CN102923778A - Method for extracting hexavalent chromium in chromium slag and harmlessly treating residual chromium slag - Google Patents
Method for extracting hexavalent chromium in chromium slag and harmlessly treating residual chromium slag Download PDFInfo
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- CN102923778A CN102923778A CN2012104727887A CN201210472788A CN102923778A CN 102923778 A CN102923778 A CN 102923778A CN 2012104727887 A CN2012104727887 A CN 2012104727887A CN 201210472788 A CN201210472788 A CN 201210472788A CN 102923778 A CN102923778 A CN 102923778A
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- chromium
- chromium slag
- slag
- residual
- buffer solution
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for extracting hexavalent chromium in chromium slag and harmlessly treating residual chromium slag. The method comprises the following steps of leaching and recycling water soluble and partial insoluble hexavalent chromiums in the chromium slag by using an acetic acid buffer solution; and then adding a reducing agent to the residual chromium slag so as to treat the residual chromium slag, so that the hexavalent chromium in the residual chromium slag is reduced to trivalent chromium; and fixing the trivalent chromium in the chromium slag. The treated nontoxic chromium slag can be used as auxiliary materials for cement and concrete or naturally landfilled. According to the invention, the chromium slag needs not to be ground and only need to be treated at normal temperature and normal pressure; as chromium slag is first sufficiently leached by using the acetic acid buffer solution, the content of the hexavalent chromium in the chromium slag can be reduced; meanwhile, the usage of the reducing agent can be also reduced and the treatment cost of the chromium slag is reduced.
Description
Technical field
The invention belongs to environmental protection technical field, particularly relate to chromic extraction and residual chromium dregs innocent treatment method in a kind of chromium slag.
Background technology
The chromium slag is the poisonous waste residue that the industries such as chromic salts and iron alloy are discharged in process of production, China is chromium salt production big country, and according to investigations, the annual new discharging chromium slag in the whole nation is 600,000 t approximately, chromium slag muck storage has reached 6,000,000 t over the years, through the less than 17% of detoxifcation processing or comprehensive utilization.The technique that domestic chromium slag produces is substantially identical, and its composition is also similar, often contains the oxide compounds such as magnesium, calcium, iron, aluminium, Cr
2O
3, water-soluble chromic acid sodium (Na
2CrO
3) and solubility in acid yellow ultramarine (CaCrO
4) etc., the Cr of solubility (VI) easily leaches in acidity or alkaline environment.
Cr in the chromium slag (VI) is listed in one of 8 kinds of chemical substances to the harm maximum, is one of 3 kinds of carcinogenic metal objects of generally acknowledging in the world, also is simultaneously one of 129 kinds of generally acknowledged priority pollutants of Environmental Protection Agency.The chromium slag is through after the long-term rain drop erosion, and the Cr of leaching (VI) has caused serious pollution to surrounding environment, such as polluted underground water, soil etc.Poisonousness of dregs mainly comes from Cr (VI), because Cr (VI) has very strong oxidisability, its toxicity is that it is to the oxygenizement of viable cell.Cr (VI) has pungency to digestive tube and the skin of human body, can cause contact dermatitis, skin ulcer, also can cause the diseases such as allergy, lung cancer.
The chromium slag is poisonous Hazardous wastes, and environment and society are caused great pollution and harm; On the other hand, the chromium slag is again available resource, if Cr (VI) wherein can be converted into the lower Cr of toxicity (III), not only can reduce its toxicity, and can substitute the multi mineral raw material, has recycling and is worth.Its harmless treatment is mainly based on following several mechanism: (1) is trivalent chromium with hexavalent chrome reduction; (2) make sexavalent chrome be formed in the physical environment the stable phase that can not clear up, also not absorb for body.(3) seal up for safekeeping securely, bury, or detoxifcation, be used after the sealing.
The processing disposal technology of present domestic chromium slag is divided into two large classes: detoxifcation is processed and comprehensive utilization.Detoxifcation is processed and is mainly contained several detoxifcation processing modes such as chemical method, microbial method, microwave method, solidification method.The main application approach of comprehensive utilization has: cement processed, glass colorant processed, sintered ironmaking, refractory materials processed, devitrified glass processed, fused(calcium magnesium)phosphate processed, build the road etc.
Although at present the improvement technology for the chromium slag has a lot, how because of complex process, treatment capacity is little, detoxifcation is not thorough, the impact of high in cost of production factor, has limited its large-scale industrialization application implementation.Developed countries adopts the security landfill mode to the final processing of chromium slag more, but needs objectionable constituent (sexavalent chrome) in the chromium slag are cured the processing such as stable, compacting before the landfill.Chemical stabilization technical finesse chromium slag is considered to a new developing direction of chromium slag stabilization, can reach the perhaps not increase-volume that reduces when realizing chromic slag harmlessness, thereby improves overall efficiency and the economy of chromic wastes disposal disposal system.Compare with other stabilization methods, chemical stabilization has the advantages such as technique is simple, stabilization effect good, expense is cheap.
Sequestrant is wherein new developing direction as the stabilization agent of heavy metal, and it can be combined with heavy metal ion and form inner complex stable, that be insoluble in water, effectively stops the leaching of heavy metal.Because the efficient of stabilizing heavy metal is high, needed chelating dosage is few, flying dust after treatment or sewage generally can reach landfill or the emission standard of country, and this harmless treatment for the chromium slag provides effective means, also will have important research and using value.
Summary of the invention
The object of the present invention is to provide chromic extraction and residual chromium dregs innocent treatment method in a kind of chromium slag.The method by the effect of its unique stabilizing heavy metal ion, is processed chromium residue with a kind of inorganic medicament or efficient heavy sequestrant effectively, makes its stable existence under envrionment conditions, reaches innoxious purpose.
Chromic extraction and residual chromium dregs innocent treatment method in a kind of chromium slag of the present invention, principal feature are to adopt vat liquor to carry out drip washing the chromium slag, and gained sexavalence chrome liquor can chromium product processed; Remaining sexavalent chrome is trivalent chromium in the medicament reduced chromium slag that residual chromium slag adding after the lixiviate processing is certain again, and is fixed in the chromium slag.Nontoxic chromium slag after the processing can be made cement, concrete auxiliary material or natural landfill disposal.
Chromic extraction and residual chromium dregs innocent treatment method in a kind of chromium slag of the present invention, realize as follows:
The acetic acid thin up is made the acetate buffer solution of pH1.5, chromium slag and acetate buffer solution are pressed mass volume ratio 1kg:10L mixing, stirring, lixiviate were filtered after 10 hours, and filter residue adds the sodium sulphite (Na of chromium slag amount 4%
2S) or the ethyl xanthate (potassium ethyl xanthonate) of chromium slag amount 1%, add again entry and make muddy, stablize and got final product in 6 hours.
Aforesaid method only need carry out at normal temperatures and pressures to chromic wastes disposal, and filtrate can be repeated lixiviate and be used, and can make chromium metal or contain the chromaking chemical product through purification; Then can be used as cement, concrete auxiliary material etc. by the chromium slag after this harmless treatment.
Advantage of the present invention is:
The chromium slag need not milled processed, only need carry out at normal temperatures and pressures, adopts acetate buffer solution first to the abundant lixiviate of chromium slag, can reduce chromic content in the chromium slag, also can reduce the reductive agent consumption simultaneously, reduces the chromic wastes disposal cost;
Extract the sexavalence chrome liquor and can produce the chromium goods, the nontoxic chromium slag after the processing, satisfy " the solid waste judging standard---leach poisonous substance and differentiate " (GB 5085.3-2007) standard-required, can make cement, concrete auxiliary material etc., good economic benefit is arranged.
Embodiment
Embodiment 1
(its main component is CaO 33.63%, and MgO 22.12%, Al to take by weighing 1 kg chromium slag
2O
35.78%, Fe
2O
39.62%, SiO
210.11%, total chromium 5.92%, Cr
2O
3(Cr
6+) 0.39%, H
2O 12.93%) sprawl in the plastic tub, add the acetate buffer solution of 10 liters of pH1.5, to stir, lixiviate is after 10 hours, and inclining supernatant liquor; In remaining filter residue, stir adding 40 g sodium sulphite (Na
2S), add entry and make muddy, stablize 6 hours after, according to the method for " solid waste judging standard---leach poisonous substance differentiate " (GB 5085.3-2007) regulation, detect the chromium slag after above the processing, Cr
6+The leaching amount be 1.42 mg/L.
Embodiment 2
(its main component is CaO 33.63%, and MgO 22.12%, Al to take by weighing 1 kg chromium slag
2O
35.78%, Fe
2O
3% 9.62%, SiO
210.11%, total chromium 5.92%, Cr
2O
3(Cr
6+) 0.39%, H
2O 12.93%) sprawl in the plastic tub, add the acetate buffer solution of 10 liters of pH1.5, to stir, lixiviate is after 10 hours, and inclining supernatant liquor; In remaining filter residue, stir adding 10 g ethyl xanthates (potassium ethyl xanthonate), add entry and make muddy, after stablizing 6 hours, according to the method for " the solid waste judging standard---the leaching poisonous substance is differentiated " (GB 5085.3-2007) regulation, the chromium slag more than detecting after the processing, Cr
6+The leaching amount be 1.16 mg/L.
Embodiment 3
(its main component is CaO 36.16%, and MgO 21.89%, Al to take by weighing 50 kg chromium slags
2O
36.13%, Fe
2O
39.54%, SiO
28.93%, total chromium 6.16%, Cr
2O
3(Cr
6+) 0.41%, H
2O 11.19%) spread in the cement pit, add the acetate buffer solution of 500L pH1.5, to stir, lixiviate was emitted supernatant liquor after 10 hours; In remaining filter residue, add 2 kg sodium sulphite (Na
2S), stir, add entry and make muddy, stablize 6 hours after, according to the method for " solid waste judging standard---leach poisonous substance and differentiate " (GB 5085.3-2007) regulation, detect the chromium slag after above the processing, Cr
6+The leaching amount be 1.39 mg/L.
Embodiment 4
(its main component is CaO 36.16%, and MgO 21.89%, Al to take by weighing 50 kg chromium slags
2O
36.13%, Fe
2O
39.54%, SiO
28.93%, total chromium 6.16%, Cr
2O
3(Cr
6+) 0.41%, H
2O 11.19%) spread in the cement pit, add the acetate buffer solution of 500L pH1.5, to stir, lixiviate was emitted supernatant liquor after 10 hours; In remaining filter residue, add 0.5 kg ethyl xanthate (potassium ethyl xanthonate), stir, add entry and make muddy, stablize 6 hours after, according to the method for " solid waste judging standard---leach poisonous substance differentiate " (GB 5085.3-2007) regulation, chromium slag after processing more than detecting, Cr
6+The leaching amount be 1.11 mg/L.
Claims (1)
1. chromic extraction and residual chromium dregs innocent treatment method in the chromium slag is characterized in that realizing as follows:
The acetic acid thin up is made the acetate buffer solution of pH1.5, chromium slag and acetate buffer solution are pressed mass volume ratio 1kg:10L mixing, stirring, lixiviate were filtered after 10 hours, filter residue adds the sodium sulphite of chromium slag amount 4% or the ethyl xanthate of chromium slag amount 1%, add again entry and make muddy, stablize and got final product in 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104727887A CN102923778A (en) | 2012-11-21 | 2012-11-21 | Method for extracting hexavalent chromium in chromium slag and harmlessly treating residual chromium slag |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104727887A CN102923778A (en) | 2012-11-21 | 2012-11-21 | Method for extracting hexavalent chromium in chromium slag and harmlessly treating residual chromium slag |
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| Publication Number | Publication Date |
|---|---|
| CN102923778A true CN102923778A (en) | 2013-02-13 |
Family
ID=47638742
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|---|---|---|---|
| CN2012104727887A Pending CN102923778A (en) | 2012-11-21 | 2012-11-21 | Method for extracting hexavalent chromium in chromium slag and harmlessly treating residual chromium slag |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103233130A (en) * | 2013-05-09 | 2013-08-07 | 贵阳中科融实新材料技术有限公司 | Chromium slag treatment method |
| CN104907532A (en) * | 2015-05-05 | 2015-09-16 | 重庆大学 | Chromium slag harmlessness processing method by taking tailings and chromium slag as sintering fusing agents after steel slag magnetic separation |
| CN105565461A (en) * | 2015-12-23 | 2016-05-11 | 曹阳 | Chromium-containing industrial wastewater processing method |
| CN105907991A (en) * | 2016-06-30 | 2016-08-31 | 华南理工大学 | Detoxification treatment method for extracting and recovering chromium from waste residues including hexavalent chromium |
| CN111348881A (en) * | 2020-03-13 | 2020-06-30 | 常熟理工学院 | Method for improving cement solidification chromium slag and product thereof |
| CN114163163A (en) * | 2021-12-22 | 2022-03-11 | 株洲宏信科技发展有限公司 | Concrete chromium reducing agent |
-
2012
- 2012-11-21 CN CN2012104727887A patent/CN102923778A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 陆清萍: "重庆市某厂含铬废渣稳定化处理技术研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103233130A (en) * | 2013-05-09 | 2013-08-07 | 贵阳中科融实新材料技术有限公司 | Chromium slag treatment method |
| CN104907532A (en) * | 2015-05-05 | 2015-09-16 | 重庆大学 | Chromium slag harmlessness processing method by taking tailings and chromium slag as sintering fusing agents after steel slag magnetic separation |
| CN104907532B (en) * | 2015-05-05 | 2017-04-26 | 重庆大学 | Chromium slag harmlessness processing method by taking tailings and chromium slag as sintering fusing agents after steel slag magnetic separation |
| CN105565461A (en) * | 2015-12-23 | 2016-05-11 | 曹阳 | Chromium-containing industrial wastewater processing method |
| CN105907991A (en) * | 2016-06-30 | 2016-08-31 | 华南理工大学 | Detoxification treatment method for extracting and recovering chromium from waste residues including hexavalent chromium |
| CN105907991B (en) * | 2016-06-30 | 2018-01-05 | 华南理工大学 | A kind for the treatment of method for detoxication of the extraction of waste residue containing Cr VI recovery chromium |
| CN111348881A (en) * | 2020-03-13 | 2020-06-30 | 常熟理工学院 | Method for improving cement solidification chromium slag and product thereof |
| CN114163163A (en) * | 2021-12-22 | 2022-03-11 | 株洲宏信科技发展有限公司 | Concrete chromium reducing agent |
| CN114163163B (en) * | 2021-12-22 | 2022-11-29 | 湖南润攸科技发展有限公司 | Concrete chromium reducing agent |
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Application publication date: 20130213 |