The preparation method of a kind of alginate-persimmon tannin composite
Technical field
The invention belongs to field of material technology, particularly the preparation method of a kind of alginate-persimmon tannin composite.
Background technology
Along with the fast development of 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 just remains strong growth, heavy metal pollution event takes place frequently, bring serious infringement to the health of environment and people, administering heavy metal pollution has become 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 some heavy metal such as manganese, copper, zinc etc. are the required trace elements of vital movement, but most of heavy metal exceedes finite concentration, just will cause damage to health, cause various disease, as: the nervous system destruction, lung pain, inflammatory eye, fash, vomiting, stomachache, pain, expiratory dyspnea, hepatic injury etc. of dehydration, stomachache, nauseating, dizzy, muscle dysfunction, children.
Except the method for middle heavy metal ion of anhydrating is 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 large, operating cost is high, operational administrative 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 large, adsorption rate is fast, cost is low, simple to operate, do not produce the advantages such as secondary pollution, be more and more subject to the favor of people.
China is original producton location and the main product state of persimmon, is distributed in 23 provinces, cities and autonomous regions, and annual persimmon total output at about 5,000,000 tons, but is not widely used in food service industry due to its puckery, and most persimmon 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 be used as polyhydroxy part and metal ion carries out ligand exchange reaction, forms netted huge legendary turtle compound, and precipitates at various ph values, utilizes this characteristic can carry out the recovery and reuse of metallic element.
But because persimmon tannin is soluble in water, be difficult to be directly used in the removal of metal ion in water body.Thus most of document carries out modification to persimmon tannin, and condensation persimmon tannin, then for Adsorption of Heavy Metals.Conventional inorganic agent/modifier/crosslinking agent/curing agent comprises acids, aldehydes, amine, calcium chloride, potassium peroxydisulfate etc.
Simultaneously, document is had to prepare persimmon tannin class compound adsorbent further, (the material Leaders such as Guilin Electronic Science and Technology Univ. college of materials science and engineering Liu wind and thunder, 2014,28 (6): 57-60) take shitosan as matrix, make crosslinking agent with glutaraldehyde, achieve the solidification of persimmon tannin, and the system research characterization of adsorption of this sorbing material to gold ion.Chinese invention patent CN201110215779.5 is with the active carbon after process: persimmon tannin solution is that raw material obtains activated carbon-persimmon tannin compound absorbent, and the method cost is low, technique 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, the preparation method of a kind of alginate-persimmon tannin composite is provided.
The present invention is achieved by following technical proposals:
(1) immature natural persimmon was pulverized 60 mesh sieves, add the enzyme of deionized water and mass fraction 0.1-0.5 ‰, carry out ultrasonic 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) be that the alginate solution of 0.1-10wt% joins the persimmon tannin solution that concentration is 0.1-10wt% by concentration, stir, regulate the pH value 5-7 of solution, obtain alginate/persimmon tannin blend solution;
(3) in blend solution, add the calcium chloride solution that concentration is 1-5wt%, after mix and blend, in composite solution, drip 1mol/L acetum, after stirring 30-120min, proceed to mould and leave standstill crosslinked 1-48h, repeatedly clean with distilled water, freeze drying.
Preferably, alginate according to claim 1 is one or more in sodium alginate, calcium alginate, potassium alginate, ammonium alginate.
Preferably, the enzyme described in step (1) is the mixture of cellulase, pectase, and its mass ratio is 1:1.
Preferably, the alginate described in step (2) and the weight ratio of persimmon tannin are 1:0.5-2.
Preferably, the calcium chloride described in step (3) is the 1%-20% of alginate quality.
Preferably, the volume ratio of the acetum described in step (3) and alginate-persimmon tannin-calcium chloride mixed solution is 1:1-1:10.
The present invention has following beneficial effect: (1) material therefor of the present invention is natural materials, abundance, cheap, environmental protection.(2) adopt enzyme-ultrasound assisted extraction persimmon tannin, compared with the solvent extraction method of routine, this method is without the need to high temperature, and security is good, and consuming time short, efficiency is high.(3) alginate prepared-persimmon tannin composite has the advantages such as good mechanical property, institutional framework is regular, porosity is high, and cost is low, technique is simple.(4) adopt the alginate-persimmon tannin composite prepared after calcium ion crosslinking can play synergistic sorption effect of alginate, persimmon tannin, the adsorption effect of heavy metal ion than single alginate or persimmon tannin all good.(5) by the alginate of Adsorption of Heavy Metal Ions-persimmon tannin composite, 1% rare H is added
2sO
4can desorb be carried out, realize the recycling of alginate-persimmon tannin composite.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.
Embodiment 1:
Immature natural persimmon was pulverized 60 mesh sieves, added the enzyme of deionized water and mass fraction 0.1 ‰, carried out ultrasonic 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.
Be that the 10ml sodium alginate soln of 1wt% joins the 10ml persimmon tannin solution that concentration is 1wt% by concentration, stir, 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 leave standstill crosslinked 10h, repeatedly clean with distilled water, freeze drying.
Configuration initial concentration is lead ion, the copper ion solution of 250mg/L, and adsorption temp is normal temperature.Alginate-persimmon tannin composite is to Pb
2+and Cu
2+absorption in 3h, 5h, reach balance respectively, saturated extent of adsorption is about 112.6mg/g and 138.7mg/g respectively.
Embodiment 2:
Immature natural persimmon was pulverized 60 mesh sieves, add the enzyme of deionized water and mass fraction 0.3 ‰, carry out ultrasonic 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.
Be that the 10ml calcium alginate solution of 5wt% joins the 10ml persimmon tannin solution that concentration is 8wt% by concentration, stir, 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 leave standstill crosslinked 24h, repeatedly clean with distilled water, freeze drying.
Embodiment 3:
Immature natural persimmon was pulverized 60 mesh sieves, add the enzyme of deionized water and mass fraction 0.5 ‰, carry out ultrasonic 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.
Be that the 10ml potassium alginate solution of 5wt% joins the 10ml persimmon tannin solution that concentration is 10wt% by concentration, stir, 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 leave standstill crosslinked 48h, repeatedly clean with distilled water, freeze drying.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, 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 give exhaustive to all embodiments.Every belong to technical scheme of the present invention the apparent change of amplifying out or variation be still in the row of protection scope of the present invention.