CN105935697A - Chromium slag detoxification method based on sludge - Google Patents
Chromium slag detoxification method based on sludge Download PDFInfo
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- CN105935697A CN105935697A CN201610370306.5A CN201610370306A CN105935697A CN 105935697 A CN105935697 A CN 105935697A CN 201610370306 A CN201610370306 A CN 201610370306A CN 105935697 A CN105935697 A CN 105935697A
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- chromium
- mud
- chromium slag
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- sulfate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
- B09C1/105—Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Mycology (AREA)
- Soil Sciences (AREA)
- Biotechnology (AREA)
- Biomedical Technology (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Botany (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a novel method for treating chromium slag. Sludge, a carbon source and ferrous sulfate are prepared into chemical agents to be applied into the chromium slag; and then a special curing manner is adopted, and hexavalent chromium slowly released in the chromium slag is gradually reduced. By means of the method, the hexavalent chromium can be efficiently reduced at low cost, and meanwhile secondary pollution of sulfate and the sludge is avoided.
Description
Technical field
The present invention provides a kind of method of novel process chromium slag, utilizes culturing sludge to go out to reduce microbial inoculum, is applied in chromium slag in conjunction with reducing agents such as ferrous sulfate; use special maintenance method subsequently; can reduction of hexavalent chromium efficiently, avoid the secondary pollution of sulfate simultaneously, belong to field of environment protection.
Background technology
Chromium slag is the by-product of discharge in bichromate production process.Having great toxicity because wherein containing water soluble hexavalent chromium, if the air storage without process, underground water source, river or marine site can be caused pollution in various degree, serious is detrimental to health and vegeto-animal growth.
How to carry out the difficult problem repairing always environmental protection circle of chromium slag.Although method of disposal is numerous, but there is various problem in great majority.Number of patent application 200710041125.9 describes one and utilizes the high temperature pyrolysis PROCESS FOR TREATMENT alkalescence method containing Cr (VI) refuse, although method effect is preferable, but the method needs expensive high-temperature service, relatively costly.The patent disclosure of Application No. CN1827247 is a kind of uses the agricultural wastes thing Testa oryzae as the method for additive dry reduction chromium slag.After Testa oryzae is mixed homogeneously with chromium slag, it is placed in microwave field and carries out redox reaction, so that the hexavalent chrome reduction in chromium slag is become trivalent chromium, be substantially capable of chromium residue detoxifying.But microwave technology is with high costs, therefore it is difficult to extensive for treatment of chromate slag.
Summary of the invention
For the deficiencies in the prior art, the present invention uses a kind of method of novel process chromium slag, mud, carbon source and ferrous sulfate are configured to pharmacy application in chromium slag, use special maintenance method subsequently, this method can avoid the secondary pollution of sulfate and mud with low cost and efficient reduction of hexavalent chromium simultaneously.It comprises the steps of
(1) sodium sulfate, mud are mixed according to a certain percentage with carbon source solution, after controlling to mix, solution dewatered sludge content is 0.1-20%, solid content 0.5-25%, organic carbon content 0.5-25%, the mass ratio of sulfate (remembering with SO4)/organic carbon is for (0-1): 1, mixed solution reaction 0-5 days, it is thus achieved that chromium slag repairs biological agent；
(2) chromium slag is crushed to below 5mm, mix with step (1) described biological agent and ferrous sulfate subsequently, mixed proportion be ferrous sulfate, the mass ratio of chromium slag and medicament be (0-0.4): 1:(0.1-1.5), be subsequently placed to closing stockyard and store up；
(3) storing up period, every 3-10 days, ground surface on the scene carried out Water spray, and the average spray flux in place is equivalent to the rainfall of 20-100mm, and natural precipitation can substitute artificial spray, and after 2-10 Water spray, site remediation terminates.
This law technology thinking is, utilizing ferrum series of reductions agent that chromium slag middle and high concentration Cr VI is reduced to sludge microbial agent can be with in tolerance range, then utilize sludge microbial agent that chromium slag is carried out long-term reparation, simultaneously by step Water spray, chromium slag is promoted to carry out alternation of wetting and drying, the Cr (VI) being difficult to inside chromium solid impurity particle separate out gradually separates out to chromium slag surface with reduction medicament effectively contacts along chromium slag capillary tube by alternation of wetting and drying, alternation of wetting and drying accelerates the mineralising of mud simultaneously, the most produced volatile organic matter and hydrogen sulfide accelerate volatilization, contribute to the rapid degraded polluted.
Comparing traditional chromic wastes disposal method, this method has a following advantage:
1. the sulfate reduction flora cultivated itself is indigenous flora, and natural tolerance is strong, easily multiplies on a large scale in place, can lasting effective reduction of hexavalent chromium, and do not result in ecological problem；
2. the sulfate in the reduction of the sulfate reducting bacteria in sludge microbial agent ferrous sulfate, generates sulfide, while more efficient reduction of hexavalent chromium, it is to avoid the secondary pollution of sulfate；
3. this sludge microbial agent reduction of hexavalent chromium has two big principles, one is that sulfate reducting bacteria inherently has the characteristic utilizing carbon source reduction of hexavalent chromium, but react slower, second is that sulfate reducting bacteria metabolite hydrogen sulfide inherently can reduction of hexavalent chromium, simultaneously because its reduction of hexavalent chromium is chemical reaction, therefore reacting very rapid, this is also that this ecological microbial agent is compared other microbial inoculum and can efficiently be disposed the reason of chromium slag；
4. the trivalent chromium after reduction and sulfate reducting bacteria metabolite sulfide form chromic sulfide precipitation so that in chromium slag, trivalent chromium is more stable, is significantly better than other biochemical process；
5. due to anaerobic sludge and the existence of carbon source, define reducing atmosphere, can effectively alleviate ferrous oxidation by air, decrease the usage amount of ferrous sulfate；The ferrous reduction of this method effective integration simultaneously is fast and advantage that Cr VI can persistently effectively be reduced by sludge microbial agent, avoids the inferior position that Cr VI can not persistently be reduced by ferrous sulfate simultaneously；
6. this method uses mud and debirs as primary raw material, greatly reduces cost.
It is embodied as example as follows:
Embodiment 1:
(1) sodium sulfate, mud are mixed according to a certain percentage with carbon source solution, after controlling to mix, solution dewatered sludge content is 0.1-5%, solid content 0.5-5%, organic carbon content 0.5-5%, the mass ratio of sulfate (remembering with SO4)/organic carbon is as 0.2:1, mixed solution reaction 1 day, it is thus achieved that chromium slag repairs medicament；
(2) chromium slag is crushed to below 5mm, mix with step (1) described biological agent and ferrous sulfate subsequently, mixed proportion be ferrous sulfate, the mass ratio of chromium slag and medicament be 0.2:1:(1-1.5), be subsequently placed to close stockyard and store up；
(3) storing up period, carry out organic solution spray every 5 days ground surfaces on the scene, the average spray flux in place is equivalent to the rainfall of 60-80mm, and natural precipitation can substitute artificial spray, and after 2 Water spray, chromium slag content of 6-valence Cr ions is less than 2mg/kg.
Embodiment 2:
(1) mud is mixed according to a certain percentage with carbon source solution, after controlling to mix, solution dewatered sludge content is 10-20%, solid content 10-25%, organic carbon content 10-25%, the mass ratio of sulfate (remembering with SO4)/organic carbon is for (0-1): 1, mixed solution reaction 0-5 days, it is thus achieved that chromium slag repairs medicament；
(2) chromium slag is crushed to below 5mm, mix with step (1) described biological agent and ferrous sulfate subsequently, mixed proportion be ferrous sulfate, the mass ratio of chromium slag and medicament be 0.2:1:(0.1-0.5), be subsequently placed to close stockyard and store up；
(3) storing up period, carry out sulfuric acid solution spray every 8 days ground surfaces on the scene, the average spray flux in place is equivalent to the rainfall of 30mm, and natural precipitation can substitute artificial spray, and after 3 Water spray, chromium slag content of 6-valence Cr ions is less than 4mg/kg.
Above example is only in order to illustrate technical scheme, rather than is limited；Although the present invention being described in detail with reference to previous embodiment, for the person of ordinary skill of the art, still the technical scheme described in previous embodiment can be modified, or wherein portion of techniques feature is carried out equivalent；And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of claimed technical solution of the invention.
Claims (5)
1. a chromium residue detoxifying method based on mud, is characterized in that, comprise the steps of
(1) sodium sulfate, mud are mixed according to a certain percentage with carbon source solution, after controlling to mix, solution dewatered sludge content is 0.1-20%, solid content 0.5-25%, organic carbon content 0.5-25%, the mass ratio of sulfate (remembering with SO4)/organic carbon is for (0-1): 1, mixed solution reaction 0-5 days, it is thus achieved that chromium slag repairs biological agent；
(2) chromium slag is crushed to below 5mm, mix with step (1) described biological agent and ferrous sulfate subsequently, mixed proportion be ferrous sulfate, the mass ratio of chromium slag and medicament be (0-0.4): 1:(0.1-0.5), be subsequently placed to closing stockyard and store up；
(3) storing up period, every 3-10 days, ground surface on the scene carried out Water spray, and the average spray flux in place is equivalent to the rainfall of 20-100mm, and natural precipitation can substitute artificial spray, and after 2-10 Water spray, site remediation terminates.
A kind of chromium residue detoxifying method based on mud, is characterized in that, described mud is anaerobic sludge produced by sewage treatment anaerobic technique, it is possible to the double oxygen mud of admixture part.
A kind of chromium residue detoxifying method based on mud, it is characterized in that, described carbon source solution can be containing organic solution such as ethanol, saccharide, protein, starch, can also be for the solution containing the industry organic solid waste such as organic waste, changing food waste, it is also possible to for industrial and municipal organic wastewater；Described sodium sulfate can be substituted by other sulfate；Described ferrous sulfate can be replaced by iron-based reducing agents such as nano zero valence irons；Described chromium cinder ladle includes chromium slag backfill soil.
A kind of chromium residue detoxifying method based on mud, is characterized in that, the described water in Water spray can be substituted by organic solution, and the organic carbon content of organic solution is 10-1000mg/L, also can add a certain amount of sulphuric acid in the water of spray；Sulphuric acid addition is every liter of water 10-1000mg sulphuric acid quality.
A kind of chromium residue detoxifying method based on mud, is characterized in that, bottom described closing stockyard and surrounding use anti-seepage geomembrane, prevent pollutant from spreading.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610370306.5A CN105935697A (en) | 2016-05-30 | 2016-05-30 | Chromium slag detoxification method based on sludge |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610370306.5A CN105935697A (en) | 2016-05-30 | 2016-05-30 | Chromium slag detoxification method based on sludge |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107199239A (en) * | 2017-06-20 | 2017-09-26 | 上海老港废弃物处置有限公司 | A kind of pesticide contaminated soil processing unit of utilization high-level oxidation technology |
| CN109486494A (en) * | 2018-09-18 | 2019-03-19 | 魏菊宁 | A kind of soil-repairing agent and preparation method thereof |
| CN110369471A (en) * | 2019-09-05 | 2019-10-25 | 中国科学院过程工程研究所 | A kind of method of chromium-polluted soil reparation |
| CN111807523A (en) * | 2020-06-15 | 2020-10-23 | 北京航空航天大学 | Efficient microbial remediation method for cadmium-polluted sediment |
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| CN102476130A (en) * | 2010-11-26 | 2012-05-30 | 李兴 | Restoration treatment reduction method for hexavalent chromium-containing soil |
| CN102598911A (en) * | 2012-03-29 | 2012-07-25 | 常熟市佳盛农业科技发展有限公司 | Method for remedying heavy metal polluted mining soil |
| WO2013116618A1 (en) * | 2012-02-03 | 2013-08-08 | The Research Foundation Of State University Of New York | Electrochemical synthesis of nitro-chitosan |
| CN104492802A (en) * | 2014-12-15 | 2015-04-08 | 山东省环境保护科学研究设计院 | Method for reducing and stabilizing chromium-contaminated soil by chemical-biological coupling |
| CN104785518A (en) * | 2015-05-01 | 2015-07-22 | 韩清洁 | Remediation method of chromium contaminated soil |
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2016
- 2016-05-30 CN CN201610370306.5A patent/CN105935697A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476130A (en) * | 2010-11-26 | 2012-05-30 | 李兴 | Restoration treatment reduction method for hexavalent chromium-containing soil |
| WO2013116618A1 (en) * | 2012-02-03 | 2013-08-08 | The Research Foundation Of State University Of New York | Electrochemical synthesis of nitro-chitosan |
| CN102598911A (en) * | 2012-03-29 | 2012-07-25 | 常熟市佳盛农业科技发展有限公司 | Method for remedying heavy metal polluted mining soil |
| CN104492802A (en) * | 2014-12-15 | 2015-04-08 | 山东省环境保护科学研究设计院 | Method for reducing and stabilizing chromium-contaminated soil by chemical-biological coupling |
| CN104785518A (en) * | 2015-05-01 | 2015-07-22 | 韩清洁 | Remediation method of chromium contaminated soil |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107199239A (en) * | 2017-06-20 | 2017-09-26 | 上海老港废弃物处置有限公司 | A kind of pesticide contaminated soil processing unit of utilization high-level oxidation technology |
| CN109486494A (en) * | 2018-09-18 | 2019-03-19 | 魏菊宁 | A kind of soil-repairing agent and preparation method thereof |
| CN109486494B (en) * | 2018-09-18 | 2021-02-02 | 浙江弄潮儿智慧科技有限公司 | Soil remediation agent and preparation method thereof |
| CN110369471A (en) * | 2019-09-05 | 2019-10-25 | 中国科学院过程工程研究所 | A kind of method of chromium-polluted soil reparation |
| CN111807523A (en) * | 2020-06-15 | 2020-10-23 | 北京航空航天大学 | Efficient microbial remediation method for cadmium-polluted sediment |
| CN111807523B (en) * | 2020-06-15 | 2022-02-25 | 北京航空航天大学 | Efficient microbial remediation method for cadmium-polluted sediment |
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Application publication date: 20160914 |
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