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CN115386127A - Preparation method of gallium adsorption resin - Google Patents

Preparation method of gallium adsorption resin Download PDF

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Publication number
CN115386127A
CN115386127A CN202210994296.8A CN202210994296A CN115386127A CN 115386127 A CN115386127 A CN 115386127A CN 202210994296 A CN202210994296 A CN 202210994296A CN 115386127 A CN115386127 A CN 115386127A
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polymer
mass
polymer precursor
polymer beads
water
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CN115386127B (en
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童海
王鹏
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Shaanxi Haihao Industrial Co ltd
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Shaanxi Haihao Industrial Co ltd
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    • 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
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • C—CHEMISTRY; METALLURGY
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    • 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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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B58/00—Obtaining gallium or indium
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    • C08J2325/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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    • 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
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    • C08J2333/20—Homopolymers or copolymers of acrylonitrile
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    • C08J2433/18—Homopolymers or copolymers of nitriles
    • C08J2433/20—Homopolymers or copolymers of acrylonitrile
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Abstract

The invention relates to a preparation method of gallium adsorption resin, aiming at controlling the particle size distribution of the obtained polymer microspheres and improving the waste loss in production; the method comprises three parts of soaking a polymer precursor, preparing polymer beads and modifying the polymer beads, wherein the polymer precursor is porous polyacrylonitrile particles containing rich nitrile groups; soaking the polymer precursor, wherein the swelling agent is a mixed solution of a polymerization monomer, a cross-linking agent and an initiator, and the polymer precursor is wrapped in a polymer bead body obtained by suspension polymerization; the modification is that polymer beads are introduced into an amidoxime group through amidoximation reaction; the invention has no introduction of pore-forming agent, reduces production procedures, improves the particle size distribution of the resin, greatly reduces the rejection rate, increases the yield of the resin from 70 percent to over 95 percent and reduces the cost.

Description

Preparation method of gallium adsorption resin
Technical Field
The invention relates to the technical field of resin preparation, in particular to a preparation method of gallium adsorption resin.
Background
At present, gallium adsorption resin is mainly used for extracting and recovering gallium metal, the particle size distribution of the gallium adsorption resin is required to be between 0.6 and 1.25mm, the effect is optimal, but in actual production, the particle size of the gallium adsorption resin generated through chemical reaction of a plurality of complicated steps is difficult to control in the particle size distribution range, and the qualified rate of the particle size is only about 70 percent generally. The large amount of gallium adsorption resin with unqualified particle size generated by the method is directly discarded as waste materials, so that the waste is relatively serious, and the reason is also one of the reasons for high production cost of the gallium adsorption resin.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a method for preparing gallium adsorbent resin, which greatly improves the yield of qualified products of resin with particle size distribution, simplifies the production process and reduces the production cost.
In order to achieve the purpose, the invention provides the following technical scheme:
the preparation method of the gallium adsorption resin comprises the following steps:
the method comprises the following steps: soaking the polymer precursor in the mixed solution at 30-35 ℃ and stirring for more than 60 min; wherein:
the polymer precursor is nitrile-group-containing polymer plastic particles with the particle size of 0.5-0.8 mm;
the mixed solution comprises a polymerization monomer, a cross-linking agent and an initiator; wherein the polymerization monomer is styrene and acrylonitrile, the cross-linking agent is divinylbenzene, and the initiator is benzoyl peroxide;
the mixed solution comprises the following components in percentage by mass: the mass of the polymerization monomer is 50-80% of that of the polymer precursor, the mass of the cross-linking agent is 30-50% of that of the polymerization monomer, and the mass of the initiator is 0.5-1% of that of the polymerization monomer.
Step two: adding the soaked polymer precursor into a reaction kettle prepared with the aqueous phase solution, heating to 70-80 ℃, carrying out heat preservation reaction for 2-3 hours, then heating to 84-88 ℃, carrying out heat preservation reaction for 4-5 hours, finally heating to 93-98 ℃, and carrying out heat preservation reaction for 4-5 hours; wherein:
the aqueous solution comprises saline water and a dispersant, the saline water comprises one or two of sodium chloride and calcium chloride, and the dispersant comprises gelatin and polyvinyl alcohol;
the saline is added in an amount of 200-300% by mass of the polymer precursor, and the dispersant is added in an amount of 1-1.5% by mass of the saline.
Step three: discharging the reaction liquid in the step two into a material washer with a filter screen, washing for more than 30min by using hot water, and vacuumizing into a drying device; drying the polymer beads by airflow and drying the polymer beads by a dryer to obtain dried polymer beads;
step four: adding the dried polymer beads into a mixed medium, stirring and swelling at the temperature of 30-50 ℃, keeping for more than 60min, pumping into a modified reagent aqueous solution and a neutralized reagent aqueous solution under continuous stirring, heating to 75-95 ℃, keeping the temperature for 14-20 h, finally cooling to 40-50 ℃, filtering out a mother solution, washing with water, and draining or draining water to obtain ion exchange resin; wherein:
the mixed medium comprises dichloroethane, ethanol and water which are added according to 250 to 500 percent of the mass of the polymer beads; the modifying reagent comprises hydroxylamine sulfate and hydroxylamine hydrochloride which are added according to 50-150% of the mass of the polymer beads; the neutralizing agent comprises sodium hydroxide and sodium carbonate which are added according to 35 to 55 percent of the mass of the polymer beads.
In the preparation method of the gallium adsorption resin, in the step one, the polymer precursor is porous polyacrylonitrile plastic particles, and the particle size distribution is 0.5-0.8 mm.
In the preparation method of the gallium adsorption resin, in the step one, the polymer precursor is soaked in the mixed solution for 30 minutes at the temperature of 30-35 ℃, and then stirred for more than 30 minutes;
in the preparation method of the gallium adsorption resin, in the step one, the preparation method of the mixed solution comprises the following steps: firstly, a polymerization monomer and a cross-linking agent are thrown into a high-order batching kettle, wherein styrene and divinylbenzene are used after a polymerization inhibitor is removed, an initiator is added, the mixture is uniformly stirred and dissolved, and then the temperature is adjusted to 30-35 ℃.
In the preparation method of the gallium adsorption resin, in the step one, the ratio of styrene to acrylonitrile is 1:1 to 1:4.
in the preparation method of the gallium adsorption resin, in the second step, the preparation method of the aqueous phase solution comprises the following steps: adding salt water into the enamel reaction kettle, dissolving the dispersing agent in water in advance, putting the mixture into the reaction kettle after all the dispersing agent is dissolved, stirring the mixture for about 30min and heating the mixture to 50 ℃.
In the preparation method of the gallium adsorption resin, in the second step, the gelatin and the polyvinyl alcohol in the dispersing agent are added in a mass ratio of 9:1-7:3.
The beneficial effects of the invention are:
the method comprises the steps of soaking a polymer precursor, preparing polymer beads and modifying the polymer beads, wherein the polymer precursor is porous polyacrylonitrile particles containing abundant nitrile groups; soaking the polymer precursor, wherein the swelling agent is a mixed solution of a polymerization monomer, a cross-linking agent and an initiator, and the polymer precursor is wrapped in a polymer bead body obtained by suspension polymerization; the modification is to introduce an amidoxime group into the polymer bead through an amidoxime reaction, and the invention has no introduction of a pore-forming agent, reduces production procedures and further improves production efficiency.
The invention uses polymer particles as the precursor of semi-finished polymer beads, so that the particle size distribution of the polymer is more controllable, the particle size distribution of the resin is improved, the rejection rate is greatly reduced, the yield of the resin is improved from 70 percent to more than 95 percent, the loss of the semi-finished product is greatly reduced, meanwhile, the effective radicals are increased by more than 10 percent, and the performance of the resin is greatly improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention relates to a preparation method of gallium adsorption resin, which comprises three parts of polymer precursor soaking, polymer bead preparation and polymer bead modification, and is carried out according to the following steps:
the method comprises the following steps: the polymer precursor is soaked in the mixed solution at the temperature of 30-35 ℃ for 30min and then stirred for more than 30 min.
The polymer precursor is polymer plastic particles with rich nitrile groups, preferably porous polyacrylonitrile plastic particles, and the particle size is 0.5-0.8 mm; the mixed solution required by soaking the polymer precursor comprises a polymerization monomer, a cross-linking agent and an initiator; wherein the polymerization monomers are styrene and acrylonitrile, and the proportion of the styrene to the acrylonitrile is 1:1 to 1:4, the cross-linking agent is divinylbenzene, and the initiator is benzoyl peroxide; the mixed solution for soaking for preparing the polymer precursor comprises the following components in percentage by mass: the mass of the polymerization monomer is 50-80% of that of the polymer precursor, the mass of the cross-linking agent is 30-50% of that of the polymerization monomer, and the mass of the initiator is 0.5-1% of that of the polymerization monomer.
Preparing a mixed solution: firstly, a polymerization monomer and a cross-linking agent are thrown into a high-order batching kettle, wherein styrene and divinylbenzene are used after a polymerization inhibitor is removed, an initiator is added, the mixture is uniformly stirred and dissolved, and then the temperature is adjusted to 30-35 ℃.
Step two: and (4) carrying out polymerization reaction.
Adding the soaked polymer precursor into a reaction kettle prepared with the aqueous phase solution, heating to 70-80 ℃, carrying out heat preservation reaction for 2-3 hours, then heating to 84-88 ℃, carrying out heat preservation reaction for 4-5 hours, finally heating to 93-98 ℃, and carrying out heat preservation reaction for 4-5 hours.
The aqueous phase solution comprises saline water and a dispersing agent, the saline water comprises one or two of sodium chloride and calcium chloride, the dispersing agent comprises gelatin and polyvinyl alcohol, the gelatin is taken as a main material, the polyvinyl alcohol is taken as an auxiliary material, and the preferable mass ratio of the gelatin to the polyvinyl alcohol is 9:1-7:3.
The saline is added in an amount of 200-300% by mass of the polymer precursor, and the dispersant is added in an amount of 1-1.5% by mass of the saline.
Preparing an aqueous phase solution: adding salt water into the enamel reaction kettle, dissolving the dispersing agent in water in advance, putting the mixture into the reaction kettle after all the dispersing agent is dissolved, stirring the mixture for about 30min and heating the mixture to 50 ℃.
Step three: after the polymerization reaction is finished, reaction liquid containing polymer beads is obtained, the reaction liquid is discharged into a washer with a filter screen after being cooled, the washer is washed for more than 30min by hot water, and the reaction liquid is vacuumized into a drying device; drying by airflow and drying by a dryer to obtain dry polymer beads.
Step four: and (3) modifying polymer beads.
Adding the dried polymer beads into a mixed medium, stirring and swelling at the temperature of 30-50 ℃, keeping for more than 60min, pumping into a modified reagent aqueous solution and a neutralized reagent aqueous solution under continuous stirring, heating to 75-95 ℃, keeping the temperature for 14-20 h, and finally cooling to 40-50 ℃. Discharging the materials into a material washer after the reaction is finished, filtering out the mother liquor, washing with water, filtering out or draining water to obtain the ion exchange resin, and packaging.
Wherein the mixed medium comprises dichloroethane, ethanol and water which are added by 250 to 500 percent of the mass of the polymer beads; the modifying reagent comprises hydroxylamine sulfate and hydroxylamine hydrochloride which are added according to 50-150% of the mass of the polymer beads; the neutralization reagent comprises sodium hydroxide and sodium carbonate which are added according to 35 to 55 percent of the mass of the polymer beads.
The method comprises the steps of soaking a polymer precursor, preparing polymer beads and modifying the polymer beads, wherein the polymer precursor is porous polyacrylonitrile particles containing abundant nitrile groups; soaking the polymer precursor, wherein the swelling agent is a mixed solution of a polymerization monomer, a cross-linking agent and an initiator, and the polymer precursor is wrapped in a polymer bead body obtained by suspension polymerization; the modification is to introduce an amidoxime group into the prepolymer beads through amidoximation reaction, and the method has the advantages of no introduction of a pore-forming agent, reduction of production procedures and further improvement of production efficiency.
The invention uses polymer particles as the precursor of semi-finished polymer beads, so that the particle size distribution of the polymer is more controllable, the gallium adsorption resin produced by the technical scheme of the invention has uniform particle size of 0.6-1.25 mm, the particle size distribution of the resin is improved, the rejection rate is greatly reduced, the yield of the resin is improved to more than 95% from 70%, the loss of the semi-finished product is greatly reduced, meanwhile, the effective groups are increased by more than 10%, and the performance of the resin is greatly improved.
Example one
10kg of styrene and 40kg of acrylonitrile, 30kg of divinylbenzene and 0.5kg of benzoyl peroxide are added into a reaction kettle at the temperature of 30 ℃, 100kg of porous polyacrylonitrile plastic particles with the particle size distribution of 0.3-1.0 mm are soaked for 30min and then are stirred for 30min;
200kg of saline, 0.9kg of gelatin and 0.1kg of polyvinyl alcohol are added into a reaction kettle; then adding the soaked porous polyacrylonitrile plastic particles, heating to 70 ℃, carrying out heat preservation reaction for 3 hours, then heating to 84 ℃, carrying out heat preservation reaction for 5 hours, finally heating to 93 ℃, and carrying out heat preservation reaction for 4 hours; then discharging into a washer with a filter screen, washing for 30min with hot water, and vacuumizing into a drying device; obtaining 212kg of polymer beads through airflow drying and drying by a dryer;
adding the dried polymer beads into 530kg of dichloroethane and ethanol aqueous solution, stirring for 90min at 30 ℃, then adding 106kg of hydroxylamine sulfate and hydroxylamine hydrochloride, 74.2kg of sodium hydroxide and sodium carbonate aqueous solution under continuous stirring, heating to 75 ℃, preserving heat for 20 h, finally cooling to 40 ℃, filtering out mother liquor, washing with water, draining water to obtain 532kg of gallium adsorption exchange resin, screening through a 0.437-1.1 mm net to obtain 511kg of gallium adsorption exchange resin, wherein the grain size distribution qualification rate of the gallium adsorption resin is 96.05%.
Example two
40kg of styrene and 40kg of acrylonitrile, 50kg of divinylbenzene and 1kg of benzoyl peroxide, 100kg of porous polyacrylonitrile plastic particles with the particle size distribution of 0.5-0.8 mm are added into a reaction kettle with the temperature of 35 ℃, soaked for 30min and stirred for 30min;
adding 300kg of saline water, 1kg of gelatin and 0.5kg of polyvinyl alcohol into a reaction kettle; then adding the soaked porous polyacrylonitrile plastic particles, heating to 80 ℃, carrying out heat preservation reaction for 2 hours, then heating to 88 ℃, carrying out heat preservation reaction for 4 hours, finally heating to 98 ℃, and carrying out heat preservation reaction for 4 hours; then discharging into a washer with a filter screen, washing for 30min with hot water, and vacuumizing into a drying device; 263kg of polymer beads are obtained after airflow drying and drying by a dryer;
adding the dried polymer beads into 1315kg of dichloroethane, ethanol and an aqueous solution, stirring for 60min at the temperature of 50 ℃, then adding 395kg of hydroxylamine sulfate and 145kg of hydroxylamine hydrochloride aqueous solution of sodium hydroxide and sodium carbonate under continuous stirring, heating to 95 ℃, preserving heat for 14 h, finally cooling to 40 ℃, filtering out mother liquor, washing with water, draining off water to obtain 613kg of gallium adsorption exchange resin, screening through a 0.6-1.25 mm net to obtain 587kg of gallium adsorption exchange resin, wherein the qualified rate of the distribution of the particle size of the gallium adsorption resin is 95.76%.
EXAMPLE III
15kg of styrene, 60kg of acrylonitrile, 40kg of divinylbenzene, 0.8kg of benzoyl peroxide and 100kg of porous polyacrylonitrile plastic particles with the particle size distribution of 0.5-0.8 mm are added into a reaction kettle at the temperature of 35 ℃ and are stirred for 30min after being soaked for 30min;
adding 250kg of saline, 1kg of gelatin and 0.3kg of polyvinyl alcohol into a reaction kettle; then adding the soaked porous polyacrylonitrile plastic particles, heating to 70 ℃, carrying out heat preservation reaction for 3 hours, then heating to 85 ℃, carrying out heat preservation reaction for 5 hours, finally heating to 95 ℃, and carrying out heat preservation reaction for 4 hours; then discharging into a washer with a filter screen, washing for 30min with hot water, and vacuumizing into a drying device; drying with air flow, and oven drying to obtain polymer beads 233kg;
adding the dried polymer beads into 932kg of dichloroethane, ethanol and aqueous solution, stirring for 60min at the temperature of 40 ℃, then adding 230kg of hydroxylamine sulfate and hydroxylamine hydrochloride, 120kg of sodium hydroxide and sodium carbonate aqueous solution under continuous stirring, heating to 90 ℃, preserving heat for 20 h, finally cooling to 50 ℃, filtering out mother liquor, washing with water, draining water to obtain 586kg of gallium adsorption exchange resin, screening through a 0.6-1.25 mm net to obtain 565kg of gallium adsorption exchange resin, wherein the grain size distribution qualification rate of the gallium adsorption resin is 96.42%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical idea of the present invention is equivalent to or changed by the present invention.

Claims (5)

1. The preparation method of the gallium adsorption resin is characterized by comprising the following steps:
the method comprises the following steps: soaking the polymer precursor in the mixed solution at 30-35 ℃ and stirring for more than 60 min; wherein:
the polymer precursor is nitrile-group-containing polymer plastic particles with the particle size distribution of 0.5-0.8 mm;
the mixed solution comprises a polymerization monomer, a cross-linking agent and an initiator; wherein the polymerization monomers are styrene and acrylonitrile, and the addition mass ratio of the styrene to the acrylonitrile is 1:1 to 1:4; the cross-linking agent is divinylbenzene; the initiator is benzoyl peroxide;
the mixed solution comprises the following components in percentage by mass: the mass of the polymerized monomer is 50-80% of that of the polymer precursor, the mass of the cross-linking agent is 30-50% of that of the polymerized monomer, and the mass of the initiator is 0.5-1% of that of the polymerized monomer.
Step two: adding the soaked polymer precursor into a reaction kettle prepared with the aqueous phase solution, heating to 70-80 ℃, carrying out heat preservation reaction for 2-3 hours, then heating to 84-88 ℃, carrying out heat preservation reaction for 4-5 hours, finally heating to 93-98 ℃, and carrying out heat preservation reaction for 4-5 hours; wherein:
the aqueous phase solution comprises saline water and a dispersing agent, the saline water comprises one or two of sodium chloride and calcium chloride, the dispersing agent comprises gelatin and polyvinyl alcohol, and the adding mass ratio of the gelatin to the polyvinyl alcohol is 9:1-7:3;
the saline is added in an amount of 200-300% by mass of the polymer precursor, and the dispersant is added in an amount of 1-1.5% by mass of the saline.
Step three: discharging the reaction solution in the step two into a material washer with a filter screen, washing for more than 30min by using hot water, and vacuumizing into a drying device; drying the polymer beads by airflow and drying the polymer beads by a dryer to obtain dried polymer beads;
step four: adding the dried polymer beads into a mixed medium, stirring and swelling at the temperature of 30-50 ℃, keeping for more than 60min, pumping into a modified reagent aqueous solution and a neutralized reagent aqueous solution under continuous stirring, heating to 75-95 ℃, keeping for 14-20 h, cooling to 40-50 ℃, filtering out a mother solution, washing with water, and draining to obtain ion exchange resin; wherein:
the mixed medium comprises dichloroethane, ethanol and water which are added according to 250 to 500 percent of the mass of the polymer beads; the modifying reagent comprises hydroxylamine sulfate and hydroxylamine hydrochloride which are added according to 50-150% of the mass of the polymer beads; the neutralization reagent comprises sodium hydroxide and sodium carbonate which are added according to 35 to 55 percent of the mass of the polymer beads.
2. The method for preparing gallium adsorbent resin according to claim 1, wherein: in the first step, the polymer precursor is porous polyacrylonitrile plastic particles, and the particle size distribution is 0.5-0.8 mm.
3. The method for preparing gallium adsorbent resin according to claim 1, wherein: in the first step, the polymer precursor is soaked in the mixed solution at 30-35 ℃ for 30 minutes and then stirred for more than 30 minutes.
4. The method for preparing gallium adsorbent resin according to claim 1, wherein: in the first step, the preparation method of the mixed solution comprises the following steps: firstly, a polymerization monomer and a cross-linking agent are thrown into a high-order batching kettle, wherein styrene and divinylbenzene are used after a polymerization inhibitor is removed, an initiator is added, the mixture is uniformly stirred and dissolved, and then the temperature is adjusted to 30-35 ℃.
5. The method for preparing gallium adsorbent resin according to claim 1, wherein: in the second step, the preparation method of the aqueous phase solution comprises the following steps: adding salt water into the enamel reaction kettle, dissolving the dispersing agent in water in advance, putting the mixture into the reaction kettle after all the dispersing agent is dissolved, stirring the mixture for about 30min and heating the mixture to 50 ℃.
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CN104292383A (en) * 2014-09-16 2015-01-21 陕西华电树脂股份有限公司 Gallium-adsorbing chelating resin and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US20130168322A1 (en) * 2010-09-14 2013-07-04 Kaneka Corporation Amidoxime-modified polyacrylonitrile porous body
CN104292383A (en) * 2014-09-16 2015-01-21 陕西华电树脂股份有限公司 Gallium-adsorbing chelating resin and preparation method thereof

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何江华: "多核型低密度聚合物微球的制备及其应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

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