CN103122044B - Sulphonic acid type macroporous ion exchange resin and preparation method thereof - Google Patents
Sulphonic acid type macroporous ion exchange resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sulphonic acid type macroporous ion exchange resin and a preparation method thereof, and mainly aims to solve the technical problem that a silver-bearing resin deiodination agent for preparing the sulphonic acid type macroporous ion exchange resin is poor in deiodination effect in the prior art. The problem is well solved by adopting the technical scheme that the sulphonic acid type macroporous ion exchange resin, a copolymer skeleton containing macroporous styrene-divinylbenzene and -SO3H are adopted, and the -SO3H is connected with a benzene ring in the copolymer skeleton through -CH2-. The technical scheme can be used for industrial production of the sulphonic acid type macroporous ion exchange resin.
Description
Technical field
The present invention relates to a kind of sulfonic acid type macroporous ion exchange resin and preparation method thereof, particularly relate to vinylbenzene--divinylbenzene crosslink multipolymer is sulfonic acid type macroporous ion exchange resin of skeleton and preparation method thereof.
Background technology
The ion exchange resin being skeleton with styrene-divinylbenzene cross-linking copolymer is divided into gel-type and macroporous type with pore structure character, and is divided into anionic and cationic with the charge property of cation exchange groups in ion exchange resin.In order to prepare macroreticular ion exchange resin, usually under the existence of pore-creating agent, first carry out vinylbenzene and divinylbenzene suspension polymerization prepare macropore styrene-divinylbenzene cross-linking copolymer (this field is called for short making large-pore white balls used, can buy from many ion exchange resin manufacturerss), such as, " syntheses and properties containing double bond wide aperture styrene-divinylbenzene microballoon " (applied chemistry [J], 1998,15 (2): 103-105) making large-pore white balls used preparation method is reported in.And then carry out to making large-pore white balls used macroporous cation or the anionite-exchange resin that chemical modification obtains having containing negatively charged ion or positively charged ion etc. ion exchanging function as required.
In prior art, with vinylbenzene--divinylbenzene crosslink multipolymer is the sulfonic group (-SO of the sulfonic acid type macroporous ion exchange resin of skeleton
3h) be directly connected with the phenyl ring in this resin, by under the existence of swelling agent, use dense H
2sO
4or SO
3to described Deng conventional sulphonating agent making large-pore white balls usedly carry out sulfonation and obtain.Such as, " sulfonation of porous vinylbenzene one divinyl benzene copolymer microballoon and the absorption to bovine serum albumin thereof " (ion-exchange and absorption [J], 2010,26 (4): 334-34) and " sulfonation reaction of high Crosslinked Macroporous styrene-divinylbenzene copolymer " (ion-exchange and absorption [J], 2000,16 (1): 1-8) method of sulfonating of making large-pore white balls used resin is reported in.This sulfonic acid type macroporous ion exchange resin all has sale at home and abroad.
In order to obtain with vinylbenzene--divinylbenzene crosslink multipolymer is the macroporous anion exchange resin of skeleton, the chloromethylation reagents that available chlorine methyl ether etc. are conventional carries out modification to making large-pore white balls used, obtain vinylbenzene phenyl ring connecting chloromethyl--divinylbenzene crosslink multipolymer (macropore chlorine ball is called for short in this field), such as, " polystyrene chloromethylation Investigation on Technological Conditions " (Yindu Journal (certainly attaining science version) [J], 1993,3:44-53) report the preparation technology of chlorine ball, then chlorine ball can be obtained by reacting macroporous anion exchange resin with amine.
In addition, " tensio-active agent and washing composition chemistry and technology " ([M] China Light Industry Press Beijing 1997 May the 1st edition 287 pages) is pointed out, alkyl chloride and sulphite react and can obtain alkylsulfonate, and this reaction is called that Strecker reacts, and its reaction formula is as follows:
RCH
2Cl+Na
2SO
3→RCH
2SO
3Na+NaCl
US Patent No. 2115192 also discloses and adopts Strecker reaction by the-CH in compound
2-Cl group is converted into-CH
2sO
3m, wherein M is K, Na etc.
As a kind of purposes of sulfonic acid type macroporous ion exchange resin, by with Ag ion exchange after obtain taking off idodine containing silver resin, this de-idodine can be used for removing the iodine in carbonyl process acetic acid.Such as, US 4,615,806 discloses and adopts sulfonic acid type macroporous ion exchange resin and AgNO
3, CH
3cOOAg carries out ion-exchange and obtains argentiferous and take off idodine, then this de-idodine is used for the iodine removed in acetic acid, the sulfonic acid type macroporous ion exchange resin adopted in embodiment is with Amberlyst 15 for representative, and its sulfonic group is directly connected with the phenyl ring in styrene diethylene benzene copoly mer.
But what the resin-made adopting sulfonic group and the phenyl ring in styrene diethylene benzene copoly mer to be directly connected was standby takes off idodine containing silver resin takes off iodine weak effect.
Summary of the invention
One of technical problem to be solved by this invention is that the silver resin that contains prepared by the sulfonic acid type macroporous ion exchange resin existed in prior art takes off the technical problem that idodine takes off iodine weak effect, there is provided a kind of new sulfonic acid type macroporous ion exchange resin, the argentiferous that this resin has a preparation takes off idodine and takes off the effective feature of iodine.
Technical problem two to be solved by this invention, is to provide a kind of preparation method with solving the problems of the technologies described above corresponding sulfonic acid type macroporous ion exchange resin.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of sulfonic acid type macroporous ion exchange resin, has macropore styrene diethylene benzene copoly mer skeleton and-SO
3h, is characterized in that described-SO
3h passes through-CH
2-be connected with the phenyl ring in described copolymerization skeleton.
The content of the styrene diethylene benzene copoly mer of macropore described in technique scheme skeleton divinylbenzene units is by weight percentage preferably 8 ~ 28%; The preferred specific surface of described sulfonic acid type macroporous ion exchange resin is 200 ~ 400m
2/ g, pore volume is preferably 0.4 ~ 0.6cm
3/ g; The quality complete exchange capacity of described sulfonic acid type macroporous ion exchange resin is preferably 3.4 ~ 5.3mmol/g.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of method preparing sulfonic acid type macroporous ion exchange resin as claimed in claim 1, comprises the steps:
(1) by phenyl ring is connected with chloromethyl macropore styrene diethylene benzene copoly mer in reaction solvent with M
2sO
3carry out being obtained by reacting ion exchange resin precursor I, wherein M is selected from Na, K, and wherein said reaction solvent is methyl-sulphoxide and/or water;
(2) the dilute aqueous soln process of described ion exchange resin precursor I strong acid, pure water are obtained described sulfonic acid type macroporous ion exchange resin.
In technique scheme, reaction solvent described in step (1) forms preferably by weight percentage: dimethyl sulfoxide (DMSO) 70 ~ 90%, water 10 ~ 30%; Cl content phenyl ring is connected with in the macropore styrene diethylene benzene copoly mer of chloromethyl is preferably 14 ~ 20% by weight percentage; Temperature of reaction in step (1) is preferably 150 ~ 170 DEG C, and the reaction times is preferably 4 ~ 8 hours; The macropore styrene diethylene benzene copoly mer being connected with chloromethyl in step (1) in chlorine, with M
2sO
3mol ratio be preferably 1: 1.05 ~ 1.2; M in step (1)
2sO
31: 5 ~ 10 are preferably with the weight ratio of described reaction solvent.
Sulfonic acid type macroporous ion exchange resin of the present invention, due to-SO
3h passes through-CH
2-be indirectly connected with the phenyl ring in described copolymerization skeleton, the environment for use of the de-idodine obtained with this resins exchange silver in use more withstand harsh.As can be seen from the experimental result that table 6 embodiment 10 to 13 and comparative example 1 to 4 provide, de-idodine evaluation experimental is carried out at 45 DEG C, resin of the present invention is close with comparative example, but the evaluation temperature of resin of the present invention be increased to 90 DEG C to 115 time, the de-iodine effect of de-idodine significantly improves along with the raising of temperature, and the de-iodine effect of comparative example improves trend in deleterious with temperature under condition on year-on-year basis, it is 1.2ppb that such as embodiment 13 processes iodine content in rear acetic acid, and on year-on-year basis in situation the iodine content of comparative example 4 up to 15.1ppb, achieve good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
1, making large-pore white balls used preparation
Carry out with reference to " syntheses and properties containing double bond wide aperture styrene-divinylbenzene microballoon " (applied chemistry [J], 1998,15 (2): 103-105).Under room temperature, in polymeric kettle, add 450 grams of vinylbenzene through underpressure distillation, (content is 49.5% to 590 grams of technical grade Vinylstyrenes, all the other are vinyl xylene, ethyl vinyl benzene), 1560 grams of pore-creating agents (being the toluene solution of the linear polystyrene (number-average molecular weight Mn=9.8 ten thousand) of 15% (weight)), 8 grams of benzoyl peroxides, stirring and dissolving.Add the aqueous solution 2000ml containing gum arabic 2% (weight) and polyvinyl alcohol (polymerization degree 1750. alcoholysis degree 88%) 2% (weight), stir lower logical nitrogen 30min.At 88 DEG C, suspension polymerization is carried out 10 hours under stirring.Suction filtration, with water and each 3 times of toluene wash filter cake.Take toluene as solvent extraction 24 hours, vacuum-drying 48 hours at 60 DEG C, obtains 1019 grams of styrene diethylene benzene copoly mer microballoons (namely making large-pore white balls used).Making large-pore white balls used middle divinyl benzene content is 28% (weight).By technical grade Vinylstyrene consumption, pore-creating agent consumption, and making large-pore white balls used middle divinyl benzene content lists in table 1.
2, the preparation of macropore chlorine ball
Carry out with reference to " polystyrene chloromethylation Investigation on Technological Conditions " (Yindu Journal (certainly attaining science version) [J], 1993,3:44-53).What add in enamel reaction still that 500 grams of steps 1 obtain is making large-pore white balls used, and (molecular formula is Cl-CH to add 3000 grams of chloromethyl methyl ethers
2-O-CH
3), swelling 6 hours, Zinc Chloride Anhydrous 195 grams is slowly added under stirring, be warming up to 40 DEG C of reactions 10 hours, filter, filter cake washing with alcohol 2 times, washing with acetone 2 times, dry 48 hours of ambient temperature in vacuum, obtains chloromethylation macropore styrene diethylene benzene copoly mer (i.e. macropore chlorine ball).Through ultimate analysis, cl content is 19.8% (weight).The cl content of chloromethyl methyl ether consumption, reaction times and macropore chlorine ball is listed in table 2.
3, the preparation of sulfonic acid type macroporous ion exchange resin
(1) ion exchange resin precursor I preparation
With reference to US 2115192.500 grams, the macropore chlorine ball that step 2 is obtained, 387 grams of Na
2sO
3(i.e. M
2sO
3for Na
2sO
3, in chlorine, macropore chlorine ball and M
2sO
3mol ratio be 1: 1.1), (namely reaction solvent is water to 3100 grams of water, M
2sO
3be 1: 8 with the weight ratio of reaction solvent), add in magnetic agitation autoclave, 160 DEG C of reactions 6 hours under stirring, be down to room temperature, filter, to be negative reaction to 1% silver nitrate aqueous solution to filtrate with deionized water wash, the filter cake obtained is ion exchange resin precursor I.M in prepared by ion exchange resin precursor I
2sO
3kind, macropore chlorine ball and M
2sO
3mol ratio, reaction solvent composition, M
2sO
3table 3 is listed in the weight ratio of reaction solvent, temperature of reaction, reaction times.
(2) sulfonic acid type macroporous ion exchange resin of the present invention is converted into by ion exchange resin precursor I
Ion exchange resin precursor I step (1) obtained whole, soak ten times with the aqueous hydrochloric acid of 5% (weight), at every turn with described hydrochloric acid soln 2000 milliliters, each 6 hours, between soak period every 30 minutes, stir once.Then filter, with deionized water wash to filtrate to 1% silver nitrate aqueous solution in neutral, obtain sulfonic acid type macroporous ion exchange resin aqueous resins of the present invention, 50 DEG C of vacuum-dryings obtain the dry thing of sulfonic acid type macroporous ion exchange resin of the present invention for 24 hours.Recording quality complete exchange capacity (being also butt complete exchange capacity) according to GB GB8144-87 method is 3.42mmol/g.
The dry thing of sulfonic acid type macroporous ion exchange resin that step (2) is obtained, with the specific surface that low temperature nitrogen determination of adsorption method obtains dried resin be 397, pore volume is 0.58; Through ultimate analysis, the sulphur content of dried resin is 11.3% (weight).Assuming that the chlorine in step (1) and (2) precursor I is all converted into sulfonic group, the sulphur theoretical content of the dried resin now calculated is 18.3% (weight).Be 61.7% according to the sulfonic group productive rate of the formulae discovery of sulfonic group productive rate=(the sulphur theoretical content of the sulphur content/dried resin of dried resin) × 100%.Sulfonic group productive rate is higher, then show that the reaction of step (1) is higher to the sulfonic selectivity of generation, more favourable to preparation sulfonic acid type macroporous ion exchange resin of the present invention.The character of sulfonic acid type macroporous ion exchange resin of the present invention is listed in table 4.
4, the preparation of de-idodine
With reference to US 4,615,806 carry out.Get the dry thing 100 grams of sulfonic acid type macroporous ion exchange resin of the present invention that step (2) obtains, add 1000 ml deionized water, add 5.65 grams of Silver Nitrates, stir 12 hours, filter, be neutral with deionized water wash filter cake to filtrate, 50 DEG C of vacuum-dryings obtain the dry thing of de-idodine.With the dry thing of de-idodine for benchmark, through ultimate analysis, silver content is 3.43% by weight percentage.The character such as silver content in the silver compound kind of employing, silver compound consumption and de-idodine are listed in table 5.
5, the evaluation of de-idodine
Get the dry thing 25 grams of de-idodine in above-mentioned steps 3, load that internal diameter is 2.5 centimetres, length is in the chromatographic column of vertical placement of 20 centimetres, with relative to de-idodine volume 4h
-1air speed (note: air speed refers to the quality of the acetic acid of the de-idodine process per hour of unit mass.) inject in the acetic acid of iodine containing methyl iodide 200ppb from chromatographic column top with peristaltic pump, controlling acetic acid temperature in chromatographic column is 90 DEG C, treated acetic acid flows out from column bottom, when outflow acetic acid reaches 250 grams, sampling from the acetic acid spout of chromatographic column, is 7.1ppb through gas chromatography determination iodine content.By evaluation temperature, list in table 6 containing the iodine content of iodine acetic acid air speed and acetic acid sample.
[embodiment 2 ~ 13]
1, making large-pore white balls used preparation
Except technical grade Vinylstyrene consumption and the change of pore-creating agent consumption, other is all identical with the step 1 of embodiment 1.By technical grade Vinylstyrene consumption, pore-creating agent consumption, and making large-pore white balls used middle divinyl benzene content lists in table 1.
2, the preparation of macropore chlorine ball
Making large-pore white balls used except what adopt in step 1, beyond chloromethyl methyl ether consumption and reaction times change, other is all identical with the step 2 of embodiment 1.The cl content of chloromethyl methyl ether consumption, reaction times and macropore chlorine ball is listed in table 2.
3, the preparation of sulfonic acid type macroporous ion exchange resin
(1) ion exchange resin precursor I preparation
Except adopting the macropore chlorine ball in step 2, and M
2sO
3kind, macropore chlorine ball and M
2sO
3mol ratio, reaction solvent composition, M
2sO
3outside changing with the weight ratio of reaction solvent, temperature of reaction, reaction times, operate identical with step (1) in embodiment 1 step 3.Main change condition is listed in table 3.
(2) sulfonic acid type macroporous ion exchange resin of the present invention is converted into by ion exchange resin precursor I
Except the ion exchange resin precursor I prepared except adopting step (1), operation steps is identical with the step (2) in embodiment 1 step 3, and the specific nature of sulfonic acid type macroporous ion exchange resin lists in table 4.
As can be seen from table 3 and table 4, embodiment 1 to embodiment 6 only changes solvent and does not change the experiment of other condition, the reaction of preparation precursor I adopts DMSO to be that solvent ratio adopts the sulfonic group productive rate of water when being solvent high, the resin quality complete exchange capacity that the present invention obtains is corresponding also high, and when adopting the mixed solvent be made up of the water of 70 ~ 90% (weight) dimethyl sulfoxide (DMSO) and 10 ~ 30% (weight), further when adopting the mixed solvent be made up of the water of 85 ~ 90% (weight) dimethyl sulfoxide (DMSO) and 10 ~ 15% (weight), the resin quality complete exchange capacity that sulfonic group productive rate and the present invention obtain is higher, there is better technique effect.
4, the preparation of de-idodine
Except adopting step (2) the sulfonic acid type macroporous ion exchange resin prepared, and outside the silver compound kind adopted, silver compound consumption change, other operation steps is with embodiment 1 step 4.The character such as silver content in the silver compound kind of employing, silver compound consumption and de-idodine are listed in table 5.
5, the evaluation of de-idodine
Except the de-idodine adopting step 4 to prepare, and evaluation temperature, to change containing iodine acetic acid air speed outside, other operation steps is with the step 5 of embodiment 1.By evaluation temperature, list in table 6 containing the iodine content of iodine acetic acid air speed and acetic acid sample.
[comparative example 1]
1, making large-pore white balls used preparation
With the step 1 in embodiment 1.
2, the preparation of sulfonic acid type macroporous ion exchange resin
Method with reference to " sulfonation reaction of high Crosslinked Macroporous styrene-divinylbenzene copolymer " (ion-exchange and absorption [J], 2000,16 (1): 1-8) is carried out.Be specially: what add in 500 grams of steps 1 in enamel sulphonation kettle is making large-pore white balls used, adds 1000 milliliters of ethylene dichloride, left at room temperature 24 hours, then the vitriol oil 1000 grams of 98% is added, under stirring, first 83 DEG C of reactions 3 hours, then react 5 hours again at 110 DEG C.After reaction terminates, reaction mixture is down to room temperature, filter, with washing with acetone 3 times, 1000 milliliters, each washing acetone, then deionized water wash is negative to washings to 5% barium chloride solution, obtains sulfonic acid type macroporous ion exchange resin aqueous resins, then within 24 hours, obtains the dry thing of sulfonic acid type macroporous ion exchange resin 50 DEG C of vacuum-dryings.
3, the preparation of de-idodine
The dry thing of the sulfonic acid type macroporous ion exchange resin prepared except adopting step 2, and the consumption of Silver Nitrate is beyond 28.43 grams, other operation is all identical with the step 4 in embodiment 1, and the character such as silver content in the silver compound kind of employing, silver compound consumption and de-idodine are listed in table 5.
4, the evaluation of de-idodine
Except the de-idodine adopting step 3 to prepare, evaluation temperature is beyond 45 DEG C, and other appreciation condition is identical with embodiment 1 step 5.The iodine content of concrete evaluation temperature, acetic acid air speed and acetic acid sample lists in table 6.
[comparative example 2 ~ 4]
Except the evaluation temperature in step 4 changes, other operation is identical with comparative example 1, and the iodine content of concrete evaluation temperature, acetic acid air speed and acetic acid sample lists in table 6.
As can be seen from table 6 embodiment 10 to 13 and comparative example 1 to 4, de-idodine evaluation experimental is carried out at 45 DEG C, resin of the present invention is close with comparative example, but when the evaluation temperature of 90 DEG C to 115 DEG C brought up to by resin of the present invention, the de-iodine effect of de-idodine improves along with the raising of temperature takes off iodine successful, and the de-iodine effect of comparative example improves trend in deleterious with temperature under condition on year-on-year basis.
The preparation that table 1 is making large-pore white balls used
The preparation of table 2 macropore chlorine ball
| Chloromethyl methyl ether consumption, g | Reaction times, h | The cl content of macropore chlorine ball, % (weight) | |
| Embodiment 1 | 3000 | 10 | 19.8 |
| Embodiment 2 | 3000 | 10 | 19.8 |
| Embodiment 3 | 3000 | 10 | 19.8 |
| Embodiment 4 | 3000 | 10 | 19.8 |
| Embodiment 5 | 3000 | 10 | 19.8 |
| Embodiment 6 | 3000 | 10 | 19.8 |
| Embodiment 7 | 3000 | 10 | 19.8 |
| Embodiment 8 | 2500 | 7 | 18.5 |
| Embodiment 9 | 2100 | 5 | 14.2 |
| Embodiment 10 | 2100 | 5 | 14.2 |
| Embodiment 11 | 2100 | 5 | 14.2 |
| Embodiment 12 | 2100 | 5 | 14.2 |
| Embodiment 13 | 2100 | 5 | 14.2 |
| Comparative example 1 | -- | -- | -- |
| Comparative example 2 | -- | -- | -- |
| Comparative example 3 | -- | -- | -- |
| Comparative example 4 | -- | -- | -- |
Prepared by table 3 ion exchange resin precursor I
★dMSO represents dimethyl sulfoxide (DMSO).
Claims (9)
1. a sulfonic acid type macroporous ion exchange resin, has macropore styrene diethylene benzene copoly mer skeleton and-SO
3h, is characterized in that described-SO
3h passes through-CH
2-be connected with the phenyl ring in described copolymer skeleton;
The preparation method of described sulfonic acid type macroporous ion exchange resin, comprises the steps:
(1) by phenyl ring is connected with chloromethyl macropore styrene diethylene benzene copoly mer in reaction solvent with M
2sO
3carry out being obtained by reacting ion exchange resin precursor I, wherein M is selected from Na, K, and wherein said reaction solvent is methyl-sulphoxide and/or water;
(2) the dilute aqueous soln process of described ion exchange resin precursor I strong acid, pure water are obtained described sulfonic acid type macroporous ion exchange resin.
2. sulfonic acid type macroporous ion exchange resin according to claim 1, is characterized in that the content of described macropore styrene diethylene benzene copoly mer skeleton divinylbenzene units is by weight percentage 8 ~ 28%.
3. sulfonic acid type macroporous ion exchange resin according to claim 1, is characterized in that the specific surface of described sulfonic acid type macroporous ion exchange resin is 200 ~ 400m
2/ g, pore volume is 0.4 ~ 0.6cm
3/ g.
4. sulfonic acid type macroporous ion exchange resin according to claim 1, is characterized in that the quality complete exchange capacity of described sulfonic acid type macroporous ion exchange resin is 3.4 ~ 5.3mmol/g.
5. sulfonic acid type macroporous ion exchange resin according to claim 1, is characterized in that described in step (1), reaction solvent consists of by weight percentage:
Dimethyl sulfoxide (DMSO) 70 ~ 90%
Water 10 ~ 30%.
6. sulfonic acid type macroporous ion exchange resin according to claim 1, is characterized in that cl content phenyl ring is connected with in the macropore styrene diethylene benzene copoly mer of chloromethyl is 14 ~ 20% by weight percentage.
7. sulfonic acid type macroporous ion exchange resin according to claim 1, it is characterized in that the temperature of reaction in step (1) is 150 ~ 170 DEG C, the reaction times is 4 ~ 8 hours.
8. sulfonic acid type macroporous ion exchange resin according to claim 1, is characterized in that the macropore styrene diethylene benzene copoly mer being connected with chloromethyl in step (1) is in chlorine, with M
2sO
3mol ratio be 1:1.05 ~ 1.2.
9. sulfonic acid type macroporous ion exchange resin according to claim 1, is characterized in that M in step (1)
2sO
3be 1:5 ~ 10 with the weight ratio of described reaction solvent.
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| CN104086692B (en) * | 2014-06-26 | 2017-01-25 | 蓝星（成都）新材料有限公司 | Super-macropore strong acid resin used as solid catalyst matrix and preparation method thereof |
| CN104693336A (en) * | 2015-03-09 | 2015-06-10 | 华东理工大学 | Sulfonyl modified strong cationic hypercrosslinked resin and preparation method thereof |
| CN107629167B (en) * | 2017-10-17 | 2019-08-27 | 厦门大学 | A kind of sulfonic acid ion exchange resin microballoon and preparation method thereof |
| CN109180850A (en) * | 2018-09-20 | 2019-01-11 | 扬州金珠树脂有限公司 | A kind of composite pore-forming is preparing the application in macroreticular ion exchange resin |
| CN111111791A (en) * | 2020-01-06 | 2020-05-08 | 凯瑞环保科技股份有限公司 | Methanesulfonic acid type cation exchange resin and preparation method thereof |
| CN111659335A (en) * | 2020-06-15 | 2020-09-15 | 浙江普尔树脂有限公司 | Cation exchange resin sulfuric acid recovery and reuse equipment and process |
| CN116333204B (en) * | 2023-05-24 | 2023-09-22 | 山东德川化工科技有限责任公司 | Preparation method of nuclear-grade cation exchange resin |
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| CN86101411A (en) * | 1985-03-07 | 1986-10-29 | 塞拉尼斯公司 | Contain the removal of iodine compound in the non-aqueous organic media |
| CN1044418A (en) * | 1989-01-23 | 1990-08-08 | 陶氏化学公司 | Reduce the extract of anionite-exchange resin |
| CN101885807A (en) * | 2010-07-09 | 2010-11-17 | 南京工业大学 | Polystyrene star-like sulfonic resin |
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|---|---|---|---|---|
| US2115192A (en) * | 1936-06-20 | 1938-04-26 | Rohm & Haas | Aryloxy polyalkylene ether sulphonates |
| CN86101411A (en) * | 1985-03-07 | 1986-10-29 | 塞拉尼斯公司 | Contain the removal of iodine compound in the non-aqueous organic media |
| CN1044418A (en) * | 1989-01-23 | 1990-08-08 | 陶氏化学公司 | Reduce the extract of anionite-exchange resin |
| CN101885807A (en) * | 2010-07-09 | 2010-11-17 | 南京工业大学 | Polystyrene star-like sulfonic resin |
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