CN101215366A - Tannin chelating resin and preparing method thereof - Google Patents
Tannin chelating resin and preparing method thereof Download PDFInfo
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- CN101215366A CN101215366A CNA2008100562747A CN200810056274A CN101215366A CN 101215366 A CN101215366 A CN 101215366A CN A2008100562747 A CNA2008100562747 A CN A2008100562747A CN 200810056274 A CN200810056274 A CN 200810056274A CN 101215366 A CN101215366 A CN 101215366A
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- tannin
- chelating resin
- linking agent
- resin
- dispersion medium
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Abstract
The invention relates to a tannin chelating resin and a process for preparation, and the process for preparation comprises adding tannin and cross linker into organic dispersant to have polymerization reaction, and extracting and purifying with organic solvent. The tannin chelating resin of the invention has the advantages of excellent ametallic ion dsorbability, easy eluting and regenerating, which can overcome the shortcomings of the toxic chemicals of synthetic resin and the mechanical property of resin, and the mechanical property of resin, and the adsorption capacity to chrome metal iron is 80mg/g.
Description
Technical field
The invention belongs to the Polymer Synthesizing field, specifically, relate to a kind of natural environmental-protective type tannin chelating resin that is used for adsorbing metal ions and preparation method thereof.
Background technology
Along with the development and the human civilization advance of society, people use the kind of metal ion and quantity more and more many, thereby contain a large amount of metal ions in runoff water, and some metal ion costliness, rare wherein is as Ag+, Pt
2+, Re
2+, Au
3+Deng, some metal ion is poisonous, as Hg
2+, Cu
2+, Cd
2+Deng.If these metal ions are abandoned in waste water and refuse, can destroy ecology, the infringement human health.
In recent years, polymer, AC are in the development and analytical characteristics test of new macromolecule chelating resin both at home and abroad, and the research of aspects such as precious metal recovery and environment protection is more active.For the synthetic and exploitation of novel chelate resin, its purpose is: select natural macromolecular material for use, prepare the high efficiency resin of more environmental protection; The thermostability of raising resin, chemical stability, mechanical property, regeneration performance, adsorption selectivity energy etc.
Utilize formaldehyde to make linking agent and in the process of synthetic resins, have residual formaldehyde, replace formalin and use the low polymerization degree Paraformaldehyde 96, both can reduce the energy consumption of dehydration, can significantly reduce wastewater treatment capacity again, and Paraformaldehyde 96 is compared with formaldehyde, it does not almost have toxicity, so this is the environmental protection engineering of benefiting the nation and the people.Tannin chelating resin can not only be used for liquid bath and can be used to adorn post, and this just requires resin to have regular shape and has certain intensity can bear the pressure of chromatographic column; In order to make its adsorption efficiency reach the standard of commercial resin, resin has bigger specific surface, preferably be microspheroidal even porous, the volume integral divergence of particle should be little, but volume can not be too small, otherwise product is a kind of aggregate and can not be arborescens, is to be unsuitable for adorning post and to adsorb under elevated pressures and there is not the resin of good mechanical properties and irregular shape.
Tannin is to multiple metal ion, particularly to transition metal ion in various degree complexing action can take place.The pH of solution plays critical effect to complexing, neutral and alkaline state absorption, desorb when acid.Because natural tannin itself is to exist with a kind of metamict, and have certain water-solublely, this has just hindered the application of tannin aspect ionic adsorption.The preparation tannin chelating resin is exactly in order to address this problem.
Summary of the invention
The purpose of this invention is to provide a kind of natural environmental-protective type tannin chelating resin that is used for adsorbing metal ions, this material can overcome the mechanical property defective of the toxic chemical substance and the resin of synthetic resins.
Another object of the present invention has provided a kind of preparation method of tannin chelating resin.
Method provided by the present invention, its concrete steps are as follows:
1) the inverse suspension polymerization reaction is taken place in vegatable tannin and linking agent in organic dispersion medium: tannin is joined in the reactor, add water, at 60 ℃～75 ℃, under preferred 70 ℃, add linking agent while stirring, treat that linking agent dissolves fully after, add dispersion medium, 350r/min～500r/min, preferred 450r/min keeps 1h～2h, preferred 1.5h, regulate agitator then to 250r/min～350r/min, the state of preferred 300r/min keeps 2h～3h, preferred 2h.After reaction is finished, Residual reactants is removed with distilled water flushing, obtain the particle of black.
2) utilize the abundant extracting of organic solvent, purifying: with the product of reaction with ether extracting 2h～4h, preferred 2h, ethanol extracting 2h～4h, preferred 2h, and then with acid solution or aqueous slkali soaking 2h～4h, preferred 4h is washed till neutrality with distilled water at last.At 60 ℃～70 ℃, the drying in oven under preferred 70 ℃ obtains product of the present invention.
In the method provided by the present invention, linking agent is a Paraformaldehyde 96; Dispersion medium is whiteruss or tetracol phenixin or diethyl phthalate; The solution that is used to soak is the NaOH solution of 5% hydrochloric acid soln or 5% or the alcoholic solution of 0.5mol/L acid.
The inventor is according to the characteristics of tannin, big quantity research and test have been carried out, by the inverse suspension polymerization method, utilize the phenolic hydroxyl group in the tannin molecule to combine first, thereby develop the resin of the spherical black wattle plant skin of adsorptive type tannin of the mechanical property defective of the toxic chemical substance that can overcome synthetic resins and resin with aldehyde radical in the linking agent.
Tannin chelating resin provided by the present invention has the improvement of two aspects than tannin ion exchange resin:
1) utilizes inexpensive, the nontoxic performance synthesis of natural environment-friendly type tannin chelating resin of vegatable tannin and Paraformaldehyde 96.
2) resin has regular shape and has certain intensity can bear pressure; Resin has bigger specific surface, makes its adsorption efficiency reach the standard of commercial resin, is microspheroidal, and resin structure is poroid, inner loose network, and the volume integral divergence of particle should be little, and the size distribution of resin is even.
Tannin chelating resin provided by the present invention utilizes tannin to have a plurality of ortho positions phenolic hydroxyl structure, as many polymerization of olefin using catalyst body, can be to metal ion generation complexing action in various degree, intend heavy metal ion being handled with the resin of preparing, realization is to separation, enrichment, the recovery of trace heavy metal, and this is the unique aspect of the present invention.
Tannin chelating resin of the present invention is about 80mg/g to the loading capacity of metal chromium ions, and adsorptivity is fine, and easily wash-out regeneration is reused effectively, and the enriching and recovering of actual chromate waste water has been obtained gratifying result.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1:
Utilize the inverse suspension polymerization that larch extract 15g is joined in the reactor, add water, the Paraformaldehyde 96 that under 70 ℃, adds 1.5g while stirring, after treating that Paraformaldehyde 96 dissolves fully, add dispersion medium 60mL whiteruss, agitator speed is transferred to 450r/min keep 1.5h, regulate agitator then and keep 2h to 300r/min.After reaction is finished, Residual reactants is removed with distilled water flushing, obtain the particle of black.With the product of reaction with ether extracting 2h, ethanol extracting 2h, and then, be washed till neutrality with distilled water at last with 5% salt acid soak 4h.Drying in oven under 70 ℃ obtains product of the present invention.
Embodiment 2:
Utilize the inverse suspension polymerization that Acacia extract 15g is joined in the reactor, add water, the Paraformaldehyde 96 that under 70 ℃, adds 1.5g while stirring, after treating that Paraformaldehyde 96 dissolves fully, add dispersion medium 60mL tetracol phenixin, agitator speed is transferred to 450r/min keep 1.5h, regulate agitator then and keep 1.5h to 300r/min.After reaction is finished, Residual reactants is removed with distilled water flushing, obtain the particle of black.With the product of reaction with ether extracting 2h, ethanol extracting 2h, and then, be washed till neutrality with distilled water at last with 5% salt acid soak 4h.Drying in oven under 70 ℃ obtains product of the present invention.
Embodiment 3:
Utilize the inverse suspension polymerization that Acacia extract 15g is joined in the reactor, add water, the Paraformaldehyde 96 that under 70 ℃, adds 1.5g while stirring, after treating that Paraformaldehyde 96 dissolves fully, add dispersion medium 60mL whiteruss, agitator speed is transferred to 450r/min keep 1.5h, regulate agitator then and keep 2h to 300r/min.After reaction is finished, Residual reactants is removed with distilled water flushing, obtain the particle of black.With the product of reaction with ether extracting 2h, ethanol extracting 2h, and then soak 4h with 5%NaOH,, be washed till neutrality with distilled water at last.Drying in oven under 70 ℃ obtains product of the present invention.
Claims (9)
1. tannin chelating resin, it is to prepare by the following method:
1) vegatable tannin and linking agent are carried out the inverse suspension polymerization reaction in organic dispersion medium;
2) utilize the abundant extracting of organic solvent, purifying.
2. tannin chelating resin as claimed in claim 1 is characterized in that described method comprises the steps:
1) tannin is joined in the reactor, add water, under 60 ℃～75 ℃, add linking agent while stirring, after treating that linking agent dissolves fully, add dispersion medium, agitator speed is transferred to 350r/min～500r/min, keep 1h～2h, regulate the state maintenance 2h～3h of agitator then, after reaction is finished, Residual reactants is removed with distilled water flushing to 250r/min～350r/min, obtain the particle of black
2) with the product of reaction ether extracting 2h～4h, ethanol extracting 2h～4h with acid solution or aqueous slkali soaking 2h～4h, is washed till neutrality with distilled water then at last, and 60 ℃～70 ℃ oven dry promptly.
3. tannin chelating resin as claimed in claim 2 is characterized in that described method comprises the steps:
1) tannin is joined in the reactor, add water, under 70 ℃, add linking agent while stirring, after treating that linking agent dissolves fully, add dispersion medium, agitator speed is transferred to 450r/min, keep 1.5h, regulate the state maintenance 3h of agitator then, after reaction is finished, Residual reactants is removed with distilled water flushing to 300r/min, obtain the particle of black
2) with the product of reaction ether extracting 2h, ethanol extracting 2h with acid solution or aqueous slkali soaking 4h, is washed till neutrality with distilled water then at last, and 70 ℃ of oven dry promptly.
4. as the arbitrary described tannin chelating resin of claim 1-3, it is characterized in that described linking agent is a Paraformaldehyde 96.
5. as the arbitrary described tannin chelating resin of claim 1-3, it is characterized in that described dispersion medium is whiteruss, tetracol phenixin or diethyl phthalate.
6. as claim 2 or 3 described tannin chelating resins, it is characterized in that the described solution that is used to soak is the NaOH solution of 5% hydrochloric acid soln or 5% or the alcoholic solution of 0.5mol/L acid.
7. as each described tannin chelating resin of claim 1-3, it is characterized in that the amount ratio of tannin and linking agent is 10: 1.
8. as the arbitrary described tannin chelating resin of claim 1-3, it is characterized in that the amount ratio of tannin and dispersion medium is 1: 4.
9. the preparation method of each described tannin chelating resin of claim 1-8 is characterized in that, comprises the steps:
1) vegatable tannin and linking agent are carried out the inverse suspension polymerization reaction in organic dispersion medium;
2) utilize the abundant extracting of organic solvent, purifying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100562747A CN101215366A (en) | 2008-01-16 | 2008-01-16 | Tannin chelating resin and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100562747A CN101215366A (en) | 2008-01-16 | 2008-01-16 | Tannin chelating resin and preparing method thereof |
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| CN101215366A true CN101215366A (en) | 2008-07-09 |
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| CNA2008100562747A Pending CN101215366A (en) | 2008-01-16 | 2008-01-16 | Tannin chelating resin and preparing method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831419A (en) * | 2010-04-06 | 2010-09-15 | 福建师范大学 | Method for preparing spherical tannin carrier |
| CN101914514A (en) * | 2010-04-06 | 2010-12-15 | 福建师范大学 | Method for preparing immobilized alpha-amylase by using spherical tannin as carrier |
| CN105107485A (en) * | 2015-10-09 | 2015-12-02 | 吉首大学 | Preparation method of immobilized tannins adsorption resin |
| CN108155383A (en) * | 2017-11-29 | 2018-06-12 | 中山大学 | A kind of lithium-sulfur cell binding agent and preparation method thereof and lithium-sulphur cell positive electrode |
| CN115850624A (en) * | 2022-12-09 | 2023-03-28 | 西南科技大学 | Preparation method of tannin resin for adsorption and separation of nuclide and heavy metal |
| CN117624262A (en) * | 2024-01-23 | 2024-03-01 | 昆明理工大学 | Method for extracting and preparing high-purity tannic acid from single Ning Zhe slag |
-
2008
- 2008-01-16 CN CNA2008100562747A patent/CN101215366A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831419A (en) * | 2010-04-06 | 2010-09-15 | 福建师范大学 | Method for preparing spherical tannin carrier |
| CN101914514A (en) * | 2010-04-06 | 2010-12-15 | 福建师范大学 | Method for preparing immobilized alpha-amylase by using spherical tannin as carrier |
| CN105107485A (en) * | 2015-10-09 | 2015-12-02 | 吉首大学 | Preparation method of immobilized tannins adsorption resin |
| CN108155383A (en) * | 2017-11-29 | 2018-06-12 | 中山大学 | A kind of lithium-sulfur cell binding agent and preparation method thereof and lithium-sulphur cell positive electrode |
| CN108155383B (en) * | 2017-11-29 | 2020-07-28 | 中山大学 | Binder for lithium-sulfur battery, preparation method of binder and lithium-sulfur battery anode |
| CN115850624A (en) * | 2022-12-09 | 2023-03-28 | 西南科技大学 | Preparation method of tannin resin for adsorption and separation of nuclide and heavy metal |
| CN117624262A (en) * | 2024-01-23 | 2024-03-01 | 昆明理工大学 | Method for extracting and preparing high-purity tannic acid from single Ning Zhe slag |
| CN117624262B (en) * | 2024-01-23 | 2024-03-29 | 昆明理工大学 | Method for extracting and preparing tannic acid from single Ning Zhe slag |
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Application publication date: 20080709 |