CN104292383A - Gallium-adsorbing chelating resin and preparation method thereof - Google Patents
Gallium-adsorbing chelating resin and preparation method thereof Download PDFInfo
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- CN104292383A CN104292383A CN201410471375.6A CN201410471375A CN104292383A CN 104292383 A CN104292383 A CN 104292383A CN 201410471375 A CN201410471375 A CN 201410471375A CN 104292383 A CN104292383 A CN 104292383A
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Abstract
The invention discloses a gallium-adsorbing chelating resin and a preparation method thereof. The preparation method comprises the following steps: mixing styrene, acrylonitrile, p-divinyl benzene, a pore-foaming agent, benzoyl peroxide and saline water, adding a dispersing agent, heating for performing suspension polymerization, thereby obtaining a reaction liquid containing copolymerization beads; separating the copolymerization beads from the reaction liquid, purifying, drying, thereby obtaining dried copolymerization beads; and carrying out an amidoximation reaction on the dried copolymerization beads, thereby preparing the gallium-adsorbing chelating resin. The preparation method disclosed by the invention is simple in process, high in operability, low in cost and high in stability. Meanwhile, the addition amount of each monomer is controlled, a proper pore-foaming agent is selected, the structure of the prepared gallium-adsorbing chelating resin is improved by the reaction medium, temperature and time, and active functional groups are increased. The test proves that the gallium-adsorbing chelating resin disclosed by the invention is excellent in hydrophilcity, proper in specific surface area and high in strength and has high adsorptive selectivity on gallium ions in a Bayer mother liquid.
Description
Technical field
The invention belongs to polymer arts, be specifically related to a kind of absorption gallium resin and preparation method.
Background technology
Gallium is a kind of rare elements, is mainly used in semi-conductor industry, normally reclaims from pregnant Bayer liquor Ga extraction method.The method reclaiming gallium from pregnant Bayer liquor has multiple, as extraction process, amalgamation process, electrolytic process and chemical enrichment method etc.But because extraction process cost is high, need to consume a large amount of extraction agent, aluminium hydroxide and alkali, and organism is brought into the Production Flow Chart of aluminum oxide; There is the shortcoming of the large and mercury pollution of mercury use in amalgamation process; There is with serious pollution shortcoming in electrolytic process; Chemical enrichment method method is a lot, but its complicated operation or gallium aluminium inferior separating effect, and the rate of recovery is not high.
At present, had application import resin Footwall drift gallium from pregnant Bayer liquor, but adsorptive capacity is lower, and Financial cost is high.Extraction recovery for metallic cation or acid metal negatively charged ion mainly still answers spent ion exchange resin and resin, but the selectivity of ion exchange resin and resin differs greatly, and not yet there is the report to utilizing amidoxim recycling gallium from Bayer mother solution by using chelate resin at present.The invention discloses a kind of chelating resin special for adsorbing of gallium and preparation method, the functional group of this chelating resin special for adsorbing of gallium is amidoxime base, first Application way prepares the resin with amidoxime base, again by the selection to factors such as the medium kind of degree of crosslinking size, pore-creating agent kind and ratio, polymerization temperature and soaking time, amidoximation and ratios, prepare a kind of chelating resin special adsorbing gallium from pregnant Bayer liquor.
Summary of the invention
The object of the present invention is to provide a kind of absorption gallium resin and preparation method, this preparation method's technique is simple, workable, cost is low, stability is high, the good hydrophilic property of the absorption gallium resin of preparation, specific surface area is preferably, and high to the gallium adsorptive capacity in pregnant Bayer liquor, intensity good, long service life, cost are low and stable performance.
In order to achieve the above object, the preparation method of gallium resin is adsorbed in the present invention, comprises the following steps:
1) by vinylbenzene, vinyl cyanide, to divinylbenzene, pore-creating agent, benzoyl peroxide and salt solution mixing after, add dispersion agent again, be then heated to 60 DEG C-70 DEG C, insulation reaction 2-3 hour, then 75 DEG C-85 DEG C are warming up to, insulation reaction 2-4 hour, is then warming up to 90 DEG C-95 DEG C, insulation reaction 3-6 hour, obtain the reaction solution containing copolymerization pearl body, separated from reaction solution by copolymerization pearl body, then purifying is also dry, obtains dry copolymerization pearl body; Wherein, vinyl cyanide and cinnamic mol ratio are 1:(0.5-1.5), be the 6%-10% of vinyl cyanide and vinylbenzene total mass to the quality of divinylbenzene, the quality of pore-creating agent is vinylbenzene, vinyl cyanide and the 60%-80% to divinylbenzene total mass; The quality of dispersion agent is vinylbenzene, vinyl cyanide and the 0.5%-1% to divinylbenzene total mass;
2) dried copolymerization pearl body is carried out amidoximation, obtained absorption gallium resin.
Described step 1) in the quality of benzoyl peroxide be vinylbenzene, vinyl cyanide and the 0.5%-1% to divinylbenzene total mass.
Described step 1) in pore-creating agent be mixed by two or three in toluene, dimethylbenzene, gasoline.
Described step 1) in dispersion agent be methylene blue and/or mass concentration be the polyvinyl alcohol of 1%.
Described step 1) in the method for purifying be: the boiling that adds water at 85 DEG C-100 DEG C after isolated copolymerization pearl body washing is extracted 3-6 hour to remove pore-creating agent, completes purifying.
Described step 1) mesohalobic mass concentration is 5%.
Described step 1) in the brine volume that adds be pore-creating agent, vinylbenzene, vinyl cyanide and the 150%-250% to divinylbenzene cumulative volume.
Described step 2) dried copolymerization pearl body is carried out amidoximation process as follows:
Dried copolymerization pearl body is added in the mixing solutions of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines, then oxammonium hydrochloride and sodium hydroxide is under agitation added, then under 65 DEG C of-85 DEG C of conditions, react 8-15 hour, be finally cooled to 40 DEG C, obtain the reaction system containing solid; Be separated by the solid of reaction system, in solid, then add mass concentration is soak 5-10 hour in the aqueous sodium hydroxide solution of 4%-5%, is finally washed to neutrality, namely completes amidoximation; Wherein, the mass ratio of oxammonium hydrochloride and dried copolymerization pearl body is (0.8-1): 1; The mol ratio of oxammonium hydrochloride and sodium hydroxide is 1:1, and the cumulative volume of mixing solutions is 3-4 times of dried copolymerization pearl body volume; And the volume ratio of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines is 1:(1-2 in mixing solutions): (0.5-1): (0.5-1.5): (1-1.5).
In described mixing solutions, the volume ratio of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines is 1:2:1:0.5:1.5.
The absorption gallium resin adopting described preparation method to prepare, its chemical structure is:
Compared with prior art, beneficial effect of the present invention is:
The present invention has obtained absorption gallium resin by suspension polymerization and amidoximation, and its method preparation method technique is simple, workable, cost is low and stability is high.Meanwhile, the present invention also by controlling the add-on of each monomer, selects suitable pore-creating agent, and reaction medium, temperature and time improve the structure of the absorption gallium resin of preparation, increase active function groups; Prove through test, absorption gallium resin wetting ability prepared by the present invention is good, and specific surface area is suitable for, and intensity is good, has higher adsorption selectivity to the gallium ion in pregnant Bayer liquor, is conducive to the adsorptive capacity improving gallium ion.In addition, this absorption gallium resin long service life, constant product quality, use cost is low.The pore-creating agent used at preparation absorption gallium resin is the mixture of toluene, dimethylbenzene, gasoline, and because toluene, dimethylbenzene are good solvent, and gasoline is poor solvent, and therefore, three mixes can regulating and controlling aperture and specific surface; Salt solution can reduce the surface tension of disperse phase, makes spherolite more even.
Embodiment
Below the present invention is described in further details.
The chemical structure that gallium resin is adsorbed in the present invention is:
The 13CNMR of this absorption gallium resin characterizes as follows:
13CNMR(300Hz,DMSO)29.9(2C,CH),30.1(1C,CH),32.0(2C,CH
2),33.5(2C,CH),34.5(2C,CH
2),36.1(1C,CH),39.2(2C,CH),128.1(4C,CH),128.3(8C,CH),125.7(2C,CH),136.6(2C,C),139.4(2C,C),164(2C,C)
The preparation method of this absorption gallium resin comprises suspension polymerization and amidoximation two step, and concrete steps are:
1) suspension polymerization
By vinylbenzene, vinyl cyanide, to divinylbenzene, pore-creating agent, benzoyl peroxide and mass concentration be 5% salt solution mixing after, add dispersion agent again, be then heated to 60 DEG C-70 DEG C, insulation reaction 2-3 hour, then 75 DEG C-85 DEG C are warming up to, insulation reaction 2-4 hour, is then warming up to 90 DEG C-95 DEG C, insulation reaction 3-6 hour, obtain the reaction solution containing copolymerization pearl body, separated from reaction solution by copolymerization pearl body, then purifying is also dry, obtains dry copolymerization pearl body; Wherein, vinyl cyanide and cinnamic mol ratio are 1:(0.5-1.5), be the 6%-10% of vinyl cyanide and vinylbenzene total mass to the quality of divinylbenzene, the quality of pore-creating agent is vinylbenzene, vinyl cyanide and the 60%-80% to divinylbenzene total mass; The quality of dispersion agent is vinylbenzene, vinyl cyanide and the 0.5%-1% to divinylbenzene total mass; The quality of benzoyl peroxide is vinylbenzene, vinyl cyanide and the 0.5%-1% to divinylbenzene total mass; Dispersion agent is methylene blue and/or mass concentration is the polyvinyl alcohol of 1%; The brine volume added is pore-creating agent, vinylbenzene, vinyl cyanide and the 150%-250% to divinylbenzene cumulative volume; And the method for purifying is: at 85 DEG C-100 DEG C after being washed by isolated copolymerization pearl body, the boiling that adds water extracts 3-6 hour to remove pore-creating agent, completes purifying.In addition, the mass concentration to divinylbenzene that the present invention adopts is 64.5%; Pore-creating agent is mixed by two or three in toluene, dimethylbenzene, gasoline; And pore-creating agent be three kinds mixing time, the ratio of toluene, dimethylbenzene and gasoline is 1:(0.6-0.8): (0.2-0.4);
2) amidoximation
Dried copolymerization pearl body is added in the mixing solutions of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines, then oxammonium hydrochloride and sodium hydroxide is under agitation added, then under 65 DEG C of-85 DEG C of conditions, react 8-15 hour, be finally cooled to 40 DEG C, obtain the reaction system containing solid; The solid of reaction system is separated, in solid, then adds the aqueous sodium hydroxide solution immersion 5-10 hour that mass concentration is 4%-5%, be finally washed to neutrality, namely complete amidoximation obtained absorption gallium resin; Wherein, the mass ratio of oxammonium hydrochloride and dried copolymerization pearl body is (0.8-1): 1; The mol ratio of oxammonium hydrochloride and sodium hydroxide is 1:1, and the cumulative volume of mixing solutions is 3-4 times of dried copolymerization pearl body volume; And the volume ratio of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines is 1:(1-2 in mixing solutions): (0.5-1): (0.5-1.5): (1-1.5), is preferably 1:2:1:0.5:1.5.
Below to the embodiment providing the present invention and prepare the method for absorption gallium resin, following examples are only explain, instead of limit.
Embodiment 1:
1) suspension polymerization
By vinylbenzene, vinyl cyanide, to divinylbenzene, adding by mass ratio after benzoyl peroxide is uniformly dissolved is the pore-creating agent that the toluene of 1:1 and dimethylbenzene form, continue to stir in the there-necked flask that is placed on and adds the salt solution having dissolved polyvinyl alcohol, and be 5% for the mass concentration of the salt solution of dissolve polyvinyl alcohol, then 60 DEG C are heated to, insulation reaction 3 hours, then 85 DEG C are warming up to, insulation reaction 4 hours, then 90 DEG C are warming up to, insulation reaction 5 hours, obtain the reaction solution containing copolymerization pearl body, copolymerization pearl body is separated from reaction solution, then purifying is also dry, obtain dry copolymerization pearl body, wherein, vinyl cyanide and cinnamic mol ratio are 1:0.5, are 6% of vinyl cyanide and vinylbenzene total mass to the quality of divinylbenzene, the quality of pore-creating agent be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 60%, the quality of polyvinyl alcohol be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 1%, the quality of benzoyl peroxide be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 0.5%, the brine volume added be pore-creating agent, vinylbenzene, vinyl cyanide and to divinylbenzene cumulative volume 150%, and the method for purifying is: at 85 DEG C after being washed by isolated copolymerization pearl body, the boiling that adds water extracts 3 hours to remove pore-creating agent, completes purifying.
2) amidoximation
Dried copolymerization pearl body is added in the mixing solutions of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines that volume ratio is 1:2:1:0.5:1.5, then under stirring at normal temperature, oxammonium hydrochloride and sodium hydroxide is added, then react 10 hours under 75 DEG C of conditions, finally be cooled to 40 DEG C, obtain the reaction system containing solid; The solid of reaction system is separated to remove mother liquor, then add in solid mass concentration be 4% aqueous sodium hydroxide solution soak 6 hours, be finally washed to neutrality, namely complete that amidoximation is obtained adsorbs gallium resin; Wherein, the mass ratio of oxammonium hydrochloride and dried copolymerization pearl body is 0.8:1; The mol ratio of oxammonium hydrochloride and sodium hydroxide is 1:1, and the cumulative volume of mixing solutions is 3 times of dried copolymerization pearl body volume, and the aqueous sodium hydroxide solution added is 5 times of solid volume.
Analytical results resin wets volume density 0.71mg/L, wet true density 1.11mg/L, resin aqueous amount 57%, resin rate of expansion 10.9%, and the pregnant Bayer liquor through gallium content 200mg/l crosses post, absorption gallium 3.25g/L.
Embodiment 2:
1) suspension polymerization
By vinylbenzene, vinyl cyanide, to divinylbenzene, adding by mass ratio after benzoyl peroxide is uniformly dissolved is the toluene of 0.5:0.4:0.1, the pore-creating agent of dimethylbenzene and gasoline composition, continue to stir in the there-necked flask that is placed on and adds the salt solution having dissolved methylene blue, and be 5% for the mass concentration of the salt solution dissolving methylene blue, then 65 DEG C are heated to, insulation reaction 2 hours, then 80 DEG C are warming up to, insulation reaction 4 hours, then 90 DEG C are warming up to, insulation reaction 4 hours, obtain the reaction solution containing copolymerization pearl body, copolymerization pearl body is separated from reaction solution, then purifying is also dry, obtain dry copolymerization pearl body, wherein, vinyl cyanide and cinnamic mol ratio are 1:0.5, are 6% of vinyl cyanide and vinylbenzene total mass to the quality of divinylbenzene, the quality of pore-creating agent be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 60%, the quality of methylene blue be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 1%, the quality of benzoyl peroxide be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 0.8%, the brine volume added be pore-creating agent, vinylbenzene, vinyl cyanide and to divinylbenzene cumulative volume 150%, and the method for purifying is: at 100 DEG C after being washed by isolated copolymerization pearl body, the boiling that adds water extracts 3 hours to remove pore-creating agent, completes purifying.
2) amidoximation
Dried copolymerization pearl body is added in the mixing solutions of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines that volume ratio is 1:2:1:0.5:1.5, then under stirring at normal temperature, oxammonium hydrochloride and sodium hydroxide is added, then react 14 hours under 70 DEG C of conditions, finally be cooled to 40 DEG C, obtain the reaction system containing solid; The solid of reaction system is separated to remove mother liquor, then add in solid mass concentration be 5% aqueous sodium hydroxide solution soak 10 hours, be finally washed to neutrality, namely complete that amidoximation is obtained adsorbs gallium resin; Wherein, the mass ratio of oxammonium hydrochloride and dried copolymerization pearl body is 0.9:1; The mol ratio of oxammonium hydrochloride and sodium hydroxide is 1:1, and the cumulative volume of mixing solutions is 3 times of dried copolymerization pearl body volume, and the aqueous sodium hydroxide solution added is 5 times of solid volume.
Analytical results resin wets volume density 0.72mg/L, wet true density 1.09mg/L, resin aqueous amount 58.5%, resin rate of expansion 11.8%, and the pregnant Bayer liquor through gallium content 200mg/L crosses post, absorption gallium 3.34g/L.
The present embodiment than adding poor solvent gasoline as pore-creating agent more in embodiment 1, have adjusted the rate of competing for speed of various raw material, obtain evengranular spherolite, the increase of initiator, shortens polymerization time.
Embodiment 3:
1) suspension polymerization
By vinylbenzene, vinyl cyanide, to divinylbenzene, adding by mass ratio after benzoyl peroxide is uniformly dissolved is the toluene of 0.5:0.4:0.1, the pore-creating agent of dimethylbenzene and gasoline composition, continue to stir in the there-necked flask that is placed on and adds the salt solution having dissolved methylene blue, and be 5% for the mass concentration of the salt solution dissolving methylene blue, then 60 DEG C are heated to, insulation reaction 2 hours, then 75 DEG C are warming up to, insulation reaction 3 hours, then 92 DEG C are warming up to, insulation reaction 4 hours, obtain the reaction solution containing copolymerization pearl body, copolymerization pearl body is separated from reaction solution, then purifying is also dry, obtain dry copolymerization pearl body, wherein, vinyl cyanide and cinnamic mol ratio are 1:0.5, are 8% of vinyl cyanide and vinylbenzene total mass to the quality of divinylbenzene, the quality of pore-creating agent be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 80%, the quality of methylene blue be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 1%, the quality of benzoyl peroxide be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 0.8%, the brine volume added be pore-creating agent, vinylbenzene, vinyl cyanide and to divinylbenzene cumulative volume 150%, and the method for purifying is: at 90 DEG C after being washed by isolated copolymerization pearl body, the boiling that adds water extracts 3 hours to remove pore-creating agent, completes purifying.
2) amidoximation
Dried copolymerization pearl body is added in the mixing solutions of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines that volume ratio is 1:2:1:0.5:1.5, then under stirring at normal temperature, oxammonium hydrochloride and sodium hydroxide is added, then react 10 hours under 65 DEG C of conditions, finally be cooled to 40 DEG C, obtain the reaction system containing solid; The solid of reaction system is separated to remove mother liquor, then add in solid mass concentration be 4.5% aqueous sodium hydroxide solution soak 5 hours, be finally washed to neutrality, namely complete that amidoximation is obtained adsorbs gallium resin; Wherein, the mass ratio of oxammonium hydrochloride and dried copolymerization pearl body is 0.9:1; The mol ratio of oxammonium hydrochloride and sodium hydroxide is 1:1, and the cumulative volume of mixing solutions is 3 times of dried copolymerization pearl body volume, and the aqueous sodium hydroxide solution added is 5 times of solid volume.
Analytical results resin wets volume density 0.73mg/L, wet true density 1.08mg/L, resin aqueous amount 60.1%, resin rate of expansion 13%, and the pregnant Bayer liquor through gallium content 200mg/L crosses post, absorption gallium 3.6g/L.
The present embodiment is compared with 2 with embodiment 1, and linking agent increases the consumption of divinylbenzene and pore-creating agent consumption, and the intensity of resin may be caused to increase specific surface area simultaneously to be increased, and finally improves the absorption property of resin.
Embodiment 4:
1) suspension polymerization
By vinylbenzene, vinyl cyanide, to divinylbenzene, adding by mass ratio after benzoyl peroxide is uniformly dissolved is the toluene of 0.5:0.3:0.2, the pore-creating agent of dimethylbenzene and gasoline composition, continue to stir in the there-necked flask that is placed on and adds the salt solution having dissolved methylene blue, and be 5% for the mass concentration of the salt solution dissolving methylene blue, then 65 DEG C are heated to, insulation reaction 2 hours, then 75 DEG C are warming up to, insulation reaction 3 hours, then 90 DEG C are warming up to, insulation reaction 5 hours, obtain the reaction solution containing copolymerization pearl body, copolymerization pearl body is separated from reaction solution, then purifying is also dry, obtain dry copolymerization pearl body, wherein, vinyl cyanide and cinnamic mol ratio are 1:0.5, are 8% of vinyl cyanide and vinylbenzene total mass to the quality of divinylbenzene, the quality of pore-creating agent be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 80%, the quality of methylene blue be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 1%, the quality of benzoyl peroxide be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 0.8%, the brine volume added be pore-creating agent, vinylbenzene, vinyl cyanide and to divinylbenzene cumulative volume 150%, and the method for purifying is: at 85 DEG C after being washed by isolated copolymerization pearl body, the boiling that adds water extracts 3 hours to remove pore-creating agent, completes purifying.
2) amidoximation
Dried copolymerization pearl body is added in the mixing solutions of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines that volume ratio is 1:2:1:0.5:1.5, then under stirring at normal temperature, oxammonium hydrochloride and sodium hydroxide is added, then react 12 hours under 75 DEG C of conditions, finally be cooled to 40 DEG C, obtain the reaction system containing solid; The solid of reaction system is separated to remove mother liquor, then add in solid mass concentration be 4.5% aqueous sodium hydroxide solution soak 8 hours, be finally washed to neutrality, namely complete that amidoximation is obtained adsorbs gallium resin; Wherein, the mass ratio of oxammonium hydrochloride and dried copolymerization pearl body is 0.8:1; The mol ratio of oxammonium hydrochloride and sodium hydroxide is 1:1, and the cumulative volume of mixing solutions is 3 times of dried copolymerization pearl body volume, and the aqueous sodium hydroxide solution added is 5 times of solid volume.
Analytical results resin wets volume density 0.72mg/L, wet true density 1.06mg/L, resin aqueous amount 62.3%, resin rate of expansion 14.7%, and the pregnant Bayer liquor through gallium content 200mg/L crosses post, absorption gallium 3.41g/L.
Change unlike the mass ratio between three kinds of pore-creating agents in the present embodiment and embodiment 3, add the weight ratio shared by non-benign agent gasoline, but the absorption property of final resin does not have the resin of synthesis in embodiment 3 high, this also just illustrates that the absorption property of this resin does not increase with the content increase of gasoline in pore-creating agent.
Embodiment 5:
1) suspension polymerization
By vinylbenzene, vinyl cyanide, to divinylbenzene, adding by mass ratio after benzoyl peroxide is uniformly dissolved is the toluene of 0.5:0.3:0.2, the pore-creating agent of dimethylbenzene and gasoline composition, continue to stir in the there-necked flask that is placed on and adds the salt solution having dissolved methylene blue, and be 5% for the mass concentration of the salt solution dissolving methylene blue, then 68 DEG C are heated to, insulation reaction 3 hours, then 75 DEG C are warming up to, insulation reaction 3 hours, then 95 DEG C are warming up to, insulation reaction 5 hours, obtain the reaction solution containing copolymerization pearl body, copolymerization pearl body is separated from reaction solution, then purifying is also dry, obtain dry copolymerization pearl body, wherein, vinyl cyanide and cinnamic mol ratio are 1:1, are 10% of vinyl cyanide and vinylbenzene total mass to the quality of divinylbenzene, the quality of pore-creating agent be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 80%, the quality of methylene blue be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 1%, the quality of benzoyl peroxide be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 1%, the brine volume added be pore-creating agent, vinylbenzene, vinyl cyanide and to divinylbenzene cumulative volume 150%, and the method for purifying is: at 85 DEG C after being washed by isolated copolymerization pearl body, the boiling that adds water extracts 3 hours to remove pore-creating agent, completes purifying.
2) amidoximation
Dried copolymerization pearl body is added in the mixing solutions of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines that volume ratio is 1:2:1:0.5:1.5, then under stirring at normal temperature, oxammonium hydrochloride and sodium hydroxide is added, then react 10 hours under 65 DEG C of conditions, finally be cooled to 40 DEG C, obtain the reaction system containing solid; The solid of reaction system is separated to remove mother liquor, then add in solid mass concentration be 4.5% aqueous sodium hydroxide solution soak 5 hours, be finally washed to neutrality, namely complete that amidoximation is obtained adsorbs gallium resin; Wherein, the mass ratio of oxammonium hydrochloride and dried copolymerization pearl body is 0.8:1; The mol ratio of oxammonium hydrochloride and sodium hydroxide is 1:1, and the cumulative volume of mixing solutions is 3 times of dried copolymerization pearl body volume, and the aqueous sodium hydroxide solution added is 5 times of solid volume.
Analytical results resin wets volume density 0.74mg/L, wet true density 1.04mg/L, and resin aqueous amount 63.5%, resin rate of expansion 15%, the pregnant Bayer liquor through gallium content 200mg/L crosses post, adsorptive capacity 3.12g/L.
From the present embodiment reaction, can see that polymerization time extends in process, polymerization temperature is higher, may because the change of proportioning raw materials causes two kinds of monomer reaction times to change, secondly the polymkeric substance that linking agent is obtained by reacting with too much vinylbenzene in reaction process can not bring functional group through amidoximation, thus the absorption property of resin do not have front four times good.
Embodiment 6:
1) suspension polymerization
By vinylbenzene, vinyl cyanide, to divinylbenzene, adding by mass ratio after benzoyl peroxide is uniformly dissolved is the toluene of 1:0.8:0.3, the pore-creating agent of dimethylbenzene and gasoline composition, continue to stir in the there-necked flask that is placed on and adds the salt solution having dissolved methylene blue, and be 5% for the mass concentration of the salt solution dissolving methylene blue, then 70 DEG C are heated to, insulation reaction 2.5 hours, then 75 DEG C are warming up to, insulation reaction 2 hours, then 95 DEG C are warming up to, insulation reaction 3 hours, obtain the reaction solution containing copolymerization pearl body, copolymerization pearl body is separated from reaction solution, then purifying is also dry, obtain dry copolymerization pearl body, wherein, vinyl cyanide and cinnamic mol ratio are 1:1.5, are 10% of vinyl cyanide and vinylbenzene total mass to the quality of divinylbenzene, the quality of pore-creating agent be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 70%, the quality of methylene blue be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 0.7%, the quality of benzoyl peroxide be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 1%, the brine volume added be pore-creating agent, vinylbenzene, vinyl cyanide and to divinylbenzene cumulative volume 200%, and the method for purifying is: at 85 DEG C after being washed by isolated copolymerization pearl body, the boiling that adds water extracts 6 hours to remove pore-creating agent, completes purifying.
2) amidoximation
Dried copolymerization pearl body is added in the mixing solutions of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines that volume ratio is 1:2:0.6:1:1.5, then under stirring at normal temperature, oxammonium hydrochloride and sodium hydroxide is added, then react 8 hours under 85 DEG C of conditions, finally be cooled to 40 DEG C, obtain the reaction system containing solid; The solid of reaction system is separated to remove mother liquor, then add in solid mass concentration be 4.5% aqueous sodium hydroxide solution soak 5 hours, be finally washed to neutrality, namely complete that amidoximation is obtained adsorbs gallium resin; Wherein, the mass ratio of oxammonium hydrochloride and dried copolymerization pearl body is 1:1; The mol ratio of oxammonium hydrochloride and sodium hydroxide is 1:1, and the cumulative volume of mixing solutions is 4 times of dried copolymerization pearl body volume, and the aqueous sodium hydroxide solution added is 5 times of solid volume.
Embodiment 7:
1) suspension polymerization
By vinylbenzene, vinyl cyanide, to divinylbenzene, adding by mass ratio after benzoyl peroxide is uniformly dissolved is the toluene of 1:0.6:0.4, the pore-creating agent of dimethylbenzene and gasoline composition, continue to stir in the there-necked flask that is placed on and adds the salt solution having dissolved methylene blue, and be 5% for the mass concentration of the salt solution dissolving methylene blue, then 70 DEG C are heated to, insulation reaction 2.5 hours, then 75 DEG C are warming up to, insulation reaction 2 hours, then 95 DEG C are warming up to, insulation reaction 6 hours, obtain the reaction solution containing copolymerization pearl body, copolymerization pearl body is separated from reaction solution, then purifying is also dry, obtain dry copolymerization pearl body, wherein, vinyl cyanide and cinnamic mol ratio are 1:1.5, are 10% of vinyl cyanide and vinylbenzene total mass to the quality of divinylbenzene, the quality of pore-creating agent be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 70%, the quality of methylene blue be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 0.7%, the quality of benzoyl peroxide be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 1%, the brine volume added be pore-creating agent, vinylbenzene, vinyl cyanide and to divinylbenzene cumulative volume 250%, and the method for purifying is: at 85 DEG C after being washed by isolated copolymerization pearl body, the boiling that adds water extracts 5 hours to remove pore-creating agent, completes purifying.
2) amidoximation
Dried copolymerization pearl body is added in the mixing solutions of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines that volume ratio is 1:1.6:0.5:0.5:1, then under stirring at normal temperature, oxammonium hydrochloride and sodium hydroxide is added, then react 15 hours under 85 DEG C of conditions, finally be cooled to 40 DEG C, obtain the reaction system containing solid; The solid of reaction system is separated to remove mother liquor, then add in solid mass concentration be 4.5% aqueous sodium hydroxide solution soak 5 hours, be finally washed to neutrality, namely complete that amidoximation is obtained adsorbs gallium resin; Wherein, the mass ratio of oxammonium hydrochloride and dried copolymerization pearl body is 1:1; The mol ratio of oxammonium hydrochloride and sodium hydroxide is 1:1, and the cumulative volume of mixing solutions is 3.5 times of dried copolymerization pearl body volume, and the aqueous sodium hydroxide solution added is 5 times of solid volume.
Embodiment 8:
1) suspension polymerization
By vinylbenzene, vinyl cyanide, to divinylbenzene, adding by mass ratio after benzoyl peroxide is uniformly dissolved is the toluene of 1:0.7:0.2, the pore-creating agent of dimethylbenzene and gasoline composition, continue to stir to be placed on to add and dissolved methylene blue and mass concentration is in the there-necked flask of the salt solution of the polyvinyl alcohol of 1%, and be 5% for dissolve methylene blue and mass concentration be the mass concentration of the salt solution of the polyvinyl alcohol of 1%, then 70 DEG C are heated to, insulation reaction 2.5 hours, then 75 DEG C are warming up to, insulation reaction 2 hours, then 95 DEG C are warming up to, insulation reaction 6 hours, obtain the reaction solution containing copolymerization pearl body, copolymerization pearl body is separated from reaction solution, then purifying is also dry, obtain dry copolymerization pearl body, wherein, vinyl cyanide and cinnamic mol ratio are 1:1.5, are 10% of vinyl cyanide and vinylbenzene total mass to the quality of divinylbenzene, the quality of pore-creating agent be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 70%, the quality of methylene blue be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 0.7%, the quality of benzoyl peroxide be vinylbenzene, vinyl cyanide and to divinylbenzene total mass 1%, the brine volume added be pore-creating agent, vinylbenzene, vinyl cyanide and to divinylbenzene cumulative volume 250%, and the method for purifying is: at 85 DEG C after being washed by isolated copolymerization pearl body, the boiling that adds water extracts 5 hours to remove pore-creating agent, completes purifying.
2) amidoximation
Dried copolymerization pearl body is added in the mixing solutions of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines that volume ratio is 1:1:1:1.5:1.2, then under stirring at normal temperature, oxammonium hydrochloride and sodium hydroxide is added, then react 15 hours under 85 DEG C of conditions, finally be cooled to 40 DEG C, obtain the reaction system containing solid; The solid of reaction system is separated to remove mother liquor, then add in solid mass concentration be 4.5% aqueous sodium hydroxide solution soak 5 hours, be finally washed to neutrality, namely complete that amidoximation is obtained adsorbs gallium resin; Wherein, the mass ratio of oxammonium hydrochloride and dried copolymerization pearl body is 1:1; The mol ratio of oxammonium hydrochloride and sodium hydroxide is 1:1, and the cumulative volume of mixing solutions is 3.5 times of dried copolymerization pearl body volume, and the aqueous sodium hydroxide solution added is 5 times of solid volume.
Above technical scheme by the selection to the selection of degree of crosslinking size, pore-creating agent, polymerization holding temperature and the selection of time, amidoximation medium and the selection of ratio, the selection etc. of amidoximation temperature and time improves amidoxim resin structure and functional group increases, improve the wetting ability of resin, prepare a kind of chelating resin special adsorbing gallium from pregnant Bayer liquor.The feature of resin prepared by the present invention is higher than the exchange capacity of existing amidoxim resin, and specific surface area is suitable for, and good hydrophilic property, has higher adsorption selectivity to gallium in pregnant Bayer liquor, is conducive to the adsorptive capacity improving gallium.Novel chelate resin prepared by the present invention has high absorbability and highly selective to gallium, the advantages such as the intensity of resin is good, long service life, constant product quality.And preparation method's technique of the present invention is simple, strong operability, cost are low, stability is high.
Claims (10)
1. adsorb a preparation method for gallium resin, it is characterized in that, comprise the following steps:
1) by vinylbenzene, vinyl cyanide, to divinylbenzene, pore-creating agent, benzoyl peroxide and salt solution mixing after, add dispersion agent again, be then heated to 60 DEG C-70 DEG C, insulation reaction 2-3 hour, then 75 DEG C-85 DEG C are warming up to, insulation reaction 2-4 hour, is then warming up to 90 DEG C-95 DEG C, insulation reaction 3-6 hour, obtain the reaction solution containing copolymerization pearl body, separated from reaction solution by copolymerization pearl body, then purifying is also dry, obtains dry copolymerization pearl body; Wherein, vinyl cyanide and cinnamic mol ratio are 1:(0.5-1.5), be the 6%-10% of vinyl cyanide and vinylbenzene total mass to the quality of divinylbenzene, the quality of pore-creating agent is vinylbenzene, vinyl cyanide and the 60%-80% to divinylbenzene total mass; The quality of dispersion agent is vinylbenzene, vinyl cyanide and the 0.5%-1% to divinylbenzene total mass;
2) dried copolymerization pearl body is carried out amidoximation, obtained absorption gallium resin.
2. the preparation method of absorption gallium resin according to claim 1, is characterized in that: described step 1) in the quality of benzoyl peroxide be vinylbenzene, vinyl cyanide and the 0.5%-1% to divinylbenzene total mass.
3. the preparation method of absorption gallium resin according to claim 1, is characterized in that: described step 1) in pore-creating agent be mixed by two or three in toluene, dimethylbenzene, gasoline.
4. the preparation method of absorption gallium resin according to claim 1, is characterized in that: described step 1) in dispersion agent be methylene blue and/or mass concentration be the polyvinyl alcohol of 1%.
5. the preparation method of absorption gallium resin according to claim 1, it is characterized in that, described step 1) in the method for purifying be: the boiling that adds water at 85 DEG C-100 DEG C after isolated copolymerization pearl body washing is extracted 3-6 hour to remove pore-creating agent, completes purifying.
6. the preparation method of absorption gallium resin according to claim 1, is characterized in that: described step 1) mesohalobic mass concentration is 5%.
7. the preparation method of absorption gallium resin according to claim 6, is characterized in that: described step 1) in the brine volume that adds be pore-creating agent, vinylbenzene, vinyl cyanide and the 150%-250% to divinylbenzene cumulative volume.
8. the preparation method of absorption gallium resin according to claim 1, is characterized in that, described step 2) process that dried copolymerization pearl body is carried out amidoximation is as follows:
Dried copolymerization pearl body is added in the mixing solutions of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines, then oxammonium hydrochloride and sodium hydroxide is under agitation added, then under 65 DEG C of-85 DEG C of conditions, react 8-15 hour, be finally cooled to 40 DEG C, obtain the reaction system containing solid; Be separated by the solid of reaction system, in solid, then add mass concentration is soak 5-10 hour in the aqueous sodium hydroxide solution of 4%-5%, is finally washed to neutrality, namely completes amidoximation; Wherein, the mass ratio of oxammonium hydrochloride and dried copolymerization pearl body is (0.8-1): 1; The mol ratio of oxammonium hydrochloride and sodium hydroxide is 1:1, and the cumulative volume of mixing solutions is 3-4 times of dried copolymerization pearl body volume; And the volume ratio of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines is 1:(1-2 in mixing solutions): (0.5-1): (0.5-1.5): (1-1.5).
9. the preparation method of absorption gallium resin according to claim 8, is characterized in that: in described mixing solutions, the volume ratio of ethylene dichloride, methyl alcohol, ethanol, water and four ethene triamines is 1:2:1:0.5:1.5.
10. the absorption gallium resin adopting the preparation method in claim 1 ~ 9 described in any one claim to prepare, it is characterized in that, its chemical structure is:
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| CN114920875B (en) * | 2022-06-15 | 2023-11-24 | 陕西海皓实业有限公司 | Preparation method of chelate resin for adsorbing gallium |
| CN115386127A (en) * | 2022-08-16 | 2022-11-25 | 陕西海皓实业有限公司 | Preparation method of gallium adsorption resin |
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