CN102657926B - Heavy metal normal temperature curing agent and method for curing heavy metal in heavy metal pollutants by use of heavy metal normal temperature curing agent - Google Patents
Heavy metal normal temperature curing agent and method for curing heavy metal in heavy metal pollutants by use of heavy metal normal temperature curing agent Download PDFInfo
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- CN102657926B CN102657926B CN201210107906.4A CN201210107906A CN102657926B CN 102657926 B CN102657926 B CN 102657926B CN 201210107906 A CN201210107906 A CN 201210107906A CN 102657926 B CN102657926 B CN 102657926B
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Abstract
The invention provides a heavy metal normal temperature curing agent, which comprises the following components of: by weight, 30.0-40.0% of magnesium oxide, 55.0-65.0% of potassium dihydrogen phosphate, 3.5-5.0% of borax, 0.1-0.5% of iron oxide and 0.1-0.5% of silica. The invention also provides a method for curing heavy metal in heavy metal pollutants by the use of the heavy metal normal temperature curing agent. Wastes containing heavy metal are cured at normal temperature by the use of the normal temperature curing agent, thus realizing resource utilization of wastes. In addition, the normal temperature curing agent has a good curing effect; the normal temperature stabilized method requires low cost; the operation process is simple and practicable; and curing is little influenced by the environment.
Description
Technical field
The invention belongs to field of environment engineering technology, relate in particular to a heavy metal species normal temperature cure agent and use the method for heavy metal in its curing heavy metal pollutant.
Background technology
Along with the high speed development of Chinese Urbanization, domestic waste discharge capacity sharply increases with annual 8% ~ 10% speed, has seriously hindered the sustainable development of China's economy and society.Burning method is the best method to urban garbage disposal at present.Burning method can effectively destroy organic toxicant, the high and recyclable secondary energy sources of volume reduction rate, but incineration of refuse flyash (MSWI) can the highly toxic heavy metal of enriched, by country, is listed in danger wastes register, need be cured rear permission security landfill to it.Realize in MSWI the harmlessness disposing of harmful constituent most important.Chinese scholars is studied targetedly to the harmlessness disposing of heavy metal in MSWI flying dust, has large quantity research report both at home and abroad.
Raw respond well (the Hui-sheng Shi that studies confirm that cement stabilizing/curing flying dust that waits obliges, Li-li Kan. Characteristics of municipal solid wastes incineration (MSWI) fly ash cement matrices and effect of mineral admixtures on composite system. Construction and Building Materials, 2009,23 (6): 2160-2166).
T. Mangialardi etc. points out flying dust to wash and can eliminate most soluble salt, can reduce flying dust to the impact of hydrated cementitious (T. Mangialardi. Disposal of MSWI fly ash through a combined washing immobili-sation process. Journal of Hazardous Materials, 2003,98 (3): 225-240).
A. the employing such as Polettini adds Na
2siO
3or CaCl
2additive reduces the impact of flying dust on hardening of cement.（A.?Polettini,?R.?Pomia,?et?al.?Properties?of?Portland?cement-stabilized?MSWI?fly?ashes.?Journal?of?Hazardous?Materials,?2001,?88?(1):?123-138）。
Glad guarantor waits employing dithiocarbamates chelating agent to replace part of cement to solidify washing flying dust (Xingbao Gao, Wei Wang, Tunmin Ye, et al. Utilization of washed MSWI fly ash as partial cement substitute with the addition of dithiocarbamic chelate. Journal of Environmental Management, 2008,88 (2) 293-299).Yet the method exists increase-volume than large, the problem such as under long-range circumstances effect the solidification effect of heavy metal is poor.
The characteristic of migrating of the research MSWI fusing fly ash heavy metals in process such as Wang Qi finds that melting method can effectively eliminate bioxin and reduce the leaching of heavy metal.（Qi?Wang,?Shulei?Tian,?Qunhui?Wang,?et?al.?Melting?characteristics?during?the?vitrification?of?MSWI?fly?ash?with?a?pilot?scale?diesel?oil?furnace.?Journal?of?Hazardous?Materials,?2008,?160(2):?376-381）。
The researchs such as Jiang Jianguo show that polyamines class and polyethyleneimine: amine heavy metal intercalating agent are obviously better than Na to the treatment effect of flying dust
2s and lime, and adding less.(Jiang Jianguo, Wang Wei, Li Guoding. heavy metal chelant is processed the stability experiment research of flying ash. Shanghai environmental science, 2001,20 (3): 134-136).
Money light people utilizes phosphoric acid class medicament to react with Si, Al in ash, Ca etc. the hydroxy phosphorus Calx mineral that generate curable heavy metal; But MSWI flying dust Zhong bioxin cannot decompose under normal temperature, and the flying dust after processing must landfill.（Guangren?Qian,?Xia?Xu,?Weimin?Sun,?et?al.?Preparation,?characterization,?and?stability?of?calcium?zinc?hydrophosphate.?Materials?Research?Bulletin,?2008,?43?(12):?3463-3473）。
In sum, current research mainly concentrates on and uses high-temperature heat treatment and chelating agent to solidify micro heavy.The method being cured for high-temperature heat treatment, first high-temperature heat treatment need to consume a large amount of energy, and can produce secondary pollution in processing procedure, and heavy metal can evaporate again, and the discarded object after processing still needs landfill, takies a large amount of soils; Secondly, the higher situation of chloride ion content in the inapplicable heavy metal discarded object of the method, because higher chloride ion content can to a certain degree damage high-temperature processing device.For the method being cured with chelating agent, its solidification effect fluctuation ratio affected by environment is larger.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of energy waste of avoiding pyroprocess, the heavy metal normal temperature cure agent that cost compare is low and use the method for heavy metal in its curing heavy metal pollutant.
The present invention solves the problems of the technologies described above taked technical scheme to be:
One heavy metal species normal temperature cure agent, is characterized in that, it is composed of the following components by weight percentage: magnesia 30.0% ~ 40.0%, potassium dihydrogen phosphate 55.0% ~ 65.0%, borax 3.5% ~ 5.0%, iron oxide 0.1% ~ 0.5%, silica 0.1% ~ 0.5%.
A method of using heavy metal in above-mentioned heavy metal normal temperature cure agent curing heavy metal pollutant, is characterized in that, it comprises the following steps:
1) be by weight percentage 30.0% ~ 40.0% magnesia, 55.0% ~ 65.0% potassium dihydrogen phosphate, 3.5% ~ 5.0% borax, 0.1% ~ 0.5% iron oxide, 0.1% ~ 0.5% silica, chooses magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica, standby;
2) magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica are fully mixed, obtain heavy metal normal temperature cure agent;
3) by the mass ratio of heavy metal contaminants and described heavy metal normal temperature cure agent, be that 5 ~ 20:100 chooses heavy metal contaminants, heavy metal contaminants is mixed with heavy metal normal temperature cure agent, stir, obtain compound;
4) add 25% ~ 35% water of described mixture quality to described compound, stir standing moulding.
In such scheme, the mixing time in described step 4) is 2min ~ 5min.
In such scheme, be also included in heavy metal contaminants and mix the steps at 105 ℃ of oven dry 2h by heavy metal contaminants before with heavy metal normal temperature cure agent.
Principle of the present invention is: the antihunt means of the present invention to heavy metal, mainly utilize the chemical reaction of magnesia and potassium dihydrogen phosphate, and chemical group and heavy metal lead, zinc, copper etc. form stable mineral salt and mineral matter.Mineral salt and mineral matter have good suction-operated to the heavy metal of low concentration, for the heavy metal of high concentration, there is chemical reaction after product be deposited in mineral surfaces.
Beneficial effect of the present invention is: through normal temperature cure agent of the present invention, heavy metal waste is cured after processing at normal temperatures, can realizes utilization of waste as resource.The solidification effect of normal temperature cure agent of the present invention is good, and ambient stable method cost is low, and operating process is simple, and solidification effect fluctuation affected by environment is less.
The specific embodiment
Below in conjunction with embodiment, the invention will be further described, and certain following embodiment should not be construed as limitation of the present invention.
The chemical composition of the heavy metal contaminants using in all embodiment is below in Table 1.
The chemical composition of table 1 heavy metal discarded object
| Composition | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | K 2O | Na 2O | Cl | SO 3 |
| Percentage by weight (%) | 16.45 | 8.72 | 6.25 | 8.27 | 3.11 | 8.75 | 2.61 | 3.72 | 3.87 |
| Composition | P 2O 5 | MnO | CuO | ZnO | CdO | Cr 2O 3 | BaO | PbO | Loss on ignition |
| Percentage by weight (%) | 2.93 | 0.12 | 6.24 | 3.11 | 6.64 | 3.12 | 5.23 | 7.74 | 3.12 |
embodiment 1
One heavy metal species normal temperature cure agent, it is composed of the following components by weight percentage: magnesia 30.0%, potassium dihydrogen phosphate 65.0%, borax 4.0%, iron oxide 0.5%, silica 0.5%.
A method of using heavy metal in above-mentioned heavy metal normal temperature cure agent curing heavy metal pollutant, it comprises the following steps:
1) heavy metal contaminants is dried to 2h at 105 ℃, standby;
2) be by weight percentage 30.0% magnesia, 65.0% potassium dihydrogen phosphate, 4.0% borax, 0.5% iron oxide, 0.5% silica, chooses magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica, standby;
3) magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica are fully mixed, obtain heavy metal normal temperature cure agent;
4) by the mass ratio of heavy metal contaminants and described heavy metal normal temperature cure agent, be that 15:100 chooses heavy metal contaminants, heavy metal contaminants is mixed with heavy metal normal temperature cure agent, stir, obtain compound;
5) add 35% water of described mixture quality to described compound, stir 2min, standing moulding, broken after 28d, according to national standard (HJ557-2010), do toxicity leaching experiment, toxicity leaches and the results are shown in Table 2.
embodiment 2
One heavy metal species normal temperature cure agent, it is composed of the following components by weight percentage: magnesia 36.0%, potassium dihydrogen phosphate 60.0%, borax 3.8%, iron oxide 0.1%, silica 0.1%.
A method of using heavy metal in above-mentioned heavy metal normal temperature cure agent curing heavy metal pollutant, it comprises the following steps:
1) be by weight percentage 36.0% magnesia, 60.0% potassium dihydrogen phosphate, 3.8% borax, 0.1% iron oxide, 0.1% silica, chooses magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica, standby;
2) magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica are fully mixed, obtain heavy metal normal temperature cure agent;
3) by the mass ratio of heavy metal contaminants and described heavy metal normal temperature cure agent, be that 18:100 chooses heavy metal contaminants, heavy metal contaminants is mixed with heavy metal normal temperature cure agent, stir, obtain compound;
4) add 33% water of described mixture quality to described compound, stir, standing moulding, broken after 28d, according to national standard (HJ557-2010), do toxicity leaching experiment, toxicity leaches and the results are shown in Table 2.
embodiment 3
One heavy metal species normal temperature cure agent, it is composed of the following components by weight percentage: magnesia 35.5%, potassium dihydrogen phosphate 59.0%, borax 5.0%, iron oxide 0.2%, silica 0.3%.
A method of using heavy metal in above-mentioned heavy metal normal temperature cure agent curing heavy metal pollutant, it comprises the following steps:
1) heavy metal contaminants is dried to 2h at 105 ℃, standby;
2) be by weight percentage 35.5% magnesia, 59.0% potassium dihydrogen phosphate, 5.0% borax, 0.2% iron oxide, 0.3% silica, chooses magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica, standby;
3) magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica are fully mixed, obtain heavy metal normal temperature cure agent;
4) by the mass ratio of heavy metal contaminants and described heavy metal normal temperature cure agent, be that 5:100 chooses heavy metal contaminants, heavy metal contaminants is mixed with heavy metal normal temperature cure agent, stir, obtain compound;
5) add 30% water of described mixture quality to described compound, stir 4min, standing moulding, broken after 28d, according to national standard (HJ557-2010), do toxicity leaching experiment, toxicity leaches and the results are shown in Table 2.
embodiment 4
One heavy metal species normal temperature cure agent, it is composed of the following components by weight percentage: magnesia 40.0%, potassium dihydrogen phosphate 55.0%, borax 4.5%, iron oxide 0.3%, silica 0.2%.
A method of using heavy metal in above-mentioned heavy metal normal temperature cure agent curing heavy metal pollutant, it comprises the following steps:
1) heavy metal contaminants is dried to 2h at 105 ℃, standby;
2) be by weight percentage 40.0% magnesia, 55.0% potassium dihydrogen phosphate, 4.5% borax, 0.3% iron oxide, 0.2% silica, chooses magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica, standby;
3) magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica are fully mixed, obtain heavy metal normal temperature cure agent;
4) by the mass ratio of heavy metal contaminants and described heavy metal normal temperature cure agent, be that 15:100 chooses heavy metal contaminants, heavy metal contaminants is mixed with heavy metal normal temperature cure agent, stir, obtain compound;
5) add 28% water of described mixture quality to described compound, stir 5min, standing moulding, broken after 28d, according to national standard (HJ557-2010), do toxicity leaching experiment, toxicity leaches and the results are shown in Table 2.
embodiment 5
One heavy metal species normal temperature cure agent, it is composed of the following components by weight percentage: magnesia 37.5%, potassium dihydrogen phosphate 58.0%, borax 3.5%, iron oxide 0.5%, silica 0.5%.
A method of using heavy metal in above-mentioned heavy metal normal temperature cure agent curing heavy metal pollutant, it comprises the following steps:
1) heavy metal contaminants is dried to 2h at 105 ℃, standby;
2) be by weight percentage 37.5% magnesia, 58.0% potassium dihydrogen phosphate, 3.5% borax, 0.5% iron oxide, 0.5% silica, chooses magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica, standby;
3) magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica are fully mixed, obtain heavy metal normal temperature cure agent;
4) by the mass ratio of heavy metal contaminants and described heavy metal normal temperature cure agent, be that 18:100 chooses heavy metal contaminants, heavy metal contaminants is mixed with heavy metal normal temperature cure agent, stir, obtain compound;
5) add 26% water of described mixture quality to described compound, stir 5min, standing moulding, broken after 28d, according to national standard (HJ557-2010), do toxicity leaching experiment, toxicity leaches and the results are shown in Table 2.
embodiment 6
One heavy metal species normal temperature cure agent, it is composed of the following components by weight percentage: magnesia 32.5%, potassium dihydrogen phosphate 63.0%, borax 3.8%, iron oxide 0.2%, silica 0.5%.
A method of using heavy metal in above-mentioned heavy metal normal temperature cure agent curing heavy metal pollutant, it comprises the following steps:
1) heavy metal contaminants is dried to 2h at 105 ℃, standby;
2) be by weight percentage 32.5% magnesia, 63.0% potassium dihydrogen phosphate, 3.8% borax, 0.2% iron oxide, 0.5% silica, chooses magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica, standby;
3) magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica are fully mixed, obtain heavy metal normal temperature cure agent;
4) by the mass ratio of heavy metal contaminants and described heavy metal normal temperature cure agent, be that 20:100 chooses heavy metal contaminants, heavy metal contaminants is mixed with heavy metal normal temperature cure agent, stir, obtain compound;
5) add 25% water of described mixture quality to described compound, stir 4min, standing moulding, broken after 28d, according to national standard (HJ557-2010), do toxicity leaching experiment, toxicity leaches and the results are shown in Table 2.
Leaching concentration (mg/L) before table 2 heavy metal contaminants is processed, after processing
As shown in Table 2, use normal temperature cure agent of the present invention to be cured heavy metal in heavy metal contaminants, leaching concentration is far below standard limited value, and solidification effect is good.
Each raw material that the present invention is cited, and the bound value of each raw material, with and interval value, can realize the present invention; And the bound value of each technological parameter (as the time), with and interval value, can realize the present invention, at this, do not enumerate embodiment.
Claims (4)
1. a heavy metal species normal temperature cure agent, it is characterized in that, it is composed of the following components by weight percentage: magnesia 30.0% ~ 40.0%, potassium dihydrogen phosphate 55.0% ~ 65.0%, borax 3.5% ~ 5.0%, iron oxide 0.1% ~ 0.5%, silica 0.1% ~ 0.5%, described heavy metal is Pb, Zn, Cd, Cr, Cu or Ba.
2. use a method for heavy metal in heavy metal normal temperature cure agent curing heavy metal pollutant as claimed in claim 1, it is characterized in that, it comprises the following steps:
1) be by weight percentage 30.0% ~ 40.0% magnesia, 55.0% ~ 65.0% potassium dihydrogen phosphate, 3.5% ~ 5.0% borax, 0.1% ~ 0.5% iron oxide, 0.1% ~ 0.5% silica, chooses magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica, standby;
2) magnesia, potassium dihydrogen phosphate, borax, iron oxide and silica are fully mixed, obtain heavy metal normal temperature cure agent;
3) by the mass ratio of heavy metal contaminants and described heavy metal normal temperature cure agent, be that 5 ~ 20:100 chooses heavy metal contaminants, heavy metal contaminants is mixed with heavy metal normal temperature cure agent, stir, obtain compound, in described heavy metal contaminants, heavy metal is Pb, Zn, Cd, Cr, Cu or Ba;
4) add 25% ~ 35% water of described mixture quality to described compound, stir standing moulding.
3. the method for heavy metal in curing heavy metal pollutant as claimed in claim 2, is characterized in that, the mixing time in described step 4) is 2min ~ 5min.
4. the method for heavy metal in curing heavy metal pollutant as claimed in claim 2, is characterized in that, is also included in heavy metal contaminants and mixes the steps at 105 ℃ of oven dry 2h by heavy metal contaminants before with heavy metal normal temperature cure agent.
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| CN102989741B (en) * | 2012-11-20 | 2015-05-27 | 盐城工学院 | Preparation method of heavy metal solid waste curing agent |
| CN103289703A (en) * | 2013-07-05 | 2013-09-11 | 浙江工业大学 | Early-strength soil solidifying agent and manufacturing method and application for same |
| CN105110671A (en) * | 2015-08-11 | 2015-12-02 | 安徽青地球环保科技有限公司 | Method for transforming lead glass into environment-friendly concrete raw material by using natural biological material |
| WO2018120051A1 (en) * | 2016-12-30 | 2018-07-05 | 深圳市能源环保有限公司 | Waste incineration fly ash stabilizing agent and preparation method therefor |
| CN112661480A (en) * | 2020-12-03 | 2021-04-16 | 嘉兴沃特泰科环保科技股份有限公司 | Solid chelating agent for life landfill standard and preparation method thereof |
| CN113648963B (en) * | 2021-09-06 | 2023-06-23 | 昆明理工大学 | Method for adsorbing ciprofloxacin in wastewater by using phosphate porous microspheres |
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| CN102180641A (en) * | 2011-01-26 | 2011-09-14 | 中国石油大学(华东) | Method and process for high strength curing of drilling waste |
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| US20070267343A1 (en) * | 2006-05-17 | 2007-11-22 | Keith Edward Forrester | Heavy metal particulate emission speciation modification wet process |
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| CN1614147A (en) * | 2003-11-07 | 2005-05-11 | 松田技研工业株式会社 | Soil solidifying agent, soil paving material and method |
| CN102180641A (en) * | 2011-01-26 | 2011-09-14 | 中国石油大学(华东) | Method and process for high strength curing of drilling waste |
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