CN1438074A - Ion exchange fiber and its preparation method and use - Google Patents
Ion exchange fiber and its preparation method and use Download PDFInfo
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- CN1438074A CN1438074A CN 03115872 CN03115872A CN1438074A CN 1438074 A CN1438074 A CN 1438074A CN 03115872 CN03115872 CN 03115872 CN 03115872 A CN03115872 A CN 03115872A CN 1438074 A CN1438074 A CN 1438074A
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- ion
- exchange fiber
- metal ion
- exchange
- fiber
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Abstract
The present invention relates to an ion-exchange fibre, its synthesis method and application. Said alkaline ion-exchange fibre adsorbent is acrylonitrile-methyl methacrylate-itaconate tripolymer containing amino functional group, can remote the acidic matter, transition metal ion and heavy metal ion from non-aqueous solution or non-aqueous solvent. Said invention is simple in preparation of product, and the adsorption volume of adsorbing acidic impurity from non-water is high, and its adsorption speed is high, its chemical property is stable. In the purification of lithium electrolyte by using said product the condition for removing impurity is moderate, at the same time of removing acidic impurity, the impurity into also can be removed.
Description
Technical field
The invention belongs to chemical field, relate to a kind of ion-exchange fiber and preparation method thereof and its application.Specifically, the present invention relates to a kind of ion-exchange fiber that can remove organic solution or solvent middle acid substance and transition metal ion and heavy metal ion.
Background technology
Along with high-tech to the highly purified strict demand of material, the enthusiasm that countries in the world are explored with research high purity material grows to even greater heights, battery industry shows significantly especially in this respect.Electrolyte for Lithium Battery purity is high more, and its performance is excellent more; The micro-HF that contains in preparation ionogen process has huge negative to the performance of lithium cell.At this problem, mainly adopt three class methods at present in the world: the first kind is the organic solvent washing that DE19805360 adopts; Second class is the heating high vacuum degassing that JP11 147705 adopts; The 3rd class is the ion exchange method that WO98/23536 adopts.The effect and the technical difficulty that compare aforesaid method, wherein ion exchange method is effectively simple.WO98/23536 adopts weakly alkaline polyvinyl pyridine resin to remove LiPF
6Acidic impurities in the organic solution, as: HF, LiPO
2F
2, LiHPO
3F.Pass through described resin when the organic solution of lithium salts, the product of gained reaches the desired standard of lithium cell, but described resin absorption capacity is low, and speed is slower, and this resin can not adsorb foreign metal ion (ppm level).
As ion-exchange fiber, SU1658444 has synthesized the fibrous sorbent material that contains carboxyl and diazanyl, is used for the purifying treatment of gas ammonia and ammonium nitrate.It is raw material that RU1051989 has introduced with the polyacrylonitrile fibre, and in succession with hydrazine hydrate or hydrazonium sulfate, the sodium hydroxide solution reaction is handled with hydrazine hydrate again, makes the synthetic method of modified polyacrylonitrile chelate fibre.RU2044748 carries out crosslinking reaction with acryl fibre and hydrazine hydrate, and then reacts with sodium hydroxide solution, has synthesized the cation exchange fibre sorbent material.In SU1512984, successively with polyacrylonitrile fibre and azanol, polyethylene polyamine reaction has prepared and has contained amino, the ion-exchange chelate fibre of hydroxyl oximido.CN1172870A and ZL97120341.5 are that skeleton has prepared respectively and contains carboxyl, hydrazide group, amino, phosphate, imidazolinyl chelate fibre with the polyacrylonitrile fibre.CN1363426A is that raw material and hydrazine hydrochloride carry out crosslinking reaction with the polyacrylonitrile fibre, and then handles with quadrol or diethylenetriamine modification, gets chelate fibre.In sum, the fibrous sorbent material of development is mainly used in metallic cation in the aqueous solution at present, as: heavy metal ion, the absorption of precious metal ion, or remove the middle harmful anion that anhydrates, and as: F
-, PO
4 3-, SO
2- 4, but to (HF, HCl, HBr, HI, H in organic solution or the solvent
2SO
4, H
3PO
4, HNO
3, LiHPO
3F etc.) ion-exchange fiber that acidic substance and transition metal ion and heavy metal ion have absorption property does not appear in the newspapers as yet; Acidic substance in report employing ion-exchange fiber absorption organic solution or the solvent are not also arranged.
Summary of the invention
The purpose of this invention is to provide a kind of ion-exchange fiber and preparation method thereof.Provide a kind of alkali ion exchange fiber that acidic substance in organic solution or the solvent is had absorption property more specifically.
Another object of the present invention provides above-mentioned ion-exchange fiber and removes organic solution or solvent middle acid substance such as HF, HCl, HBr, HI, H in absorption
2SO
4, H
3PO
4, HNO
3, LiHPO
3F, and the purposes of transition metal ion and heavy metal ion.
Vinyl cyanide-methymethacrylate that alkali ion exchange fiber of the present invention is an amino-contained functional group-itaconic ester trimer, wherein the content of amido is 3-13.5% (weight).
The synthetic preparation of ion-exchange fiber of the present invention is simple, and raw material is easy to get, and processing unit is few, and to the loading capacity height of on-waterborne acidic impurities, speed is fast, and chemical property is stable, and regeneration is convenient.Can adsorptivity remove in organic solution or the solvent as: HF, HCl, HBr, HI, H
2SO
4, H
3PO
4, HNO
3, LiHPO
3The acidic substance of F etc. and transition metal ion and heavy metal ion.
The synthetic schemes of alkalinous ion-exchange fibre absorbent of the present invention is to adopt vinyl cyanide-methymethacrylate-itaconic ester trimer and amine and analogue reaction thereof, generates the ion-exchange fiber that is insoluble to organic solution.
The preparation method of alkalinous ion-exchange fibre absorbent of the present invention, as described below:
With vinyl cyanide-methymethacrylate-itaconic ester trimer under 60-150 ℃, with concentration of volume percent be that the diethylenetriamine of 5-25% carried out crosslinking reaction 5-10 hour; Be reacting ethylenediamine 5-7 hour of 5-25% down at 60-150 ℃ then with concentration of volume percent; With 20-60 ℃ distilled water wash of the product of gained, 100-150 ℃ water vapour washing; Use 20-60 ℃ distilled water wash then, under 50-60 ℃, vacuum-drying gets the alkali ion exchange fiber.
The agents useful for same raw material is commercial in the aforesaid method.
Alkali ion exchange fiber of the present invention has following advantage:
1) preparation is simple, and raw material is easy to get, and processing unit is few.
2) loading capacity height, speed is fast, and chemical property is stable, and regeneration is convenient.
3) can remove in organic solution or the solvent as HF HCl, HBr, HI, H
2SO
4, H
3PO
4, HNO
3, LiHPO
3The acidic substance of F etc. and transition metal ion and heavy metal ion.
The present invention also provides a kind of acidic substance in organic solution or the solvent and method of transition metal ion and heavy metal ion of removing, and comprising:
To pack in the ion exchange column by vacuum drying above-mentioned alkalinous ion-exchange fibre absorbent, with the ion-exchange fiber in this post of organic solvent washing; Inject the organic solution of lithium hexafluoro phosphate then from the top of exchange column, by gravity, organic solution is passed this ion-exchange fiber post.From the acidic substance of lithium hexafluoro phosphate organic solution and the basic group generation chemical reaction on the ion-exchange fiber, acidic substance are bonded on this ion-exchange fiber as a result in post; Chelatropic reaction takes place in transition metal ion and the functional group on heavy metal ion and the ion-exchange fiber from lithium hexafluoro phosphate organic solution simultaneously, and these transition metal ions and heavy metal ion are bonded on this ion-exchange fiber as a result.When the organic solution of lithium hexafluoro phosphate when flow out the bottom of exchange column, removed most of acidic substance and transition metal ion and heavy metal ion.The organic solution of lithium hexafluoro phosphate can enter one or more ion exchange columns, also is that the length of ion exchange column can be decided according to the requirement of removing impurity.Lithium hexafluoro phosphate after the alkali ion exchange fiber exchange column of certain-length is handled includes hydrogen fluoride and is less than 10ppm, and its transition metal ion and heavy metal ion also meet the requirement of lithium cell institute.Absorbed the alkali ion exchange fiber of impurity, after the basic solution washing, can regenerate.
Aforesaid method has the impurity of removing mild condition, removes obvious, the fireballing advantage of foreign ion and decon effect when removing acidic impurities.
Embodiment
Embodiment 1:
Take by weighing vinyl cyanide-methymethacrylate-itaconic ester trimer fiber 5g, place the 250ml round-bottomed flask, adding 150ml concentration of volume percent is 20% diethylenetriamine, under 105 ℃, carries out crosslinking reaction 8 hours; After reaction finishes, this fiber is placed the round-bottomed flask of 500ml, under 120 ℃, with the 300ml concentration of volume percent be 15% reacting ethylenediamine 5-7 hour; With the product of gained distilled water wash with 60 ℃, 110 ℃ water vapour washing; Use 20-60 ℃ distilled water wash then, under 50-60 ℃, vacuum-drying gets the alkali ion exchange fiber.
Embodiment 2:
Take by weighing vinyl cyanide-methymethacrylate-itaconic ester trimer fiber 5g, place the 150ml round-bottomed flask, adding 30ml concentration of volume percent is 15% diethylenetriamine, under 100 ℃, carries out crosslinking reaction 5 hours; After reaction finishes, this fiber is placed the round-bottomed flask of 250ml, under 90 ℃, with the 150ml concentration of volume percent be 15% reacting ethylenediamine 7 hours; With 20-60 ℃ distilled water wash of the product of gained, 150 ℃ water vapour washing; Use 20-60 ℃ distilled water wash then, under 50-60 ℃, vacuum-drying gets the alkali ion exchange fiber.
Embodiment 3:
To pack in the ion exchange column by vacuum drying above-mentioned alkalinous ion-exchange fibre absorbent 100g, wash ion-exchange fiber in this post with organic solvent 3000ml; Inject the organic solution 5000ml of lithium hexafluoro phosphate (commercial) then from the top of exchange column, by gravity, organic solution is passed this ion-exchange fiber post.From the acidic substance of lithium hexafluoro phosphate organic solution and the basic group generation chemical reaction on the ion-exchange fiber, acidic substance are bonded on this ion-exchange fiber as a result in post; Simultaneously, from the transition metal ion and the generation chelatropic reaction of the functional group on heavy metal ion and the ion-exchange fiber of lithium hexafluoro phosphate organic solution, these transition metal ions and heavy metal ion are bonded on this ion-exchange fiber as a result.The original organic solution of lithium hexafluoro phosphate contains the HF of 250ppm, contains multiple transition metal ion that exceeds standard and heavy metal ion; When flowing out from the bottom of exchange column, lithium hexafluoro phosphate includes hydrogen fluoride and is less than 10ppm, and its transition metal ion and heavy metal ion also meet the requirement of lithium cell institute.Absorb the alkali ion exchange fiber of impurity, after 1M sodium hydroxide solution 500ml washing, obtained regeneration.
Embodiment 4:
To pack in the ion exchange column by vacuum drying above-mentioned alkalinous ion-exchange fibre absorbent 150g, wash ion-exchange fiber in this post with organic solvent 5000ml; Inject the organic solution 6000ml of lithium hexafluoro phosphate then from the top of exchange column, by gravity, organic solution is passed this ion-exchange fiber post.From the acidic substance of lithium hexafluoro phosphate organic solution and the basic group generation chemical reaction on the ion-exchange fiber, acidic substance are bonded on this ion-exchange fiber as a result in post; Simultaneously, from the transition metal ion and the generation chelatropic reaction of the functional group on heavy metal ion and the ion-exchange fiber of lithium hexafluoro phosphate organic solution, these transition metal ions and heavy metal ion are bonded on this ion-exchange fiber as a result.The original organic solution of lithium hexafluoro phosphate contains the HF of 1500ppm, contains multiple transition metal ion that exceeds standard and heavy metal ion; When flowing out from the bottom of exchange column, lithium hexafluoro phosphate includes hydrogen fluoride and is less than 10ppm, and its transition metal ion and heavy metal ion also meet the requirement of lithium cell institute.Absorb the alkali ion exchange fiber of impurity, after 1M sodium hydroxide solution 1500ml washing, obtained regeneration.
Claims (5)
1, a kind of ion-exchange fiber is characterized in that described ion-exchange fiber is the vinyl cyanide-methymethacrylate-itaconic ester trimer of amino-contained functional group.
2, by the described ion-exchange fiber of claim 1, it is characterized in that described ion-exchange fiber wherein amido content be 3-13.5%.
3, a kind of preparation method of ion-exchange fiber of claim 1 is characterized in that adopting the reaction of vinyl cyanide-methymethacrylate-itaconic ester trimer and amine and analogue thereof, generates the ion-exchange fiber that is insoluble to organic solution.
4, by the preparation method of the ion-exchange fiber of claim 3, it is characterized in that vinyl cyanide-methymethacrylate-itaconic ester trimer at 60-150 ℃, with concentration of volume percent be diethylenetriamine reaction 5-10 hour of 5-25%; Be reacting ethylenediamine 5-7 hour of 5-25% down at 60-150 ℃ then with concentration of volume percent; With 20-60 ℃ distilled water wash, vacuum-drying.
5, according to the ion-exchange fiber of claim 1, the purposes in removing non-aqueous solution or non-aqueous solvent middle acid substance and transition metal ion and heavy metal ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031158722A CN1181924C (en) | 2003-03-18 | 2003-03-18 | Ion exchange fiber and its preparation method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031158722A CN1181924C (en) | 2003-03-18 | 2003-03-18 | Ion exchange fiber and its preparation method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1438074A true CN1438074A (en) | 2003-08-27 |
| CN1181924C CN1181924C (en) | 2004-12-29 |
Family
ID=27674149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031158722A Expired - Fee Related CN1181924C (en) | 2003-03-18 | 2003-03-18 | Ion exchange fiber and its preparation method and use |
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|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103502527A (en) * | 2011-04-27 | 2014-01-08 | 株式会社钟化 | Ion-exchange fiber and method for producing same, method for removing and adsorbing chemical substance in water, and device for removing and adsorbing chemical substance in water |
| CN105186038A (en) * | 2005-10-20 | 2015-12-23 | 三菱化学株式会社 | Lithium Secondary Cell And Nonaqueous Electrolytic Solution For Use Therein |
| CN114042437A (en) * | 2021-11-12 | 2022-02-15 | 河南省科学院化学研究所有限公司 | Preparation process of amino weakly-alkaline anion exchange fiber |
-
2003
- 2003-03-18 CN CNB031158722A patent/CN1181924C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105186038A (en) * | 2005-10-20 | 2015-12-23 | 三菱化学株式会社 | Lithium Secondary Cell And Nonaqueous Electrolytic Solution For Use Therein |
| CN105186038B (en) * | 2005-10-20 | 2017-07-28 | 三菱化学株式会社 | Lithium secondary battery and the nonaqueous electrolytic solution wherein used |
| US11769871B2 (en) | 2005-10-20 | 2023-09-26 | Mitsubishi Chemical Corporation | Lithium secondary batteries and nonaqueous electrolyte for use in the same |
| CN103502527A (en) * | 2011-04-27 | 2014-01-08 | 株式会社钟化 | Ion-exchange fiber and method for producing same, method for removing and adsorbing chemical substance in water, and device for removing and adsorbing chemical substance in water |
| CN103502527B (en) * | 2011-04-27 | 2015-11-25 | 株式会社钟化 | The removing adsorbent equipment of the chemical substance in the removing adsorption method of the chemical substance in ion-exchange fibre and manufacture method thereof, water and water |
| CN114042437A (en) * | 2021-11-12 | 2022-02-15 | 河南省科学院化学研究所有限公司 | Preparation process of amino weakly-alkaline anion exchange fiber |
| CN114042437B (en) * | 2021-11-12 | 2023-11-10 | 河南省科学院化学研究所有限公司 | Preparation process of amino weak-alkaline anion exchange fiber |
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| Publication number | Publication date |
|---|---|
| CN1181924C (en) | 2004-12-29 |
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Granted publication date: 20041229 Termination date: 20100318 |