CN102580698A - Persimmon tannin adsorption material and preparation method thereof - Google Patents
Persimmon tannin adsorption material and preparation method thereof Download PDFInfo
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- CN102580698A CN102580698A CN2012100436666A CN201210043666A CN102580698A CN 102580698 A CN102580698 A CN 102580698A CN 2012100436666 A CN2012100436666 A CN 2012100436666A CN 201210043666 A CN201210043666 A CN 201210043666A CN 102580698 A CN102580698 A CN 102580698A
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Abstract
The invention discloses a persimmon tannin adsorption material and a preparation method of the persimmon tannin adsorption material. The preparation method comprises the steps of: adding 2-5 parts of cattle-hide collagen fiber and 5-8 parts of persimmon powder which are treated into 100 parts of deionized water to be mixed and dissolved, and stirring for 10-20h at the normal temperature; adding 3-8 parts of cross-linking agent into the mixed solution, adjusting the pH value of the mixed solution to 6.0-6.6 by NaOH or HCl water solution, and carrying out reaction for 1-3 hours at the normal temperature; leading reactant to carry out water bath reaction for 3-5h at the temperature of 50-60 DEG C; taking out products of the reaction and filtering, carrying out vacuum drying at the temperature of 60 DEG C; and after drying, grinding the products into fine powder by a grinding machine to obtain the cattle-hide collagen fiber-cured persimmon tannin adsorption material. The persimmon tannin adsorption material is good in physical stability, remarkable in adsorption effect, low in cost and free from secondary pollution for the environment, and can be used in a circulating way; the persimmon tannin adsorption material is used for carrying out adsorption recovery test on noble metals such as Cu, Cr, Fe, Ag and the like, and the average adsorption rate reaches more than 95%, so that better adsorption effect can be achieved; and the persimmon tannin adsorption material disclosed by the invention is suitable for adsorbing, separating and recovering the heavy metal ions in industrial waste water with low concentration.
Description
Technical field
The invention belongs to functional high polymer material field, specifically is a kind of persimmon tannin sorbing material and preparation method thereof.
Background technology
At present, the method for handling heavy metal-containing waste water, waste residue both at home and abroad mainly contains three kinds: the one, and chemical precipitation method, the 2nd, biological treatment, the 3rd, absorption method.Absorption method is to handle the particularly comparatively effective method of low-concentration heavy metal ion waste water of effluent containing heavy metal ions, and sorbing material commonly used comprises active carbon, synthetic resin, mineral matter, microorganism and natural biomass etc.; People such as the Zhang Huiping of South China Science & Engineering University, Zhu Liguo study the activated carbon fiber counterweight Adsorption Properties for Metal Ions of activated carbon fiber and modification, and the result shows: activated carbon fiber is to Cu
2+, Ni
2+Saturated extent of adsorption be respectively 5.1mg/g, 6.6mg/g, the activated carbon fiber of modification is to Cu
2+, Ni
2+Saturated extent of adsorption reached 20.6mg/g, 8.0mg/g, adsorption capacity is still less than normal; These sorbing materials also come with some shortcomings in industrial applications, and the one, adsorption capacity is lower, only a few metal ion is had suction-operated and adsorption capacity usually between 5-20mg/g like active carbon; The 2nd, absorption and desorption rate are slow, and present employed sorbing material mainly depends on the porous character of sorbing material self, and heavy metal ion mainly is adsorbed through the surface that gets into the sorbing material endoporus, so its adsorption rate is slower; The 3rd, can't regenerate and reuse after a lot of sorbing material absorption are saturated, can only carry out processing such as landfill or burning as solid waste, often cause secondary pollution.
Tannin is a kind of natural polyphenol compound, and it extensively is present in the plant, a plurality of ortho positions phenolic hydroxyl group that tannin has; It can be combined and complex reaction with multiple metal ion generation static, is swift in response, but tannin soluble in water with polar organic solvent in; Therefore be difficult to directly be used for Industrial Wastewater Treatment, existing research shows: can tannin and aldehyde compound reaction be generated tannin resin, perhaps use macromolecular material as backing material; Tannin is solidificated on these macromolecular materials, processes solidified tannin adsorptive material, but still it is not firm to exist tannin to solidify; Be prone to come off problems such as poor stability.
Summary of the invention
Technical problem to be solved by this invention provides a kind of persimmon tannin sorbing material and preparation method thereof.The persimmon tannin sorbing material adsorption capacity of this method preparation is big, and easy desorption; Can be applicable to separate, reclaim noble metal, and can be recycled.
The technical scheme that realizes the object of the invention is:
Adopt the source of natural puckery persimmon extract, combine formation to solidify persimmon tannin with cattle-hide collagen fibers through aldehyde is crosslinked tannin in the puckery persimmon powder as tannin.This curing persimmon tannin has good physical stability, through modification, and under various conditions, can the selective absorption precious metal ion.
A kind of preparation method of persimmon tannin sorbing material comprises the steps:
(1) takes by weighing by 2 ~ 5 parts of the cattle-hide collagen fibers of having handled of following weight portion and 5 ~ 8 parts of persimmon powders, join mixed dissolution in 100 parts of deionized waters, stirred at normal temperatures 10 ~ 20 hours;
(2) add 3 ~ 8 parts of crosslinking agents, the pH of mixed solution is adjusted to 6.0 ~ 6.6, reacted at normal temperatures 1 ~ 3 hour with NaOH or the HCl aqueous solution; Crosslinking agent can be glutaraldehyde or formaldehyde, and concentration can be 25% the aqueous solution;
(3) with reacted product 50 ~ 60 ℃ of following water-baths 3 ~ 5 hours;
(4) take out filtration, 60 ℃ of following vacuum drying, dry back is ground into fine powder with pulverizer, just obtains collagen fiber solidified persimmon tannin sorbing material.
The present invention has the following advantages and characteristic:
1, physical stability is good:
The thermal denaturation temperature that records the curing persimmon tannin sorbing material that several groups of different persimmon powders and cattle-hide collagen fibers proportioning make with the DSC differential scanning calorimetry is respectively 156.9 ~ 175.2 ℃, 160.7 ~ 177.7 ℃, 148.1 ~ 179.1 ℃; It is much higher to compare the thermal denaturation temperature that has the research of reporting to solidify hair Baybery tannin (90～96 ℃) or curing larch tannin (93～98 ℃), promptly has higher heat endurance.
2, adsorption capacity is big, and the scope of application is big, and is effective: with active carbon; Sorbing materials such as mineral matter can only adsorb a few metal ion and absorption is slow; Be difficult for desorb, adsorption capacity is less to be compared, and the scope of application of solidifying the persimmon tannin adsorbent wants big; Multiple metal ion has all been demonstrated the good adsorption performance, like metals such as copper, iron, chromium, cadmium, silver.Wherein, be 91.65% to the adsorption rate of copper, be 98.92% to the adsorption rate of iron, be 99.95% to the adsorption rate of chromium, and through after the screening, the adsorption effect of the curing persimmon tannin powder that particle diameter is little be better than the big particle adsorbent.
3, cost is low: it is raw material that this product adopts persimmon powder and materials with hide glue fibril, makes costs such as spent ion exchange resin or synthetic resin much lower than tradition.
4, environment friendly and pollution-free: as to carry out landfill or burning after making heavy metal ion generate water-fast deposit with chemical precipitation method in the industry; Essence but is a kind of transfer of pollution; By contrast; The raw material of this product are natural persimmon powder and collagenous fibres, are easier to desorption after absorption is used and can produce secondary pollution to environment.
5, can be recycled: can't regenerate after traditional charcoal absorption is saturated, can not reuse; And solidified tannin adsorptive material all can recycle multiple precious metal ion, after different stripping liquid desorbs, the sample that obtains is adsorbed again; Three absorption property tests; The result shows that adsorbance descends to some extent but be also not obvious, explains that this product has good regenerability.
The specific embodiment
Through embodiment the present invention is further described below, but is not qualification content of the present invention.
Embodiment 1:
To be according to publication number: persimmon powder 60g, materials with hide glue fibril 15g that the application for a patent for invention method of CN101328194 is produced join in the 1000ml distilled water, 25 ℃ of following stirring reactions 20 hours; Add the 22.5ml laboratory and use 25% glutaraldehyde water solution, 25 ℃ of following stirring reactions 1 hour; After reaction finished, the pH that uses the pH tester to record solution was 5.0; Regulate pH to 6.4 with the NaOH aqueous solution of 1mol/L again, then reactant is put into there-necked flask, 50 ℃ of following water-baths 3 hours; Take out with circulation ability of swimming vavuum pump vacuumizing filtration, 60 ℃ of following vacuum drying 12 hours; Take out with pulverizer at last and be ground into fine powder, obtain collagen fiber solidified tannin 60g.Through absorption Fe
3+Test records absorption back concentration by AAS, and calculating its adsorption rate is 90.1%, is 98.92% and use the adsorption rate of the fine grained adsorbent that 120 mesh filter out.
Embodiment 2:
FD persimmon powder 60g, materials with hide glue fibril 40g with buying joined in the 1000ml distilled water, 25 ℃ of following stirring reactions 20 hours; Add the 60ml laboratory with 25% glutaraldehyde water solution 25 ℃ of following stirring reactions 1 hour; After reaction finished, the pH that uses the pH tester to record solution was 5; Regulate pH to 6.4 with the NaOH aqueous solution of 1mol/L again, then reactant is put into there-necked flask, 50 ℃ of following water-baths 3 hours; Take out with circulation ability of swimming vavuum pump vacuumizing filtration, 60 ℃ of following vacuum drying 12 hours; Take out with pulverizer at last and be ground into fine powder, obtain collagen fiber solidified tannin 79g.Through Adsorption of Cu
2+Test records absorption back concentration by AAS, and calculating its adsorption rate is 91.65%.
Embodiment 3:
FD persimmon powder 60g, materials with hide glue fibril 40g with buying joined in the 1000ml distilled water, 25 ℃ of following stirring reactions 20 hours; Add the 60ml laboratory with 25% glutaraldehyde water solution 25 ℃ of following stirring reactions 1 hour; After reaction finished, the pH that uses the pH tester to record solution was 5; Regulate pH to 6.4 with the NaOH aqueous solution of 1mol/L again, then reactant is put into there-necked flask, 50 ℃ of following water-baths 3 hours; Take out with circulation ability of swimming vavuum pump vacuumizing filtration, 60 ℃ of following vacuum drying 12 hours; Take out with pulverizer at last and be ground into fine powder, obtain collagen fiber solidified tannin 79g.Through absorption Ag
+Test records absorption back concentration by AAS, and calculating its adsorption rate is 95.2%.
Embodiment 4:
FD persimmon powder 60g, materials with hide glue fibril 60g with buying joined in the 1000ml distilled water, 25 ℃ of following stirring reactions 20 hours; Add the 60ml laboratory with 25% glutaraldehyde water solution 25 ℃ of following stirring reactions 1 hour; After reaction finished, the pH that uses the pH tester to record solution was 5; Regulate pH to 6.4 with the NaOH aqueous solution of 1mol/L again, then reactant is put into there-necked flask, 50 ℃ of following water-baths 3 hours; Take out with circulation ability of swimming vavuum pump vacuumizing filtration, 60 ℃ of following vacuum drying 12 hours; Take out with pulverizer at last and be ground into fine powder, obtain collagen fiber solidified tannin 98g.Through absorption Cr
6+Test, calculating its adsorption rate is 99.95%.
Claims (3)
1. persimmon tannin sorbing material, it is characterized in that: this sorbing material is processed by following raw material by weight:
Cattle-hide collagen fibers 2 ~ 5
Persimmon powder 5 ~ 8
Crosslinking agent 3 ~ 8.
2. the preparation method of the described persimmon tannin sorbing material of claim 1 is characterized in that: comprise the steps:
(1) takes by weighing cattle-hide collagen fibers and the persimmon powder of having handled, join mixed dissolution in the deionized water, stirred at normal temperatures 10 ~ 20 hours;
(2) add crosslinking agent, the pH of mixed solution is adjusted to 6.0 ~ 6.6, reacted at normal temperatures 1 ~ 3 hour with NaOH or the HCl aqueous solution;
(3) reactant that step (2) is drawn was 50 ~ 60 ℃ of following water-baths 3 ~ 5 hours;
(4) take out filtration, 60 ℃ of following vacuum drying, dry back is ground into fine powder with pulverizer, just obtains collagen fiber solidified persimmon tannin sorbing material.
3. persimmon tannin sorbing material according to claim 1 is characterized in that: said crosslinking agent is to adopt glutaraldehyde or formaldehyde, and concentration is 25% the aqueous solution.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899489A (en) * | 2012-11-05 | 2013-01-30 | 桂林电子科技大学 | Method for recovering gold from electronic wastes by using solidified persimmon tannin |
| CN102925683A (en) * | 2012-11-05 | 2013-02-13 | 桂林电子科技大学 | Indium-iron separation method by using persimmontannin |
| CN105079842A (en) * | 2015-09-15 | 2015-11-25 | 江苏锦宇环境工程有限公司 | Preparation method of poultry farm deodorant |
| CN105727907A (en) * | 2016-04-12 | 2016-07-06 | 桂林电子科技大学 | Magnetic persimmon tannin composite adsorption material and preparing method thereof |
| CN108031450A (en) * | 2017-11-15 | 2018-05-15 | 四川大学 | A kind of solidified tannin polyamide miillpore filter and its preparation method and application |
| CN114522675A (en) * | 2022-04-07 | 2022-05-24 | 四川大学 | Adsorption separation material for adsorbing boron and separating boron isotope and preparation method thereof |
| CN115254021A (en) * | 2022-08-01 | 2022-11-01 | 广西壮族自治区农业科学院 | Green preparation method and application of biochar loaded nano-iron material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410157A (en) * | 2002-11-27 | 2003-04-16 | 四川大学 | Collagen fiber solidified tannin adsorptive material and its preparation method and its adsorption and separation of metallic ion |
| CN101294349A (en) * | 2008-06-19 | 2008-10-29 | 四川大学 | Collagen fiber stem grafting tannic acid and method for loading palladium catalyst |
-
2012
- 2012-02-24 CN CN2012100436666A patent/CN102580698A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410157A (en) * | 2002-11-27 | 2003-04-16 | 四川大学 | Collagen fiber solidified tannin adsorptive material and its preparation method and its adsorption and separation of metallic ion |
| CN101294349A (en) * | 2008-06-19 | 2008-10-29 | 四川大学 | Collagen fiber stem grafting tannic acid and method for loading palladium catalyst |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899489A (en) * | 2012-11-05 | 2013-01-30 | 桂林电子科技大学 | Method for recovering gold from electronic wastes by using solidified persimmon tannin |
| CN102925683A (en) * | 2012-11-05 | 2013-02-13 | 桂林电子科技大学 | Indium-iron separation method by using persimmontannin |
| CN102925683B (en) * | 2012-11-05 | 2013-11-06 | 桂林电子科技大学 | Indium-iron separation method by using persimmontannin |
| CN105079842A (en) * | 2015-09-15 | 2015-11-25 | 江苏锦宇环境工程有限公司 | Preparation method of poultry farm deodorant |
| CN105727907A (en) * | 2016-04-12 | 2016-07-06 | 桂林电子科技大学 | Magnetic persimmon tannin composite adsorption material and preparing method thereof |
| CN105727907B (en) * | 2016-04-12 | 2018-06-08 | 桂林电子科技大学 | A kind of magnetism persimmon tannin composite adsorbing material and preparation method thereof |
| CN108031450A (en) * | 2017-11-15 | 2018-05-15 | 四川大学 | A kind of solidified tannin polyamide miillpore filter and its preparation method and application |
| CN114522675A (en) * | 2022-04-07 | 2022-05-24 | 四川大学 | Adsorption separation material for adsorbing boron and separating boron isotope and preparation method thereof |
| CN115254021A (en) * | 2022-08-01 | 2022-11-01 | 广西壮族自治区农业科学院 | Green preparation method and application of biochar loaded nano-iron material |
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Application publication date: 20120718 |