CN104307490B - A kind of preparation method of alginate-persimmon tannin composite - Google Patents
A kind of preparation method of alginate-persimmon tannin composite Download PDFInfo
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- CN104307490B CN104307490B CN201410565425.7A CN201410565425A CN104307490B CN 104307490 B CN104307490 B CN 104307490B CN 201410565425 A CN201410565425 A CN 201410565425A CN 104307490 B CN104307490 B CN 104307490B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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Abstract
The preparation method that the present invention relates to a kind of alginate-persimmon tannin composite, method initially with enzyme-ultrasound assisted extraction obtains persimmon tannin, then the alginate solution that concentration is 0.1-10wt% is joined the persimmon tannin solution that concentration is 0.1-10wt%, obtain alginate/persimmon tannin blend solution, it is eventually adding calcium chloride and mixed solution is carried out calcium ion crosslinking, finally prepare alginate-persimmon tannin composite。The present invention adopts enzyme-ultrasound assisted extraction persimmon tannin, compared with conventional solvent extraction method, it is not necessary to high temperature, safety be good, consuming time short, efficiency is high。The alginate that the present invention prepares-persimmon tannin composite has the advantages such as good mechanical property, organizational structure is regular, porosity is high, and cost is low, technique is simple, and heavy metal ionic adsorption is effective。
Description
Technical field
The invention belongs to field of material technology, particularly to the preparation method of a kind of alginate-persimmon tannin composite。
Background technology
Fast development along with China's economy, society, the continuous growth of the size of population, the quickening of industrialization and urbanization advances, the industry relating to heavy metal pollution is just remain strong growth, heavy metal pollution event takes place frequently, bring serious infringement to the health of environment and people, administer heavy metal pollution and have become as an instant task。
Heavy metal pollution refers to the environmental pollution caused by heavy metal or its compound。Heavy metal can not be biodegradable, but can under the biological magnification of food chain, and thousands of times of ground enrichments finally enter human body。Although the trace element that to be vital movement required such as some heavy metal such as manganese, copper, zinc etc., but major part heavy metal exceedes finite concentration, just health will be caused damage, cause various disease, as: dehydration, stomachache, feel sick, dizziness, muscle dysfunction, the nervous system destruction of child, pain in the lung, inflammatory eye, erythra, vomiting, stomachache, pain, dyspnea, hepatic injury etc.。
Remove the method for heavy metal ion in water a lot, traditional has chemical precipitation method, oxidation-reduction method, ferrite process, electrolysis, evaporation concentration method, ion-exchange-resin process etc., but these methods exist mostly, and investment is big, operating cost is high, operation management bothers and can produce secondary pollution and can not solve the problem such as metal and water resource recycling well。And biomass adsorbent has that adsorbance is big, adsorption rate is fast, cost is low, simple to operate, do not produce the advantages such as secondary pollution, be increasingly subject to the favor of people。
China is original producton location and the main product state of Fructus Kaki, is distributed in 23 provinces, cities and autonomous regions, and annual Fructus Kaki total output is at about 5,000,000 tons, but owing to its puckery is without being widely used in food service industry, most Fructus Kaki is not all utilized effectively and naturally addles。During astringent persimmon fruit is real, tannin content is between 0.13%-1.54%, is a kind of fruit that tannin content is the highest。Persimmon tannin is a kind of natural polymer polyphenolic substance。Multiple ortho positions phenolic hydroxyl group that tannin contains, can carry out ligand exchange reaction as polyhydroxy part and metal ion, form netted sequestration thing, and precipitate at various ph values, utilize this characteristic can carry out the recycling and reuse of metallic element。
But owing to persimmon tannin is soluble in water, the removal of the metal ion that is difficult to be directly used in water body。Thus persimmon tannin is modified by most of document, condensation persimmon tannin, it is subsequently used for Adsorption of Heavy Metals。Conventional inorganic agent/modifying agent/cross-linking agent/firming agent includes acids, aldehydes, amine, calcium chloride, potassium peroxydisulfate etc.。
Simultaneously, document is had to be prepared for persimmon tannin class compound adsorbent further, (the material Leaders such as Guilin Electronic Science and Technology Univ.'s college of materials science and engineering Liu's wind and thunder, 2014,28 (6): 57-60) with chitosan for substrate, cross-linking agent is made, it is achieved that the solidification of persimmon tannin with glutaraldehyde, and systematic study this adsorbing material characterization of adsorption to gold ion。Chinese invention patent CN201110215779.5 is with the activated carbon after processing: persimmon tannin solution prepares activated carbon-persimmon tannin compound absorbent for raw material, and the method cost is low, technique is simple, and prepared compound adsorbent has the good feature of adsorption effect。But the research of alginate-persimmon tannin composite has no report temporarily。
Summary of the invention
The present invention is directed to the deficiency that prior art exists, it is provided that the preparation method of a kind of alginate-persimmon tannin composite。
The technical scheme is that:
(1) immature natural Fructus Kaki was pulverized 60 mesh sieves, add the enzyme of deionized water and mass fraction 0.1-0.5 ‰, carry out supersound extraction, ultrasonic power 80-120w, ultrasonic time 10-60min, ultrasonic temperature 30-50 DEG C, enzymolysis pH value 5-6, solid-liquid ratio is 1:5-1:20, by the extraction vacuum filtration at night after process, dries and obtains persimmon tannin；
(2) alginate solution that concentration is 0.1-10wt% is joined the persimmon tannin solution that concentration is 0.1-10wt%, stir, regulate the pH value 5-7 of solution, obtain alginate/persimmon tannin blend solution；
(3) adding concentration in blend solution is the calcium chloride solution of 1-5wt%, after mix and blend, drips 1mol/L acetum in composite solution, after stirring 30-120min, proceeds to mould and stands crosslinking 1-48h, repeatedly clean with distilled water, lyophilization。
Preferably, the alginate described in claim 1 is one or more in sodium alginate, calcium alginate, potassium alginate, ammonium alginate。
Preferably, the mixture that enzyme is cellulase, pectase described in step (1), its mass ratio is 1:1。
Preferably, the alginate described in step (2) is 1:0.5-2 with the weight ratio of persimmon tannin。
Preferably, the 1%-20% that calcium chloride is alginate quality described in step (3)。
Preferably, the acetum described in step (3) is 1:1-1:10 with the volume ratio of alginate-persimmon tannin-calcium chloride mixed solution。
There is advantages that (1) material therefor of the present invention is natural materials, abundance, cheap, environmental protection。(2) adopting enzyme-ultrasound assisted extraction persimmon tannin, compared with conventional solvent extraction method, this method is without high temperature, and safety is good, consuming time short, and efficiency is high。(3) alginate prepared-persimmon tannin composite has the advantages such as good mechanical property, organizational structure is regular, porosity is high, and cost is low, technique is simple。(4) alginate-persimmon tannin composite prepared after adopting calcium ion crosslinking can play synergistic sorption effect of alginate, persimmon tannin, and the adsorption effect of heavy metal ion will be good than single alginate or persimmon tannin。(5) by the alginate of Adsorption of Heavy Metal Ions-persimmon tannin composite, 1% rare H is added2SO4Desorbing can be carried out, it is achieved the recycling of alginate-persimmon tannin composite。
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further。
Embodiment 1:
Immature natural Fructus Kaki was pulverized 60 mesh sieves, adds the enzyme of deionized water and mass fraction 0.1 ‰, carry out supersound extraction, ultrasonic power 80w, ultrasonic time 10min, ultrasonic temperature 30 DEG C, enzymolysis pH value 5, solid-liquid ratio is 1:5, by the extraction vacuum filtration at night after process, dries and obtains persimmon tannin。Wherein enzyme is the mixture of cellulase, pectase, and mass ratio is 1:1。
The 10ml sodium alginate soln that concentration is 1wt% is joined the 10ml persimmon tannin solution that concentration is 1wt%, stirs, regulate the pH value 5 of solution, obtain sodium alginate/persimmon tannin blend solution。In blend solution, add the 1ml calcium chloride solution that concentration is 1wt%, after mix and blend, in composite solution, drip the 5ml acetum of 1mol/L, after stirring 60min, proceed to mould and stand crosslinking 10h, repeatedly clean with distilled water, lyophilization。
Configuration initial concentration is the lead ion of 250mg/L, copper ion solution, and adsorption temp is room temperature。Alginate-persimmon tannin composite is to Pb2+And Cu2+Absorption respectively reach in 3h, 5h balance, saturated extent of adsorption respectively may be about 112.6mg/g and 138.7mg/g。
Embodiment 2:
Immature natural Fructus Kaki was pulverized 60 mesh sieves, adds the enzyme of deionized water and mass fraction 0.3 ‰, carry out supersound extraction, ultrasonic power 100w, ultrasonic time 30min, ultrasonic temperature 40 DEG C, enzymolysis pH value 6, solid-liquid ratio is 1:10, by the extraction vacuum filtration at night after process, dries and obtains persimmon tannin。Wherein enzyme is the mixture of cellulase, pectase, and mass ratio is 1:1。
The 10ml calcium alginate solution that concentration is 5wt% is joined the 10ml persimmon tannin solution that concentration is 8wt%, stirs, regulate the pH value 6 of solution, obtain calcium alginate/persimmon tannin blend solution。In blend solution, add the 5ml calcium chloride solution that concentration is 2wt%, after mix and blend, in composite solution, drip the 10ml acetum of 1mol/L, after stirring 100min, proceed to mould and stand crosslinking 24h, repeatedly clean with distilled water, lyophilization。
Embodiment 3:
Immature natural Fructus Kaki was pulverized 60 mesh sieves, adds the enzyme of deionized water and mass fraction 0.5 ‰, carry out supersound extraction, ultrasonic power 120w, ultrasonic time 60min, ultrasonic temperature 50 DEG C, enzymolysis pH value 6, solid-liquid ratio is 1:20, by the extraction vacuum filtration at night after process, dries and obtains persimmon tannin。Wherein enzyme is the mixture of cellulase, pectase, and mass ratio is 1:1。
The 10ml potassium alginate solution that concentration is 5wt% is joined the 10ml persimmon tannin solution that concentration is 10wt%, stirs, regulate the pH value 7 of solution, obtain potassium alginate/persimmon tannin blend solution。In blend solution, add the 3ml calcium chloride solution that concentration is 5wt%, after mix and blend, in composite solution, drip the 10ml acetum of 1mol/L, after stirring 120min, proceed to mould and stand crosslinking 48h, repeatedly clean with distilled water, lyophilization。
Obviously, the above embodiment of the present invention is only for clearly demonstrating example of the present invention, and is not the restriction to embodiments of the present invention。For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description。Here cannot all of embodiment be given exhaustive。Every belong to apparent change that technical scheme amplified out or the variation row still in protection scope of the present invention。
Claims (3)
1. the preparation method of alginate-persimmon tannin composite, it is characterised in that this preparation method includes following operating procedure:
(1) immature natural Fructus Kaki was pulverized 60 mesh sieves, adding the enzyme of deionized water and mass fraction 0.1-0.5 ‰, wherein said enzyme is the mixture of cellulase, pectase, and its mass ratio is 1:1, then supersound extraction is carried out, ultrasonic power 80-120w, ultrasonic time 10-60min, ultrasonic temperature 30-50 DEG C, enzymolysis pH value 5-6, solid-liquid ratio is 1:5-1:20, by the extracting solution vacuum filtration after process, dries and obtains persimmon tannin；
(2) alginate solution that concentration is 0.1-10wt% is joined the persimmon tannin solution that concentration is 0.1-10wt%, stir, regulating the pH value 5-7 of solution, the weight ratio obtaining alginate/persimmon tannin blend solution, wherein said alginate and persimmon tannin is 1:0.5-2；
(3) adding concentration in blend solution is the calcium chloride solution of 1-5wt%, wherein said calcium chloride is the 1%-20% of alginate quality, after mix and blend, 1mol/L acetum is dripped in composite solution, after stirring 30-120min, proceed to mould and stand crosslinking 1-48h, repeatedly clean with distilled water, lyophilization。
2. the preparation method of a kind of alginate-persimmon tannin composite according to claim 1, it is characterised in that described alginate is one or more in sodium alginate, calcium alginate, potassium alginate, ammonium alginate。
3. the preparation method of a kind of alginate-persimmon tannin composite according to claim 1, it is characterised in that the volume ratio of the acetum described in step (3) and alginate-persimmon tannin-calcium chloride mixed solution is 1:1-1:10。
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| CN112108123B (en) * | 2020-08-31 | 2022-04-22 | 西安交通大学 | Modified sodium alginate composite ball, preparation method thereof and application of modified sodium alginate composite ball as heavy metal ion capturing agent |
| CN112551631A (en) * | 2020-12-01 | 2021-03-26 | 长春工业大学 | Method for rapidly reducing concentration of heavy metal chromium ions in water |
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| CN103551585A (en) * | 2013-07-17 | 2014-02-05 | 苏州正业昌智能科技有限公司 | Method for preparing nano-silver by utilizing persimmon tannin as reductant |
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Effective date of registration: 20190102 Address after: 221000 Room 213, Xuzhou High-tech Venture Center, Quanshan District, Xuzhou City, Jiangsu Province Patentee after: Zhong Jianwen Address before: 215000 No. 2 Taishan Road, Suzhou High-tech Zone, Suzhou City, Jiangsu Province Patentee before: Suzhou Zhengyechang Intelligent Technology Co., Ltd. |
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Effective date of registration: 20191030 Address after: 314500 shangfenggang West, Hebei side of Changshan, zhouquan Town, Tongxiang City, Jiaxing City, Zhejiang Province Patentee after: Tongxiang Jianchun Plastic Industry Co., Ltd Address before: Room 213, Xuzhou hi tech entrepreneurship center, Quanzhan District Patentee before: Zhong Jianwen |
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