CN101249424A - Solidify tannin large hole adsorption resin and method of preparing the same - Google Patents
Solidify tannin large hole adsorption resin and method of preparing the same Download PDFInfo
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- CN101249424A CN101249424A CNA2008101031317A CN200810103131A CN101249424A CN 101249424 A CN101249424 A CN 101249424A CN A2008101031317 A CNA2008101031317 A CN A2008101031317A CN 200810103131 A CN200810103131 A CN 200810103131A CN 101249424 A CN101249424 A CN 101249424A
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Abstract
The invention provides solidified tannin macroporous adsorptive resin containing 0.25-1% vegetable tannin and preparation method thereof. The Mannich reaction is adopted to solidify vegetable tannin on styrene-divinylbenzene copolymer to preparing a kind of novel solidified tannin macroporous adsorptive resin. The obtained solidified tannin macroporous adsorptive resin has the advantages of good absorbability to phenols substances in aqueous solution, easy elution and regeneration, and good reutilization effect. The resin has a satisfied result for enriching and recovering practical phenols substances-containing waste water and can overcome toxic chemical substances of synthetic resin.
Description
Technical field
The present invention relates to a kind of macroporous absorbent resin, specifically, the present invention relates to a kind of macroporous absorbent resin that contains tannin and preparation method thereof.
Background technology
Macroporous absorbent resin is a kind of cation exchange groups that do not contain, and has the macromolecule bead-like body adsorbent of macroporous netlike structure.It is one of important development in the later 1960s ion exchange technique field.All obtained remarkable effect in fields such as environmental protection, medical industry, chemical industry, analytical chemistry, clinical treatments at present.
Macroporous absorbent resin fast development is in recent decades got up, because it has the physical and chemical stability height, and the adsorptive selectivity uniqueness, the influence that not existed by inorganic matter, it is easy to regenerate, the desorption condition gentleness, life cycle is long, be suitable for the formation closed cycle, plurality of advantages such as cost saving, thus obtained using widely in a lot of fields, processing as organic wastewater, pharmacy, bio-separation, chromatographic isolation and enrichment etc.
But polymeric adsorbent crosslinked polystyrene hydrophobicity is strong, and the interface energy between water and the resin is bigger, limits its application in wastewater treatment to a certain extent, and novel polymeric adsorbent becomes the problem that the research worker feels more interest.Particularly utilize natural polymer that it is prepared, have multiple effects such as nontoxic, safety, environmental protection.
Summary of the invention
The purpose of this invention is to provide a kind of natural environmental-protective type vegatable tannin macroporous absorbent resin that is used for the absorbing phenolic material, this resin can overcome the defective of the toxic chemical substance of synthetic resin.
Another object of the present invention provides a kind of preparation method of solidify tannin large hole adsorption resin.
In order to realize the object of the invention, a kind of solidify tannin large hole adsorption resin of the present invention, it contains the vegatable tannin of 0.25～1% amount.
Wherein, percentage is percetage by weight.
Macroporous absorbent resin of the present invention is the solidify tannin large hole adsorption resin of styrene-divinylbenzene copolymer.
The preparation method of solidify tannin large hole adsorption resin of the present invention, it comprises the steps:
1) amine resin preparation
The chloromethylated polystyrene resin adds the methyl-sulfoxide swelling, adds ethylenediamine then at 60～80 ℃ of reaction 12～36h, reactant cooling back suction filtration, and washing, drying makes amine resin;
2) mannich reaction prepares resin
Get amine resin, after adding the oxolane swelling, add distilled water and formalin, regulator solution pH is 3～5, and at 99～100 ℃ down behind reaction 20～40min, adding the pH value again and be 3～5 the tannin aqueous solution, to make the tannin concentration of aqueous solution of system be 0.5～2%, continue reaction 6～8h, washing is dry.
Wherein, in the step 1), the mass volume ratio of chloromethylated polystyrene resin and methyl-sulfoxide is 0.5～0.7: 1～2 (g/ml), and swelling time is 0.5～1.5h.
The amount of described ethylenediamine is 2～5 times of amounts of methyl-sulfoxide.
Step 2) in, the mass volume ratio of described amine resin and oxolane is 0.2～0.6: 1～2 (g/ml), and swelling time is 1.5～2.5h.
The amount of described distilled water is 3～6 times of amounts of oxolane; The amount of described formalin (mass concentration 37%, i.e. formalin) is 0.2～1 times of amount of oxolane.
The chloromethylated polystyrene resin is commercially available, and particle diameter is about 1mm.
Described tannin is commercially available, again the autogamy aqueous solution.
Described suction filtration adopts ethanol to carry out Soxhlet extracting 4～6h.
Described washing is to adopt earlier washing, uses 3～5% NaOH solution oscillation treatment again 2～3 hours, is washed to neutrality.
The physical property of solidify tannin large hole adsorption resin of the present invention is as follows:
The present invention is fixed on vegatable tannin on the styrene-divinylbenzene copolymer, prepare plant polyphenol type hydrophily tannin and solidify macroporous absorbent resin, utilize the polarities match of plant polyphenol and the phenols structural similarity and the phenolic hydroxyl group of this resin, phenol wastewater is handled, realized Pyrogentisinic Acid's separation, enrichment, recovery.
The present invention utilizes natural polymer--vegatable tannin first, successfully synthesized safe, nontoxic novel macroporous absorbent resin, particularly the curing of carrying out tannin first with the reaction scheme in Manny west prepares macroporous absorbent resin, and its thinking and method are innovated.
Solidify tannin large hole adsorption resin of the present invention shows good adsorption property to the aldehydes matter in the aqueous solution, and easily wash-out regeneration is reused effectively, and the actual enriching and recovering that contains aldehydes matter waste water has all been obtained gratifying result.Can overcome the toxic chemical substance of synthetic resin, its Pyrogentisinic Acid's adsorption capacity is 60～80mg/g, and with commercially available NKA-II resin contrast, NKA-II Pyrogentisinic Acid's adsorbance is 25mg/g, and product of the present invention is apparently higher than the NKA-II resin.
The specific embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
The solidify tannin large hole adsorption resin of present embodiment is that the vegatable tannin that contains 0.5% amount is fixed in styrene-divinylbenzene copolymer.
Concrete preparation process is as follows:
(1) amine resin preparation
In the 250mL there-necked flask, add 7.0g chloromethylated polystyrene resin, add 10mL dimethyl sulfoxide (DMSO) swelling 1h, add the 20mL ethylenediamine then at 70 ℃ of reaction 24h, after the reactant cooling, adopt ethanol to carry out Soxhlet extracting 4h, washing was used 5% NaOH solution oscillation treatment 3 hours again, be washed to neutrality, drying makes amine resin.
(2) mannich reaction prepares resin
Get the 2g amine resin, after adding 5mL oxolane swelling 2h, add 25mL distilled water and 1mL formalin (mass concentration 37%), with hydrochloric acid conditioning solution pH is 4, adding down the 25mL tannin aqueous solution (regulating the pH value in advance is 4) behind the reaction 30min again at 99～100 ℃, to make the tannin concentration of system be 0.8%, continue reaction 7h, resin is fully washed drying obtain product of the present invention.
After testing, the physical property of solidify tannin large hole adsorption resin is as follows:
Its Pyrogentisinic Acid's adsorption capacity is 60mg/g.
Embodiment 2
The solidify tannin large hole adsorption resin of present embodiment is that the vegatable tannin that contains 0.8% amount is fixed in styrene-divinylbenzene copolymer.
Concrete preparation process is as follows:
(1) amine resin preparation
In the 250mL there-necked flask, add 7.0g chloromethylated polystyrene resin, add 10mL dimethyl sulfoxide (DMSO) swelling 0.5h, add the 40mL ethylenediamine then at 60 ℃ of reaction 12h, after the reactant cooling, adopt ethanol to carry out Soxhlet extracting 6h, washing was used 3% NaOH solution oscillation treatment 2 hours again, be washed to neutrality, drying makes amine resin.
(2) mannich reaction prepares resin
Get the 2g amine resin, after adding 5mL oxolane swelling 1.5h, add 30mL distilled water and 1.5mL formalin (mass concentration 37%), with hydrochloric acid conditioning solution pH is 3, adding down the 20mL tannin aqueous solution (regulating the pH value in advance is 4) behind the reaction 20min again at 99～100 ℃, to make the tannin concentration of system be 1%, continue reaction 6h, resin is fully washed drying, obtain product of the present invention.
After testing, the physical property of solidify tannin large hole adsorption resin is as follows:
Its Pyrogentisinic Acid's adsorption capacity is 70mg/g.
Embodiment 3
The solidify tannin large hole adsorption resin of present embodiment is that the vegatable tannin that contains 1% amount is fixed in styrene-divinylbenzene copolymer.
Concrete preparation process is as follows:
(1) amine resin preparation
In the 250mL there-necked flask, add 5.0g chloromethylated polystyrene resin, add 20mL dimethyl sulfoxide (DMSO) swelling 1.5h, add the 50mL ethylenediamine then at 80 ℃ of reaction 36h, after the reactant cooling, adopt ethanol to carry out Soxhlet extracting 5h, washing was used 4% NaOH solution oscillation treatment 2 hours again, be washed to neutrality, drying makes amine resin.
(2) mannich reaction prepares resin
Get the 3g amine resin, after adding 10mL oxolane swelling 2.5h, add 40mL distilled water and 2mL formalin (mass concentration 37%), with hydrochloric acid conditioning solution pH is 4, adding down the 30mL tannin aqueous solution (regulating the pH value in advance is 4) behind the reaction 40min again at 99～100 ℃, to make the tannin concentration of system be 1.5%, continue reaction 8h, resin is fully washed drying, obtain product of the present invention.
After testing, the physical property of solidify tannin large hole adsorption resin is as follows:
Its Pyrogentisinic Acid's adsorption capacity is 80mg/g.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. a solidify tannin large hole adsorption resin is characterized in that, it contains the vegatable tannin of 0.25～1% amount.
2. the described solidify tannin large hole adsorption resin of claim 1 is characterized in that, described resin is a styrene-divinylbenzene copolymer.
3. prepare the method for claim 1 or 2 described solidify tannin large hole adsorption resins, it is characterized in that it comprises the steps:
1) amine resin preparation
The chloromethylated polystyrene resin adds the methyl-sulfoxide swelling, adds ethylenediamine then at 60～80 ℃ of reaction 12～36h, reactant cooling back suction filtration, and washing, drying makes amine resin;
2) mannich reaction prepares resin
Get amine resin, after adding the oxolane swelling, add distilled water and formalin, regulator solution pH is 3～5, and at 99～100 ℃ down behind reaction 20～40min, adding the pH value again and be 3～5 the tannin aqueous solution, to make the tannin concentration of aqueous solution of system be 0.5～2%, continue reaction 6～8h, washing is dry.
4. the preparation method of solidify tannin large hole adsorption resin according to claim 3, it is characterized in that, in the step 1), the mass volume ratio of chloromethylated polystyrene resin and methyl-sulfoxide is 0.5～0.7: 1～2 (g/ml), and swelling time is 0.5～1.5h.
5. according to the preparation method of claim 3 or 4 described solidify tannin large hole adsorption resins, it is characterized in that the amount of described ethylenediamine is 2～5 times of amounts of methyl-sulfoxide.
6. according to the preparation method of any described solidify tannin large hole adsorption resin of claim 3-5, it is characterized in that, step 2) in, the mass volume ratio of described amine resin and oxolane is 0.2～0.6: 1～2 (g/ml), and swelling time is 1.5～2.5h.
7. according to the preparation method of any described solidify tannin large hole adsorption resin of claim 3-6, it is characterized in that the amount of described distilled water is 3～6 times of amounts of oxolane; The amount of described formalin is 0.2～1 times of amount of oxolane.
8. according to the preparation method of any described solidify tannin large hole adsorption resin of claim 3-7, it is characterized in that described suction filtration adopts ethanol to carry out Soxhlet extracting 4～6h.
9. according to the preparation method of any described solidify tannin large hole adsorption resin of claim 3-8, it is characterized in that described washing is to adopt earlier washing, used 3～5% NaOH solution oscillation treatment again 2～3 hours, be washed to neutrality.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101031317A CN101249424A (en) | 2008-03-31 | 2008-03-31 | Solidify tannin large hole adsorption resin and method of preparing the same |
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| CNA2008101031317A CN101249424A (en) | 2008-03-31 | 2008-03-31 | Solidify tannin large hole adsorption resin and method of preparing the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013152492A1 (en) * | 2012-04-12 | 2013-10-17 | 淮北中润生物能源技术开发有限公司 | Method for adsorbing phenolic chemicals from water phase |
| CN105037669A (en) * | 2015-07-08 | 2015-11-11 | 王金明 | Preparation method for adsorbent for sugar liquor refining |
| CN105727906A (en) * | 2016-03-29 | 2016-07-06 | 苏州蔻美新材料有限公司 | Plant tannin modified resin and preparation method thereof |
| CN111422942A (en) * | 2020-03-23 | 2020-07-17 | 浙江工业大学 | Method for synchronously reducing and adsorbing hexavalent chromium in water by using ethylenediamine-based resin |
| CN116078362A (en) * | 2023-04-11 | 2023-05-09 | 四川大学 | Boron isotope separation material of amino resin grafted plant polyphenol, preparation method and application |
-
2008
- 2008-03-31 CN CNA2008101031317A patent/CN101249424A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013152492A1 (en) * | 2012-04-12 | 2013-10-17 | 淮北中润生物能源技术开发有限公司 | Method for adsorbing phenolic chemicals from water phase |
| CN105037669A (en) * | 2015-07-08 | 2015-11-11 | 王金明 | Preparation method for adsorbent for sugar liquor refining |
| CN105727906A (en) * | 2016-03-29 | 2016-07-06 | 苏州蔻美新材料有限公司 | Plant tannin modified resin and preparation method thereof |
| CN111422942A (en) * | 2020-03-23 | 2020-07-17 | 浙江工业大学 | Method for synchronously reducing and adsorbing hexavalent chromium in water by using ethylenediamine-based resin |
| CN116078362A (en) * | 2023-04-11 | 2023-05-09 | 四川大学 | Boron isotope separation material of amino resin grafted plant polyphenol, preparation method and application |
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Open date: 20080827 |