pure water than the ratio that is 1: 19, is stirred to dissolving; Just make the lysine mass fraction and be 5% lysine solution, collect 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, be used to prepare the lysine grafting reactant.
(2) preparation lysine grafting reactant
(1) step be a raw material with commercially available macropore acidulous acrylic acid cationic ion-exchange resin (being the D113 resin) after accomplishing, and according to the quality (g) of macropore acidulous acrylic acid cationic ion-exchange resin: (1) goes on foot the lysine solution volume (mL) that makes than the ratio that is 1: 3; Earlier described resin is joined in the described lysine solution; Stir, and carry out stirring and adsorbing after 1 hour, add the dicyclohexylcarbodiimide ethanolic solution that (1) step made again; Carried out graft reaction 1 hour; And the collection grafting reactant, be the lysine grafting reactant of preparing, 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 accomplishing, and carried out vacuum filtration, collected suction filtration slag and suction filtration liquid respectively.For the suction filtration liquid of collecting,, be used for recycling because of containing unreacted lysine.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, in washing with alcohol liquid, till the no dicyclohexyl isourea, collect washing with alcohol liquid and washing with alcohol slag respectively.The washing with alcohol liquid that merges each time collection at last; Washing with alcohol slag to last collection carries out cyclic washing with distilled water again, in cleaning solution, till the no lysine, collects distilled water cleaning solution and distilled water washed-residue respectively.To the distilled water washed-residue of last collection, be and prepare polylysine modification both sexes macroporous ion exchange resin, be positioned over 4 ℃ and preserve subsequent use down; Merge the distilled water cleaning solution of each time collection at last, and pump into biochemical treatment tank, carry out biochemical treatment, back up to standard discharging.
(4) recycling
After the completion of (3) step; The suction filtration liquid that (3) step was collected places vacuum concentrator, under the condition that temperature is 60 ℃, vacuum for-0.05MPa, carries out vacuum and concentrates; Soluble solid content reaches at 25% o'clock only in concentrate; Collect concentrate, be the lysine of recovery, be used for (1) step preparation lysine solution.To the last washing with alcohol liquid (containing the dicyclohexyl isourea) that merges of (3) step, deliver to dicyclohexylcarbodiimide factory and reclaim, be used to prepare 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, and stirring and adsorbing was carried out graft reaction 1.5 hours after 2 hours again.
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, the distilled water washed-residue of collecting at last is positioned over 4.5 ℃ preserves down.
In (4) step, to be 70 ℃, vacuum be-0.07MPa to the temperature of vacuum concentrator, and soluble solid content reaches at 30% o'clock and ends in 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 graft reaction again 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, the distilled water washed-residue of collecting at last is positioned over 5 ℃ preserves down.
In (4) step, under the condition that the temperature of vacuum concentrator is 80 ℃, vacuum for-0.08MPa, soluble solid content reaches at 35% o'clock and ends in concentrate.
Claims (1)
1. method for preparing polylysine modification both sexes macroporous ion exchange resin is characterized in that the concrete grammar step of said method is following:
(1) preparing reaction solution
With commercially available lysine and dicyclohexylcarbodiimide is 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
After the completion of (1) step; With commercially available macropore acidulous acrylic acid cationic ion-exchange resin, promptly D113 resin or D155 resin or D111 resin are raw material, and according to the quality of macropore acidulous acrylic acid cationic ion-exchange resin: the lysine solution volume ratio that (1) step made is the ratio of 1g: 3～6mL; Earlier described resin is joined in the described lysine solution; Mix, and carry out stirring and adsorbing after 1～3 hour, add the dicyclohexylcarbodiimide ethanolic solution that (1) step made again; Carry out graft reaction 1～2 hour, and collected grafting reactant;
(3) preparation both sexes macroporous ion exchange resin
After the completion of (2) step; The lysine grafting reactant of (2) step preparation is pumped in the vacuum filtration machine, carry out vacuum filtration, collect suction filtration slag and suction filtration liquid respectively; 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, and the suction filtration slag of collecting with the ethanolic solution cyclic washing again is in washing with alcohol liquid till the no dicyclohexyl isourea; Collect washing with alcohol liquid and washing with alcohol slag respectively, merge the washing with alcohol liquid of each time collection at last; Washing with alcohol slag to last collection carries out cyclic washing with distilled water again; In cleaning solution till the no lysine; Collect distilled water cleaning solution and distilled water washed-residue respectively; The distilled water washed-residue of collecting at last is the polylysine modification both sexes macroporous ion exchange resin product of preparing, and is positioned over 4～5 ℃ and preserves down;
(4) recycling
After the completion of (3) step; The suction filtration liquid of earlier (3) step being collected places vacuum concentrator; Temperature be 60～80 ℃, vacuum be-0.05～-condition of 0.08MPa under, carry out vacuum and concentrate, soluble solid content reaches at 25～35% o'clock and ends in concentrate; Collect concentrate, the last washing with alcohol liquid that merges of (3) step is delivered to dicyclohexylcarbodiimide factory reclaim.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN102580791A true CN102580791A (en) | 2012-07-18 |
| CN102580791B CN102580791B (en) | 2013-10-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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