CN104761039A - Composite chelating agent used for treating cadmium-containing waste water and application method thereof - Google Patents
Composite chelating agent used for treating cadmium-containing waste water and application method thereof Download PDFInfo
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- CN104761039A CN104761039A CN201410775639.7A CN201410775639A CN104761039A CN 104761039 A CN104761039 A CN 104761039A CN 201410775639 A CN201410775639 A CN 201410775639A CN 104761039 A CN104761039 A CN 104761039A
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Abstract
The invention provides a composite chelating agent used for treating cadmium-containing waste water and application thereof. The composite chelating agent is prepared by compounding, by mass, 20 to 65% of trisodium thiocyanate and 35 to 80% of sodium dimethyldithiocarbamate. Application of the composite chelating agent in treatment of cadmium-containing waste water comprises the following steps: adding the composite chelating agent into the cadmium-containing waste water, wherein a mass ratio of the added composite chelating agent to the waste water is 1: 200 to 1: 5000; carrying out stirring for 5 to 30 min and then adding aluminum polychlorid, wherein a mass ratio of the aluminum polychlorid to the waste water is 1: 200 to 1: 5000; carrying out stirring for 5 to 30 min and then carrying out standing at normal temperature for 0.5 to 12 h; and subjecting obtained turbid liquid to filtering with a filter, wherein effluent obtained after filtering has cadmium content lower than cadmium content prescribed in national first-class discharge standard in China. The application method has the advantages of simple process flow, low cost, convenient operation, high efficiency, energy saving, a few sediments, no toxicity and exemption from incurrence of secondary pollution.
Description
Technical field
The present invention relates to technical field of sewage, specifically a kind of association complex and application method thereof processing cadmium wastewater.
Background technology
In process of production, the volume of smoke produced during smelting contains a large amount of heavy metal substances, after the process of use wet dust collector, most heavy metal substance can enter into acidity and to gather dust spray liquid, form the waste water that heavy metal content is higher, if this part waste water is without heavy Cadmium treated direct reuse, cadmium can continuous circulative accumulation in the entire system, finally has influence on the quality of matallurgical products.Meanwhile, be directly discharged in environment if the high waste water of cadmium content is not treated, serious heavy metal contamination can be caused.If cadmium wastewater exhaust emission soil, cadmium can be made to enter into plant by root system of plant, if the mankind's edible food high containing cadmium for a long time, or drink containing the high water of cadmium, cadmium can be made to enter human body in a large number, reduce the content of Skeleton System calcium, cause bone brittleness easy to break; Meanwhile, cadmium enters human body and also by biomagnification and accumulation, can cause a series of damage to lung, liver, kidney, immunity system and reproductive system.In addition, cadmium seriously can also suppress microbial growth, and when cadmium concentration is 0.1 ~ 1mg/l, microbial death rate can reach 50%, when cadmium mass concentration is 0.1mg/l in water, just can suppress self-purification of waters.
For this reason, China " integrated wastewater discharge standard " (GB8978-1996) clear stipulaties, cadmium is first kind pollutent, and the highest permission discharge quality concentration is 0.1mg/l, can not dilution process." sewage enters town sewer water quality standard " (CJ 343-2010) according to up-to-date revision specifies, the concentration of the water quality requirement cadmium of A, B, C tri-kinds of grades, can not dilution process not higher than 0.1mg/l.Therefore, the process of cadmium wastewater, has great society, economy and environment meaning.
Process cadmium wastewater has the methods such as chemical precipitation method, electrolytic process, absorption method, ion exchange method, membrane separation technique and biological process.In actual applications, the many existing defects of aforesaid method are as large in absorption method reagent injected volume; The processing cost such as membrane separation technique, electrolytic process is high, and chemical precipitation method easily causes secondary pollution, and biological process is difficult to reach the degree of depth except cadmium etc., and time especially to a large amount of cadmium wastewater process, these shortcomings seem particularly outstanding.Flocculation sedimentation is conventional pollutant effluents treatment technology, improves water quality and has irreplaceable advantage, as few in reagent dosage, easy and simple to handle, cost is low and be beneficial to a large amount of wastewater treatment.But flocculation agent does not have removes water soluble ion performance, and therefore cause except cadmium is incomplete in waste water, in waste water, cadmium content is difficult to reach emission standard.
China Patent Publication No. is 103773958A, the patent that name is called " a kind of method for removing cadmium ", and the method described in patent is, first carries out one section of pre-copper removal of purification; First add the pre-copper removal of crude zinc powder according to copper, cadmium content in middle supernatant, the copper grade obtained after filtering be higher, liquid after copper-cadmium slag that cadmium grade is lower and copper removal; After pre-copper removal liquid add blowing zinc powder continue copper removal, cadmium again, obtain the copper-cadmium slag that copper grade is lower, cadmium grade is higher after filtration; China Patent Publication No. is: 103060555A, the patent that name is called " a kind of method of the purifying and cadmium removing from nickel and cobalt solution containing cadmium ", method described in patent is, cadmium concentration is selected to be less than the nickel and cobalt solution of 0.1g/L, first the cadmium in nickel and cobalt solution is enriched in cobalt liquor or washing lotion by solvent extraction and goes, make the concentration of cadmium reach 0.1 ~ 1.0g/L; Then adopt resin anion(R.A) by the cadmium removing in cobalt liquor or washing lotion.
For the defect in cadmium wastewater treatment process, the present invention is at the upper composite chelate group introducing seizure cadmium ion in flocculation sediment basis, make it have and cadmium ion sequestering action and two kinds of performances of flocculating, expection can obtain effective cadmium wastewater flocculating settling process practical approach simultaneously.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art existence, there is provided a kind of association complex from cadmium wastewater, remove the method for cadmium, to lower concentration cadmium wastewater, can purify more thoroughly and recycle, except the concentration of cadmium in solution after cadmium is lower than 0.05mg/l, non-secondary pollution also carries out the recycle of water.
The technical solution used in the present invention is: a kind of association complex processing cadmium wastewater, and this association complex is 20% ~ 65% by trithiocyanuric acid trisodium salt by mass percentage, and Sodium dimethyldithiocarbamate 40min salt is 35% ~ 80% compositely to form.
Described association complex preparation method step is: add in container by the ratio of trithiocyanuric acid trisodium salt and pure water 1:1 in mass ratio, stir 5min furnishing solution, the ratio of Sodium dimethyldithiocarbamate 40min salt and pure water 1:1 is in mass ratio added in another container, stir 5min furnishing solution, the trithiocyanuric acid trisodium-salt solution mixed up and Sodium dimethyldithiocarbamate 40min salts solution are added in another container simultaneously and stirs 5min, make liquid after still aging 10min, be described association complex.
The application of described association complex in process cadmium wastewater, that described association complex is joined in cadmium wastewater, the association complex added and wastewater quality are than being 1:200 ~ 1:5000, after stirring 5 ~ 30min, the polymerize aluminum chloride added and wastewater quality, than being 1:200 ~ 1:5000, after stirring 5 ~ 30min, leave standstill 0.5 ~ 12 hour at normal temperatures, the suspension liquid of gained is after filter filters, and water outlet contains cadmium lower than national grade one discharge standard.
Compared with the conventional method, advantage of the present invention and effect are:
1, technological operation is simple, and flow process is unobstructed, makes the removing process of cadmium in cadmium wastewater become simple possible.
2, the removal efficiency of cadmium is high, and uses reagent cost cheap, and consumption is low.Precipitation non-toxic substance leaches.Water outlet can directly serve as industrial production Treated sewage reusing.
3. the cadmium wastewater handled by, containing cadmium concentration at 1500 ~ 0.1mg/l, except cadmium is applied widely.
4, in cadmium wastewater after treatment the density loss of cadmium ion to below 0.05mg/l, water outlet contains cadmium lower than national grade one discharge standard, China " integrated wastewater discharge standard " (GB8978-1996) clear stipulaties, cadmium is first kind pollutent, the highest permission discharge quality concentration is 0.1mg/l, can not dilution process.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of association complex for the treatment of cadmium wastewater of process cadmium wastewater of the present invention.
Embodiment
Below by way of specific embodiment, technical scheme of the present invention is described further.
Embodiment 1
By mass percentage, by trithiocyanuric acid trisodium salt 65%, Sodium dimethyldithiocarbamate 40min salt 35% is made into association complex, process containing cadmium in certain smelting wastewater, in waste water, cadmium content is 1500mg/l, and test is got 5g association complex and joined in 1L cadmium wastewater, stirs 30min, add 5g polymerize aluminum chloride again, staticly settle 24h, after filtering with filter, in water outlet, cadmium content is 0.022mg/l, clearance is more than 99.9%, and water outlet is lower than national grade one discharge standard.
Embodiment 2
By mass percentage, by trithiocyanuric acid trisodium salt 55%, Sodium dimethyldithiocarbamate 40min salt 45% is made into association complex, process containing cadmium in certain smelting wastewater, in waste water, cadmium content is 1000mg/l, and test is got 4g association complex and joined in 1L cadmium wastewater, stirs 20min, add 4g polymerize aluminum chloride again, staticly settle 20h, after filtering with filter, in water outlet, cadmium content is 0.028mg/l, clearance is more than 99.9%, and water outlet is lower than national grade one discharge standard.
Embodiment 3
By mass percentage, by trithiocyanuric acid trisodium salt 45%, Sodium dimethyldithiocarbamate 40min salt 55% is made into association complex, process containing cadmium in certain smelting wastewater, in waste water, cadmium content is 350mg/l, and test is got 2g association complex and joined in 1L cadmium wastewater, stirs 15min, add 2g polymerize aluminum chloride again, staticly settle 12h, after filtering with filter, in water outlet, cadmium content is 0.030mg/l, clearance is more than 99.9%, and water outlet is lower than national grade one discharge standard.
Embodiment 4
By mass percentage, by trithiocyanuric acid trisodium salt 35%, Sodium dimethyldithiocarbamate 40min salt 65% is made into association complex, process containing cadmium in certain smelting wastewater, in waste water, cadmium content is 100mg/l, and test is got 1g association complex and joined in 1L cadmium wastewater, stirs 10min, add 1g polymerize aluminum chloride again, staticly settle 8h, after filtering with filter, in water outlet, cadmium content is 0.033mg/l, clearance is more than 99.9%, and water outlet is lower than national grade one discharge standard.
Embodiment 5
By mass percentage, by trithiocyanuric acid trisodium salt 20%, Sodium dimethyldithiocarbamate 40min salt 80% is made into association complex, process containing cadmium in certain smelting wastewater, in waste water, cadmium content is 0.1mg/l, and test is got 0.02g association complex and joined in 1L cadmium wastewater, stirs 5min, add 0.02g polymerize aluminum chloride again, staticly settle 0.5h, after filtering with filter, in water outlet, cadmium content is 0.02mg/l, clearance is more than 99.9%, and water outlet is lower than national grade one discharge standard.
Claims (2)
1. process an association complex for cadmium wastewater, it is characterized in that, described association complex is that trithiocyanuric acid trisodium salt is 20% ~ 65% by percentage in mass ratio, and Sodium dimethyldithiocarbamate 40min salt is 35% ~ 80% compositely to form,
Described association complex preparation method is: add in container by the ratio of trithiocyanuric acid trisodium salt and pure water 1:1 in mass ratio, stir 5min furnishing solution, the ratio of Sodium dimethyldithiocarbamate 40min salt and pure water 1:1 is in mass ratio added in another container, stir 5min furnishing solution, the trithiocyanuric acid trisodium-salt solution mixed up and Sodium dimethyldithiocarbamate 40min salts solution are added in another container simultaneously and stirs 5min, make liquid after still aging 10min, obtain described association complex.
2. the application of association complex according to claim 1 in process cadmium wastewater, it is characterized in that, described association complex is joined in cadmium wastewater, the association complex added and wastewater quality are than being 1:200 ~ 1:5000, and after stirring 5 ~ 30min, the polymerize aluminum chloride added and wastewater quality are than being 1:200 ~ 1:5000, after stirring 5 ~ 30min, leave standstill 0.5 ~ 12 hour at normal temperatures, the suspension liquid of gained is after filter filters, and water outlet contains cadmium lower than national grade one discharge standard.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336071A (en) * | 2016-08-23 | 2017-01-18 | 广州超邦化工有限公司 | Treatment method of cadmium ion in EDTA-free acidic non-cyanide cadmium plating wastewater |
| CN109265383A (en) * | 2018-10-08 | 2019-01-25 | 泰山医学院 | A kind of synthetic method of good fortune U.S. potassium and application in the treatment of waste water |
| CN110577269A (en) * | 2019-10-15 | 2019-12-17 | 湖南亿康环保科技有限公司 | Composite reagent for removing manganese and ammonia nitrogen in wastewater and application method thereof |
| CN111265810A (en) * | 2019-09-20 | 2020-06-12 | 连云港新江环保材料有限公司 | Efficient fly ash chelating agent and preparation method thereof |
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| CN102145945A (en) * | 2011-02-21 | 2011-08-10 | 中国科学院生态环境研究中心 | Method for removing trace cadmium in high salt wastewater by combining polymer chelation with adsorption |
| CN102249388A (en) * | 2011-05-05 | 2011-11-23 | 长安大学 | Method for performing synergetic degradation on cadmium ammonia complex in underground water |
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- 2014-12-15 CN CN201410775639.7A patent/CN104761039B/en not_active Expired - Fee Related
Patent Citations (5)
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| JP2002194328A (en) * | 2000-12-26 | 2002-07-10 | Mitsubishi Rayon Co Ltd | Heavy metal fixing agent and method for fixing heavy metal using the same |
| CN101456939A (en) * | 2008-12-02 | 2009-06-17 | 天津壹生环保科技有限公司 | Water-soluble high molecule intercalating agent containing thiourea group and preparation method |
| CN102145945A (en) * | 2011-02-21 | 2011-08-10 | 中国科学院生态环境研究中心 | Method for removing trace cadmium in high salt wastewater by combining polymer chelation with adsorption |
| CN102249388A (en) * | 2011-05-05 | 2011-11-23 | 长安大学 | Method for performing synergetic degradation on cadmium ammonia complex in underground water |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336071A (en) * | 2016-08-23 | 2017-01-18 | 广州超邦化工有限公司 | Treatment method of cadmium ion in EDTA-free acidic non-cyanide cadmium plating wastewater |
| CN106336071B (en) * | 2016-08-23 | 2019-08-13 | 广州超邦化工有限公司 | The processing method of cadmium ion in a kind of acid non-cyanide plating cadmium waste water without EDTA |
| CN109265383A (en) * | 2018-10-08 | 2019-01-25 | 泰山医学院 | A kind of synthetic method of good fortune U.S. potassium and application in the treatment of waste water |
| CN111265810A (en) * | 2019-09-20 | 2020-06-12 | 连云港新江环保材料有限公司 | Efficient fly ash chelating agent and preparation method thereof |
| CN110577269A (en) * | 2019-10-15 | 2019-12-17 | 湖南亿康环保科技有限公司 | Composite reagent for removing manganese and ammonia nitrogen in wastewater and application method thereof |
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| CN104761039B (en) | 2016-07-20 |
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