CN101342481B - Preparation method for iron-tannic acid adsorption agent with high-ctivity dephosphorization and uses thereof - Google Patents
Preparation method for iron-tannic acid adsorption agent with high-ctivity dephosphorization and uses thereof Download PDFInfo
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- CN101342481B CN101342481B CN2008101179494A CN200810117949A CN101342481B CN 101342481 B CN101342481 B CN 101342481B CN 2008101179494 A CN2008101179494 A CN 2008101179494A CN 200810117949 A CN200810117949 A CN 200810117949A CN 101342481 B CN101342481 B CN 101342481B
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Abstract
The invention discloses a preparation method and an application, belonging to the technical field of water treatment and relating to the preparation method and the application of a high active dephosphorizing iron-tannin adsorbent prepared by polyvinyl alcohol embedded iron-tannin. Firstly, an iron-tannin compound is embedded within the polyvinyl alcohol to constitute an iron-tannin embedded body; phosphorus in water is diffused into the embedded body and reacts with the iron in the embedded body to form a ferric phosphate-tannin compound. The phosphorus adsorbent prepared by the method has an adsorption capacity in 2 to 5 times of activated aluminium oxide and is easy to use; when the adsorbent is saturated, the adsorbent can be took out directly and used as a delayed release fertilizer. Compared with the prior chemical dephosphorizing operation, the high active dephosphorizing iron-tannin adsorbent has the advantages of simple operation, reduced operating cost, lightened workload, simple making technology and easy resource recycling of the product of the saturated phosphorus adsorbent.
Description
Technical field
The invention belongs to water-treatment technology field, particularly adopt the iron-tannic acid adsorbent preparation method and the application thereof of a kind of high activity dephosphorization of polyvinyl alcohol embedding iron-tannic acid making.
Background technology
Excessive phosphorus causes the eutrophication of water body with other superfluous nutrient in the environment water, prevents that by the phosphorus of removing in the water body method that eutrophication takes place is proved to be permanently effective method.Conventional wastewater biological dephosphorization method adopts the form of chemical precipitation usually, needs to add flocculant, and needs supporting sewage disposal device, and the operating cost of dephosphorization is higher, and is easy to generate secondary pollution, can not reclaim the defective of phosphor resource.And the adsorption and dephosphorization method has that operation is simple and reliable, can be used for slow-release phosphate fertilizer after adsorbents adsorb is saturated, can be used as resource and utilizes.
In adsorbent for phosphate removal technology, the absorption method dephosphorization is to utilize the absorption affinity of the solid matter of some porous or Large ratio surface to phosphate anion in the water, realizes the dephosphorization and the phosphorus of waste water are reclaimed.Dephosphorization adsorbent should have the adsorption capacity height, anti-interference, be easy to regeneration, characteristics such as price is low.Natural material and part industrial slags such as kaolin, bentonite and natural zeolite all have certain suction-operated to phosphate anion in the water.People are also in research and utilization activated alumina and some other artificial synthetic adsorbent dephosphorization.Activated alumina is traditional phosphorus adsorbent, and application at present is wider, but because the phosphorus adsorption capacity is not high enough, and the adsorbent cycle of operation is also shorter, and aluminium is harmful, the phosphorus of absorption is difficult to carry out recycling.Yet the industrial applications of waste water dephosphorization requires adsorbent that must be arranged long service cycle, must take all factors into consideration adsorbent expense, cost of equipment and operating cost, therefore, the requirement of efficient dephosphorization adsorbent is become inevitable.
Summary of the invention
At the deficiencies in the prior art and defective, the purpose of this invention is to provide a kind of iron-tannic acid adsorbent preparation method and application thereof of high activity dephosphorization, it is characterized in that the iron of described high activity dephosphorization-tannic acid adsorbent preparation method carries out according to following step:
1) is mixed with 5 ~ 15% the macromolecule aqueous solution with water miscible hydroxy polymer;
2) with water-soluble trivalent inorganic molysite and NaOH 1:3 hybrid reaction generation in molar ratio flco, the stoichiometry of flco according to molar concentration 1.5-2.0M added in the aforementioned macromolecule aqueous solution, stirring is dissolved it fully;
3) then under condition of stirring, adding concentration is the tannic acid of 1.0-10.0g/L, mixes;
4) above-mentioned mixed solution is splashed in saturated boric acid or the ethanedioic acid solution, form the spherical condensate of diameter 0.5-3mm;
5) the gained precipitated product is washed, promptly obtained polyvinyl alcohol embedding iron-tannic acid adsorbent after the drying.
Described water soluble hydroxy polymer is a polyvinyl alcohol, and the degree of polymerization is 40-55.
Described trivalent inorganic molysite is iron chloride, ferric sulfate or ferric nitrate.
Described tannic acid is condensed tannin acid.
The application of the described iron of a kind of claim 1-tannic acid adsorbent, comprise and be used for removing the superfluous phosphorus of water bodys such as waste water, sanitary sewage and eutrophication river and lake, and adsorb containing ferrophosphorus-tannic acid adsorbent and can be used as slow release fertilizer after saturated, realize the utilization again of phosphor resource.
The present invention compared with prior art, have the following advantages and outstanding effect: adsorbents adsorb capacity height, its Unit Weight adsorbance are 2-3 times of activated alumina; The density height of the effective iron ion of adsorbent, and form a lot of small spaces after the embedding, even the iron ion of embedding body inside also can play a role; The adsorbent that adsorbs after saturated can be used as slow release fertilizer, realizes the utilization again of resource; And because tannic acid and iron ion isochela cooperation usefulness, the iron ion stripping meets all kinds of water standards, does not have other metal ion stripping problem.
The specific embodiment
The invention provides a kind of highly active Fe-tannic acid preparation of adsorbent method and application thereof.Described highly active Fe-tannic acid preparation of adsorbent method is carried out according to following step:
With the degree of polymerization is the macromolecule aqueous solution of 40-55 water-soluble poval preparation 5-15wt%; Water-soluble trivalent inorganic molysite (as iron chloride, ferric nitrate or ferric sulfate etc.) and NaOH (mol ratio 1:3) reaction are generated flco, the stoichiometry of flco according to molar concentration 1.5-2.0M added in the aforementioned macromolecule aqueous solution, and stirring is dissolved it fully; Then under condition of stirring, adding concentration is the tannic acid of 1.0-10.0g/L, then above-mentioned solution is dropped in the saturated BAS with dropper, above-mentioned solution forms the spheric granules that diameter is 1-3mm in boric acid, to above-mentioned precipitated product through washing, dehydration, drying process after, can obtain highly active Fe-tannic acid adsorbent.
Embodiment 1
Get the aqueous solution that polyvinyl alcohol is prepared 10wt% with mean molecule quantity 1455 (degree of polymerization 55),, add the tannic acid of 5g/L then, be made into the mixed solution of 1.5M with the flco that this solution dissolving ferric trichloride and NaOH (mol ratio 1:3) generate.Under stirring at normal temperature with above-mentioned drips of solution in saturated BAS, forming diameter is the polyvinyl alcohol embedding iron-tannic acid embedding body of the form of spherical particles of 1-3mm.To precipitation wash, dewater, drying, adsorbent sample 1.
Sample 1 is used for absorption to phosphate solution phosphorus, in the phosphorus in the water is diffused into the embedding body and the ferro element in the embedding body react, form the compound of ferric phosphate-tannic acid.In temperature is 25 ℃, and initial pH is 6.0, carries out adsorption test under the condition of initial phosphorus concentration 20mg/l.Two 100ml water samples are added 0.1g sample 1 and 0.1g reactive powder aluminium polychloride respectively, and the adsorbance that records after the adsorption equilibrium is respectively: sample 1:41mg-P/g; Powder aluminium polychloride: 18.5mg-P/g.Sample 1 is 2.2 times of alumina powder Unit Weight adsorbance.Wherein sample 1 can be used as slow release fertilizer, realizes the utilization again of resource; And the powder aluminium polychloride is harmful, is difficult to carry out recycling.
Embodiment 2
Press the poly-vinyl alcohol solution of embodiment 1 preparation 5wt%, react the sediment that forms and add tannic acid with this solution dissolving ferric sulfate and NaOH (mol ratio 1:3).Under stirring at normal temperature above-mentioned solution is dripped in the saturated BAS, forming diameter is the polyvinyl alcohol embedding iron-tannic acid embedding body of the form of spherical particles of 1-3mm.To particle wash, dewater, dry, adsorbent sample 2.
Sample 2 is used for absorption to phosphate solution phosphorus.In temperature is 25 ℃, and initial pH is 7.0, carries out adsorption test under the condition of initial phosphorus concentration 80mg/L.Two 100ml water samples are added 0.1g test 2 and 0.1g powder aluminium polychloride respectively, and the adsorbance that records after the adsorption equilibrium is respectively: sample 2:48.9mg-P/g; Powder aluminium oxide: 19.6mg-P/g.Sample 2 is 2.5 times of aluminium oxide Unit Weight adsorbance.Wherein sample 2 can be used as slow release fertilizer, realizes the utilization again of resource; And the powder aluminium polychloride is harmful, is difficult to carry out recycling.
Claims (4)
1. the iron of a high activity dephosphorization-tannic acid adsorbent preparation method is characterized in that, the iron of described high activity dephosphorization-tannic acid adsorbent preparation method carries out according to following step:
1) with the degree of polymerization is the macromolecule aqueous solution that the polyvinyl alcohol of 40-55 is mixed with 5-15%;
2) water-soluble trivalent inorganic molysite and NaOH were mixed in 1: 3 in molar ratio, reaction generates flco, and the stoichiometry of flco according to molar concentration 1.5-2.0M added in the aforementioned macromolecule aqueous solution, stirs it is dissolved fully;
3) then under condition of stirring, adding concentration is the tannic acid of 1.0-10.0g/L, mixes to obtain mixed solution;
4) above-mentioned mixed solution is splashed in saturated boric acid or the ethanedioic acid solution, form the spherical condensate of diameter 0.5-3mm, promptly obtain precipitated product;
5) the gained precipitated product is washed, promptly obtained polyvinyl alcohol embedding iron-tannic acid adsorbent after the drying.
2. according to the iron-tannic acid adsorbent preparation method of the described high activity dephosphorization of claim 1, it is characterized in that described trivalent inorganic molysite is iron chloride, ferric sulfate or ferric nitrate.
3. according to the iron-tannic acid adsorbent preparation method of the described high activity dephosphorization of claim 1, it is characterized in that described tannic acid is condensed tannin acid.
4. application of iron-tannic acid adsorbent of making of preparation method according to claim 1, it is characterized in that, comprise being used for removing waste water and the superfluous phosphorus of river course eutrophication water, and adsorb and contain ferrophosphorus-tannic acid adsorbent as slow release fertilizer after saturated, realize the utilization again of resource.
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| CN103663641B (en) * | 2013-12-09 | 2016-01-20 | 余苏祥 | A kind of flocculation agent for the treatment of paper waste |
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Inventor after: Feng Quan Inventor after: Bi Xianrong Inventor after: Liang Peng Inventor before: Feng Quan Inventor before: Xing Xinhui Inventor before: Bi Xianrong Inventor before: Liang Peng |
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Address after: 100084 room 476, Department of chemical engineering, Tsinghua University, Beijing, Haidian District Patentee after: BEIJING CAPITAL QING YUAN ENVIRONMENTAL TECHNOLOGY CO., LTD. Address before: 100084 room 476, Department of chemical engineering, Tsinghua University, Beijing, Haidian District Patentee before: Beijing Siqingyuan Bioscience Co., Ltd. |