CN102936116A - Method for solidifying-stabilizing bottom mud polluted by heavy metals by using cement and organic sulfides and application of obtained solidified body - Google Patents
Method for solidifying-stabilizing bottom mud polluted by heavy metals by using cement and organic sulfides and application of obtained solidified body Download PDFInfo
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- CN102936116A CN102936116A CN2012104640845A CN201210464084A CN102936116A CN 102936116 A CN102936116 A CN 102936116A CN 2012104640845 A CN2012104640845 A CN 2012104640845A CN 201210464084 A CN201210464084 A CN 201210464084A CN 102936116 A CN102936116 A CN 102936116A
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 64
- 239000004568 cement Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 42
- 150000003568 thioethers Chemical class 0.000 title 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000011105 stabilization Methods 0.000 claims description 23
- 239000012990 dithiocarbamate Substances 0.000 claims description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 11
- 238000010348 incorporation Methods 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 238000012423 maintenance Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 7
- 238000010276 construction Methods 0.000 claims description 7
- 239000011133 lead Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000004566 building material Substances 0.000 abstract 1
- 150000004763 sulfides Chemical class 0.000 abstract 1
- 239000011499 joint compound Substances 0.000 description 31
- 238000002386 leaching Methods 0.000 description 27
- 230000006835 compression Effects 0.000 description 9
- 238000007906 compression Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 6
- 238000003916 acid precipitation Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 150000004659 dithiocarbamates Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000004162 soil erosion Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
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- Treatment Of Sludge (AREA)
Abstract
The invention relates to a method for solidifying-stabilizing bottom mud polluted by heavy metals by using cement and organic sulfides and application of an obtained solidified body. The method comprises the steps of adding aminodithioformic acid into the bottom mud polluted by heavy metals, stirring fully, adding cement, stirring the obtained mixture uniformly, and curing for 3d-14d to obtain the solidified body, so that a solidifying-stabilizing process is completed. The method has the advantages that the usage amount of the cement can be reduced, the cost is reduced, the capacity increasing rate of the solidified body is reduced, secondary pollution is avoided, the solidifying-stabilizing effect of the bottom mud polluted by heavy metals is improved, the cured solidified body can be used for landfill disposal or can serve as a building material.
Description
Technical field
The present invention relates to a kind of curing-stabilization treatment method of heavy metal polluted bed mud, relate in particular to a kind of the utilize method of stablizer curing-stabilization heavy metal polluted bed mud and the application of gained cured body.
Background technology
Along with the fast development of industrial economy, the environmental problem that trade effluent brings is day by day serious, and the pollutents such as heavy metal enter water body by industrial wastewater discharge, finally accumulates in the bed mud, and water ecosystem is constituted a threat to.Therefore, Heavy Metal Pollution in Sediments becomes a global environmental problem.Bed mud refers to the superficial deposit material of water bottom, is comprised of soil ulmin, microorganism, silt and soil etc.Heavy metal can enter Sediments by atmospheric falling dust, precipitation, soil erosion, rainwash etc., and Sediments can be regarded as the storage vault of heavy metal to a certain extent.When the bed mud external environment changes, heavy metal may be again from bed mud stripping cause secondary pollution of water.In addition, heavy metal can not be biodegradable, but has the characteristic of biological accumulation, can produce biomagnification and concentrated effect by aquatic food chain, and the top biology that finally has influence on " food chain " is namely human.
At present, utilizing curing-stabilization method to process heavy metal polluted bed mud is one of more technology of domestic and international application.Wherein cement is modal gelling material.Simple not only cost is too high with cement solidification-stabilization bed mud, and when processing the high-content heavy metal polluted bed mud, need add the usage quantity of large cement with the assurance solidification effect, thereby can cause the problems such as cured body increase-volume ratio is large, processing cost is high.In the last few years, the chemical stabilization technology was owing to had the advantages such as increase-volume is simpler than little, technique, good stability, was more and more widely used in heavy metal refuse stable.Common heavy metal stabilizer can be divided into two kinds of inorganic type and organic types, wherein the organic type medicament is take sequestrant as main, the inner complex hydrophobic, indissoluble that it and the reaction of bed mud heavy metal form can keep stable in wider pH value scope, thereby reduced the quadratic risk function of product, in actual application, have more advantage, but the rarely seen report of application of the combination curing-stabilization treatment heavy metal polluted bed mud such as itself and cement.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide a kind of and can reduce processing cost, improve solidification effect, can satisfy again the ultimate compression strength requirement of cured body landfill and the heavy metal polluted bed mud security processing of leaching concentration index, the application of the method aspect landfill disposal and material of construction also is provided.
For solving the problems of the technologies described above, the present invention proposes a kind of method of utilizing cement and organic sulfide curing-stabilization heavy metal polluted bed mud, the steps include: dithiocar-bamate (DTCR) is added in the heavy metal polluted bed mud, after fully stirring, add cement, the mixture that obtains is stirred to evenly, obtains cured body through maintenance, finish curing-stabilization procedures.
In the above-mentioned method, the incorporation of described cement 〉=50% (preferred 50%～70%), the incorporation of described dithiocar-bamate 〉=1.5% (preferred 1.5%～2.5%).Incorporation refers to the cement that mixes in the dry bottom mud or the mass percent of DTCR.
In the above-mentioned method, the described well-beaten time is 20min～50min.
In the above-mentioned method, the water ratio of described heavy metal polluted bed mud is 50%～65%.
In the above-mentioned method, described heavy metal comprises one or more in cadmium, zinc, lead, chromium, the copper.
In the above-mentioned method, the temperature of described maintenance is 15 ℃～30 ℃, and the time is 3d～14d.
In the above-mentioned method, the starting stage of described maintenance processes (starting stage is generally about 24h) is to place rectangular parallelepiped or square mould to carry out.
As a total technical conceive, the present invention also provides the application of aforesaid method gained cured body in landfill is disposed, or the application of aforesaid method gained cured body in material of construction.
When the method gained cured body of the invention described above is used as material of construction, be especially suitable for use as the material of construction of building river course slope protection or roadbed.
Compared with prior art, the invention has the advantages that: the adding of organic sulfide can reduce the usage quantity of cement among the present invention, and can make cured body keep preferably ultimate compression strength.With respect to the plain cement curing technology, curing of the present invention has not only reduced the processing cost to heavy metal polluted bed mud, increase-volume ratio and the Leaching of Heavy Metals concentration of cured body have also been reduced simultaneously, make cured body Leaching of Heavy Metals concentration be lower than the admission standard of landfill yard, effectively prevented secondary pollution, improved significantly the curing-stabilization effect of heavy metal polluted bed mud, for the safe handling of heavy metal polluted bed mud provides new approach, can be widely used in that direct landfill is disposed and as material of construction.
Description of drawings
Fig. 1 is the graph of a relation of cured body ultimate compression strength in the embodiment of the invention, cement mixed weight and DTCR incorporation.
Fig. 2 is the Electronic Speculum figure of embodiment of the invention Central Plains heavy metal polluted bed mud.
Fig. 3 is the Electronic Speculum figure that plain cement solidifies bed mud in the embodiment of the invention.
Fig. 4 is the Electronic Speculum figure of cement and organic sulfide combination curing-stabilization bed mud in the embodiment of the invention.
Embodiment
Embodiment:
Basic physical and chemical for the heavy metal polluted bed mud that tries is: pH is 7.79, water ratio is 53.90%, heavy metal comprises Cd, Zn, Pb, Cr and Cu, wherein, Cd content is 121.00mg/kg, and Zn content is 7850.30mg/kg, and Pb content is 1032.00mg/kg, Cr content is 595mg/kg, and Cu content is 398.62mg/kg.Leaching situation for the heavy metal polluted bed mud that tries is as shown in table 1 below, and the photo of its microtexture as shown in Figure 2.
Table 1: the Leaching (mg/L) that supplies the heavy metal polluted bed mud of examination among the embodiment
DTCR is added in the heavy metal polluted bed mud, fully stir 30min after, add cement, the incorporation of DTCR and cement is as shown in table 2.The mixture that obtains is stirred to evenly, then joins in the square mould of 100mm * 100mm * 100mm, adition process is carried out at shaking table, make mixture vibratory compaction, the demoulding behind the maintenance 24h is then at 25 ℃ of lower maintenance 7d, obtain cured body, finish curing-stabilization procedures.
Table 2: the consumption scheme of cement and DTCR among the embodiment
In the present embodiment, cured body behind the maintenance 7d (HJ/T300-2007) is carried out Leaching Heavy Metals with reference to " solid waste Leaching leaching method-hac buffer method " to be tested, measure the concentration of Cd, Zn, Pb, Cr, Cu in the leach liquor, test result is as shown in table 3 below, wherein, the microtexture photo of C4D1 group sample as shown in Figure 3, the microtexture photo of C4D5 group sample is as shown in Figure 4.
The Leaching Heavy Metals (mg/L) of cured body when table 3: embodiment tests with reference to the HJ/T300-2007 method
As shown in Table 3, when successively adding heavy metal polluted bed mud, DTCR and cement is cured-during stabilization the leaching concentration that Leaching of Heavy Metals concentration is significantly less than plain cement when solidifying.When cement mixed weight was determined, along with the increase of DTCR incorporation, Leaching of Heavy Metals concentration was the trend of continuous minimizing, and the pH value stabilization of leach liquor is between 7～8.5.The leaching concentration of Zn is maximum, reason may be Zn as amphiprotic substance, in cement cementitious system easily and the OH in the cement
-And CO
3 2-Ion generates precipitation, and most of form with oxyhydroxide, metal hydration phase and calcium-metal mixture exists, when leach liquor is alkalescence, and the dissolving of the throw out of Zn, the Zn leaching concentration increases.
The leaching result of table 3 shows, when utilizing cement solidification separately, cured body (Cd, Pb and Cr have surpassed household refuse landfill sites and have polluted control criterion limit value (as shown in table 4) among the C1D1～C6D1), add DTCR after, 8 groups of samples (C5D4, C6D4 are arranged; C4D5, C5D5, C6D5; C4D6, C5D6, C6D6) Leaching of Heavy Metals concentration be lower than standard limited value.Therefore, consider the volume that solidifies cost and cured body, leach the factor such as stability, the cured body C4D5 that selection reaches the minimum cement dosage of safety standards and the minimum DTCR consumption corresponding with it is as optimal proportion: namely cement mixed weight is that 50%, DTCR incorporation is 2%.Under this proportioning, greatly reduced the consumption of cement, thereby reduced cost.
As shown in Figure 4, be the microscopic appearance photo of C4D5 group sample of the present invention.From photo, can find out, the cured body that method of the present invention obtains has presented many reticular substance structures and the needle crystal structure of matter, and these all are the configuration of surface features that cement aquation forms C-S-H (hydrated calcium silicate) and Aft (ettringite).Solidify the discrete particle shape form that bed mud (as shown in Figure 3) presents than former heavy metal contamination bed mud (as shown in Figure 2) and plain cement, method of the present invention wraps up heavy metal polluted bed mud by cement aquation, so that heavy metal and DTCR reaction, generated and had the stable cancellated heavy metal chelate in crosslinked space, make heavy metal ion be difficult to leach, thereby make cured body possess better curing-stabilization effect.
Table 4: household refuse landfill sites pollutes control criterion
Employing digestion agent pH value is 3 acetum, the Simulated Acid Rain condition, and (C4D1～C6D6) as leaching object, study the Leaching Heavy Metals of cured body under the acid rain condition with this, it is as shown in table 5 below to leach the result take cured body.
Table 5: the Leaching Heavy Metals (mg/L) of the lower cured body of acid rain condition (pH=3)
When (pH=3) leaches under the acid rain condition, the leaching concentration of 5 heavy metal species all is higher than the leaching concentration that obtains when testing with reference to the HJ/T300-2007 method, pollute the control criterion limit value than household refuse landfill sites, except Cu and Zn leaching concentration are lower than the standard limited value, the leaching concentration of Cd, Pb, Cr all is higher than standard limited value.Leaching concentration when Leaching of Heavy Metals concentration mostly is lower than cement and solidifies separately in the cured body take DTCR as additive illustrates that DTCR can stabilizing heavy metal, prevents leaching ability of heavy metal.This test is that modeling effort destroys the (leaching of particle diameter≤9.5mm), and in landfill yard, (pH≤3) and cured body particle actual spoilage probability are very low under the acid rain condition, so practical situation can be safer of cured body particle.
In the present embodiment, cured body has also been carried out compressive strength determination, the experimental result that draws as shown in Figure 1.As shown in Figure 1, cured body ultimate compression strength is determined that by cement along with cement mixed weight increases, cured body ultimate compression strength constantly increases.Under identical cement mixing content, along with the increase of DTCR incorporation, the ultimate compression strength of cured body decreases, this may be because DTCR is organism, form DTCR salt with the heavy metal reaction, a small amount of DTCR salt may stop the hydration reaction of part of cement, can not effectively form continuous network-like structure.Research shows that also organic existence can make cured body ultimate compression strength slightly reduce.Cause the heavy metal secondary pollution for preventing that cured body from breaking, can use for reference " consumer waste incineration processing engineering legislation " (CJJ90-2002) remains on more than the 0.98MPa cured body 7d ultimate compression strength, when cement mixed weight 〉=50%, ultimate compression strength can both meet the demands.
Claims (10)
1. method of utilizing cement and organic sulfide curing-stabilization heavy metal polluted bed mud, it is characterized in that, may further comprise the steps: dithiocar-bamate is added in the heavy metal polluted bed mud, after fully stirring, add cement, the mixture that obtains is stirred to evenly, obtains cured body through maintenance, finish curing-stabilization procedures.
2. the method for utilizing cement and organic sulfide curing-stabilization heavy metal polluted bed mud according to claim 1 is characterized in that the incorporation of described cement 〉=50%, the incorporation of described dithiocar-bamate 〉=1.5%.
3. the method for utilizing cement and organic sulfide curing-stabilization heavy metal polluted bed mud according to claim 1 and 2 is characterized in that the described well-beaten time is 20min～50min.
4. the method for utilizing cement and organic sulfide curing-stabilization heavy metal polluted bed mud according to claim 1 and 2 is characterized in that the water ratio of described heavy metal polluted bed mud is 50%～65%.
5. the method for utilizing cement and organic sulfide curing-stabilization heavy metal polluted bed mud according to claim 1 and 2 is characterized in that described heavy metal comprises one or more in cadmium, zinc, lead, chromium, the copper.
6. the method for utilizing cement and organic sulfide curing-stabilization heavy metal polluted bed mud according to claim 1 and 2 is characterized in that, the temperature of described maintenance is 15 ℃～30 ℃, and the time is 3d～14d.
7. the method for utilizing cement and organic sulfide curing-stabilization heavy metal polluted bed mud according to claim 1 and 2 is characterized in that, the starting stage of described maintenance processes is to place rectangular parallelepiped or square mould to carry out.
8. one kind such as method obtains as described in each in the claim 1～7 the application of cured body in landfill is disposed.
9. one kind such as method obtains as described in each in the claim 1～7 the application of cured body in material of construction.
10. application according to claim 9 is characterized in that, described cured body is the material of construction as river course slope protection or roadbed.
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| CN201210464084.5A CN102936116B (en) | 2012-11-16 | 2012-11-16 | Method for solidifying-stabilizing bottom mud polluted by heavy metals by using cement and organic sulfides and application of obtained solidified body |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104787994A (en) * | 2015-03-23 | 2015-07-22 | 湖南大学 | Method for stabilizing heavy metal lead in bottom sediment by using modified nano-chlorapatite |
| CN105967470A (en) * | 2016-05-12 | 2016-09-28 | 江西洁地环境治理生态科技有限公司 | Cadmium copper lead polluted bottom mud curing agent and curing method thereof |
| CN105964652A (en) * | 2016-05-10 | 2016-09-28 | 苏州大学 | Curing and stabilizing treatment method for garbage incineration fly ash |
| CN108503085A (en) * | 2018-04-20 | 2018-09-07 | 广东华矿高新技术有限公司 | The fractional precipitation process of iron/copper in a kind of recycling acidic mine waste water |
| CN110668748A (en) * | 2019-09-25 | 2020-01-10 | 上海市政工程设计研究总院（集团）有限公司 | Method suitable for curing sludge incineration ash for making bricks |
| CN112851282A (en) * | 2021-01-27 | 2021-05-28 | 中钢集团马鞍山矿山研究总院股份有限公司 | Gelling agent for solidifying heavy metal ions in tailings and application method thereof |
| CN112851283A (en) * | 2021-01-27 | 2021-05-28 | 中钢集团马鞍山矿山研究总院股份有限公司 | Cementing material capable of solidifying and stabilizing heavy metal ions in tailings |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104787994A (en) * | 2015-03-23 | 2015-07-22 | 湖南大学 | Method for stabilizing heavy metal lead in bottom sediment by using modified nano-chlorapatite |
| CN105964652A (en) * | 2016-05-10 | 2016-09-28 | 苏州大学 | Curing and stabilizing treatment method for garbage incineration fly ash |
| CN105967470A (en) * | 2016-05-12 | 2016-09-28 | 江西洁地环境治理生态科技有限公司 | Cadmium copper lead polluted bottom mud curing agent and curing method thereof |
| CN105967470B (en) * | 2016-05-12 | 2019-06-11 | 江西洁地环境治理生态科技有限公司 | A kind of cadmium copper lead contamination bed mud curing agent and its curing method |
| CN108503085A (en) * | 2018-04-20 | 2018-09-07 | 广东华矿高新技术有限公司 | The fractional precipitation process of iron/copper in a kind of recycling acidic mine waste water |
| CN110668748A (en) * | 2019-09-25 | 2020-01-10 | 上海市政工程设计研究总院（集团）有限公司 | Method suitable for curing sludge incineration ash for making bricks |
| CN112851282A (en) * | 2021-01-27 | 2021-05-28 | 中钢集团马鞍山矿山研究总院股份有限公司 | Gelling agent for solidifying heavy metal ions in tailings and application method thereof |
| CN112851283A (en) * | 2021-01-27 | 2021-05-28 | 中钢集团马鞍山矿山研究总院股份有限公司 | Cementing material capable of solidifying and stabilizing heavy metal ions in tailings |
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| CN102936116B (en) | 2014-12-10 |
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