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
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- cement
- bed mud
- polluted bed
- stabilization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Processing Of Solid Wastes (AREA)
- 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102936116A true CN102936116A (en) | 2013-02-20 |
| CN102936116B CN102936116B (en) | 2014-12-10 |
Family
ID=47695052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210464084.5A Active 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102936116B (en) |
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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139387A (en) * | 1993-12-29 | 1997-01-01 | 巴科曼实验室国际公司 | Composition and process for reducing or preventing metal and acid contamination in rock drainage |
| JP2002241166A (en) * | 2000-12-11 | 2002-08-28 | Taiheiyo Cement Corp | Hydraulic composition |
| JP2005146275A (en) * | 2003-10-24 | 2005-06-09 | Growth Factor:Kk | Agent for improving, solidifying, and stabilizing soil and its quality |
| CN101921090A (en) * | 2010-08-03 | 2010-12-22 | 湖南大学 | Heavy metal pollution bottle sediment curing agent and curing method thereof |
| CN102274605A (en) * | 2010-06-09 | 2011-12-14 | 栗田工业株式会社 | Stabilization treatment method for heavy metal containing heavy metal dust |
-
2012
- 2012-11-16 CN CN201210464084.5A patent/CN102936116B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139387A (en) * | 1993-12-29 | 1997-01-01 | 巴科曼实验室国际公司 | Composition and process for reducing or preventing metal and acid contamination in rock drainage |
| JP2002241166A (en) * | 2000-12-11 | 2002-08-28 | Taiheiyo Cement Corp | Hydraulic composition |
| JP2005146275A (en) * | 2003-10-24 | 2005-06-09 | Growth Factor:Kk | Agent for improving, solidifying, and stabilizing soil and its quality |
| CN102274605A (en) * | 2010-06-09 | 2011-12-14 | 栗田工业株式会社 | Stabilization treatment method for heavy metal containing heavy metal dust |
| CN101921090A (en) * | 2010-08-03 | 2010-12-22 | 湖南大学 | Heavy metal pollution bottle sediment curing agent and curing method thereof |
Cited By (8)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102936116B (en) | 2014-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102936116B (en) | Method for solidifying-stabilizing bottom mud polluted by heavy metals by using cement and organic sulfides and application of obtained solidified body | |
| Kogbara et al. | Mechanical and leaching behaviour of slag-cement and lime-activated slag stabilised/solidified contaminated soil | |
| CN102267788B (en) | Nitrate slow-release material and preparation method thereof | |
| CN104560046A (en) | Contaminated soil passivator and preparation method and application thereof | |
| CN105948589B (en) | A kind of method of electroplating sludge harmless treatment | |
| Quina et al. | Stabilisation/solidification of APC residues from MSW incineration with hydraulic binders and chemical additives | |
| CN103170488B (en) | The treatment process of incineration of refuse flyash solidifying agent and incineration of refuse flyash | |
| Al-Kindi | Evaluation the solidification/stabilization of heavy metals by Portland cement | |
| CN104628324B (en) | The reagent combination and method of the innoxious gelling processing of well drilling detritus | |
| CN105254166B (en) | A kind of dewatered sludge curing agent, preparation method and application method | |
| CN102503274A (en) | Curing agent for heavy-metal polluted bottom sludge | |
| CN101921090A (en) | Heavy metal pollution bottle sediment curing agent and curing method thereof | |
| CN107117843B (en) | A kind of method that nature of glass solidifies electroplating sludge | |
| CN102093027A (en) | Sludge curing agent and method for curing sludge | |
| CN104129900A (en) | Method for preparing covering soil for refuse landfill from raw sludge | |
| CN105417978A (en) | Cement additive for curing organic waste and application of cement additive | |
| CN105967470A (en) | Cadmium copper lead polluted bottom mud curing agent and curing method thereof | |
| CN102485666A (en) | Technology of in situ harmless treatment on waste drilling mud | |
| CN104759454B (en) | Flyash curing stabilization method | |
| CN104761168B (en) | Flying dust building materials reuse method | |
| Zhang et al. | Risk assessment for the long-term stability of fly ash-based cementitious material containing arsenic: Dynamic and semidynamic leaching | |
| CN103224335A (en) | Sludge wet-processing technology and equipment | |
| CN105439507A (en) | Cadmium-containing waste residue solidified body and preparation method thereof | |
| EP2982450A1 (en) | In-situ process for stabilization and solidification of contaminated soil into composite material - building material | |
| Yang et al. | Long-term leaching behaviours of cement composites prepared by hazardous wastes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |