CN1974427A - One-step preppn process of ecologically safe composite high efficiency flocculant - Google Patents
One-step preppn process of ecologically safe composite high efficiency flocculant Download PDFInfo
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- CN1974427A CN1974427A CN 200610129809 CN200610129809A CN1974427A CN 1974427 A CN1974427 A CN 1974427A CN 200610129809 CN200610129809 CN 200610129809 CN 200610129809 A CN200610129809 A CN 200610129809A CN 1974427 A CN1974427 A CN 1974427A
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Abstract
The present invention relates to sewage treating technology, and is especially the one-step preparation process of ecologically safe composite high efficiency flocculant for treating industrial waste water and domestic sewage. The flocculant is prepared with inorganic aluminum salt, starch, water and sodium hydroxide as material, and through adding the material in certain proportion into the reaction system in certain order under controlled temperature for starch causticization, aluminum salt polymerization, composition, product curing, etc. to obtain the product. The ecologically safe composite high efficiency flocculant is economic, efficient, wide in application range and without secondary pollution.
Description
Technical field
The present invention relates to sewage disposal, specifically a kind of preparation method of ecologically safe composite efficient flocculant of be used for feeding water pre-treatment, trade effluent or sanitary sewage disposal.
Background technology
Current, the flocculation agent of widespread use roughly can be divided into two classes in feedwater and sewage disposal: inorganic flocculating agent, organic floculant.Wherein inorganic flocculating agent is representative with aluminium salt, molysite and polymkeric substance thereof, and is cheap, and flocculating effect is better; Organic floculant comprises natural organic high-molecular flocculant and synthetic polymeric flocculant.Natural macromolecule flocculating agent mainly comprises starch, tannin etc.The synthetic polymeric flocculant is representative with the polyacrylamide, and they also are popular on market because flocculating effect is good, adding less.Raising along with industrialization degree, the wastewater flow rate that industrial production produces is in rising trend, the consumption of flocculation agent significantly increases, these flocculation agents have been brought into play bigger effect in the treating water process, but the flocculation agent of these types is in production, use and subsequent disposal, also brought very big pressure, and human beings'health has been constituted obviously or potential harm to environment.Available data shows:
1, the aluminium in the aluminum salt flocculant is after each channel enters human body, by accumulating and participating in many biochemical reactions, nutritive element essential in the body and trace element displacement can be run off or deposition, hinder and damage the physiological function at each position, cause human body to occur such as clinical poisoning by aluminum illnesss such as aluminum encephalopathy, aluminium osteopathy, aluminium anaemias.Simultaneously, the toxicity of aluminium salt also shows the toxic effect to hydrobiont, plant, when the concentration of aluminium is big, also may produce detrimentally affect to the microorganism in the biological wastewater treatment process.The World Health Organization is 0.2mg/L to the limitation standard of residual aluminum content in the water, and the U.S. is decided to be 0.05mg/L.Also in provisional water quality objective in 2000, the standard value that has increased aluminium is 0.2mg/L in China.
2, the synthetic organic polymer coargulator polyacrylamide that range of application is the widest, usage quantity is maximum at present is a low toxicity, most of products are skin irritation not, some product can be used for drinking water treatment, but synthetic cost is high and in building-up process acrylamide monomer very big to human health damage, use the most of polymer in back to be difficult to by environment degradable, a large amount of accumulation and long-term existence are brought huge pressure to environment in physical environment; Small portion can be degraded to small molecules such as acrylamide monomer then is a toxic substance, neural toxic effect to mammal, cat is the most responsive to acrylamide toxicity, and its toxicological harmless daily ingested dose is 0.3mg/kg, and common people's toxicological harmless daily ingested dose is 0.5mg/kg.Some hydrolysis body has remaining alkalescence, repeatedly, have pungency when contacting for a long time.The polyacrylamide maximum permitted concentration of U.S.'s approval is 1mg/L, and it is 0.5mg/L that Britain's regulation polyacrylamide on average adds concentration, and maximum dosage must not surpass 1mg/L, and acrylamide should be less than 0.05% at the residual volume of polymkeric substance.
3, natural macromolecule flocculating agent mainly contains: starch, tannin, Mierocrystalline cellulose, guar gum, gelatin and gelatinum or the like.Natural polymer can be dextrin, causticization starch, phosphorous hydrochlorate-CH as the starch correctability through various chemical modifications to adapt to different needs also
2OPO (CH)
2And amino-contained-CH
2CH
2NH
2Starch etc.In general, natural macromolecule flocculating agent is cheap, but molecular weight is lower and unstable, consumption height during use, poor effect and might produce problems such as BOD.
4, the china natural resources utilization ratio is lower, has all to contain aluminium element in a lot of waste residues and the waste liquid, and the discharging of these waste residues and waste liquid has increased the pressure to environment.These waste residues and waste liquid are carried out suitable processing, recycle useful component wherein, can alleviate environmental stress, turn waste into wealth, realize the utilization again of resource.
Summary of the invention
The object of the present invention is to provide the preparation method of the ecological safety type efficient flocculant of a kind of economy, efficient, applied range, non-secondary pollution.
The invention discloses the preparation method of ecological safety type efficient flocculant, it is characterized in that: with aluminium salt, starch, water and NaOH is raw material, as follows preparation:
1) press NaOH and starch quality than scope 1: 15-5: 1 mixes the NaOH solution of 2%-20% starch solution and 10%-35%, and heated and stirred is even, makes prefinished products A.
2) press NaOH and aluminium element mass ratio 1: 1-4: NaOH solution and the inorganic aluminate mixed solution of 1 preparation 10%-35% make prefinished products B.
3) according to aluminium element and starch quality than scope 1: 3-5: 3 slowly add B among the A.
4) control reaction temperature 30-55 ℃, carried out complex reaction 0.5-4 hour under the pH value 2-5 condition, get white milk flocculation agent pH value 3-5 product;
5) products obtained therefrom slaking at normal temperatures is 12 hours, obtains the ecological safety type efficient flocculant.
The principle of the invention is as follows:
On the basis of the advanced abroad flocculation agent research of the present invention, according to polluting the control principles of chemistry, use the ecotoxicology method, make up by multisystem, having improved its ecological safety performance, is raw material with cheap natural polymer W-Gum and aluminium salt, by distinctive poly-hydroxy in the starch compound with inorganic aluminate (complexing) after the modification causticization, form compound (complexing) thing, change aluminum ions chemical form.The composite macromolecular flocculant flocculation mechanism of natural polymer starch and aluminium salt formation is among the present invention: at the flocculation initial stage, aluminium salt is by electrically charged formation charge neutrality effect (compression double electric layer), the net of polymer composite performance is subsequently caught and (playing a major role in the flocculation process) characteristic of building bridge makes molecule and contaminants formation flocs unit in the water body, in addition, mixture space structure and the high molecular optimized, the very fast sedimentation of the flco that helps forming, this is the place of the efficient key of this flocculation agent just.
The present invention has the following advantages:
1. has ecological security.The present invention is synthetic by above-mentioned prescription and manufacture craft by natural polymer starch and inorganic polymer aluminium salt, distinctive poly-hydroxy is compound with inorganic aluminate after the modification causticization in the starch, change aluminum ions combining form, the concentration of active aluminum is reduced greatly, reduce to greatest extent even eliminated aluminium salt toxicity.
2. flocculating property is good.Product of the present invention is the polymeric flocculant of natural polymer starch and aluminium salt formation, pass through electrically charged formation charge neutrality effect (compression double electric layer) at flocculation initial stage aluminium salt, the net of polymer composite performance is subsequently caught and the characteristic of building bridge makes molecule and contaminants formation flocs unit (playing a major role in the flocculation process) in the water body, the very fast sedimentation of flocs unit that forms, therefore has good flocculating effect, be in particular in: handle sanitary sewage with polymerize aluminum chloride in the prior art and compare, dosage of the present invention has reduced 1/3-1/2, in other words, its flocculating effect be equivalent to common commercially available flocculant poly aluminum chloride 1.5-2 doubly.
3. applied widely.By adjusting formula rate, can be used for various forms of sewage disposals, comprise various industrial sewages, sanitary sewage, also can be used for to water treatment.
4. non-secondary pollution.The employing W-Gum is a raw material, and the flocculation agent residue is easy to do not had the secondary pollution problem by the microbiological deterioration in the environment.
5. turn waste into wealth resource reutilization.Inorganic aluminate in the prescription can utilize the waste liquid of the various Al of containing or waste residue is prepared or directly utilization, and starch can utilize various forms of starch based " refuse " to carry out innoxious, resource utilization recycle.
6. method is simple, and a step can finish, and is convenient to suitability for industrialized production.This method is not high to equipment requirements, the reaction conditions gentleness, and making processes is simple, according to the difference of process object sewage character, suitably adjusts formula rate, reaches best treatment effect.
7. handle in flocculating effect, product price and other functions (as pollutents such as removal heavy metals) and flocculate precipitate, have remarkable advantages than other class flocculant product on the market.
Embodiment
Flocculation agent of the present invention is a raw material with inorganic aluminate, starch, water and sodium hydroxide (NaOH), and single stage method is produced the ecological safety type efficient flocculant.Wherein: inorganic aluminate, starch are major ingredient, and NaOH is used for the causticization processing of starch and the prepolymerization of inorganic aluminate.Described inorganic aluminate can be aluminum chloride, Tai-Ace S 150 or aluminiferous waste liquid, waste etc. in pretreated aluminium industrial production.Described starch can be W-Gum, or other cereal starch, potato starch, legume starch etc.
According to the difference of process object sewage character, can in proper range, adjust formula for a product, if concentration of metal ions height in the sewage can improve the ratio of starch; If when handling slant acidity sewage, suitably improve the composition of aluminium salt, can make the maximization of target contaminant processing efficiency like this; Aluminium element in the inorganic aluminate in the products material prescription: starch (mass ratio)=1: 2.5-5: 3;
Concrete preparation method: inorganic aluminate, starch, water, NaOH are added reaction system according to following method, and regulate and control temperature of reaction successively according to reaction process, carry out starch conversion, the polymerization of aluminium salt, the processes such as compound and product slaking of the two, until obtaining the finished product:
1) proportioning causticization starch: the quality by NaOH and starch is 1 than scope: 5-2: 1 gets NaOH solution and the mass concentration 4%-20% starch solution solution thorough mixing of the mass concentration 10-22% of certain mass, carries out the starch causticization and handles.
2) reduced lyes formula inorganic aluminate begins complex reaction: is 2.2 by aluminium element quality in NaOH and the inorganic aluminate than scope: 1-3.7: 1, and in the inorganic aluminate quality of aluminium element and causticization starch than scope 1: 2.5-5: 3 join 1 with NaOH solution and the inorganic aluminate of the mass concentration 15%-35% of certain mass successively) reaction system in.
3) control reaction temperature 35-45 ℃, carry out under the pH value 2-5 that the starch causticization is handled, the prepolymerization of aluminium salt and the complex reaction 0.5-4 of the two hour, white milk flocculation agent.
4) products obtained therefrom slaking at normal temperatures 12 hours in the above step 3) obtains the ecological safety type efficient flocculant.
Economy of the present invention, efficient, suitability wide, non-secondary pollution, is the ecological safety type efficient flocculant.
The present invention is described in more detail below by embodiment.
Embodiment 1
The present invention is a raw material with aluminium salt, W-Gum, sodium hydroxide (NaOH), wherein: aluminium salt (AlCl
3), W-Gum is major ingredient, NaOH is used for the modification of W-Gum and the prepolymerization of inorganic aluminate; AlCl
3The mass ratio of middle aluminium element and W-Gum is 1: 1;
Its preparation method is:
1) proportioning causticization starch: got 25% NaOH solution and 10% starch solution thorough mixing than 1: 4 with starch quality by NaOH.
2) in reaction system reduced lyes formula AlCl3: successively 25% NaOH solution and inorganic aluminate are joined 1), wherein NaOH and aluminium element mass ratio (2.9: 1), aluminium element and 1) in W-Gum mass ratio 1: 1.
3) control reaction temperature is 40 ℃, and pH value 3 was carried out starch causticization, the prepolymerization of aluminium salt and complex reaction 1 hour, white emulsus flocculation agent.
4) with 3) in products obtained therefrom slaking at normal temperatures 12 hours, obtain the ecological safety type efficient flocculant.
Embodiment 2
The present invention is a raw material with aluminium salt, W-Gum, sodium hydroxide (NaOH), wherein: aluminium salt (Al
2(SO
4)
3), W-Gum is major ingredient, NaOH is used for the modification of W-Gum and the prepolymerization of inorganic aluminate; AlCl
3The mass ratio of middle aluminium element and W-Gum is 2: 1;
Its preparation method is:
1) proportioning causticization starch: got 15% NaOH solution and 8% starch solution thorough mixing than 1: 3 with starch quality by NaOH.
2) reduced lyes formula Al
2(SO
4)
3: successively 15% NaOH solution and inorganic aluminate are joined 1) reaction system in, wherein NaOH and aluminium element mass ratio (2.5: 1), aluminium element and 1) in W-Gum mass ratio 2: 1.
3) control reaction temperature is 45 ℃, and pH value 4 was carried out starch causticization, the prepolymerization of aluminium salt and complex reaction 2 hours, white emulsus flocculation agent.
4) with 3) in products obtained therefrom slaking at normal temperatures 12 hours, obtain the ecological safety type efficient flocculant.
Embodiment 3
The present invention is a raw material with aluminium salt, W-Gum, sodium hydroxide (NaOH), wherein: aluminium salt (AlCl
3), W-Gum is major ingredient, sodium hydroxide is used for the modification of W-Gum and the prepolymerization of inorganic aluminate; AlCl
3The mass ratio of middle aluminium element and W-Gum is 2: 3;
Its preparation method is:
1) proportioning causticization starch: got 30% NaOH solution and 20% starch solution thorough mixing than 2: 1 with starch quality by NaOH.
2) reduced lyes formula AlCl
3: successively 25% NaOH solution and inorganic aluminate are joined 1) reaction system in, wherein NaOH and aluminium element mass ratio (3.1: 1), aluminium element and 1) in W-Gum mass ratio 2: 3.
3) control reaction temperature is 55 ℃, and pH value 3 was carried out starch causticization, the prepolymerization of aluminium salt and complex reaction 4 hours, white emulsus flocculation agent.
4) with 3) in products obtained therefrom slaking at normal temperatures 12 hours, obtain the ecological safety type efficient flocculant.
Embodiment 4
The present invention is a raw material with aluminium salt, W-Gum, sodium hydroxide (NaOH), wherein: aluminium salt (Al
2(SO
4)
3), W-Gum is major ingredient, NaOH is used for the modification of W-Gum and the prepolymerization of inorganic aluminate; AlCl
3The mass ratio of middle aluminium element and W-Gum is 1: 2;
Its preparation method is:
1) proportioning causticization starch: got 20% NaOH solution and 15% starch solution thorough mixing than 1: 1 with starch quality by NaOH.
2) reduced lyes formula Al
2(SO
4)
3: successively 25% NaOH solution and inorganic aluminate are joined 1) reaction system in, wherein NaOH and aluminium element mass ratio (2.55: 1), aluminium element and 1) in W-Gum mass ratio 1: 2.
3) control reaction temperature is 50 ℃, and pH value 3 was carried out starch causticization, the prepolymerization of aluminium salt and complex reaction 3 hours, white emulsus flocculation agent.
4) with 3) in products obtained therefrom slaking at normal temperatures 12 hours, obtain the ecological safety type efficient flocculant.
Embodiment 5
Be with example difference before: aluminium salt is anthraquinone mother liquor, wherein Al in the present embodiment raw material
3+Ionic concn is 4%.Concrete preparation method is:
1) proportioning treated starch: got 25% NaOH solution and 10% starch solution thorough mixing than 1: 4 with starch quality by NaOH.
2) reduced lyes formula AlCl
3: successively 25% NaOH solution and anthraquinone mother liquor are joined 1) reaction system in, aluminium element mass ratio 2.96: 1 in NaOH and the anthraquinone mother liquor wherein, aluminium element and 1) in W-Gum mass ratio 1: 1.
3) control reaction temperature is 45 ℃, and the pH value was carried out complex reaction for 2 times 1.5 hours, obtains light yellow translucent milky product.
4) with 3) in products obtained therefrom slaking at normal temperatures 24 hours, obtain the ecological safety type efficient flocculant.
Claims (10)
1. the preparation method of an ecological safety type efficient flocculant, it is characterized in that: with inorganic aluminate, starch, water and NaOH is raw material, as follows preparation:
1) press NaOH and starch quality than scope 1: 15-5: 1 mixes the NaOH solution of 2%-20% starch solution and 10%-35%, and heated and stirred is evenly carried out the starch causticization, makes prefinished products A.
2) press NaOH and aluminium element mass ratio 1: 1-4: NaOH solution and the inorganic aluminate mixed solution of 1 preparation 10%-35% make prefinished products B.
3) according to aluminium element and starch quality than scope 1: 3-5: 3 slowly add B among the A.
4) control reaction temperature 30-55 ℃, carried out complex reaction 0.5-4 hour under the pH value 2-5 condition, get white milk flocculation agent pH value 3-5 product;
5) products obtained therefrom slaking at normal temperatures is 12 hours, obtains the ecological safety type efficient flocculant.
2. according to the preparation method of the described ecological safety type efficient flocculant of claim 1, it is characterized in that described inorganic aluminate is aluminum chloride, Tai-Ace S 150 or aluminiferous waste liquid, waste in pretreated aluminium industrial production.
3. according to the preparation method of claim 1 or 2 described ecological safety type efficient flocculants, it is characterized in that described starch is W-Gum, or other cereal starch, potato starch, legume starch.
4 preparation methods according to the described ecological safety type efficient flocculant of claim 1 is characterized in that the described NaOH that is used for the starch causticization and the quality of starch are 1 than scope: 5-2: 1.
5. according to the preparation method of the described ecological safety type efficient flocculant of claim 1, it is characterized in that described be used for the prepolymerized NaOH of aluminium salt with inorganic aluminate aluminium element quality be 2.2 than scope: 1-3.7: 1.
6. according to the preparation method of the described ecological safety type efficient flocculant of claim 1, it is characterized in that the mass ratio of aluminium element and starch is 1 in the described inorganic aluminate: 2.5-5: 3.
7. according to the preparation method of the described ecological safety type efficient flocculant of claim 1, it is characterized in that the described starch solution mass concentration scope that is used for causticization is 4%-20%.
8. according to the preparation method of the described ecological safety type efficient flocculant of claim 1, it is characterized in that the described NaOH solution quality concentration range that is used for the starch causticization is 10%-22%.
9 preparation methods according to the described ecological safety type efficient flocculant of claim 1 is characterized in that described to be used for the prepolymerized NaOH solution quality of aluminium salt concentration range be 15%-30%.
10 preparation methods according to the described ecological safety type efficient flocculant of claim 1 is characterized in that described complex reaction temperature is controlled at 35-45 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610129809XA CN100519436C (en) | 2006-12-01 | 2006-12-01 | One-step preppn process of flocculant |
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|---|---|---|---|
| CNB200610129809XA CN100519436C (en) | 2006-12-01 | 2006-12-01 | One-step preppn process of flocculant |
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|---|---|
| CN1974427A true CN1974427A (en) | 2007-06-06 |
| CN100519436C CN100519436C (en) | 2009-07-29 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106335944A (en) * | 2016-10-20 | 2017-01-18 | 郑州丽福爱生物技术有限公司 | Multifunctional sewage treatment agent |
| CN106564971A (en) * | 2016-10-20 | 2017-04-19 | 郑州丽福爱生物技术有限公司 | Multifunctional domestic sewage treating agent |
-
2006
- 2006-12-01 CN CNB200610129809XA patent/CN100519436C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106335944A (en) * | 2016-10-20 | 2017-01-18 | 郑州丽福爱生物技术有限公司 | Multifunctional sewage treatment agent |
| CN106564971A (en) * | 2016-10-20 | 2017-04-19 | 郑州丽福爱生物技术有限公司 | Multifunctional domestic sewage treating agent |
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| Publication number | Publication date |
|---|---|
| CN100519436C (en) | 2009-07-29 |
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Granted publication date: 20090729 Termination date: 20111201 |