CN101875004B - Chelating resin special for adsorbing of gallium and preparation method and application thereof - Google Patents
Chelating resin special for adsorbing of gallium and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a chelating ion-exchange resin special for the adsorbing of gallium and a preparation method thereof. The chelating ion-exchange resin comprises the copolymer of styrene-divinylbenzene in the formulas (I) and (II) and is prepared by suspension polymerization. The method comprises the following steps of: mixing a cross linking agent, styrene, a porogenic agent, an initiator and water; performing the suspension polymerization on the mixture in the presence of a conventional dispersing agent; reacting the obtained product at the temperature of between 65 and 70 DEG C for 2 to 3h, at the temperature of between 75 and 80 DEG C for 2 to 4h and at the temperature of between 85 and 98 DEG C for 4 to 7h sequentially; and performing washing, chloridization, functionalization and amidoximation on the reaction product to obtain the chelating ion-exchange resin special for the adsorbing of the gallium. The method has the advantages of simple and short operation procedure, convenient operation, and no need of any reagents added into sodium aluminate solution, non-pollution and no waste during the adsorbing of the gallium.
Description
Technical field
The present invention relates to a kind of new type functional macromolecular compound, be specifically related to a kind of special-purpose chelating ion exchange resin of gallium that adsorbs, the invention still further relates to the preparation method and the application thereof of the special-purpose chelating ion exchange resin of above-mentioned absorption gallium.
Background technology
Gallium is a kind of rarer element, and important application is arranged in semi-conductor industry, thereby expection will increase the demand of gallium in the future, and the source of gallium is rare, more than its product from the accessory substance of aluminium industry etc.The method that from the Bayer mill solution, reclaims gallium is adopted in the extraction of gallium usually, and this is the method for universally acknowledged best recovery gallium.
The method that from bayer liquor, reclaims gallium has multiple, and commonly used at present have amalgam process, step-by-step precipitation method, solvent extraction, an ion-exchange etc.Amalgam process is to make negative electrode with mercury metal, electroextraction gallium from circulation fluid.In electrolytic process, gallium is separated out on the mercury metal negative electrode and is formed the gallium amalgam with mercury.After electrolysis contains gallium 0.3%-1.0% to amalgam, will contain gallium and be transferred to together in the closed reactor, add people NaOH and boil to closely boiling, gallium mercury is decomposed, just can obtain containing the NaGaO of gallium 10-60g/L
2Liquid, this rich Gallium solution can be produced gallium through electrolysis.But there is the shortcoming of the too big and mercury pollution of mercury use in this method.Step-by-step precipitation method is in circulating mother liquor, to feed carbon dioxide earlier to make the co-precipitation of gallium aluminium, uses milk of lime causticization dealuminzation again, and gallium is separated with aluminium; In containing Gallium solution, lead to people's carbon dioxide carbonating once more then; Just obtain to contain the sediment of gallium, behind this sediment of dissolution of sodium hydroxide, electrolysis promptly obtains gallium again; The major defect of this method is that the consumption of carbon dioxide is bigger, and can produce a large amount of calcium aluminate residues.Solvent extraction is to use extractant from sulphuric leachate, to reclaim and sows, and extractant commonly used mainly contains alkyl phosphoric acid, hydroxamic acid and mixed extractant.Alkyl phosphoric acid commonly used in the industry mainly contains single alkyl phosphonic acid and dialkyl group phosphoric acid, in extraction process, the hydrogen ion generation ion-exchange reactions in gallium ion and the phosphoric acid and with oxygen atom on lone pair electrons formation coordinate bond; In the low acidity solution of pH＞2; Above-mentioned two kinds of extractants can extract gallium effectively, but the easy hydrolysis of gallium in pH＞2 solution, if pH＜2; The extraction yield of gallium has only about 50%, but there is the high and with serious pollution problem of extract of cost in extraction.
CN1210099C discloses a kind of chelating resin special for adsorbing of gallium and preparation method, and this chelating resin special for adsorbing of gallium is on the basis of amidoxim chelating resin, through the selection of degree of cross linking size and the 3rd component and ratio; The selection of pore-foaming agent kind and ratio; The selection of polymerization temperature and temperature retention time; The selection of hydrolysising alkali concentration, reaction temperature and time; The selection in amidoxime reaction medium and ratio, reaction temperature and reaction time; To the improvement of amidoxim resin pore structure and the increase and the ratio adjustment of functional group; Improve zwitterion total exchange capacity and selected suitable resin specific area; And improve the hydrophily of resin, prepared a kind of from the Baeyer mother liquor chelating resin special of absorption gallium, but this resinoid exists that intensity is low, service life defective such as weak point, unstable properties.
Summary of the invention
Technical problem to be solved by this invention is that existing method existence of from bayer liquor, reclaiming gallium is polluted greatly, cost is high and produce a large amount of discarded objects; The invention provides a kind of special-purpose chelating ion exchange resin of gallium that adsorbs for this reason; It is brief that it has operating process; Easy to operate, need not in sodium aluminate solution, to add any reagent, pollution-free and do not produce any discarded object, and this kind resin has good characteristic such as adsorbance height, intensity are good, long service life, stable performance.
Another object of the present invention provides the preparation method of the special-purpose chelating ion exchange resin of above-mentioned absorption gallium.
Another object of the present invention provides the special-purpose chelating ion exchange resin of above-mentioned absorption gallium adsorbs gallium in the Bayer mother liquor application.
For realizing the foregoing invention purpose, technical scheme of the present invention is:
A kind of special-purpose chelating ion exchange resin of gallium that adsorbs, described chelating ion exchange resin contains the copolymer of the styrene-divinylbenzene of formula (I) and formula (II):
Wherein R is methylene or ethylidene.
A kind of method for preparing the special-purpose chelating ion exchange resin of absorption gallium, said method comprises the steps:
After crosslinking agent, styrene, pore-foaming agent, initator and water mixing; In the presence of conventional dispersant, carry out suspension polymerisation, reaction is 2-3 hour under 65 ℃ of-70 ℃ of temperature conditions; 75 ℃-80 ℃ reactions 2-4 hour; Reaction is 4-7 hour under 85 ℃ of-98 ℃ of conditions, and product makes the special-purpose chelating ion exchange resin of absorption gallium through washing, chlorination, functionalization and amidoxim reaction;
Said pore-foaming agent is the 120%-180% of crosslinking agent and styrene gross weight;
Said initator is the 0.8-1.0% of crosslinking agent and styrene gross weight;
Described water is the 238-300% of crosslinking agent, styrene and pore-foaming agent gross weight.
Described crosslinking agent is a divinylbenzene solution, and above-mentioned crosslinking agent is divinylbenzene solution.
Described pore-foaming agent is a kind of in isooctane, toluene, xylenes, the atoleine or several kinds mixture wherein; Described initator is benzoyl peroxide or azodiisobutyronitrile; Described dispersant is a gelatin, carboxymethyl cellulose, hydroxyethylcellulose, a kind of in polyvinyl alcohol or the sodium lignin sulfonate or several kinds mixture wherein.
Described washing is with after the product washing, places extract 3-6 hour, extracts pore-foaming agent, gets copolymer pearl body.
Described extract is an acetone, a kind of in ethanol or the benzinum or several kinds mixture wherein.
Described chlorination is at normal temperatures, with the product after the washing in chloromethyl ether swelling 2-3 hour, adds zinc chloride again, is warmed up to 38-46 ℃, is incubated 16-24 hour;
The mass ratio 1 of wherein said product and chloromethyl ether: 5-6;
The quality of said zinc chloride is the 0.8%-1.1% of product.
Described functionalization is in reactor, to add product, N, and N '-dimethyl formamide (DMF) and imino group dintrile stirred 20-50 hour at 95 ℃-115 ℃, preferably stirred 20-50 hour washing, drying at 100 ℃.
Described product and N, the volume ratio of N '-dimethyl formamide is 1: 3-6, the mass ratio of said product and imino group dintrile is 1: 2-5.
Described imino group dintrile is imido grpup diacetonitrile and/or iminodipropioditrile.
Described amidoxim reaction is dissolved in product in the 30-50wt% methanol aqueous solution; Stir and add hydroxylamine hydrochloride and alkali down; After approaching temperature 62-64 ℃ of refluxing reacted 10-20 hour, and be cooled to 30 ℃, adding alkali adjusting pH value was 12-13; Washing promptly obtains the special-purpose chelating ion exchange resin of absorption gallium to neutral;
Wherein the mass ratio of product and hydroxylamine hydrochloride is 1: 0.5-2.0;
The mol ratio of described hydroxylamine hydrochloride and alkali is 1: 1.
Described alkali is NaOH or caustic alcohol or sodium carbonate.
A kind of described chelating resin special for adsorbing of gallium adsorbs the application of gallium in the Bayer mother liquor.
Particularly, the present invention is adsorbed the special-purpose chelating ion exchange resin of gallium and is adopted and be prepared as follows step:
(1) suspension polymerisation: after crosslinking agent divinylbenzene, styrene, pore-foaming agent, initator and water mixing; In the presence of conventional dispersant; Carry out suspension polymerisation, reaction was 2-3 hour under 65 ℃ of-70 ℃ of temperature conditions, 75 ℃-80 ℃ reactions 2-4 hour; Under 85 ℃ of-98 ℃ of conditions the reaction 4-7 hour, wash then copolymerization pearl body (1);
Described pore-foaming agent is a kind of in isooctane, toluene, xylenes, the atoleine or several kinds mixture wherein, and said pore-foaming agent is the 120%-180% of crosslinking agent and styrene gross weight; Described initator is benzoyl peroxide or azodiisobutyronitrile, and said initator is the 0.8-1% of crosslinking agent and styrene gross weight; Described dispersant is a gelatin, carboxymethyl cellulose, hydroxyethylcellulose, a kind of in polyvinyl alcohol or the sodium lignin sulfonate or several kinds mixture wherein.
Described water is pure water or salt solution, and its consumption is the 250-300% of crosslinking agent, styrene and pore-foaming agent gross weight.
(2) extract dry: use acetone, the pore-foaming agent in the extraction copolymerization pearl bodies (1) such as ethanol and benzinum gets copolymerization pearl body (2), to copolymerization pearl body (2) wash and carry out dry must copolymerization pearl body (3).
(3) chlorination: under the normal temperature, copolymerization pearl body (3) in chloromethyl ether swelling 2-3 hour, the mass ratio 1 of copolymerization pearl body (3) and chloromethyl ether: 5-6.Add the zinc chloride that accounts for copolymerization pearl body (3) quality 0.8%-1.1% afterwards, be warmed up to 38-46 ℃, be incubated 16-24 hour.Product is washed processing obtain copolymerization pearl body (4).
(4) functionalization: add the N of 3-6 times of copolymerization pearl body (4) volume in the reactor, the imido grpup diacetonitrile of N '-dimethyl formamide (DMF) and 2-5 times of copolymerization pearl body (4) quality or in the iminodipropioditrile one or both.Stirred washing, the dry copolymerization pearl body (5) that gets 20-50 hour in 100 ℃.
(5) amidoxim reaction: copolymerization pearl body (5) carries out the amidoxim reaction in the 30-50wt% methanol aqueous solution, stirs to add hydroxylamine hydrochloride down, and the mole dosage of hydroxylamine hydrochloride is 1.5-2.5 a times of copolymer pearl body; Mol alkali such as adding again; Like NaOH or caustic alcohol or sodium carbonate, make azanol free, reacting 10-20 hour near temperature 62-64 ℃ that refluxes; After being cooled to 30 ℃; Adding NaOH is adjusted to the pH value and is 12-13, and washing is extremely neutral again, i.e. the special-purpose chelating ion exchange resin of acquisition absorption gallium.
The special-purpose chelating ion exchange resin total exchange capacity of the absorption gallium of the present invention preparation is higher than existing amidoxim resin, and is except to being adsorbed with the higher selectivity of gallium in the Bayer mother liquor, also higher to the adsorbance of gallium.This resin zwitterion exchange capacity >=6.0mmol/g; In mother liquor, under the gallium content 200mg/l condition, inhale the gallium amount all more than 3.5g/l.Therefore novel chelate resin of the present invention is a kind of gallium to be had high adsorption and high selectivity dedicated ion exchange resin; Stability is high; Strong operability, constant product quality, and this kind resin has good characteristic such as adsorbance height, intensity are good, long service life, stable performance.
The specific embodiment
Below in conjunction with embodiment the present invention is done further explanation.
Embodiment 1
A kind of special-purpose chelating ion exchange resin of gallium that adsorbs, its preparation method is:
(1) suspension polymerisation
65.63% divinylbenzene 137kg, styrene 163kg, isooctane 120kg, toluene 120kg, atoleine 120kg, benzoyl peroxide 2.56kg mixes, and places agitated reactor.Add the water 2000L dissolved the dispersant gelatin, carry out suspension polymerisation, each grade temperature retention time be respectively 65 ℃ 3 hours, 75 ℃ 2 hours, 90 ℃ 4 hours, wash then copolymerization pearl body (1);
Wherein said pore-foaming agent is the mixture of isooctane, toluene and atoleine, and its consumption is 120% of crosslinking agent divinylbenzene and a styrene gross weight, and specific algorithm is: (120+120+120) ÷ (137+163) * 100%=120%.
Said initator benzoyl peroxide is 0.85% of crosslinking agent divinylbenzene and a styrene gross weight, and concrete computational methods are: 2.56 ÷ (137+163) * 100%=0.85%;
Described water is 300% of crosslinking agent divinylbenzene, styrene and pore-foaming agent gross weight, and concrete computational methods are: 2000 ÷ (137+163+120+120+120) * 100%=300%.
(2) washing
Copolymerization pearl body (1) was placed extract acetone 3 hours, extract pore-foaming agent and get copolymerization pearl body (2),, wash and the dry copolymerization pearl body (3) that gets copolymerization pearl body (2);
(3) chlorination
Under the normal temperature, get 100kg copolymerization pearl body (3) swelling 2 hours in the 500L chloromethyl ether.The zinc chloride that adds 0.8kg afterwards is warmed up to 38 ℃, is incubated 16 hours.Product is washed processing obtain copolymerization pearl body (4).
(4) functionalization
Get 100kg copolymerization pearl body (4) and place agitated reactor, add the N of 500L, N '-dimethyl formamide (DMF) and 300kg imido grpup diacetonitrile stirred washing afterwards, the dry again copolymerization pearl body (5) that gets 20 hours in 100 ℃.
(5) amidoxim reaction
Get 100kg copolymerization pearl body (5) and place agitated reactor, add the 30wt% methanol aqueous solution of 400L, normal temperature condition is thought; Stir adding 50kg hydroxylamine hydrochloride, the NaOH that adds 28.8kg afterwards made azanol free, 64 ℃ of reactions of the approaching temperature that refluxes 10 hours; After being cooled to 30 ℃; Adding naoh treatment to pH value is 12-13, and washing promptly obtains the special-purpose chelating ion exchange resin of absorption gallium to neutral again;
Wherein copolymerization pearl body (5) is 1: 0.5 with the mass ratio of hydroxylamine hydrochloride;
The mol ratio of described hydroxylamine hydrochloride and alkali is 1: 1.
Embodiment 2
A kind of special-purpose chelating ion exchange resin of gallium that adsorbs, its preparation method is:
(1) suspension polymerisation
65.63% divinylbenzene 137kg, styrene 163kg, isooctane 240kg, xylenes 240kg, atoleine 60kg, azodiisobutyronitrile 3kg mixes, and places agitated reactor.Add the salt solution 2000L dissolved the dispersant hydroxyethylcellulose, carry out suspension polymerisation, each grade temperature retention time be respectively 70 ℃ 2 hours, 80 ℃ 2 hours, 98 ℃ 7 hours, wash then copolymerization pearl body (1)
Wherein said pore-foaming agent is the mixture of isooctane, xylenes and atoleine, and its consumption is 180% of crosslinking agent divinylbenzene and a styrene gross weight, and specific algorithm is: (240+240+60) ÷ (137 *+163) * 100%=180%.
Said initator azodiisobutyronitrile is 1% of crosslinking agent divinylbenzene and a styrene gross weight, and concrete computational methods are: 3 ÷ (137+163) * 100%=1%;
Described water is 238% of crosslinking agent divinylbenzene, styrene and pore-foaming agent gross weight, and concrete computational methods are: 2000 ÷ (137+163+240+240+60) * 100%=238%.。
(2) washing
Copolymerization pearl body (1) was placed extract ethanol 6 hours, extract pore-foaming agent and get copolymerization pearl body (2),, wash and the dry copolymerization pearl body (3) that gets copolymerization pearl body (2);
(3) chlorination
Under the normal temperature, get 100kg copolymerization pearl body (3) swelling 3 hours in the 500L chloromethyl ether.The zinc chloride that adds 1kg afterwards is warmed up to 46 ℃, is incubated 24 hours.Product is washed processing obtain copolymerization pearl body (4).
(4) functionalization
Get 100kg copolymerization pearl body (4) and place agitated reactor, add the N of 500L, N '-dimethyl formamide (DMF) and 500kg iminodipropioditrile stirred washing afterwards, the dry again copolymerization pearl body (5) that gets 50 hours in 100 ℃.
(5) amidoxim reaction
Get 100kg copolymerization pearl body (5) and place agitated reactor, add the 50wt% methanol aqueous solution of 500L, carry out the amidoxim reaction.Normal temperature; Stir adding 200kg hydroxylamine hydrochloride down, the NaOH that adds 115.2kg afterwards made azanol free, 62 ℃ of reactions of the approaching temperature that refluxes 20 hours; After being cooled to 30 ℃; Adding naoh treatment to pH value is 12-13, and washing promptly obtains the special-purpose chelating ion exchange resin of absorption gallium to neutral again;
Wherein copolymerization pearl body (5) is 1: 2.0 with the mol ratio of hydroxylamine hydrochloride;
The mol ratio of described hydroxylamine hydrochloride and alkali is 1: 1.
Embodiment 3
A kind of special-purpose chelating ion exchange resin of gallium that adsorbs, its preparation method is:
(1) suspension polymerisation
65.63% divinylbenzene 45.7kg, styrene 254.3kg, isooctane 105kg, toluene 105kg, xylenes 105kg, atoleine 105kg, each 1.5kg of benzoyl peroxide and azodiisobutyronitrile mixes, and places agitated reactor.Add the salt solution 2000L of the good polyethylene of dispersing agent alcohol of dissolving, carry out suspension polymerisation, each grade temperature retention time be respectively 70 ℃ 2 hours, 85 ℃ 2 hours, 95 ℃ 5 hours, wash then copolymerization pearl body (1);
Wherein said pore-foaming agent is the mixture of isooctane, toluene, xylenes and atoleine, and its consumption is 140% of crosslinking agent divinylbenzene and a styrene gross weight, and specific algorithm is: (105+105+105+105) ÷ (45.7+254.3) * 100%=140%.
Said initator benzoyl peroxide and azodiisobutyronitrile are 1% of crosslinking agent divinylbenzene and styrene gross weight, and concrete computational methods are: (1.5+1.5) ÷ (45.7+254.3) * 100%=1%;
Described water is 278% of crosslinking agent divinylbenzene, styrene and pore-foaming agent gross weight, and concrete computational methods are: 2000 ÷ (45.7+254.3+105+105+105+105) * 100%=278%.
(2) washing
Copolymerization pearl body (1) was placed the extract benzinum 5 hours, extract pore-foaming agent and get copolymerization pearl body (2),, wash and the dry copolymerization pearl body (3) that gets copolymerization pearl body (2);
(3) chlorination
Under the normal temperature, get 100kg copolymerization pearl body (3) swelling 2.5 hours in the 500L chloromethyl ether.The zinc chloride that adds 0.8kg afterwards is warmed up to 40 ℃, is incubated 20 hours.Product is washed processing obtain copolymerization pearl body (4).
(4) functionalization
Get 100kg copolymerization pearl body (4) and place agitated reactor, add the N of 500L, N '-dimethyl formamide (DMF) and 400kg imido grpup diacetonitrile stirred washing afterwards, the dry again copolymerization pearl body (5) that gets 40 hours in 100 ℃.
(5) amidoxim reaction
Get 100kg copolymerization pearl body (5) and place agitated reactor, add the 40wt% methanol aqueous solution of 500L, carry out the amidoxim reaction.Normal temperature; Stir adding 100kg hydroxylamine hydrochloride down, the NaOH that adds 57.6kg afterwards made azanol free, 63 ℃ of reactions of the approaching temperature that refluxes 18 hours; After being cooled to 30 ℃; Adding naoh treatment to pH value is 12-13, and washing promptly obtains the special-purpose chelating ion exchange resin of absorption gallium to neutral again;
Wherein copolymerization pearl body (5) is 1: 1 with the mass ratio of hydroxylamine hydrochloride;
The mol ratio of described hydroxylamine hydrochloride and alkali is 1: 1.
Embodiment 4
A kind of special-purpose chelating ion exchange resin of gallium that adsorbs, its preparation method is:
(1) suspension polymerisation
65.63% divinylbenzene 91.4kg, styrene 208.6kg, toluene 330kg, atoleine 150kg, benzoyl peroxide 2.5kg mixes, and places agitated reactor.Add the pure water 2000L dissolved the carboxymethyl cellulose dispersant, carry out suspension polymerisation, each grade temperature retention time be respectively 70 ℃ 2.5 hours, 80 ℃ 2 hours, 85 ℃ 6 hours, wash then copolymerization pearl body (1);
Wherein said pore-foaming agent is the mixture of toluene and atoleine, and its consumption is 160% of crosslinking agent divinylbenzene and a styrene gross weight, and specific algorithm is: (330+150) ÷ (91.4+208.6) * 100%=160%.
Said initator Oxybenzene formyl is 0.83% of crosslinking agent divinylbenzene and a styrene gross weight, and concrete computational methods are: 2.5 ÷ (91.4+208.6) * 100%=0.83%;
Described water is 256% of crosslinking agent divinylbenzene, styrene and pore-foaming agent gross weight, and concrete computational methods are: 2000 ÷ (91.4+208.6+330+150) * 100%=256%.
(2) washing
Copolymerization pearl body (1) is placed extract acetone, in the benzinum 4 hours, extract pore-foaming agent and get copolymerization pearl body (2), to copolymerization pearl body (2), wash and dry copolymerization pearl body (3);
(3) chlorination
Under the normal temperature, get 100kg copolymerization pearl body (3) swelling 3 hours in the 600L chloromethyl ether.The zinc chloride that adds 0.9kg afterwards is warmed up to 44 ℃, is incubated 16 hours.Product is washed processing obtain copolymerization pearl body (4).
(4) functionalization
Get 100kg copolymerization pearl body (4) and place agitated reactor, add the N of 500L, N '-dimethyl formamide (DMF) and 440kg imido grpup diacetonitrile stirred washing afterwards, the dry again copolymerization pearl body (5) that gets 35 hours in 100 ℃.
(5) amidoxim reaction
Get 100kg copolymerization pearl body (5) and place agitated reactor, add the 45wt% methanol aqueous solution of 500L, carry out the amidoxim reaction.Normal temperature; Stir adding 80kg hydroxylamine hydrochloride down, the NaOH that adds 46.0kg afterwards made azanol free, 62 ℃ of reactions of the approaching temperature that refluxes 16 hours; After being cooled to 30 ℃; Adding naoh treatment to pH value is 12-13, and washing promptly obtains the special-purpose chelating ion exchange resin of absorption gallium to neutral again;
Wherein copolymerization pearl body (5) is 1: 0.8 with the mol ratio of hydroxylamine hydrochloride;
The mol ratio of described hydroxylamine hydrochloride and alkali is 1: 1.
Embodiment 5
A kind of special-purpose chelating ion exchange resin of gallium that adsorbs, its preparation method is:
(1) suspension polymerisation
65.63% divinylbenzene 68.6kg, styrene 231.4kg, toluene 270kg, atoleine 150kg, benzoyl peroxide 2.4kg mixes, and places agitated reactor.Add the pure water 2160L dissolved the dispersant gelatin, carry out suspension polymerisation, each grade temperature retention time be respectively 70 ℃ 2.5 hours, 80 ℃ 5.5 hours, 90 ℃ 4.5 hours, wash then copolymerization pearl body (1);
Wherein said pore-foaming agent is the mixture of toluene and atoleine, and its consumption is 140% of crosslinking agent divinylbenzene and a styrene gross weight, and specific algorithm does; (270+150) ÷ (68.6+231.4) * 100%=140%.
Said initator Oxybenzene formyl is 0.8% of crosslinking agent divinylbenzene and a styrene gross weight, and concrete computational methods are: 2.4 ÷ (68.6 *+231.4) * 100%=0.8%;
Described water is 300% of crosslinking agent divinylbenzene, styrene and pore-foaming agent gross weight, and concrete computational methods are: 2160 ÷ (68.6+231.4+270+150) * 100%=300%.
(2) washing
Copolymerization pearl body (1) is placed extract acetone, in the benzinum 5 hours, extract pore-foaming agent and get copolymerization pearl body (2), to copolymerization pearl body (2), wash and dry copolymerization pearl body (3);
(3) chlorination
Under the normal temperature, get 100kg copolymerization pearl body (3) swelling 2.3 hours in the 600L chloromethyl ether.The zinc chloride that adds 1.1kg afterwards is warmed up to 45 ℃, is incubated 20 hours.Product is washed processing obtain copolymerization pearl body (4).
(4) functionalization
Get 100kg copolymerization pearl body (4) and place agitated reactor, add the N of 600L, N '-dimethyl formamide (DMF) and 200kg imido grpup diacetonitrile stirred washing afterwards, the dry again copolymerization pearl body (5) that gets 35 hours in 100 ℃.
(5) amidoxim reaction
Get 100kg copolymerization pearl body (5) and place agitated reactor, add the 45wt% methanol aqueous solution of 500L, carry out the amidoxim reaction.Normal temperature; Stir adding 150kg hydroxylamine hydrochloride down, the NaOH that adds 86.3kg afterwards made azanol free, 62 ℃ of reactions of the approaching temperature that refluxes 16 hours; After being cooled to 30 ℃; Adding naoh treatment to pH value is 12-13, and washing promptly obtains the special-purpose chelating ion exchange resin of absorption gallium to neutral again;
Wherein copolymerization pearl body (5) is 1: 1.5 with the mass ratio of hydroxylamine hydrochloride;
The mol ratio of described hydroxylamine hydrochloride and alkali is 1: 1.
Embodiment is used to further specify the present invention, instructs those skilled in the art to realize the present invention, can not be interpreted as the restriction to protection domain of the present invention.
Claims (12)
1. one kind prepares the method for adsorbing the special-purpose chelating ion exchange resin of gallium, and said method comprises the steps:
After crosslinking agent, styrene, pore-foaming agent, initator and water mixing; In the presence of conventional dispersant, carry out suspension polymerisation, reaction is 2-3 hour under 65 ℃ of-70 ℃ of temperature conditions; 75 ℃-80 ℃ reactions 2-4 hour; Reaction is 4-7 hour under 85 ℃ of-98 ℃ of conditions, and product makes the special-purpose chelating ion exchange resin of absorption gallium through washing, chlorination, functionalization and amidoxim reaction;
Described crosslinking agent is a divinylbenzene solution;
Said pore-foaming agent is the 120%-180% of crosslinking agent and styrene gross weight;
Said initator is the 0.8-1.0% of crosslinking agent and styrene gross weight;
Described water is the 238-300% of crosslinking agent, styrene and pore-foaming agent gross weight;
Described washing is with after the product washing, places extract 3-6 hour, extracts pore-foaming agent, gets copolymer;
Described chlorination is at normal temperatures, with the product after the washing in chloromethyl ether swelling 2-3 hour, adds zinc chloride again, is warmed up to 38-46 ℃, is incubated 16-24 hour;
Described functionalization is in reactor, to add product, N, and N '-dimethyl formamide (DMF) and imino group dintrile stirred 20-50 hour washing, drying at 95 ℃-115 ℃;
Described amidoxim reaction is dissolved in product in the 30-50 wt% methanol aqueous solution; Stir and add hydroxylamine hydrochloride and alkali down; After approaching temperature 62-64 ℃ of refluxing reacted 10-20 hour, and be cooled to 30 ℃, adding alkali adjusting pH value was 12-13; Washing promptly obtains the special-purpose chelating ion exchange resin of absorption gallium to neutral.
2. method according to claim 1 is characterized in that described pore-foaming agent is a kind of in isooctane, toluene, xylenes, the atoleine or several kinds mixture wherein.
3. method according to claim 1 is characterized in that described initator is benzoyl peroxide or azodiisobutyronitrile.
4. method according to claim 1 is characterized in that described dispersant is a gelatin, carboxymethyl cellulose, hydroxyethylcellulose, a kind of in polyvinyl alcohol or the sodium lignin sulfonate or several kinds mixture wherein.
5. method according to claim 1 is characterized in that the extract in the said washing step is an acetone, a kind of in ethanol or the benzinum or several kinds mixture wherein.
6. according to the described method of claim 1, it is characterized in that in the said chlorinating step mass ratio 1:5-6 of product and chloromethyl ether; The quality of said zinc chloride is the 0.8%-1.1% of product.
7. method according to claim 1 is characterized in that in the described functionalization step, product and N, and the volume ratio of N '-dimethyl formamide is 1: 3-6, the mass ratio of said product and imino group dintrile is 1: 2-5.
8. method according to claim 7 is characterized in that described imino group dintrile is iminodiacetonitrile and/or iminobis-propanenitrile.
9. method according to claim 1 is characterized in that in the said amidoxim step,
The mass ratio of product and hydroxylamine hydrochloride is 1: 0.5-2.0; The mol ratio of hydroxylamine hydrochloride and alkali is 1: 1.
10. method according to claim 9 is characterized in that described alkali is NaOH or caustic alcohol or sodium carbonate.
11. method according to claim 1 is characterized in that:
Described pore-foaming agent is a kind of in isooctane, toluene, xylenes, the atoleine or several kinds mixture wherein;
Described initator is benzoyl peroxide or azodiisobutyronitrile;
Described dispersant is a gelatin, carboxymethyl cellulose, hydroxyethylcellulose, a kind of in polyvinyl alcohol or the sodium lignin sulfonate or several kinds mixture wherein;
Extract in the said washing step is an acetone, a kind of in ethanol or the benzinum or several kinds mixture wherein;
In the said chlorinating step, the mass ratio 1:5-6 of product and chloromethyl ether; The quality of said zinc chloride is the 0.8%-1.1% of product;
In the described functionalization step, product and N, the volume ratio of N '-dimethyl formamide is 1: 3-6, the mass ratio of said product and imino group dintrile is 1: 2-5; Described imino group dintrile is iminodiacetonitrile and/or iminobis-propanenitrile;
In the said amidoxim step, the mass ratio of product and hydroxylamine hydrochloride is 1: 0.5-2.0; The mol ratio of hydroxylamine hydrochloride and alkali is 1: 1; Described alkali is NaOH or caustic alcohol or sodium carbonate.
12. the special-purpose chelating ion exchange resin of absorption gallium for preparing according to the described method of arbitrary claim among the claim 1-11 adsorbs gallium in the Bayer mother liquor application.
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| CN103012644B (en) * | 2012-11-27 | 2016-02-24 | 安徽皖东化工有限公司 | The preparation method of superacicd styrene system exchange resin |
| CN103894241B (en) * | 2013-10-28 | 2016-04-20 | 上海长翊科技股份有限公司 | Non-alkaline gallium ion exchanger resin |
| 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 |
| CN106824138A (en) * | 2017-03-21 | 2017-06-13 | 四川大学 | A kind of cross-linking type polyacrylonitrile-radical amidoxim fiber and its preparation method and application |
| JP6904563B2 (en) * | 2017-08-25 | 2021-07-21 | 国立研究開発法人森林研究・整備機構 | Method of manufacturing composite particles and composite particles obtained by the manufacturing method |
| CN109776744B (en) * | 2019-01-12 | 2021-08-03 | 广西大学 | Preparation method of amidoxime-silicon dioxide resin for adsorbing gallium |
| CN110818830B (en) * | 2019-11-29 | 2021-08-17 | 广东先导稀材股份有限公司 | Amidoxime group-containing polymer, and preparation method and application thereof |
| CN111675782A (en) * | 2020-03-03 | 2020-09-18 | 南京浩普新材料科技有限公司 | Special chelate resin for adsorbing gallium and preparation method thereof |
| CN112642411B (en) * | 2020-12-17 | 2023-05-05 | 江苏大学 | Preparation method and application of porous/ion-rich channel microsphere adsorbent |
| CN113546611A (en) * | 2021-07-23 | 2021-10-26 | 江苏金杉新材料有限公司 | Preparation method of porous adsorption resin |
| CN115286789B (en) * | 2022-07-29 | 2023-08-11 | 扬州中天利新材料股份有限公司 | Chelating resin special for adsorbing gallium and preparation method |
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| CN101538659A (en) * | 2008-03-21 | 2009-09-23 | 北京合创同盛科技有限公司 | Method for recovering metal gallium |
| CN101735372A (en) * | 2009-12-28 | 2010-06-16 | 西安蓝晓科技有限公司 | Novel chelate resin and production method and application thereof |
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| JPS5842737A (en) * | 1981-09-07 | 1983-03-12 | Unitika Ltd | Recovering method for gallium |
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| CN101538659A (en) * | 2008-03-21 | 2009-09-23 | 北京合创同盛科技有限公司 | Method for recovering metal gallium |
| CN101735372A (en) * | 2009-12-28 | 2010-06-16 | 西安蓝晓科技有限公司 | Novel chelate resin and production method and application thereof |
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