CN110252426A - Bisulfate ion-sulfate radical type anion exchange resin preparation method - Google Patents
Bisulfate ion-sulfate radical type anion exchange resin preparation method Download PDFInfo
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- CN110252426A CN110252426A CN201910503938.8A CN201910503938A CN110252426A CN 110252426 A CN110252426 A CN 110252426A CN 201910503938 A CN201910503938 A CN 201910503938A CN 110252426 A CN110252426 A CN 110252426A
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- anion exchange
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
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Abstract
The invention discloses bisulfate ion-sulfate radical type anion exchange resin preparation methods, including following four step: using commercially available chloride ion type anion exchange resin as starting material, with purifying water rinse resin to efflux clear, colorless, and it sufficiently impregnates, resin elution is rinsed with H2SO4 aqueous solution, then with purifying water rinse resin up to efflux to faintly acid, resin elution is rinsed with NaOH aqueous solution, then with purifying water rinse resin up to efflux to faintly acid to neutrality, resin elution is rinsed with H2SO4 aqueous solution, after detection is qualified, again with purifying water rinse resin up to efflux to faintly acid or neutrality, water to be purified, which no longer flows out, collects to obtain bisulfate ion type anion exchange resin.Bisulfate ion (sulfate radical type) anion exchange resin that the present invention prepares has the very strong ability and higher stability for improving HSO4- ion, and Chloride residue is few, can achieve medicinal requirements, integrated artistic simplification is, it can be achieved that industrialized production.
Description
Technical field
The present invention relates to chemical technology fields, specially bisulfate ion-sulfate radical type anion exchange resin preparation side
Method.
Background technique
Ion exchange resin is a kind of high molecular material with ion exchanging function, is a kind of height with cross-linked structure
Molecular substance combines many cation exchange groups, i.e., so-called fixed ion and and fixed ion on matrix with chemical bond, ionic bond
In conjunction with meet opposite ion.Wherein, counter ion can dissociate in the solution comes, and can exchange with other ions
Reaction.Under normal circumstances, ion-exchange reactions is reversible, and by certain method, the ion exchanged can be desorbed, make from
Sub-exchange resin is restored to original ionic formula, recycles so ion exchange resin can regenerate.
According to the difference of cation exchange groups, ion exchange resin has been segmented into two major classes cation exchange resin, can with it is molten
Cation swaps reaction in liquid, can dissociate hydrogen ion or metal cation.Anion exchange resin, can be with yin in solution
Ion swaps reaction, can dissociate hydroxide ion or other acid ions.
Ion exchange resin is widely used in water process, food industry, chemical industry environmental protection and pharmaceuticals industry.And current city
The overwhelming majority belongs to chloride ion type in the anion exchange resin sold, i.e., by the anion exchange resin regeneration of chloride ion type
Reason obtains hydroxyl type strong alkalinity anion exchange resin.But bisulfate ion (the sulphur for needing to use for certain special industries
Acid group) the existing sale on the market of type anion exchange resin, it is also not carried out industrialization production, relevant document and patent are also fresh
It has been reported that.
With extensive use of bisulfate ion (sulfate radical) the type anion exchange resin in chemical industry, pharmaceutical industry, such as
Sulfate radical type anion-exchange resin method improves PAC flocculating property, such as using using bisulfate ion/sulfate radical type anion friendship
It changes resin and carries out salt form conversion etc. of the ion exchange realization drug free alkali from the salt of other acid ion forms to sulfate,
The market demand will be increasing, and application prospect is more and more wider, and quality requirement also will be higher and higher.
Summary of the invention
The purpose of the present invention is to provide bisulfate ion-sulfate radical type anion exchange resin preparation method, pass through by
Commercially available anion exchange resin (chloride ion type), is eluted by sulfuric acid solution, is eluted using sodium hydroxide solution, using
Sulfuric acid solution elution, solution out is drenched in detection whether there is chloride ion, and after determining chloride ion exchange, hydrogen sulfate can be obtained
Root/sulfate radical type anion exchange resin.Its bisulfate ion prepared (sulfate radical type) anion exchange resin has very strong
Offer HSO4- ion ability and higher stability, the replacement result of original chloride ion is good, and Chloride residue is few, can be with
Reach medicinal requirements, integrated artistic is simplified, it can be achieved that industrialized production, to solve the problems mentioned in the above background technology.
To achieve the above object, the invention provides the following technical scheme: bisulfate ion-sulfate radical type anion exchange resin
Preparation method, including following four step:
Step 1: using commercially available chloride ion type anion exchange resin as starting material, with purifying water rinse resin to efflux
Clear, colorless, and sufficiently impregnate, it is used for next step afterwards；
Step 2: resin, control certain flow rate elution, then with purifying water rinse resin until stream are rinsed with H2SO4 aqueous solution
Liquid is to faintly acid out；
Step 3: resin, control certain flow rate elution, then with purifying water rinse resin until outflow are rinsed with NaOH aqueous solution
Liquid to faintly acid to neutrality；
Step 4: resin is rinsed with H2SO4 aqueous solution, control certain flow rate elution after detection is qualified, then is rinsed with purified water and set
For rouge until efflux is to faintly acid or neutrality, water to be purified, which no longer flows out, collects to obtain bisulfate ion type anion exchange resin.
Further, commercially available chloride ion type anion exchange resin described in step 1 can be strong basicity quaternary ammonium system
Anion exchange resin, or alkalescent styrene series anion exchanges resin, and purifying water rinse resin is clear to efflux
It is clear colourless and sufficiently impregnate, soaking time 5-36h.
Further, H2SO4 concentration of aqueous solution described in step 2 is 1%-30%, and rate of flow in rinse is controlled in 0.3 ~ 8 times of column
Volume/h.
Further, H2SO4 concentration of aqueous solution is 5%, and rate of flow in rinse is controlled in 1.0 ~ 2.0 times of column volume/h.
Further, NaOH concentration of aqueous solution described in step 3 is 1%-30%, and rate of flow in rinse is controlled in 0.3 ~ 8 times of cylinder
Product/h.
Further, NaOH concentration of aqueous solution is 5%, and rate of flow in rinse is controlled in 1.0 ~ 2.0 times of column volume/h.
Further, H2SO4 concentration of aqueous solution described in step 4 is 1%-30%, and rate of flow in rinse is controlled in 0.3 ~ 8 times of column
Volume/h.
Further, H2SO4 concentration of aqueous solution is 5%, and rate of flow in rinse is controlled in 1.0 ~ 2.0 times of column volume/h.
Compared with prior art, the beneficial effects of the present invention are:
The preparation method of this bisulfate ion-sulfate radical type anion exchange resin, by by commercially available anion exchange resin (chlorine
Ionic), it is eluted by sulfuric acid solution, is eluted using sodium hydroxide solution, eluted using sulfuric acid solution, detection is drenched molten out
Liquid whether there is chloride ion, and after determining chloride ion exchange, bisulfate ion/sulfate radical type anion exchange tree can be obtained
Rouge.Its bisulfate ion prepared (sulfate radical type) anion exchange resin have it is very strong improve HSO4- ion ability and
Higher stability, better than the replacement result of original chloride ion, Chloride residue is few, can achieve medicinal requirements, integrated artistic
Simplify, it can be achieved that industrialized production.
Specific embodiment
It will be detailed below the embodiment of the present invention, however, the embodiment of the present invention is not limited thereto.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts,
It shall fall within the protection scope of the present invention.
Sulfuric acid, sodium hydroxide in following embodiment are commercially available chemical grade product.Anion exchange resin is 201*7 highly basic
Property polystyrene series anion exchange resin and D301 type alkalescent polystyrene series anion exchange resin.As nothing is especially said
Bright, other reagents are ordinary commercial products.
Embodiment 1
Bisulfate ion-sulfate radical type anion exchange resin preparation method weighs the 201*7 strong basicity polyphenyl second of 10.00Kg
Alkene series anion exchange resin (apparent density 0.72g/mL) purifying water rinse resin to efflux clear, colorless, and sufficiently soak
Steep 12 ~ 16h.Then resin is successively rinsed as steps described below:
Resin is rinsed with the 5%H2SO4 aqueous solution of 6 ~ 8 times of column volumes, coutroi velocity is in 1.0 ~ 1.5 times of column volume/h, then with pure
Change water rinse resin until efflux pH ≈ 6；
Resin is rinsed with the 5%NaOH aqueous solution of 6 ~ 8 times of column volumes, coutroi velocity is in 1.0 ~ 1.5 times of column volume/h, then with pure
Change water rinse resin until efflux pH=6 ~ 7；
Resin, 1.0 ~ 1.5 times of column volume/h of coutroi velocity, after flushing are rinsed with the 5%H2SO4 aqueous solution of 6 ~ 8 times of column volumes
According to 99-100 pages of chlorination object detecting method detection stream of 2015 editions pharmacopeia go out liquid Cl- concentration it is qualified after (turbidity is lower than chloride ion
The satd aq NaCl of concentration 10-6g/ml), then with purifying water rinse resin until efflux pH=6 ~ 7, water to be purified is no longer
Bisulfate ion (sulfate radical) type anion exchange resin is collected to obtain in outflow.
Detection method is as follows: preparing c [Cl-]=10- according to 99-100 pages of 0801 chlorination object detecting method of 2015 editions pharmacopeia
The satd aq NaCl of 6g/ml is as reference substance.Efflux is also according to 99-100 pages of 0801 chlorination quality testing of 2015 editions pharmacopeia
The preparation of survey method is compared with reference substance, and efflux Cl- concentration is no more than the Cl- concentration in satd aq NaCl.
Embodiment 2
Bisulfate ion-sulfate radical type anion exchange resin preparation method weighs the D301 type alkalescent polyphenyl second of 10.00Kg
Alkene series anion exchange resin with purifying water rinse resin to efflux clear, colorless, and sufficiently impregnates 10 ~ 18h.Then according to
Following step successively rinses resin:
Resin is rinsed with the 10%H2SO4 aqueous solution of 5 ~ 7 times of column volumes, then coutroi velocity is used in 1.5 ~ 2.0 times of column volume/h
Water rinse resin is purified until efflux pH ≈ 6；
Resin is rinsed with the 10%NaOH aqueous solution of 5 ~ 7 times of column volumes, coutroi velocity is in 1.5 ~ 2.0 times of column volume/h, then with pure
Change water rinse resin until efflux pH=6 ~ 7；
Resin, 1.5 ~ 2.0 times of column volume/h of coutroi velocity are rinsed with the 10%H2SO4 aqueous solution of 5 ~ 7 times of column volumes, flushing finishes
Afterwards according to 99-100 pages of chlorination object detecting method detection stream of 2015 editions pharmacopeia go out liquid Cl- concentration it is qualified after (turbidity lower than chlorine from
The satd aq NaCl of sub- concentration 10-6g/ml), then with purifying water rinse resin until efflux pH=6 ~ 7, water to be purified is not
It flows out again and collects to obtain bisulfate ion (sulfate radical) type anion exchange resin.
Detection method is as follows: preparing c [Cl-]=10- according to 99-100 pages of 0801 chlorination object detecting method of 2015 editions pharmacopeia
The satd aq NaCl of 6g/ml is as reference substance.Efflux is also according to 99-100 pages of 0801 chlorination quality testing of 2015 editions pharmacopeia
The preparation of survey method is compared with reference substance, and efflux Cl- concentration is no more than the Cl- concentration in satd aq NaCl.
In summary: the preparation method of this bisulfate ion-sulfate radical type anion exchange resin, by by it is commercially available yin from
Sub-exchange resin (chloride ion type), is eluted by sulfuric acid solution, is eluted using sodium hydroxide solution, drenched using sulfuric acid solution
It washes, solution out is drenched in detection whether there is chloride ion, and after determining chloride ion exchange, bisulfate ion/sulfate radical type can be obtained
Anion exchange resin.Its bisulfate ion prepared (sulfate radical type) anion exchange resin has very strong raising HSO4-
The ability of ion and higher stability, better than the replacement result of original chloride ion, Chloride residue is few, can achieve medicinal want
It asks, integrated artistic simplification is, it can be achieved that industrialized production.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (8)
1. bisulfate ion-sulfate radical type anion exchange resin preparation method, which is characterized in that including following four step:
Step 1: using commercially available chloride ion type anion exchange resin as starting material, with purifying water rinse resin to efflux
Clear, colorless, and sufficiently impregnate, it is used for next step afterwards；
Step 2: resin, control certain flow rate elution, then with purifying water rinse resin until stream are rinsed with H2SO4 aqueous solution
Liquid is to faintly acid out；
Step 3: resin, control certain flow rate elution, then with purifying water rinse resin until outflow are rinsed with NaOH aqueous solution
Liquid to faintly acid to neutrality；
Step 4: resin is rinsed with H2SO4 aqueous solution, control certain flow rate elution after detection is qualified, then is rinsed with purified water and set
For rouge until efflux is to faintly acid or neutrality, water to be purified, which no longer flows out, collects to obtain bisulfate ion type anion exchange resin.
2. bisulfate ion according to claim 1-sulfate radical type anion exchange resin preparation method, feature exist
In commercially available chloride ion type anion exchange resin described in step 1 can be strong basicity quaternary ammonium series anion exchange tree
Rouge, or alkalescent styrene series anion exchanges resin, and purifying water rinse resin to efflux clear, colorless is simultaneously abundant
It impregnates, soaking time 5-36h.
3. bisulfate ion according to claim 1-sulfate radical type anion exchange resin preparation method, feature exist
In H2SO4 concentration of aqueous solution described in step 2 is 1%-30%, and rate of flow in rinse is controlled in 0.3 ~ 8 times of column volume/h.
4. bisulfate ion according to claim 3-sulfate radical type anion exchange resin preparation method, feature exist
In H2SO4 concentration of aqueous solution is 5%, and rate of flow in rinse is controlled in 1.0 ~ 2.0 times of column volume/h.
5. bisulfate ion according to claim 1-sulfate radical type anion exchange resin preparation method, feature exist
In NaOH concentration of aqueous solution described in step 3 is 1%-30%, and rate of flow in rinse is controlled in 0.3 ~ 8 times of column volume/h.
6. bisulfate ion according to claim 5-sulfate radical type anion exchange resin preparation method, feature exist
In NaOH concentration of aqueous solution is 5%, and rate of flow in rinse is controlled in 1.0 ~ 2.0 times of column volume/h.
7. bisulfate ion according to claim 1-sulfate radical type anion exchange resin preparation method, feature exist
In H2SO4 concentration of aqueous solution described in step 4 is 1%-30%, and rate of flow in rinse is controlled in 0.3 ~ 8 times of column volume/h.
8. bisulfate ion according to claim 7-sulfate radical type anion exchange resin preparation method, feature exist
In H2SO4 concentration of aqueous solution is 5%, and rate of flow in rinse is controlled in 1.0 ~ 2.0 times of column volume/h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113457750A (en) * | 2021-07-19 | 2021-10-01 | 南通秋之友生物科技有限公司 | Anion exchange resin recovery process applied to biological extraction |
| CN114602553A (en) * | 2022-03-31 | 2022-06-10 | 南京大学 | Macroporous weak-base anion resin loaded tungsten-based catalyst, microchannel continuous flow oxidation system and application thereof |
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| CN86100573A (en) * | 1986-05-10 | 1987-04-15 | 中国石油化工总公司上海石油化工总厂 | Method with purification of sodium thiocyanate solution via anionic exchange resin |
| JP2002263507A (en) * | 2001-03-13 | 2002-09-17 | Mitsubishi Gas Chem Co Inc | Method for preparing ion exchange resin |
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2019
- 2019-06-12 CN CN201910503938.8A patent/CN110252426A/en active Pending
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113457750A (en) * | 2021-07-19 | 2021-10-01 | 南通秋之友生物科技有限公司 | Anion exchange resin recovery process applied to biological extraction |
| CN114602553A (en) * | 2022-03-31 | 2022-06-10 | 南京大学 | Macroporous weak-base anion resin loaded tungsten-based catalyst, microchannel continuous flow oxidation system and application thereof |
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