CN113024718A - Preparation method of macroporous acrylic acid weak base anion exchange resin - Google Patents
Preparation method of macroporous acrylic acid weak base anion exchange resin Download PDFInfo
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- CN113024718A CN113024718A CN202110212744.XA CN202110212744A CN113024718A CN 113024718 A CN113024718 A CN 113024718A CN 202110212744 A CN202110212744 A CN 202110212744A CN 113024718 A CN113024718 A CN 113024718A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
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Abstract
The invention discloses a preparation method of macroporous acrylic weak base anion exchange resin, which comprises the following steps: step one, preparing white balls: taking aqueous solution of gelatin and hydroxyethyl cellulose as water phase, and adding inorganic dispersant and methylene blue solution as water phase polymerization inhibitor; using a mixture of acrylonitrile and divinylbenzene dissolved with BPO and a pore-foaming agent as an oil phase; preparing macroporous cross-linked polyacrylonitrile polymer microspheres from the oil phase and the water phase by a suspension polymerization method, recovering the pore-forming agent by reduced pressure distillation, washing the polymer microspheres with hot water and cold water in sequence, and drying to obtain white spheres; step two, preparation of resin: and (3) reacting the white balls prepared in the step one with polyethylene polyamine at a certain temperature to prepare the macroporous acrylic weak base anion exchange resin. The resin prepared by the method can be used in the water treatment industry, and can effectively remove anions such as chloride radicals, sulfate radicals and the like in organic acid when being used in the food industry.
Description
Technical Field
The invention relates to the technical field of ion exchange resin, in particular to a preparation method of macroporous acrylic acid weak base anion exchange resin.
Background
Ion exchange resin products are of a wide variety. According to the property of active groups carried by the resin, the resin can be divided into strong acid cation, weak acid cation, strong base anion, weak base anion, chelating property, amphoteric property and redox resin; according to different functions and principles of action, the water treatment resin, the adsorption resin and the resin catalyst can be divided into a gel type and a macroporous type according to different pore types.
The adsorption resin is a resin adsorbent which is characterized by adsorption and has a porous three-dimensional structure; in recent years, the acrylic acid type weak-base anion exchange resin is fully utilized in the fields of medicine extraction, biological fermentation liquor decolorization, primary separation and purification of tea polysaccharide, acid removal and decolorization of sugar liquor, molybdenum extraction by hydrometallurgy, and extraction and decolorization of organic acid biochemical substances such as citric acid, vitamins and the like.
The existing macroporous acrylic weak base anion exchange resin basically adopts methyl acrylate as a framework and is synthesized by organic amine such as propane diamine and the like, and the resin is widely used in the water treatment industry and has the advantages of high exchange capacity, strong organic pollution resistance and the like. With the promotion of ion exchange application to the food industry, the resin has the defect of low elution efficiency in the aspect of removing chloride and sulfate radicals in organic acids such as tartaric acid, citric acid and the like. This is due to the pore structure of the resin itself and the molecular weight of the organic amine.
Disclosure of Invention
The invention aims to provide a preparation method of macroporous acrylic acid weak base anion exchange resin aiming at the defects in the prior art, and the resin prepared by the method can be used in the water treatment industry and can effectively remove anions such as chloride radicals, sulfate radicals and the like in organic acid when being used in the food industry.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of macroporous acrylic weak base anion exchange resin, which comprises the following steps:
step one, preparing white balls:
taking aqueous solution of gelatin and hydroxyethyl cellulose as water phase, and adding inorganic dispersant and methylene blue solution as water phase polymerization inhibitor; using a mixture of acrylonitrile and divinylbenzene dissolved with BPO and a pore-foaming agent as an oil phase; preparing macroporous cross-linked polyacrylonitrile polymer microspheres from the oil phase and the water phase by a suspension polymerization method, recovering the pore-forming agent by reduced pressure distillation, washing the polymer microspheres with hot water and cold water in sequence, and drying to obtain white spheres;
step two, preparation of resin:
reacting the white balls prepared in the step one with polyethylene polyamine at a certain temperature to prepare the macroporous acrylic acid weak base anion exchange resin
Preferably, in step one, the gelatin: hydroxyethyl cellulose: inorganic dispersant: methylene blue: the mass ratio of water is
Preferably, in the first step, sodium chloride is used as the inorganic dispersant.
Preferably, in step one, the acrylonitrile: BPO: divinylbenzene: the mass ratio of the pore-foaming agent is (88-93%): (4-8 ‰): (7-12%): (18-30%).
Preferably, in the first step, isobutanol or mineral spirit is used as the porogen.
Preferably, in the first step, the suspension polymerization process comprises the following specific reaction processes: mixing the oil phase and the water phase, starting stirring, adjusting the rotating speed to 100r/min, heating the oil bath to 75 ℃, preserving the heat for 4 hours, then heating to 95 ℃, and preserving the heat for 6 hours.
Preferably, in the first step, the degree of crosslinking of the white spheres is 5 to 10.
Preferably, in the second step, the polyethylene polyamine is selected from one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
Preferably, in the second step, the mass ratio of the white balls to the polyethylene polyamine is 1: 3-5.
Preferably, in the second step, the reaction temperature is 160-170 ℃, and the reaction time is 10-15 h.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
the preparation method of the invention selects the novel pore-foaming agent to synthesize the white ball, adjusts the crosslinking degree of the macroporous white ball by controlling the proportion of divinylbenzene in a monomer phase, and adopts polyethylene polyamine to synthesize the macroporous acrylic acid weak base anion exchange resin which can be used in the water treatment industry, can effectively remove anions such as chloride radicals, sulfate radicals and the like in organic acid when being used in the food industry, and has the advantages of high exchange capacity, good adsorption effect, high regeneration elution rate and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
Adding 5g of gelatin, 3g of hydroxyethyl cellulose and 60g of sodium chloride into a three-neck flask filled with 1000ml of pure water for dissolving, adding 5 drops of a 0.1% methylene blue solution by mass fraction, adding 420.5g of acrylonitrile and 79.5g of divinylbenzene into a beaker as monomer phases, adding BPO (methyl propyl ketone) accounting for 0.8% of the total monomer phase into the monomer phases, adding 150g of isobutanol as a pore-forming agent, mixing an oil phase and a water phase, starting stirring, regulating the rotating speed to 100r/min, heating an oil bath to 75 ℃, keeping the temperature for 4 hours, heating to 95 ℃, keeping the temperature for 6 hours, recovering the pore-forming agent by reduced pressure distillation, washing polymer microspheres with hot water and cold water in sequence, and drying; adding 450ml of diethylenetriamine into 100g of the synthesized macroporous white spheres, heating to 165 ℃, preserving heat for 12h, and cleaning reaction products with water to obtain the macroporous acrylic acid weak base anion exchange resin; the total cross-linking, water content and strength performance indexes of the synthesized resin are measured.
Wherein, the total cross-linking of the macroporous absorption resin with high specific surface area: 8.65mmol/g (dry); water content: 51.02 percent; penetration and grinding sphericity: 95.12 percent.
Application example 1
1. Tartaric acid test
Regenerating the resin prepared in example 1 with 4BV1mol/L sodium hydroxide solution, washing with pure water to pH 8, loading about 70ml OH type resin into a Phi 20mm X270 mm organic glass exchange column, passing the prepared tartaric acid solution from top to bottom through OH type macroporous weak base anion resin at a flow rate of 2BV/h, collecting the effluent with a beaker, and detecting Cl in the effluent during operation-Concentration, control of Cl-The concentration is less than 50 mg/L. The dechlorination of the resin tartaric acid is 42 BV.
2. Citric acid test
Regenerating the resin prepared in example 1 with 4BV1mol/L sodium hydroxide solution, washing with pure water to pH 8, loading about 200ml OH type resin into a Phi 20mm X270 mm organic glass exchange column, passing the prepared citric acid solution from top to bottom through OH type macroporous weak base anion resin at a flow rate of 0.3BV/h, collecting the effluent with a beaker, and detecting Cl in the effluent during operation-Concentration, controlled discharge without Cl-. The dechlorination of the resin citric acid is 98 BV.
Example 2
Adding 5g of gelatin, 3g of hydroxyethyl cellulose and 60g of sodium chloride into a three-neck flask filled with 1000ml of pure water for dissolving, adding 5 drops of a 0.1% methylene blue solution by mass fraction, adding 411g of acrylonitrile and 89g of divinylbenzene into a beaker as a monomer phase, adding BPO (boron-doped barium oxide) accounting for 0.8% of the total monomer amount into the monomer phase, adding 180g of isobutanol as a pore-forming agent, mixing an oil phase and a water phase, starting stirring, regulating the rotating speed to 100r/min, heating an oil bath to 75 ℃, preserving heat for 4 hours, then heating to 95 ℃, preserving heat for 6 hours, carrying out reduced pressure distillation to recover the pore-forming agent, washing polymer microspheres with hot water and cold water in sequence, and drying; adding 500ml of triethylene tetramine into 100g of synthesized macroporous white spheres, heating to 170 ℃, preserving heat for 15h, and cleaning reaction products with water to obtain the macroporous acrylic weak base anion exchange resin; the total cross-linking, water content and strength performance indexes of the synthesized resin are measured.
Wherein, the total cross-linking of the macroporous absorption resin with high specific surface area: 8.20mmol/g (dry); water content: 50.27 percent; penetration and grinding sphericity: 95.67 percent.
Application example 2
1. Tartaric acid test
Regenerating the resin prepared in example 2 with 4BV1mol/L sodium hydroxide solution, washing with pure water to pH 8, loading about 70ml OH type resin into a Phi 20mm X270 mm organic glass exchange column, passing the prepared tartaric acid solution from top to bottom through OH type macroporous weak base anion resin at a flow rate of 2BV/h, collecting the effluent with a beaker, and detecting Cl in the effluent during operation-Concentration, control of Cl-The concentration is less than 50 mg/L. The dechlorination of the resin tartaric acid is 39 BV.
2. Citric acid test
Regenerating the resin prepared in example 2 with 4BV1mol/L sodium hydroxide solution, washing with pure water to pH 8, loading about 200ml OH type resin into a Phi 20mm X270 mm organic glass exchange column, passing the prepared citric acid solution from top to bottom through OH type macroporous weak base anion resin at a flow rate of 0.3BV/h, collecting the effluent with a beaker, and detecting Cl in the effluent during operation-Concentration, controlled discharge without Cl-. The dechlorination of the resin citric acid is 117 BV.
Example 3
Adding 5g of gelatin, 3g of hydroxyethyl cellulose and 60g of sodium chloride into a three-neck flask filled with 1000ml of pure water for dissolving, adding 5 drops of a 0.1% methylene blue solution by mass fraction, adding 415g of acrylonitrile and 85g of divinylbenzene into a beaker as a monomer phase, adding BPO (methyl methacrylate) accounting for 0.8% of the total monomer phase into the monomer phase, adding 160g of isobutanol as a pore-forming agent, mixing an oil phase and a water phase, starting stirring, regulating the rotating speed to 100r/min, heating an oil bath to 75 ℃, preserving heat for 4 hours, then heating to 95 ℃, preserving heat for 6 hours, carrying out reduced pressure distillation to recover the pore-forming agent, washing polymer microspheres with hot water and cold water in sequence, and drying; adding 400ml of diethylenetriamine into 100g of the synthesized macroporous white spheres, heating to 160 ℃, preserving heat for 10h, and cleaning reaction products with water to obtain the macroporous acrylic acid weak base anion exchange resin; the total cross-linking, water content and strength performance indexes of the synthesized resin are measured.
Wherein, the total cross-linking of the macroporous absorption resin with high specific surface area: 8.03mmol/g (dry); water content: 50.22 percent; penetration and grinding sphericity: 95.37 percent.
Application example 3
1. Tartaric acid test
Regenerating the resin prepared in example 3 with 4BV1mol/L sodium hydroxide solution, washing with pure water to pH 8, loading about 70ml OH type resin into a Phi 20mm X270 mm organic glass exchange column, passing the prepared tartaric acid solution from top to bottom through OH type macroporous weak base anion resin at a flow rate of 2BV/h, collecting the effluent with a beaker, and detecting Cl in the effluent during operation-Concentration, control of Cl-The concentration is less than 50 mg/L. The dechlorination of the resin tartaric acid is 40 BV.
2. Citric acid test
Regenerating the resin prepared in example 3 with 4BV1mol/L sodium hydroxide solution, washing with pure water to pH 8, loading about 200ml OH type resin into a Phi 20mm X270 mm organic glass exchange column, passing the prepared citric acid solution from top to bottom through OH type macroporous weak base anion resin at a flow rate of 0.3BV/h, collecting the effluent with a beaker, and detecting Cl in the effluent during operation-Concentration, controlled discharge without Cl-. The dechlorination of the resin citric acid is 116 BV.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of macroporous acrylic weak base anion exchange resin is characterized by comprising the following steps:
step one, preparing white balls:
taking aqueous solution of gelatin and hydroxyethyl cellulose as water phase, and adding inorganic dispersant and methylene blue solution as water phase polymerization inhibitor; using a mixture of acrylonitrile and divinylbenzene dissolved with BPO and a pore-foaming agent as an oil phase; preparing macroporous cross-linked polyacrylonitrile polymer microspheres from the oil phase and the water phase by a suspension polymerization method, recovering the pore-forming agent by reduced pressure distillation, washing the polymer microspheres with hot water and cold water in sequence, and drying to obtain white spheres;
step two, preparation of resin:
reacting the white balls prepared in the step one with polyethylene polyamine at a certain temperature to prepare the macroporous acrylic acid weak base anion exchange resin
2. The method for preparing macroporous acrylic weak base anion exchange resin as claimed in claim 1, wherein in step one, the gelatin: hydroxyethyl cellulose: inorganic dispersant: methylene blue: the mass ratio of water is
3. The method for preparing macroporous acrylic weak base anion exchange resin as claimed in claim 1, wherein in step one, sodium chloride is used as the inorganic dispersant.
4. The method for preparing macroporous acrylic weak base anion exchange resin as claimed in claim 1, wherein in step one, the acrylonitrile: BPO: divinylbenzene: the mass ratio of the pore-foaming agent is (88-93%): (4-8 ‰): (7-12%): (18-30%).
5. The method for preparing macroporous acrylic weak base anion exchange resin as claimed in claim 1, wherein in step one, isobutanol or mineral spirit is used as the porogen.
6. The method for preparing macroporous acrylic weak base anion exchange resin as claimed in claim 1, wherein in the first step, the suspension polymerization method comprises the following specific reaction processes: mixing the oil phase and the water phase, starting stirring, adjusting the rotating speed to 100r/min, heating the oil bath to 75 ℃, preserving the heat for 4 hours, then heating to 95 ℃, and preserving the heat for 6 hours.
7. The method for preparing macroporous acrylic weak base anion exchange resin as claimed in claim 1, wherein in step one, the degree of cross-linking of the white spheres is 5 to 10.
8. The method for preparing macroporous acrylic weak base anion exchange resin as claimed in claim 1, wherein in the second step, the polyethylene polyamine is selected from one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
9. The method for preparing macroporous acrylic weak base anion exchange resin as claimed in claim 1, wherein in the second step, the mass ratio of the white spheres to the polyethylene polyamine is 1: 3-5.
10. The method as claimed in claim 1, wherein the reaction temperature is 160-170 ℃ and the reaction time is 10-15 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115999651A (en) * | 2022-12-26 | 2023-04-25 | 宁波争光树脂有限公司 | Zirconium-carrying resin and preparation method thereof |
| CN118307706A (en) * | 2024-06-07 | 2024-07-09 | 安徽一帆新材料科技有限公司 | Acrylic acid macroporous anion resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0194994A (en) * | 1987-10-06 | 1989-04-13 | Sumitomo Chem Co Ltd | Removal of lower aldehydes |
| CN110505914A (en) * | 2017-02-09 | 2019-11-26 | 嬴晟运营私人有限公司 | Polymeric beads and its application |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0194994A (en) * | 1987-10-06 | 1989-04-13 | Sumitomo Chem Co Ltd | Removal of lower aldehydes |
| CN110505914A (en) * | 2017-02-09 | 2019-11-26 | 嬴晟运营私人有限公司 | Polymeric beads and its application |
Non-Patent Citations (1)
| Title |
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| N.R.MEICHIK ET AL: "~", 《POLYMER SCIENCE SERIES B》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115999651A (en) * | 2022-12-26 | 2023-04-25 | 宁波争光树脂有限公司 | Zirconium-carrying resin and preparation method thereof |
| CN118307706A (en) * | 2024-06-07 | 2024-07-09 | 安徽一帆新材料科技有限公司 | Acrylic acid macroporous anion resin and preparation method thereof |
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