CN116253816A - Chelate resin and preparation method thereof - Google Patents
Chelate resin and preparation method thereof Download PDFInfo
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- CN116253816A CN116253816A CN202211732702.XA CN202211732702A CN116253816A CN 116253816 A CN116253816 A CN 116253816A CN 202211732702 A CN202211732702 A CN 202211732702A CN 116253816 A CN116253816 A CN 116253816A
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- acrylic
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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
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
- C01D3/145—Purification by solid ion-exchangers or solid chelating agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
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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
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of resin synthesis, and provides a preparation method of chelate resin, which comprises the following steps: after the amino resin is placed in a swelling solution for swelling treatment, adding acrylic acid, acrylic sulfonic acid, acrylic acid salt, acrylic sulfonate, acrylic ester or acrylic sulfonate for addition reaction, and after the reaction is finished, adopting a detergent for washing treatment to obtain chelate resin; the invention adopts the amino resin with high exchange capacity, and synthesizes the methylene amino carboxylic acid chelate resin or the methylene amino sulfonic acid chelate resin through the addition reaction with acrylic acid, acrylic sulfonic acid, acrylic acid salt, acrylic sulfonate, acrylic ester or acrylic sulfonate.
Description
Technical Field
The invention relates to the field of resin synthesis, in particular to chelating resin and a preparation method thereof.
Background
The existing methylene amino carboxylic acid chelate resin or methylene amino sulfonic acid chelate resin is synthesized by adopting primary amine resin as a framework and chloroacetic acid through substitution reaction, and the resin is widely used in hydrometallurgy industry, is particularly suitable for absorbing alkaline earth and heavy metal cations from diluted and concentrated brine solution, and has the advantages of high exchange capacity, strong selectivity and the like. However, chloroacetic acid has the defects of corrosiveness, skin and respiratory tract irritation and extremely high toxicity to aquatic organisms, so that the chloroacetic acid is dangerous in the using and post-treatment processes; secondly, chloroacetic acid substitution reaction can be carried out in a heating environment, and the energy consumption is high.
Therefore, there is a need for a chelate resin which is green, safe, low in energy consumption, and has a high exchange capacity, and a method for preparing the same.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a chelating resin and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a preparation method of chelate resin, comprising the following steps: and (3) placing the amino resin into a swelling solution for swelling treatment, adding acrylic acid, acrylic sulfonic acid, acrylic acid salt, acrylic sulfonate, acrylic ester or acrylic sulfonate for addition reaction, and washing with a detergent after the reaction is finished to obtain the chelate resin.
Preferably, the amine-based resin comprises: at least one of a benzylamine resin, a primary amine resin, or a secondary amine resin.
Preferably, the swelling liquid includes: at least one of an alcohol solution, a liquid aliphatic hydrocarbon, a liquid aromatic hydrocarbon, a liquid halogenated hydrocarbon, an ester solution, an ether solution or deionized water.
More preferably, the alcoholic solution comprises: at least one of a methanol solution, an ethanol solution, or an n-butanol solution; the liquid aliphatic hydrocarbon comprises: at least one of cyclohexane, octane, or dodecane; the liquid aromatic hydrocarbon includes: at least one of benzene or toluene; the liquid halogenated hydrocarbon comprises: at least one of chloroform, carbon tetrachloride or chlorobenzene; the ester solution comprises: at least one of an ethyl acetate solution, a butyl acetate solution, or an acrylate solution; the ether solution comprises: at least one of an ether solution, a tetrahydrofuran solution, or a dioxane solution.
Preferably, the mass ratio of the swelling liquid to the amino resin is 2-10; the swelling treatment time is 2-12 h.
Preferably, the addition reaction comprises: adding the acrylic acid, the acrylic sulfonic acid, the acrylic acid salt or the acrylic sulfonic acid salt and reacting for 8-40 h at the temperature of 10-40 ℃.
Preferably, the addition reaction comprises: adding the acrylic ester or the propylene sulfonate, reacting for 8-40 h at 10-40 ℃, adding sodium hydroxide solution, and heating to 80-100 ℃ for reacting for 8-12 h.
Preferably, the mass ratio of the acrylic acid, the acrylic sulfonic acid, the acrylic acid salt or the acrylic sulfonic acid salt to the amine-based resin is 0.5 to 4.
Preferably, the detergent comprises: at least one of methanol, ethanol or deionized water.
In a second aspect, the present invention provides a chelate resin prepared by the preparation method, wherein the chelate resin is shown as formula I or formula II;
wherein R is selected from-H, - (CH) 2 ) n 、-CH 2 COOM、-CH 2 CH 2 COOM or-CH 2 CH 2 SO 3 M；
Wherein n is selected from integers from 1 to 6;
wherein M is-H or a metal cation.
Compared with the prior art, the invention has the following technical effects:
the invention adopts the amino resin with high exchange capacity, and synthesizes the methylene amino carboxylic acid chelate resin or the methylene amino sulfonic acid chelate resin through the addition reaction with acrylic acid, acrylic sulfonic acid, acrylic acid salt, acrylic sulfonate, acrylic ester or acrylic sulfonate.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention will be further illustrated, but is not limited, by the following examples.
Example 1
The embodiment provides a preparation method of methylene amino carboxylic acid chelate resin, which comprises the following steps: and (3) putting 20g of benzylamine resin into 100mL of methanol to swell for 2 hours, adding 40g of acrylic acid, stirring uniformly, continuing stirring, reacting for 8.2 hours at 20 ℃, filtering and washing with deionized water after the reaction is finished, and thus obtaining the methylene amino carboxylic acid chelate resin.
The detection shows that the total exchange capacity of the methylene amino carboxylic acid chelate resin is 6.4mmol/g (dry), the water content is 57.9 percent, and Cu 2+ The adsorption amount was 1.72mmol/g (dry).
The reaction chemical formula is as follows:
example 2
The embodiment provides another preparation method of methylene sulfamic acid chelate resin, which comprises the following steps: and (3) placing 20g of benzylamine resin into 200mL of dioxane to swell for 4 hours, adding 60g of sodium acrylate, stirring uniformly, continuing stirring, reacting at 30 ℃ for 12.5 hours, filtering after the reaction is finished, and washing with deionized water to obtain the methylene sulfamic acid chelate resin.
Through detection, the total exchange capacity of the methylene sulfamic acid chelate resin is 6.2mmol/g (dry), the water content is 49.5 percent, and Cu 2+ The adsorption amount was 1.05mmol/g (dry).
The reaction chemical formula is as follows:
example 3
The embodiment provides a preparation method of a methylene amino carboxylic acid chelating resin, which comprises the following steps: and (3) placing 20g of benzylamine resin into 150mL of deionized water to swell for 6 hours, adding 40g of methyl acrylate, stirring uniformly, continuing stirring, reacting for 20 hours at 25 ℃, adding 30g of sodium hydroxide solution after the reaction is finished, heating to 90 ℃ to perform hydrolysis reaction for 10 hours, filtering and washing with deionized water after the hydrolysis reaction is finished, and thus obtaining the methylene amino carboxylic acid chelate resin.
The detection shows that the total exchange capacity of the methylene amino carboxylic acid chelate resin is 3.9mmol/g (dry), the water content is 56.7 percent, and Cu 2+ The adsorption amount was 2.12mmol/g (dry).
The reaction chemical formula is as follows:
in summary, the invention adopts the amino resin with high exchange capacity, and the amino resin and acrylic acid, acrylic sulfonic acid, acrylic acid salt, acrylic sulfonate, acrylic ester or acrylic sulfonate are synthesized into methylene amino carboxylic acid chelate resin or methylene amino sulfonic acid chelate resin through addition reaction, the resin not only avoids using chloroacetic acid which is a reactant with strong toxicity, but also is more environment-friendly, the addition reaction can be carried out at normal temperature, the energy consumption is reduced, the amino resin is suitable for absorbing various alkaline earth and heavy metal cations from diluted and concentrated brine solution, and the amino resin has the advantages of green safety, low energy consumption, high exchange capacity and the like.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, and it will be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the teachings of the present invention, which are intended to be included within the scope of the invention.
Claims (10)
1. A preparation method of chelate resin is characterized by comprising the following steps: and (3) placing the amino resin into a swelling solution for swelling treatment, adding acrylic acid, acrylic sulfonic acid, acrylic acid salt, acrylic sulfonate, acrylic ester or acrylic sulfonate for addition reaction, and washing with a detergent after the reaction is finished to obtain the chelate resin.
2. The method of preparing according to claim 1, wherein the amine-based resin comprises: at least one of a benzylamine resin, a primary amine resin, or a secondary amine resin.
3. The production method according to claim 1, wherein the swelling liquid comprises: at least one of an alcohol solution, a liquid aliphatic hydrocarbon, a liquid aromatic hydrocarbon, a liquid halogenated hydrocarbon, an ester solution, an ether solution or deionized water.
4. A method of preparing according to claim 3, wherein the alcoholic solution comprises: at least one of a methanol solution, an ethanol solution, or an n-butanol solution; the liquid aliphatic hydrocarbon comprises: at least one of cyclohexane, octane, or dodecane; the liquid aromatic hydrocarbon includes: at least one of benzene or toluene; the liquid halogenated hydrocarbon comprises: at least one of chloroform, carbon tetrachloride or chlorobenzene; the ester solution comprises: at least one of an ethyl acetate solution, a butyl acetate solution, or an acrylate solution; the ether solution comprises: at least one of an ether solution, a tetrahydrofuran solution, or a dioxane solution.
5. The method according to claim 1, wherein the mass ratio of the swelling liquid to the amine-based resin is 2 to 10; the swelling treatment time is 2-12 h.
6. The method of preparation according to claim 1, wherein the addition reaction comprises: adding the acrylic acid, the acrylic sulfonic acid, the acrylic acid salt or the acrylic sulfonic acid salt and reacting for 8-40 h at the temperature of 10-40 ℃.
7. The method of preparation according to claim 1, wherein the addition reaction comprises: adding the acrylic ester or the propylene sulfonate, reacting for 8-40 h at 10-40 ℃, adding sodium hydroxide solution, and heating to 80-100 ℃ for reacting for 8-12 h.
8. The method according to claim 1, wherein a mass ratio of the acrylic acid, the acrylic sulfonic acid, the acrylic acid salt or the acrylic sulfonic acid salt to the amine-based resin is 0.5 to 4.
9. The method of preparing according to claim 1, wherein the detergent comprises: at least one of methanol, ethanol or deionized water.
10. A chelating resin prepared by the preparation method according to any one of claims 1 to 9, wherein the chelating resin is represented by formula I or formula II;
wherein R is selected from-H, - (CH) 2 ) n 、-CH 2 COOM、-CH 2 CH 2 COOM or-CH 2 CH 2 SO 3 M；
Wherein n is selected from integers from 1 to 6;
wherein M is-H or a metal cation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211732702.XA CN116253816A (en) | 2022-12-30 | 2022-12-30 | Chelate resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211732702.XA CN116253816A (en) | 2022-12-30 | 2022-12-30 | Chelate resin and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN116253816A true CN116253816A (en) | 2023-06-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211732702.XA Pending CN116253816A (en) | 2022-12-30 | 2022-12-30 | Chelate resin and preparation method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN116253816A (en) |
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2022
- 2022-12-30 CN CN202211732702.XA patent/CN116253816A/en active Pending
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