CN102335494B - Heavy metal stabilizing treatment method for dust containing heavy metals - Google Patents
Heavy metal stabilizing treatment method for dust containing heavy metals Download PDFInfo
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Abstract
The invention relates to a heavy metal stabilizing treatment method. According to the method, an alkaline reagent and a heavy metal fixative are added to heavy-metal-containing dust showing P-alkalinity; and the materials are mixed. The alkaline reagent comprises an Mg compound and/or a Ca compound. The heavy metal fixative comprises a phosphoric acid compound and a dithiocarbamic acid compound. With the heavy metal stabilizing treatment method provided by the invention, dust containing heavy metals can be stably treated for a long term. According to a PRC HJT300-2007 testing method used for extracting solid waste toxic extract through an acetic acid buffering solution method, the pollution controlling efficiency of the method provided by the invention can stably satisfy a standard value of a domestic waste landfill pollution controlling standard GB16889-2008. Also, the cost of the method is low. With the method, environmental load can be reduced.
Description
Technical field
The present invention relates to a kind of make burn or burn till the general discarded object of melting or industrial waste time the dust that produces in the innoxious method of the heavy metal that contains, especially according to People's Republic of China (PRC) HJT300-2007 solid waste Leaching leaching method hac buffer method, stably heavy metal can be processed.Make innoxious process ash can landfill disposal etc.
Background technology
For heavy metal dusts, general adds a certain amount of cement, water, the method making heavy metal innoxious by cement solidification.Again, what also have the standard value using not meeting household refuse landfill sites Environmental capacity standard GB16889-2008 contains heavy metal dusts as danger, carries out the situation of danger process.
As in the cement solidification technology of conventional art, when the occasion of the high dust of the content of beary metal such as Pb, Cd, Zn, Cu, in the test of the method according to People's Republic of China (PRC) HJT300-2007 solid waste Leaching leaching method hac buffer method, existence stably can not meet the problem of the standard value of household refuse landfill sites Environmental capacity standard GB16889-2008, and i.e. enable process, cement addition is also very many, produces the problem needing landfill disposal amount significantly to increase thus.Special under the condition that pH value is low, the Pb that content is high, the heavy metals such as Cd, Cu, Zn can with higher concentration digestion.
Summary of the invention
The present invention puts forward for solving problem existing for above-mentioned prior art, the object of the invention is to, a kind of heavy metal stabilization processing method is provided, it can be stablized and process contains heavy metal dusts chronically, especially, according in the test method of People's Republic of China (PRC) HJT300-2007 solid waste Leaching leaching method hac buffer method, stably can meet the standard value of household refuse landfill sites Environmental capacity standard GB16889-2008, and cost is low, and carrying capacity of environment can be alleviated.
To achieve these goals, the present invention proposes following technical scheme:
(1) a heavy metal stabilization processing method, is characterized in that:
The heavy metal dusts that contains to display P-basicity adds alkaline reagent and heavy metal fixative, mix, above-mentioned alkaline reagent is Mg compound and/or Ca compound, as above-mentioned heavy metal fixative, and with phosphate compound and aminodithioformic acid compounds.
(2) in the heavy metal stabilization processing method described in technique scheme (1), it is characterized in that:
Add water to above-mentioned dust, mix.
(3) in the heavy metal stabilization processing method described in technique scheme (1) or (2), it is characterized in that:
Above-mentioned Mg compound is at least one material selected from magnesia, magnesium hydroxide.
(4) in the heavy metal stabilization processing method described in technique scheme (1) or (2), it is characterized in that:
Above-mentioned Ca compound is at least one material selected from calcium oxide, calcium hydroxide.
(5), in the heavy metal stabilization processing method in technique scheme (1) ~ (4) described in any one, it is characterized in that:
Above-mentioned phosphate compound is at least one material selected from phosphoric acid, dibastic sodium phosphate, potassium hydrogen phosphate, sodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphate hydrogen tri-sodium, phosphoric acid hydrogen tripotassium, calcium phosphate, magnesium phosphate.
(6), in the heavy metal stabilization processing method in technique scheme (1) ~ (4) described in any one, it is characterized in that:
Above-mentioned aminodithioformic acid compounds is at least one material selected from diethyldithiocar bamic acid or its salt, piperazine aminodithioformic acid or its salt, dimethyl dithiocarbamic acid or its salt, polyamine aminodithioformic acid or its salt.
(7), in the heavy metal stabilization processing method in technique scheme (1) ~ (6) described in any one, it is characterized in that:
As above-mentioned alkaline reagent and above-mentioned heavy metal fixative, both uses are mixed into the chemicals of potion.
(8), in the heavy metal stabilization processing method in technique scheme (1) ~ (7) described in any one, it is characterized in that:
After adding above-mentioned alkaline reagent, add above-mentioned heavy metal fixative, mix.
(9), in the heavy metal stabilization processing method in technique scheme (1) ~ (8) described in any one, it is characterized in that:
Containing heavy metal dusts be burn or burn till the general discarded object of melting or industrial waste time the dust that produces.
In the present invention, water is not necessary, but, except alkaline reagent and heavy metal fixative, add water further, by mixing, alkaline reagent and heavy metal fixative homogeneous/dispersiveness becomes good, therefore, can more stable, effectively implement heavy metal process.
Below, the distinctive effect of the present invention is described.
As the MgO/Mg (OH) of alkaline reagent
2effect be make the ability raising pH value excellent, meanwhile, there is about pH9.5 ~ 10.5 pH value pooling feature.In addition, also there is the function of similarly to solidify with cement containing heavy metal dusts.
As the CaO/Ca (OH) of alkaline reagent
2effect, identical with Mg compounds, the ability raising pH value is excellent, and meanwhile, when adding phosphate compound, this reagent also has and improves the insoluble effect of heavy metal.And also there is the function of solidification containing heavy metal dusts.
Phosphate compound is by making Pb, and the heavy metallic mineral of Cd, Cu, Zn etc., has stabilisation, thawless function.
In dust, add phosphoric acid, carry out mixing:
1. Pb
2++ PO
4 3-+ Cl
-→ Pb
5(PO
4)
3cl (pyromorphite)
2. Ca
2++ PO
4 3-+ OH
-→ Ca
5(PO
4)
3oH (hydroxyapatite) ... major part hydroxyapatite has the immobilized character of heavy metal class such as making Pb or Cd.
Ca
5(PO
4)
3oH+Pb
2+→ Pb
5(PO
4)
3oH (pyromorphite)+Ca
2+
Finally, plumbous and phosphoric acid combines, and becomes the most stable insoluble compound.
Again, the product of phosphate compound and heavy metal reaction is indissoluble, insoluble compound, has long-term stability.But phosphate compound and heavy metal delay of response, slowly react with heavy metal, forms stable compound.
On the other hand, aminodithioformic acid compounds have identical with phosphate compound, make Pb, the thawless effect of the heavy metals such as Cd, Cu, Zn, but immobilization mechanism is different from phosphate compound.
Aminodithioformic acid compounds can form the chelate of slightly solubility with heavy metal, makes heavy metal insoluble.
[the insoluble mechanism of aminodithioformic acid compounds]
Aminodithioformic acid compounds is organic sequestering agent, different with phosphate compound, reacts have quick-acting with heavy metal.But, because be organic matter, so, through after a while, can because of oxidation Decomposition etc., aminodithioformic acid compounds decomposes, and has the shortcoming (that is, not having long-term stability) of heavy metal stripping again.
Be used alone the function that alkaline reagent (Mg, Ca compounds) only has adjusted to ph, stably can not process heavy metal.
Be used alone phosphoric acid system fixative, and the reactivity of heavy metal is slow, therefore, needs to add considerable amount, be actually difficult to fixing heavy metal.
Be used alone aminodithioformic acid compounds, although the fixed effect quick-acting of heavy metal is high, but, when not adding alkaline reagent, need considerable addition, and pernicious gas (carbon disulfide, hydrogen sulfide etc.) can be produced when pH is little, and there is no long-term stability, deposit the problem of the stripping again of heavy metal after a period of time has passed.
The present invention passes through and uses phosphate compound and aminodithioformic acid compounds, as heavy metal fixative, can realize the fixing quick-acting of heavy metal and long-time stability.Further, by adding MgO, the CaO as alkaline reagent, the addition (reactivity of fixative can be improved) of fixative can be reduced.
Again, by adding Mg system, Ca based compound, the curing performance identical with cement can be obtained, therefore, do not need cement.In addition, also there is the pernicious gas suppressing to occur because aminodithioformic acid compounds produces.
Can be used alone the process of Mg compounds as alkaline reagent, but the reactivity with heavy metal can be improved by adding Ca compounds.
[definition containing heavy metal dusts]
Tie up to burn or burn till the general discarded object of melting or industrial waste time produce containing the dust of heavy metal, mean dust, boiler ash, the gas cooling ash of exhaust cooling tower, the ash etc. of exhaust purge tower collected by dust arrester.
Accompanying drawing explanation
Fig. 1 represents the curve map of relation between elapsed time and leaching ability of heavy metal concentration.
Detailed description of the invention
The application of the invention, according in the test method of People's Republic of China (PRC) HJT300-2007 solid waste Leaching leaching method hac buffer method, stably can meet the standard value of household refuse landfill sites Environmental capacity standard GB16889-2008, can be used as general discarded object landfill disposal.
Below, the embodiment of the heavy metal stabilization processing method containing heavy metal dusts of the present invention is described in detail.In following embodiment, although to inscape, kind, combination, various restriction has been done in configuration etc., these only exemplify, and the present invention is not limited thereto.
As evaluating the test method that whether stably can process heavy metal, use People's Republic of China (PRC) HJT300-2007 solid waste Leaching leaching method hac buffer method.
The present invention relates to the heavy metal processing method containing heavy metal dusts, Mg compounds and/or Ca compounds is used as alkaline reagent, as fixative interpolation, mixed phosphate compounds and aminodithioformic acid compounds, discarded object after mixed processing stably meets the standard value of household refuse landfill sites Environmental capacity standard GB16889-2008, can be used as general discarded object landfill disposal.
As the Mg compounds of alkaline reagent, magnesia, magnesium hydroxide can be used.
As the Ca compounds of alkaline reagent, calcium oxide, calcium hydroxide can be used.
As the phosphate compound of heavy metal fixative, phosphoric acid, dibastic sodium phosphate, potassium hydrogen phosphate, sodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphate hydrogen tri-sodium, phosphoric acid hydrogen tripotassium, calcium phosphate, magnesium phosphate can be used.
As the aminodithioformic acid compounds of heavy metal fixative, diethyldithiocar bamic acid or its salt, piperazine aminodithioformic acid or its salt, dimethyl dithiocarbamic acid or its salt, polyamine aminodithioformic acid or its salt can be used.
Alkaline reagent and heavy metal fixative can be powder, slurry or liquid, are not particularly limited.
As the adding rate of Mg compounds, be preferably, relatively containing heavy metal dusts 100 % by weight, add 3 ~ 50 % by weight, be more preferably 5 ~ 40 % by weight scopes.
As the adding rate of Ca compounds, be preferably, relatively containing heavy metal dusts 100 % by weight, add 3 ~ 50 % by weight, be more preferably 5 ~ 40 % by weight scopes.
As the adding rate of phosphate compound, be preferably, relatively containing heavy metal dusts 100 % by weight, add 0.05 ~ 30 % by weight, be more preferably 0.1 ~ 20 % by weight scope.
As the adding rate of aminodithioformic acid compounds, be preferably, relatively containing heavy metal dusts 100 % by weight, add 0.05 ~ 30 % by weight, be more preferably 0.1 ~ 20 % by weight scope.
As adding method, alkaline reagent and heavy metal fixative can be added respectively, also alkaline reagent and heavy metal fixative can be mixed into potion and add.
When adding alkaline reagent and heavy metal fixative respectively, be preferably, after adding alkaline reagent, then add the mixing of heavy metal fixative.Add the dust after alkaline reagent and the process of heavy metal fixative according to People's Republic of China (PRC) HJT300-2007 solid waste Leaching leaching method hac buffer method, be preferably the pH scope of its dissolution fluid 5.0 ~ 12.5.
Again, in heavy metal processing method of the present invention, the dust proterties containing heavy metal ash of discharge, be preferably, relative dust weight 1, pure water weight is the liquid-solid ratio of more than 5, mixing time more than 1 minute, display P-basicity.
Fig. 1 represents the curve map of relation between elapsed time and leaching ability of heavy metal concentration.As shown in Figure 1, use mode occasion in the past, when adopting inorganic process, when adopting organic process, no matter with or without auxiliary agent, along with time process, can there is heavy metal stripping again in difficult treatment.
And pass through the mixed processing (using organic+inorganic+auxiliary agent) of the present invention one embodiment, there is quick-acting, and there are long-time stability.
[embodiment]
Use the dust of discharging from municipal refuse disposal area as powder sample.
The composition analysis result of powder sample is as shown in table 1.
Table 1
| Analysis project | Unit | Dust SJ |
| Former Di | mg-CaCo 3/ g-dust | 110 |
| Moisture content | ％ | 1.0＞ |
| Scorching hot decrement | ％ | 4.1 |
| Ca | mg/kg | 156000 |
| T-Cr | mg/kg | 110 |
| Zn | mg/kg | 8700 |
| Cd | mg/kg | 95 |
| Pb | mg/kg | 3800 |
| Hg | mg/kg | 6.8 |
| As | mg/kg | 14 |
| Se | mg/kg | 3 |
| Ni | mg/kg | 85 |
| Cu | mg/kg | 1120 |
Embodiment and comparative example as shown in table 2.
Test method: add a certain amount of alkaline reagent, heavy metal fixative in sample dust 100g, pure water 25 % by weight (relative dust), with spatula after mixing about 3 minutes, obtained mixing thing, as process ash, implements the dissolution test according to People's Republic of China (PRC) HJT300-2007 solid waste Leaching leaching method.
Obtained process ash (making 300g) is taken care of after two weeks, after surrounding, is again implemented above-mentioned dissolution test respectively, implement the stability confirmation test along with time variations under air.
Alkaline reagent and the heavy metal fixative of test are as follows:
Alkaline reagent:
1. calcium oxide → purity more than 96% (commercial goods)
2. magnesia → purity more than 95% (commercial goods)
3. calcium hydroxide → purity more than 96% (commercial goods)
4. magnesium hydroxide → purity more than 99% (commercial goods)
Remarks: 1.-be 4. all powder product
Heavy metal fixative:
1. Na
3pO
4→ content more than 99% (commercial goods)
2. Na
2hPO
4→ content more than 99% (commercial goods)
3. three hydration sodium diethyldithiocarbamate → content about 95% (commercial goods)
4. diethyldithiocar bamic acid potassium → content about 52% (commercial goods)
Remarks: 1.-be 3. powder product, be 4. liquid product
Table 2-1
Table 2-2
Note 1:Pb, Cd, Hg, Cu, Zn, Be, Ba, Ni, As, Se, Cr
6+, the dimension of T-Cr is " mg/L "
Note 2:GB16889-2008 system " household refuse landfill sites Environmental capacity standard GB16889-2008 " is note slightly.
From above-mentioned result of the test, in embodiments, the method of the application of the invention, according in the test method of People's Republic of China (PRC) HJT300-2007 solid waste Leaching leaching method hac buffer method, result of the test data stably can meet the requirement of household refuse landfill sites Environmental capacity standard GB16889-2008, can be used as general discarded object landfill disposal.
Above with reference to illustrating embodiments of the invention, but the present invention is not limited to above-mentioned embodiment.Can do all changes in the technology of the present invention thought range, they all belong to protection scope of the present invention.
Claims (11)
1. a heavy metal stabilization processing method, is characterized in that:
Add alkaline reagent and heavy metal fixative to display P-basicity containing heavy metal dusts, mix, above-mentioned alkaline reagent is Mg compound, as above-mentioned heavy metal fixative, and with phosphate compound and aminodithioformic acid compounds.
2. heavy metal stabilization processing method as claimed in claim 1, is characterized in that:
Above-mentioned alkaline reagent also comprises Ca compound.
3. heavy metal stabilization processing method as claimed in claim 1, is characterized in that:
Add water to above-mentioned dust, mix.
4. heavy metal stabilization processing method as claimed in claim 2, is characterized in that:
Add water to above-mentioned dust, mix.
5., as the heavy metal stabilization processing method in Claims 1 to 4 as described in any one, it is characterized in that:
Above-mentioned Mg compound is at least one material selected from magnesia, magnesium hydroxide.
6. the heavy metal stabilization processing method as described in claim 2 or 4, is characterized in that:
Above-mentioned Ca compound is at least one material selected from calcium oxide, calcium hydroxide.
7., as the heavy metal stabilization processing method in Claims 1 to 4 as described in any one, it is characterized in that:
Above-mentioned phosphate compound is at least one material selected from phosphoric acid, dibastic sodium phosphate, potassium hydrogen phosphate, sodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphate hydrogen tri-sodium, phosphoric acid hydrogen tripotassium, calcium phosphate, magnesium phosphate.
8., as the heavy metal stabilization processing method in Claims 1 to 4 as described in any one, it is characterized in that:
Above-mentioned aminodithioformic acid compounds is at least one material selected from diethyldithiocar bamic acid or its salt, piperazine aminodithioformic acid or its salt, dimethyl dithiocarbamic acid or its salt, polyamine aminodithioformic acid or its salt.
9., as the heavy metal stabilization processing method in Claims 1 to 4 as described in any one, it is characterized in that:
As above-mentioned alkaline reagent and above-mentioned heavy metal fixative, both uses are mixed into the chemicals of potion.
10., as the heavy metal stabilization processing method in Claims 1 to 4 as described in any one, it is characterized in that:
After adding above-mentioned alkaline reagent, add above-mentioned heavy metal fixative, mix.
11., as the heavy metal stabilization processing method in Claims 1 to 4 as described in any one, is characterized in that:
Containing heavy metal dusts be burn or burn till the general discarded object of melting or industrial waste time the dust that produces.
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| CN104138884B (en) * | 2013-05-09 | 2018-12-14 | 栗田工业株式会社 | The insolubilizing agent of heavy metal and the insoluble method of heavy metal |
| CN104492024A (en) * | 2014-12-12 | 2015-04-08 | 江苏中宜生态土研究院有限公司 | Fly ash treatment method for waste incineration |
| CN104610972B (en) * | 2014-12-18 | 2017-12-08 | 淄博金鼎光电科技有限公司 | It is a kind of to be used to administer inorganic agent of heavy-metal contaminated soil and preparation method thereof |
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