CN102336458A - Heavy metal high-polymer flocculating agent and preparation and application methods thereof - Google Patents
Heavy metal high-polymer flocculating agent and preparation and application methods thereof Download PDFInfo
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- CN102336458A CN102336458A CN2011102494962A CN201110249496A CN102336458A CN 102336458 A CN102336458 A CN 102336458A CN 2011102494962 A CN2011102494962 A CN 2011102494962A CN 201110249496 A CN201110249496 A CN 201110249496A CN 102336458 A CN102336458 A CN 102336458A
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Abstract
The invention discloses a heavy metal high-polymer flocculating agent and preparation and application methods thereof. The heavy metal high-polymer flocculating agent is modified and synthesized by polysilicate aluminium ferric and dimethyldiallylammoniumchloride. The pH value of the heavy metal waste water is regulated to 8 to 9 by alkali, the novel high-polymer flocculating agent is added during the stirring, and the efficient separation of heavy metals of Cd, Zn, As, Cr, Pb and the like in waste water can be realized through reaction and precipitation. Special Si-O structures in active silicic acid and C-N structures of the dimethyldiallylammoniumchloride are utilized for developing the flocculating agent with the advantages that the molecular weight is high, the precipitation speed is high, and the high-concentration heavy metal waste water can be effectively precipitated. After the waste water is treated, the precipitated flocculated bodies have higher heavy metal contents and can be returned to the smelting process to be recovered and utilized, and the water outlet water quality is stable and can reach or be superior to the national sewage integral discharge standard GB 8978-1996. The heavy metal high-polymer flocculating agent and the preparation and application methods have the advantages that the operation is simple and is easy to control, the operation time is short, the cost is low, good social, environment and economic benefits are realized, and the application prospects are wide.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to a kind of high-polymeric flocculent and methods for making and using same thereof of heavy metal containing wastewater treatment.
Background technology
Heavy metal contamination is one of severe problem of facing of China's water surrounding, also is the huge water pollution problems of harm.Because its high toxicity, cumulative bad and persistence, water surrounding ecology and drinking water safety in serious threat.Pollution extensively derives from industries such as mining, ore dressing, smelting, chemical industry, metal processing, and the major pollution factor is lead, cadmium, chromium, mercury, arsenic, zinc etc.Country's Eleventh Five-Year Plan water special project is also administered Xiang River basin heavy metal as the major control target.The high density heavy metal containing wastewater treatment realizes very difficulty of pollution factor qualified discharge, thereby the medicament of exploitation highly economical processing heavy metal wastewater thereby is extremely important with technology.
At present; Mainly contain four types to process for treating heavy-metal waste water: 1) physical treatment process: mainly be through physical action; To separate, to reclaim the undissolved method of wastewater treatment that is the suspended state pollution substance in the waste water, like gravity centrifuging (air supporting, flotation etc.), centrifugal separation and sieving blocking cut-off process etc.2) method of chemical treatment: be to separate, remove pollution substance that is dissolving, colloidal state in the waste water or the waste water treatment process that is translated into innoxious substance with effect of mass transmitting, like coagulation, neutralization, redox, absorption, IX or r-o-etc. through chemical reaction.3) physico-chemical processes: be to utilize physics chemical action to remove the method for pollutants in waste water matter, like adsorption method of separation, the gentle formulation of extraction process etc.4) biochemical treatment method: be the method for removing pollution substance in the waste water through the metabolism of mikrobe.Method the most commonly used remains method of chemical treatment.
The heavy metal wastewater thereby complicated component; Concentration difference is bigger; Handle comparatively strictness of requirement up to standard, traditional treatment technology exists: shortcomings such as the treatment agent usage quantity is big, energy consumption is high, reaction is wayward, reaction is slow, effect is undesirable, water quality inferiority, residue instability, recovery precious metal difficulty.Therefore, development and utilization effect is good, cost is low, environment is not had the surrogate and the nontoxic novel water-treatment medicament that influence medicament is the development trend of handling heavy metal wastewater thereby.
Summary of the invention
The objective of the invention is to seek the weak point that can overcome existing treatment technology; A kind of high-polymeric flocculent and methods for making and using same thereof of novel treatment heavy metal wastewater thereby are provided; This high-polymeric flocculent can efficiently be removed the heavy metal in the industry waste water such as smelting, and have the treatment time short, adapt to advantages such as wide and easy to control.
A kind of preparation method of novel heavy metal high-polymeric flocculent; Be that the polymeric silicicacid ferrum sulfuricum oxydatum solutum is mixed under 70-100 ℃ with dimethyl diallyl ammonium chloride solution; Stir, (mix fast earlier, stir at a slow speed afterwards) is red-brown to mixed solution and gets final product.
Described polymeric silicicacid ferrum sulfuricum oxydatum solutum mass concentration 20-30%.
The mass concentration 50-70% of described dimethyl diallyl ammonium chloride solution.
The volume ratio of described polymeric silicicacid ferrum sulfuricum oxydatum solutum and dimethyl diallyl ammonium chloride solution is 5-8: 1.
The preparation of described polymeric silicicacid ferrum sulfuricum oxydatum solutum is following: at mol ratio Fe: Si=1: under the 0.2-1 condition, bodied ferric sulfate is slowly added in the active silicic acid solution, stir, reaction 1.5-2h; Behind static, the ageing 2-5h, obtain brown polymeric silicicacid ferrum sulfuricum oxydatum solutum;
Described active silicic acid formulations prepared from solutions: take by weighing the 5.7g water glass and be dissolved in to 120ml water, process sodium silicate solution, use 6mol/L H then
2SO
4Titration to pH value of solution value is 1-1.5, stirs; After the room temperature activation 1.5 hours, promptly get active silicic acid solution.
Described high-polymeric flocculent be applied to heavy metal containing wastewater treatment.Specifically be that heavy metal wastewater thereby is added described high-polymeric flocculent 8-10mL/L.After adding high-polymeric flocculent, stir at first fast (100-200r/min), even back to be mixed reduces stirring velocity (50-70r/min), and the alumen ustum of avoiding forming is broken, then standing sedimentation.
Before adding high-polymeric flocculent, the pH value of heavy metal wastewater thereby is adjusted in 8-9; In this pH value scope, can realize best flocculating effect, also satisfy the requirement of water outlet pH value 6-9.Described heavy metal wastewater thereby derives from mining, ore dressing, smelting, plating or heavy metal processing waste water (comprise one or more of following heavy metal ion: Pb, Cd, As, Zn, Cr, Mn, Fe, Cu etc.);
Advantage of the present invention is:
(1) the present invention utilizes Si-O and the special C-N structure of dimethyl diallyl ammonium chloride in the active silicic acid, develops that molecular weight is big, sedimentation speed fast, flocculation agent that can effectively sedimentation high density heavy metal wastewater thereby; The inventive method handles that heavy metal wastewater thereby is simple to operate, the settling time short, and is easy to control, effectively sedimentation heavy metal and remove colourity.
(2) to the heavy metal wastewater thereby of nonferrous smelting industry, behind the Wastewater Pretreatment flocculating settling, the deposition flco can return the recycling that smelting technology carries out heavy metal.
(3) heavy metal wastewater thereby of lower concentration, carry out flocculating settling after, but the heavy metal concentration qualified discharge.
(4) high density heavy metal wastewater thereby most of heavy metal behind flocculating settling migrates in the flco, creates advantageous conditions for follow-up processing, lightens the load.
(5) high-polymeric flocculent settling velocity of the present invention is fast, need not add the coagulant aids SEPIGEL 305, practices thrift cost for wastewater treatment.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1,
The preparation high-polymeric flocculent:
(1) preparation active silicic acid solution: take by weighing the 5.7g water glass and be dissolved in to 120ml water, process sodium silicate solution, use 6mol/L H then
2SO
4Titration is stirred to pH to 1.5; Room temperature activation 1.5 hours;
(2) preparation polymeric silicicacid ferrum sulfuricum oxydatum solutum: at mol ratio Fe: Si=1: under 0.2 condition; 24% polymeric ferrous sulphate solution is slowly added in the active silicic acid solution; Stir, obtain brown polymeric silicicacid ferrum sulfuricum oxydatum solutum behind the reaction 1.5-2h, static, ageing 2-5h;
(3) 20% polymeric silicicacid ferrum sulfuricum oxydatum solutum is mixed with 60% dimethyl diallyl ammonium chloride solution, synthetic down at 70-100 ℃.
The amount ratio of polymeric silicicacid ferrum sulfuricum oxydatum solutum and dimethyl diallyl ammonium chloride solution is 6: 1.
Embodiment 2
Contain the multiple heavy metal As, Cd, Zn that environment is had huge pollution etc. in the comprehensive wastewater of zinc smelting enterprise discharging.The comprehensive wastewater of choosing the large-scale smelting enterprise in Hunan Province is a research object, under the waste water ph nominal situation between 5-6; Measure waste water 500mL; At first use alkali (sodium hydroxide) that the pH value of waste water is adjusted to 8.9, stir fast make waste water mix, then after slowly adding the novel flocculant 5mL of modification after synthetic under the slower stirring velocity, leaving standstill 30min after mixing fully; Detect the concentration of heavy metal ions in wastewater: As is reduced to 23.5ug/L by 9.5mg/L; Cd is reduced to 37ug/L by 24.7mg/L, and Zn is reduced to 1.2mg/L by 217mg/L, can realize standard wastewater discharge.
Embodiment 3
, pH value lower to heavy metal concentration is neutral waste water, and adjust pH 8 directly adds novel flocculant.Get waste water 500mL, add high-polymeric flocculent 4mL, the back sedimentation 30min that stirs detects: heavy metal concentration Pb is reduced to 0.18mg/L by 0.7mg/L, and Zn is reduced to 1.48mg/L by 5.7mg/L, and colourity is reduced to 8 times by 20 times.
Embodiment 4
Choose Hunan Province enterprise vanadium smelting waste water for supplying the examination object, water quality pH 6-7, total Cr2.76-5.10mg/L, Cd 0.97-2.33mg/L.Measure waste water 1L, regulate pH value to 8.2, add high-polymeric flocculent 8mL, behind the stirring 5min, free setting 30min.Detect the pollution factor content: total Cr 0.3-0.5mg/L, Cd 30-46ug/L.
Embodiment 5
Contain a large amount of poisonous and hazardous heavy metal ion in the waste water that the electrolytic manganese industry produces, if it is not handled the serious harm ecological environment security.The waste water of choosing certain electrolytic manganese enterprise is for supplying examination material, former water pH value 2.89; Measure waste water 1L, regulate pH to 8.7, add high-polymeric flocculent 9mL; Stir, detect after leaving standstill 30min: Mn is reduced to 0.7mg/L by 158mg/L in the former water; Fe is by 16.1mg/L reduction value 1.3mg/L, and Cu realizes the waste water quality qualified discharge by 1.96mg/L reduction value 0.41mg/L.
Claims (10)
1. the preparation method of a heavy metal species high-polymeric flocculent is characterized in that, is the polymeric silicicacid ferrum sulfuricum oxydatum solutum is mixed under 70-100 ℃ with dimethyl diallyl ammonium chloride solution, stirs, and is red-brown to mixed solution and gets final product.
2. method according to claim 1 is characterized in that, described polymeric silicicacid ferrum sulfuricum oxydatum solutum mass concentration is 20-30%.
3. method according to claim 1 is characterized in that, the mass concentration 50%-70% of described dimethyl diallyl ammonium chloride solution.
4. according to claim 1 or 2 or 3 described methods, it is characterized in that the volume ratio of described polymeric silicicacid ferrum sulfuricum oxydatum solutum and dimethyl diallyl ammonium chloride solution is 5-8: 1.
5. the high-polymeric flocculent of a heavy metal containing wastewater treatment is characterized in that, is the high-polymeric flocculent that is prepared by the described method of claim 4.
6. the application method of the described high-polymeric flocculent of claim 5 is characterized in that, is used for heavy metal containing wastewater treatment.
7. the application method of high-polymeric flocculent according to claim 6 is characterized in that, heavy metal wastewater thereby is added described high-polymeric flocculent 8-10mL/L.
8. the application method of high-polymeric flocculent according to claim 7 is characterized in that, add described high-polymeric flocculent after, stir at first fast, even back to be mixed reduces stirring velocity, the alumen ustum of avoiding forming is broken, then standing sedimentation.
9. the application method of high-polymeric flocculent according to claim 7 is characterized in that, before adding described high-polymeric flocculent, the pH value of described heavy metal wastewater thereby is adjusted in 8-9.
10. the application method of high-polymeric flocculent according to claim 6 is characterized in that, described heavy metal wastewater thereby derives from mining, ore dressing, smelting, electrolysis, plating or heavy metal processing waste water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613182A (en) * | 2013-12-10 | 2014-03-05 | 成应向 | Heavy-metal high flocculant and application thereof |
| CN104445563A (en) * | 2014-12-08 | 2015-03-25 | 厦门福润源环保科技有限公司 | High-molecular heavy metal flocculant and preparation method thereof |
| CN105523620A (en) * | 2016-02-01 | 2016-04-27 | 仲恺农业工程学院 | Polysilicate ferric sulfate based inorganic-organic composite flocculant and preparation method thereof |
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| CN1778701A (en) * | 2005-10-14 | 2006-05-31 | 哈尔滨工业大学 | Oxidation polysilacidiron coagulant and preparation thereof |
| CN101525173A (en) * | 2009-03-17 | 2009-09-09 | 济南大学 | Oxygenation and dimethyl diallyl ammonium chloride composite modification silicoferrite coagulating agent and preparation method thereof |
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| US6184257B1 (en) * | 2000-04-10 | 2001-02-06 | Calgon Corporation | Composition of ferric chloride and a dialkyl diallyl ammonium polymer and process of preparing the same |
| CN1778701A (en) * | 2005-10-14 | 2006-05-31 | 哈尔滨工业大学 | Oxidation polysilacidiron coagulant and preparation thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613182A (en) * | 2013-12-10 | 2014-03-05 | 成应向 | Heavy-metal high flocculant and application thereof |
| CN103613182B (en) * | 2013-12-10 | 2015-12-02 | 湖南省环境保护科学研究院 | A kind of heavy metal high-polymer flocculating agent and application thereof |
| CN104445563A (en) * | 2014-12-08 | 2015-03-25 | 厦门福润源环保科技有限公司 | High-molecular heavy metal flocculant and preparation method thereof |
| CN105523620A (en) * | 2016-02-01 | 2016-04-27 | 仲恺农业工程学院 | Polysilicate ferric sulfate based inorganic-organic composite flocculant and preparation method thereof |
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Application publication date: 20120201 |