CN103073100B - Dextrin-modified polysilicon ferric sulfate composite flocculating agent and preparation method thereof - Google Patents
Dextrin-modified polysilicon ferric sulfate composite flocculating agent and preparation method thereof Download PDFInfo
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- CN103073100B CN103073100B CN201310050032.8A CN201310050032A CN103073100B CN 103073100 B CN103073100 B CN 103073100B CN 201310050032 A CN201310050032 A CN 201310050032A CN 103073100 B CN103073100 B CN 103073100B
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Abstract
The invention discloses a dextrin-modified polysilicon ferric sulfate composite flocculating agent. The flocculating agent comprises polysilicon ferric sulfate and dextrin in the mass ratio of (3-250):1. A preparation method of the flocculating agent comprises the following steps of: (i) dissolving sodium silicate into water, mixing uniformly to obtain a sodium silicate solution, adding the sodium silicate solution into a sulfuric acid solution in a stirring state, and adjusting the pH value of the solution to 2-4 by using an alkali to obtain a polysilicic acid solution; (ii) preparing a ferrous sulfate solution, mixing the polysilicic acid solution and the ferrous sulfate solution in the molar ratio of Si and Fe being 1, adding an oxidation liquid in a stirring state, and curing to obtain polyferric silicate sulfate; and (iii) mixing the polyferric silicate sulfate and the dextrin in the abovementioned mass ratio, and stirring. The flocculating agent provided by the invention has the characteristics of high storage stability, high flocculating capability, high turbidity removing performance, high COD (Chemical Oxygen Demand) removing rate and the like; and moreover, a preparation process is simple, is convenient to operate and use, and can be widely applied to treatment of various industrial waste water.
Description
Technical field
The present invention relates to a kind of sewage treatment flocculating agent, specifically a kind of dextrin modified ferric sulfate of polymerized silica composite flocculation agent and preparation method thereof.
Background technology
Flocculation sedimentation is current widely used a kind of method for cleaning treatment of sewage, and it is mainly by add appropriate flocculation agent in trade effluent, makes flocculation agent and wastewater suspended substance aggegation sedimentation reach the object of purification of water quality.The quality of purification of water quality depends on the performance of flocculation agent to a great extent, and therefore, developing various high-performance flocculation agents is one of main study hotspots of current sewage disposal.
The kind of flocculation agent is a lot, is mainly divided into inorganic, organic and composite flocculation agent three major types.Wherein inorganic flocculating agent price is relatively cheap, but large usage quantity, and part flocculation agent can produce some adverse influences to HUMAN HEALTH and ecotope; Organic polymer coargulator consumption is few, and scum silica frost output is few, and flocculation ability is strong, and oil removing and oil removal are effective, but the residual monomer of this class superpolymer (as acrylamide) has the effects such as teratogenesis, carcinogenic, mutagenesis; And though composite flocculation agent can overcome inorganic, organic floculant shortcoming separately has the high and COD of soil removal efficiency to remove the strong characteristic of ability, the problem of the high and contaminate environment of ubiquity poor storage stability, cost.
Ferric sulfate of polymerized silica is the composite type inorganic polymer flocculation agent growing up on the basis of poly-silicic acid and traditional Ferric Salt Flocculants, it has simple, efficient, nontoxic, the reduced investment of preparation, characteristic that flocculation ability is strong, is one of recent domestic popular flocculation agent of processing trade effluent.
Dextrin is the incomplete hydrolysis ring-type polyhydroxylated polymer being linked by more than six glucose being obtained after acid or thermal treatment or enzymolysis cyclization by starch, is the starch hydrolysate of lower molecular weight, high branched structure, and molecular formula is (C
6h
10o
5)
nh
2o; Yellow or white amorphous powder; Be soluble in hot water, be slightly dissolved in cold water, be insoluble to ethanol and ether.Dextrin is divided into yellow starch gum and white dextrin by purity; It is mainly used in preparing water soluble adhesive, suspension agent, be widely used in the tackiness agent of medicine, food, papermaking, casting, wallpaper, label, stamp, adhesive tape etc., also as the excipient of medicine and the surrogate of Sudan Gum-arabic, also can be as weighting agent on various Chemical Solvents are produced, be used for improving the stability of product, extend and use preservation period.
At present, in the research of existing inorganic organic composite coagulator, also do not find the relevant report of dextrin modified ferric sulfate of polymerized silica composite flocculation agent.
Summary of the invention
Object of the present invention is just to provide a kind of dextrin modified ferric sulfate of polymerized silica composite flocculation agent and preparation method thereof, developing a kind of good stability, go that turbid rate is high, COD removes the strong and eco-friendly high-performance environment-friendly flocculation agent of ability.
The object of the invention is to be achieved through the following technical solutions:. a kind of dextrin modified ferric sulfate of polymerized silica composite flocculation agent, this flocculation agent comprises ferric sulfate of polymerized silica and dextrin, the mass ratio of described ferric sulfate of polymerized silica and dextrin is: 3～250:1.
The mass ratio of ferric sulfate of polymerized silica of the present invention and dextrin is: 13.6～250:1.
The mass ratio of ferric sulfate of polymerized silica of the present invention and dextrin is: 13.6～134:1.
The mass ratio of ferric sulfate of polymerized silica of the present invention and dextrin is: 13.6～25:1.
The mass ratio of ferric sulfate of polymerized silica of the present invention and dextrin is: 25:1.
Dextrin of the present invention is preferably white dextrin.
The preparation method of dextrin modified ferric sulfate of polymerized silica composite flocculation agent of the present invention, comprises the following steps:
(i) by soluble in water water glass, mix, obtain sodium silicate solution, under whipped state, sodium silicate solution is joined in sulphuric acid soln, with pH to 2～3 of alkali regulator solution, obtain poly-silicate solution;
(ii) preparing copperas solution, is 1 to mix above-mentioned poly-silicate solution and copperas solution by the mol ratio of Si:Fe, under whipped state, adds oxidation solution, and at 45～50 ℃, slaking 110～120min, obtains ferric sulfate of polymerized silica;
(iii) ferric sulfate of polymerized silica is mixed by above-mentioned mass ratio with dextrin, mixture is stirred 2～3 hours at normal temperatures, obtain dextrin modified ferric sulfate of polymerized silica composite flocculation agent.
Step of the present invention (i) in pH value preferably 3.
The oxygenant preferred hydrogen peroxide of step of the present invention described in (ii).
The dextrin of step of the present invention described in is (iii) white dextrin.
Important innovations part of the present invention is to adopt organic polymer dextrin to carry out modification to inorganic polymer ferric sulfate of polymerized silica, by both suitable quality formula tests a kind of new inorganic organic composite coagulator, i.e. dextrin modified poly-ferrosilicon composite flocculation agent.
The present invention carries out modification by dextrin to inorganic ferric sulfate of polymerized silica, fully utilized that ferric sulfate of polymerized silica is efficient, nontoxic, cost is low, flocculation ability is strong and the advantage of the safety non-pollution of dextrin, made up the defect that ferric sulfate of polymerized silica flocculation agent exists short, unfavorable preservation transportation steady time simultaneously, prepared and had that stability in storage is good, flocculation ability strong, turbidity removal performance is good, COD clearance is high and the novel flocculant of the characteristic such as environmental friendliness.In addition, this flocculation agent cost of material is cheap, and technique is simple, easy to operate, is suitable for scale operation and use, can be widely used in the processing of the trade effluents such as papermaking, printing and dyeing, medicine, chemical industry.
Flocculation agent provided by the invention is applicable to the wastewater treatment that pH value is 5～10 scopes; Suggestion dosage is 19～120 mg/L.
Embodiment
Embodiment is used for further describing the present invention below, but does not limit in any form the present invention.
Embodiment 1
(1) water glass is dissolved in distilled water and is mixed, the mass percent concentration sodium silicate solution that is 35%, under whipped state, it is in 20% sulphuric acid soln that sodium silicate solution is dropwise joined to mass percent concentration, use again the pH to 2 of sodium hydroxide solution regulator solution, obtain poly-silicate solution;
(2) get ferrous sulfate and be dissolved in distilled water, heating makes to dissolve completely, after stirring, obtains mass percent concentration and be 25% copperas solution;
(3) by poly-silicate solution and copperas solution, by the mol ratio of Si:Fe, be 1 to mix, under whipped state, add the hydrogen peroxide 4.5ml that quality is 30% than concentration, slaking 110min at 45 ℃, obtains mass percent concentration and is 53% ferric sulfate of polymerized silica flocculant solution;
(4) get 53% ferric sulfate of polymerized silica 10mL in beaker, then to add 100mL mass percent concentration be 2% yellow starch gum, obtain the mixture that ferric sulfate of polymerized silica and dextrin mass ratio are 3:1, stir 2 hours, obtain dextrin modified ferric sulfate of polymerized silica composite flocculation agent.
Embodiment 2
(1) water glass is dissolved in distilled water and is mixed, the mass percent concentration sodium silicate solution that is 35%, under whipped state, it is in 20% sulphuric acid soln that sodium silicate solution is dropwise joined to mass percent concentration, with sodium hydroxide solution, be adjusted to again the pH to 3 of solution, obtain poly-silicate solution;
(2) get ferrous sulfate and be dissolved in distilled water, heating makes to dissolve completely, after stirring, obtains mass percent concentration and be 25% copperas solution;
(3) by poly-silicate solution and copperas solution, by the mol ratio of Si:Fe, be 1 to mix, under whipped state, add the hydrogen peroxide 4.5ml that quality is 30% than concentration, slaking 120min at 48 ℃, obtains mass percent concentration and is 53% ferric sulfate of polymerized silica flocculant solution;
(4) get 53% ferric sulfate of polymerized silica 50mL in beaker, adding 100mL mass percent concentration is 2% white dextrin again, obtain the mixture that ferric sulfate of polymerized silica and dextrin mass ratio are 13.6:1, stir 2.5 hours, obtain dextrin modified ferric sulfate of polymerized silica composite flocculation agent.
Embodiment 3
(1) water glass is dissolved in distilled water and is mixed, the mass percent concentration sodium silicate solution that is 35%, under whipped state, it is in 20% sulphuric acid soln that sodium silicate solution is dropwise joined to mass percent concentration, with sodium hydroxide solution, be adjusted to again the pH to 3 of solution, obtain poly-silicate solution;
(2) get ferrous sulfate and be dissolved in distilled water, heating makes to dissolve completely, after stirring, obtains mass percent concentration and be 25% copperas solution;
(3) by poly-silicate solution and copperas solution, by the mol ratio of Si:Fe, be 1 to mix, under whipped state, add the hydrogen peroxide 4.5ml that quality is 30% than concentration, slaking 110min at 50 ℃, obtains mass percent concentration and is 53% ferric sulfate of polymerized silica flocculant solution;
(4) get 53% ferric sulfate of polymerized silica 100mL in beaker, adding 100mL mass percent concentration is 2% white dextrin again, obtain the mixture that ferric sulfate of polymerized silica and dextrin mass ratio are 25:1, stir 2.5 hours, obtain dextrin modified ferric sulfate of polymerized silica composite flocculation agent.
Embodiment 4
(1) water glass is dissolved in distilled water and is mixed, the mass percent concentration sodium silicate solution that is 35%, under whipped state, it is in 20% sulphuric acid soln that sodium silicate solution is dropwise joined to mass percent concentration, with sodium hydroxide solution, be adjusted to again the pH to 3 of solution, obtain poly-silicate solution;
(2) get ferrous sulfate and be dissolved in distilled water, heating makes to dissolve completely, after stirring, obtains mass percent concentration and be 25% copperas solution;
(3) by poly-silicate solution and copperas solution, by the mol ratio of Si:Fe, be 1 to mix, under whipped state, adding quality is 30 than concentration) hydrogen peroxide 4.5ml, slaking 110min at 50 ℃, obtains mass percent concentration and is 53% ferric sulfate of polymerized silica flocculant solution;
(4) get 53% ferric sulfate of polymerized silica 100mL in beaker, then to add 20mL mass percent concentration be 2% white dextrin, obtain the mixture that ferric sulfate of polymerized silica and dextrin mass ratio are 134:1, stir 3 hours, obtain dextrin modified ferric sulfate of polymerized silica composite flocculation agent.
Embodiment 5
(1) water glass is dissolved in distilled water and is mixed, the mass percent concentration sodium silicate solution that is 35%, under whipped state, it is in 20% sulphuric acid soln that sodium silicate solution is dropwise joined to mass percent concentration, with sodium hydroxide solution, be adjusted to again the pH to 3 of solution, obtain poly-silicate solution;
(2) get ferrous sulfate and be dissolved in distilled water, heating makes to dissolve completely, after stirring, obtains mass percent concentration and be 25% copperas solution;
(3) by poly-silicate solution and copperas solution, by the mol ratio of Si:Fe, be 1 to mix, under whipped state, add the hydrogen peroxide 4.5ml that quality is 30% than concentration, slaking 115min at 50 ℃, obtains mass percent concentration and is 53% ferric sulfate of polymerized silica flocculant solution;
(4) get 53% ferric sulfate of polymerized silica 100mL in beaker, then to add 10mL mass percent concentration be 2% white dextrin, obtain the mixture that ferric sulfate of polymerized silica and dextrin mass ratio are 250:1, stir 3 hours, obtain dextrin modified ferric sulfate of polymerized silica composite flocculation agent.
Comparative example
(1) water glass is dissolved in distilled water and is mixed, the mass percent concentration sodium silicate solution that is 35%, under whipped state, it is in 20% sulphuric acid soln that sodium silicate solution is dropwise joined to mass percent concentration, with sodium hydroxide solution, be adjusted to again the pH to 3 of solution, obtain poly-silicate solution;
(2) get ferrous sulfate and be dissolved in distilled water, heating makes to dissolve completely, after stirring, obtains mass percent concentration and be 25% copperas solution;
(3) by poly-silicate solution and copperas solution, by the mol ratio of Si:Fe, be 1 to mix, under whipped state, add the hydrogen peroxide 4.5ml that quality is 30% than concentration, slaking 110min at 50 ℃, obtains mass percent concentration and is 53% ferric sulfate of polymerized silica flocculation agent.
The Performance Detection of flocculation agent prepared by embodiment 6 specific embodiment of the invention
Detection method:
Sewage is from Shijiazhuang pharmaceutical factory equalizing tank waste water, and the COD content of raw waste water is 7120 mg/L.
(1) flocculation agent steady time: the time that keeps transparent and homogeneous state before solids precipitation or gel appears in flocculation agent, to investigate flocculation agent stable storing performance, unit: day.
(2) COD clearance: adopt potassium dichromate feedback method; Clearance=(supernatant C OD after COD of sewage-flocculation sediment)/COD of sewage × 100%, unit: %.
(3) go turbid rate: with turbidimeter, measure each supernatant liquor and raw water turbidity, go turbid rate=add flocculation agent to go to turbidity/raw water turbidity × 100% after turbid, unit: %.
During Performance Detection of the present invention, the flocculation agent of every liter of sewage input is 120mg, after dropping into, stirs 20 minutes, precipitates 10 minutes, carries out index detection.
Detected result: refer to table 1
Table 1 flocculation agent detergency ability detects
| Project | Flocculation agent steady time/sky | COD clearance/% | Remove turbid rate % |
| Embodiment 1 | 7 | 6.44 | 92.39 |
| Embodiment 2 | 8 | 19.3 | 93.80 |
| Embodiment 3 | 14 | 32.3 | 96.57 |
| Embodiment 4 | 7 | 10.8 | 95.80 |
| Embodiment 5 | 8 | 8.2 | 97.09 |
| Comparative example | 4 | 13.4 | 54.69 |
By above data presentation, dextrin modified polyacrylamide composite flocculation agent stability in storage provided by the invention is good, in sewage disposal, show away the superperformance that turbid performance is good and COD clearance is high, can extensively in the purifying treatment of all types of industries waste water, promote the use of.
Claims (4)
1. a preparation method for dextrin modified ferric sulfate of polymerized silica composite flocculation agent, this flocculation agent comprises ferric sulfate of polymerized silica and dextrin, the mass ratio of described ferric sulfate of polymerized silica and dextrin is: 13.6～25:1, it is characterized in that, comprise the following steps:
(i) by soluble in water water glass, mix, obtain sodium silicate solution, under whipped state, sodium silicate solution is joined in sulphuric acid soln, with pH to 2～3 of alkali regulator solution, obtain poly-silicate solution;
(ii) preparing copperas solution, is 1 to mix above-mentioned poly-silicate solution and copperas solution by the mol ratio of Si:Fe, under whipped state, adds oxygenant, and at 45～50 ℃, slaking 110～120min, obtains ferric sulfate of polymerized silica;
(iii) ferric sulfate of polymerized silica is mixed by above-mentioned mass ratio with dextrin, mixture is stirred 2～3 hours at normal temperatures, obtain dextrin modified ferric sulfate of polymerized silica composite flocculation agent.
2. the preparation method of dextrin modified ferric sulfate of polymerized silica composite flocculation agent according to claim 1, is characterized in that, step (i) middle pH value is 3.
3. the preparation method of dextrin modified ferric sulfate of polymerized silica composite flocculation agent according to claim 1, is characterized in that, step (ii) described oxygenant is hydrogen peroxide.
4. the preparation method of dextrin modified ferric sulfate of polymerized silica composite flocculation agent according to claim 1, is characterized in that, step (iii) described dextrin is white dextrin.
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| CN104445550B (en) * | 2014-11-13 | 2016-04-13 | 南京新美汇电子科技有限公司 | A kind of preparation method of heavy metal-polluted water treatment agent |
| CN105692828B (en) * | 2016-02-03 | 2019-04-12 | 长沙矿冶研究院有限责任公司 | The methods and applications of polysilicate sulfuric acid ferric flocculant are prepared with niobium-tantalum ore waste residue |
| CN105668750B (en) * | 2016-04-26 | 2019-05-21 | 河北冀泽生物科技有限公司 | The preparation process and system of modified ferric sulfate of polymerized silica flocculant |
| CN108996634A (en) * | 2018-07-24 | 2018-12-14 | 河南工程学院 | It is a kind of for handling the preparation method of the polymeric ferric sulfate flocculant of waste water from dyestuff |
| CN114516681A (en) * | 2022-01-21 | 2022-05-20 | 丁金萍 | Composite flocculant for industrial wastewater treatment and preparation method thereof |
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