CN101875004A - 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
- Publication number
- CN101875004A CN101875004A CN2010102069643A CN201010206964A CN101875004A CN 101875004 A CN101875004 A CN 101875004A CN 2010102069643 A CN2010102069643 A CN 2010102069643A CN 201010206964 A CN201010206964 A CN 201010206964A CN 101875004 A CN101875004 A CN 101875004A
- Authority
- CN
- China
- Prior art keywords
- gallium
- product
- styrene
- exchange resin
- hour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 69
- 229920001429 chelating resin Polymers 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title abstract description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 66
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 32
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 32
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims abstract description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 48
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 239000004088 foaming agent Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 20
- 239000000284 extract Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims description 11
- 238000005660 chlorination reaction Methods 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 235000005074 zinc chloride Nutrition 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- CSIFGMFVGDBOQC-UHFFFAOYSA-N 3-iminobutanenitrile Chemical compound CC(=N)CC#N CSIFGMFVGDBOQC-UHFFFAOYSA-N 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 108010010803 Gelatin Proteins 0.000 claims description 5
- 229920000159 gelatin Polymers 0.000 claims description 5
- 239000008273 gelatin Substances 0.000 claims description 5
- 235000019322 gelatine Nutrition 0.000 claims description 5
- 235000011852 gelatine desserts Nutrition 0.000 claims description 5
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- BSRDNMMLQYNQQD-UHFFFAOYSA-N iminodiacetonitrile Chemical compound N#CCNCC#N BSRDNMMLQYNQQD-UHFFFAOYSA-N 0.000 claims 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 abstract description 2
- 238000010557 suspension polymerization reaction Methods 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 description 68
- 238000000205 computational method Methods 0.000 description 10
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 229910000497 Amalgam Inorganic materials 0.000 description 4
- -1 alkyl phosphoric acid Chemical compound 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical group [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical compound C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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 chelating ion exchange resin that adsorbs the gallium special use, the invention still further relates to the preparation method and the application thereof of the chelating ion exchange resin of above-mentioned absorption gallium special use.
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, the source rareness of gallium, more than its product from the accessory substance of aluminium industry etc.The method that reclaims gallium from the Bayer mill solution is adopted in the extraction of gallium usually, and this is the method for universally acknowledged best recovery gallium.
The method that reclaims gallium from bayer liquor 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 to feed carbon dioxide earlier to make the co-precipitation of gallium aluminium in circulating mother liquor, use milk of lime causticization dealuminzation again, 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 to reclaim from sulphuric leachate and sows, and extractant commonly used mainly contains alkyl phosphoric acid, hydroxamic acid and mixed extractant.Industrial alkyl phosphoric acid commonly used mainly contains single alkyl phosphonic acid and dialkyl group phosphoric acid, in extraction process, hydrogen ion generation ion-exchange reactions in gallium ion and the phosphoric acid also forms coordinate bond with lone pair electrons on the oxygen atom, 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, by 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 the hydrophily of raising 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 reclaiming gallium from bayer liquor is polluted greatly, cost is high and produce a large amount of discarded objects, the invention provides a kind of chelating ion exchange resin that adsorbs the gallium special use 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 chelating ion exchange resin of above-mentioned absorption gallium special use.
Another object of the present invention provides the chelating ion exchange resin of above-mentioned absorption gallium special use adsorbs gallium in the Bayer mother liquor application.
For achieving the above object, technical scheme of the present invention is:
A kind of chelating ion exchange resin that adsorbs the gallium special use, described chelating ion exchange resin contain 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 chelating ion exchange resin of absorption gallium special use, described 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 pore-foaming agent is the 120%-180% of crosslinking agent and styrene gross weight;
Described 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 or wherein several mixture in isooctane, toluene, dimethylbenzene, the atoleine; Described initator is benzoyl peroxide or azodiisobutyronitrile; Described dispersant is a gelatin, carboxymethyl cellulose, hydroxyethylcellulose, a kind of or wherein several mixture in polyvinyl alcohol or the sodium lignin sulfonate.
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 or wherein several mixture in ethanol or the benzinum.
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 described zinc chloride is the 0.8%-1.1% of product.
Described functionalization is to add product, N in reactor, 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 described 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, reacting 10-20 hour near temperature 62-64 ℃ that refluxes, after being cooled to 30 ℃, adding alkali adjusting pH value is 12-13, be washed to neutrality, promptly obtain the special-purpose chelating ion exchange resin of absorption gallium;
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's chelating ion exchange resin of adsorbing the gallium special use adopts and to 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 is 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 or wherein several mixture in isooctane, toluene, dimethylbenzene, the atoleine, and described pore-foaming agent is the 120%-180% of crosslinking agent and styrene gross weight; Described initator is benzoyl peroxide or azodiisobutyronitrile, and described initator is the 0.8-1% of crosslinking agent and styrene gross weight; Described dispersant is a gelatin, carboxymethyl cellulose, hydroxyethylcellulose, a kind of or wherein several mixture in polyvinyl alcohol or the sodium lignin sulfonate.
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, stir and add hydroxylamine hydrochloride down, the mole dosage of hydroxylamine hydrochloride is 1.5-2.5 a times of copolymer pearl body, mol alkali such as adding again, as 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, be washed to neutrality again, promptly obtain the special-purpose chelating ion exchange resin of absorption gallium.
The chelating ion exchange resin total exchange capacity of the absorption gallium special use 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
The present invention is described further below in conjunction with embodiment.
Embodiment 1
A kind of chelating ion exchange resin that adsorbs the gallium special use, 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 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%.
Described 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 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 reactor, the 30wt% methanol aqueous solution that adds 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, is washed to neutrality again, promptly obtains the special-purpose chelating ion exchange resin of absorption gallium;
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 chelating ion exchange resin that adsorbs the gallium special use, its preparation method is:
(1) suspension polymerisation
65.63% divinylbenzene 137kg, styrene 163kg, isooctane 240kg, dimethylbenzene 240kg, atoleine 60kg, azodiisobutyronitrile 3kg mixes, and places 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, dimethylbenzene 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%.
Described 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 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 reactor, add the 50wt% methanol aqueous solution of 500L, carry out the amidoxim reaction.Normal temperature, stir and add the 200kg hydroxylamine hydrochloride down, the NaOH that adds 115.2kg afterwards makes azanol free, reacting 20 hours for 62 ℃ near the temperature that refluxes, after being cooled to 30 ℃, adding naoh treatment to pH value is 12-13, is washed to neutrality again, promptly obtains the special-purpose chelating ion exchange resin of absorption gallium;
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 chelating ion exchange resin that adsorbs the gallium special use, its preparation method is:
(1) suspension polymerisation
65.63% divinylbenzene 45.7kg, styrene 254.3kg, isooctane 105kg, toluene 105kg, dimethylbenzene 105kg, atoleine 105kg, each 1.5kg of benzoyl peroxide and azodiisobutyronitrile mixes, and places 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, dimethylbenzene and atoleine, 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%.
Described 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 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 reactor, add the 40wt% methanol aqueous solution of 500L, carry out the amidoxim reaction.Normal temperature, stir and add the 100kg hydroxylamine hydrochloride down, the NaOH that adds 57.6kg afterwards makes azanol free, reacting 18 hours for 63 ℃ near the temperature that refluxes, after being cooled to 30 ℃, adding naoh treatment to pH value is 12-13, is washed to neutrality again, promptly obtains the special-purpose chelating ion exchange resin of absorption gallium;
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 chelating ion exchange resin that adsorbs the gallium special use, 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 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%.
Described 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 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 reactor, add the 45wt% methanol aqueous solution of 500L, carry out the amidoxim reaction.Normal temperature, stir and add the 80kg hydroxylamine hydrochloride down, the NaOH that adds 46.0kg afterwards makes azanol free, reacting 16 hours for 62 ℃ near the temperature that refluxes, after being cooled to 30 ℃, adding naoh treatment to pH value is 12-13, is washed to neutrality again, promptly obtains the special-purpose chelating ion exchange resin of absorption gallium;
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 chelating ion exchange resin that adsorbs the gallium special use, 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 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 is; (270+150) ÷ (68.6+231.4) * 100%=140%.
Described 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 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 reactor, add the 45wt% methanol aqueous solution of 500L, carry out the amidoxim reaction.Normal temperature, stir and add the 150kg hydroxylamine hydrochloride down, the NaOH that adds 86.3kg afterwards makes azanol free, reacting 16 hours for 62 ℃ near the temperature that refluxes, after being cooled to 30 ℃, adding naoh treatment to pH value is 12-13, is washed to neutrality again, promptly obtains the special-purpose chelating ion exchange resin of absorption gallium;
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 limiting the scope of the invention.
Claims (15)
1. chelating ion exchange resin that adsorbs the gallium special use is characterized in that described chelating ion exchange resin contains the copolymer of the styrene-divinylbenzene of formula (I) and formula (II):
Wherein R is methylene or ethylidene.
2. method for preparing the chelating ion exchange resin of absorption gallium special use, described 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 pore-foaming agent is the 120%-180% of crosslinking agent and styrene gross weight;
Described 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.
3. method according to claim 2 is characterized in that described crosslinking agent is a divinylbenzene solution.
4. method according to claim 2 is characterized in that described pore-foaming agent is a kind of or wherein several mixture in isooctane, toluene, dimethylbenzene, the atoleine.
5. method according to claim 2 is characterized in that described initator is benzoyl peroxide or azodiisobutyronitrile.
6. method according to claim 2 is characterized in that described dispersant is a gelatin, carboxymethyl cellulose, hydroxyethylcellulose, a kind of or wherein several mixture in polyvinyl alcohol or the sodium lignin sulfonate.
7. method according to claim 2 is characterized in that described washing is with after the product washing, places extract 3-6 hour, extracts pore-foaming agent, gets copolymer.
8. method according to claim 7 is characterized in that described extract is an acetone, a kind of or wherein several mixture in ethanol or the benzinum.
9. according to claim 2 or 7 described methods, it is characterized in that described chlorination is at normal temperatures,, add zinc chloride again, be warmed up to 38-46 ℃, be incubated 16-24 hour the product after the washing in chloromethyl ether swelling 2-3 hour;
The mass ratio 1 of wherein said product and chloromethyl ether: 5-6;
The quality of described zinc chloride is the 0.8%-1.1% of product.
10. method according to claim 9 is characterized in that described functionalization is to add product, N in reactor, and N '-dimethyl formamide (DMF) and imino group dintrile stirred 20-50 hour washing, drying at 95 ℃-115 ℃.
11. method according to claim 10 is characterized in that described product and N, the volume ratio of N '-dimethyl formamide is 1: 3-6, the mass ratio of described product and iminodiacetonitrile are 1: 2-5.
12., it is characterized in that described imino group dintrile is imido grpup diacetonitrile and/or iminodipropioditrile according to claim 10 or 11 described methods.
13. method according to claim 10, it is characterized in that described amidoxim reaction is dissolved in product in the 30-50wt% methanol aqueous solution, stir and add hydroxylamine hydrochloride and alkali down, reacting 10-20 hour near temperature 62-64 ℃ that refluxes, after being cooled to 30 ℃, adding alkali adjusting pH value is 12-13, is washed to neutrality, promptly obtains the special-purpose chelating ion exchange resin of absorption gallium;
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.
14. method according to claim 10 is characterized in that described alkali is NaOH or caustic alcohol or sodium carbonate.
15. a described chelating resin special for adsorbing of gallium adsorbs the application of gallium in the Bayer mother liquor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102069643A CN101875004B (en) | 2010-06-23 | 2010-06-23 | A special chelating resin for adsorbing gallium, its preparation method and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102069643A CN101875004B (en) | 2010-06-23 | 2010-06-23 | A special chelating resin for adsorbing gallium, its preparation method and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101875004A true CN101875004A (en) | 2010-11-03 |
| CN101875004B CN101875004B (en) | 2012-05-23 |
Family
ID=43017748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102069643A Active CN101875004B (en) | 2010-06-23 | 2010-06-23 | A special chelating resin for adsorbing gallium, its preparation method and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101875004B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012644A (en) * | 2012-11-27 | 2013-04-03 | 安徽皖东化工有限公司 | Preparation method of strongly acidic styrene exchange resin |
| CN103894241A (en) * | 2013-10-28 | 2014-07-02 | 上海长翊科技股份有限公司 | Non-alkaline gallium ion exchange 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 |
| JP2019038949A (en) * | 2017-08-25 | 2019-03-14 | 国立研究開発法人森林研究・整備機構 | Method for producing composite particle and composite particle obtained by production method |
| CN109776744A (en) * | 2019-01-12 | 2019-05-21 | 广西大学 | A kind of preparation method of amidoxime-silica resin for adsorbing gallium |
| CN110818830A (en) * | 2019-11-29 | 2020-02-21 | 广东先导稀材股份有限公司 | A kind of polymer containing amidoxime group and its preparation method and application |
| 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 |
| CN112642411A (en) * | 2020-12-17 | 2021-04-13 | 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 |
| CN115286789A (en) * | 2022-07-29 | 2022-11-04 | 扬州中天利新材料股份有限公司 | Chelate resin special for adsorbing gallium and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5842737A (en) * | 1981-09-07 | 1983-03-12 | Unitika Ltd | Recovering method for gallium |
| 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 |
-
2010
- 2010-06-23 CN CN2010102069643A patent/CN101875004B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5842737A (en) * | 1981-09-07 | 1983-03-12 | Unitika Ltd | Recovering method for gallium |
| 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 |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012644A (en) * | 2012-11-27 | 2013-04-03 | 安徽皖东化工有限公司 | Preparation method of strongly acidic styrene exchange resin |
| 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 |
| CN103894241A (en) * | 2013-10-28 | 2014-07-02 | 上海长翊科技股份有限公司 | Non-alkaline gallium ion 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 |
| JP2019038949A (en) * | 2017-08-25 | 2019-03-14 | 国立研究開発法人森林研究・整備機構 | Method for producing composite particle and composite particle obtained by production method |
| CN109776744A (en) * | 2019-01-12 | 2019-05-21 | 广西大学 | A kind of preparation method of amidoxime-silica resin for adsorbing gallium |
| CN110818830A (en) * | 2019-11-29 | 2020-02-21 | 广东先导稀材股份有限公司 | A kind of polymer containing amidoxime group and its preparation method and application |
| CN110818830B (en) * | 2019-11-29 | 2021-08-17 | 广东先导稀材股份有限公司 | A kind of polymer containing amidoxime group and its preparation method and application |
| 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 |
| CN112642411A (en) * | 2020-12-17 | 2021-04-13 | 江苏大学 | Preparation method and application of porous/ion-rich channel microsphere adsorbent |
| CN112642411B (en) * | 2020-12-17 | 2023-05-05 | 江苏大学 | A kind of preparation method and application of porous/ion channel-rich 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 |
| CN115286789A (en) * | 2022-07-29 | 2022-11-04 | 扬州中天利新材料股份有限公司 | Chelate resin special for adsorbing gallium and preparation method thereof |
| CN115286789B (en) * | 2022-07-29 | 2023-08-11 | 扬州中天利新材料股份有限公司 | A kind of chelating resin special for adsorbing gallium and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101875004B (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101875004A (en) | Chelating resin special for adsorbing of gallium and preparation method and application thereof | |
| CN103539952B (en) | Novel humic acid sulfonatiion process | |
| CN103145160A (en) | Method for producing alumina by using high-alumina fly ash | |
| CN116440873B (en) | An adsorbent for adsorbing lithium from the semen of Bayer process for producing alumina and a method for using the same | |
| KR20220140396A (en) | Method for recovering and manufacturing crude lithium carbonate from the battery meterial raffinate | |
| CN104292383A (en) | Gallium-adsorbing chelating resin and preparation method thereof | |
| WO2025001404A1 (en) | System and method for recovering alkali by carbonizing red mud | |
| CN113955753A (en) | Method for recovering waste lithium iron phosphate battery powder | |
| CN111484046A (en) | A kind of method for extracting lithium from salt lake brine with high magnesium-lithium ratio | |
| CN118724031A (en) | A hydrogenation method for purifying industrial-grade lithium carbonate and a process for purifying industrial-grade lithium carbonate using the method | |
| CN108658111A (en) | A method of improving alumina producing Bayer process efficiency | |
| WO2019144475A1 (en) | Method for preparing high-valence iron salt | |
| CN103303955B (en) | Production method of calcium carbonate whisker | |
| CN109110741B (en) | Method for recycling mother liquor step by step in preparation process of iron phosphate manganese | |
| CN110669938B (en) | Extraction system for separating magnesium from magnesium-containing brine by using secondary amide/alkyl ketone composite solvent and extracting lithium, extraction method and application thereof | |
| CN108428893A (en) | Preparation method of brine battery-grade lithium carbonate | |
| CN116161691A (en) | Method for preparing magnesium-aluminum hydrotalcite from sludge | |
| CN110451472B (en) | Preparation method of anhydrous iron phosphate in organic system | |
| CN104843752B (en) | Method for removing iron from sodium aluminate solution | |
| CN106517260A (en) | Process for preparing lithium carbonate from lithium-bearing saline lake brine | |
| CN115286789B (en) | A kind of chelating resin special for adsorbing gallium and preparation method thereof | |
| CN111233651A (en) | A method for recovering and preparing L(+)-2,3-dihydroxysuccinic acid from dopa production wastewater | |
| CN114849664B (en) | A kind of phosphorous acid modified polyphenolamine adsorption material and its preparation method and application | |
| CN117142499B (en) | A method for enhancing the short-range carbonization preparation of battery-grade lithium carbonate | |
| CN117049578B (en) | Method for recovering lithium from hydrochloric acid desorption solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: High tech Zone technology two road 710075 Shaanxi city of Xi'an province No. 72 Chak tower 4 Applicant after: Sunresin New Materials Co., Ltd., Xi'an Address before: High tech Zone technology two road 710075 Shaanxi city of Xi'an province No. 72 Chak tower 4 Applicant before: Xian Sunresin Technology Co., Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: XI AN LANXIAO SCI-TECH CO., LTD. TO: XI AN SUNRESIN NEW MATERIALS CO., LTD. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |