CN101112647A - Technics for expelling poison for chromic slag - Google Patents
Technics for expelling poison for chromic slag Download PDFInfo
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- CN101112647A CN101112647A CNA2007100288150A CN200710028815A CN101112647A CN 101112647 A CN101112647 A CN 101112647A CN A2007100288150 A CNA2007100288150 A CN A2007100288150A CN 200710028815 A CN200710028815 A CN 200710028815A CN 101112647 A CN101112647 A CN 101112647A
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Abstract
The invention relates to a chrome slag decontamination process. The process is characterized in that the barium chloride is dissolved and diluted into solution by water, barium carbonate is dissolved and diluted into suspension, which is put into a ball mill with the chrome slag for mixing grinding; when mixing grinding, the chrome slag is crushed; the hexavalent chromium in the chrome slag is continuously dissolved in the crushing process and is reacted with the barium ion to create the barium chromate not dissolved in the water. The invention has the advantages of short disposal process, simple process, good decontamination effect, large industrialization scale, high automation of production pipeline, trivalence chromium in the chrome slag after disposal not easy to be reverted into hexavalent chromium and the chrome slag after disposal mixed with the cement, lime and sand stone used for the stabilization soil of the earthwork.
Description
Technical field
The present invention relates to a kind of technics for expelling poison for chromic slag.
Background technology
Contain the water-soluble Cr VI that is confirmed to be strong carcinogen in the waste residue that in chromium salt production, is discharged, and Cr VI permeability extra-heavy by to soil, underground water, river infiltration, causes serious pollution to environment.Adopt of existing improvement method becomes trivalent chromium with hexavalent chrome reduction more, but the trivalent chromium after the reduction under field conditions (factors), and the oxidation of oxygen can be oxidized into Cr VI again in air, can not thoroughly remove poison.Application number is 98113225.1, name is called the disclosed improvement method of Chinese patent that the chromium pulp water dissolves malicious comprehensive use and is: the water wet method is broken and soak more than 24 hours in clear water with the chromium ground-slag, regularly stir, carry out Separation of Solid and Liquid then and obtain filter cake and filtrate.In the Separation of Solid and Liquid process, filter cake is carried out stepless hydro-peening, add excess chlorination barium in the filter cake behind hydro-peening, make the Cr VI that remains in the filter cake generate the barium chromate of insoluble in water with fresh water; Slag after detoxifcation slurry is carried out Separation of Solid and Liquid once more.Filter residue and cement, sandstone, barium chloride, brium carbonate are mixed and made into the cement lump.Add an amount of barium chloride solution in the filtrate after the first time Separation of Solid and Liquid, reaction generates the barium chromate precipitation.This method detoxifying effect is reliable, but because crushing rear material should soak more than 24 hours at clear water, and through the Separation of Solid and Liquid and the stepless hydro-peening of secondary, so long flow path, floor space is big again, and water consumption is big, and production scale is little, investment is big, and automaticity is not high.And the cement brick that detoxifcation back chromium slag is made, market sales volume has certain limitation, can't utilize the chromium slag after the detoxifcation in a large number.
Summary of the invention
The purpose of this invention is to provide that a kind of technological process is short, technology is simple, remove the effective technics for expelling poison for chromic slag of poison.
Realize a kind of technics for expelling poison for chromic slag of the present invention, technical process comprises: water becomes solution or brium carbonate dissolved dilution to become suspension the barium chloride dissolved dilution, put into the ball mill mix grinding simultaneously with the chromium slag, during mix grinding that the chromium ground-slag is broken, Cr VI in the chromium slag is constantly stripping in crushing process, with barium ions reaction in the solution, generate water-fast barium chromate.Chromium slag and solution or suspension run foul of each other with the iron ball of ball mill in ball mill and make the chromium ground-slag broken during mix grinding, ball milling stirs violent, the continuous stripping in the collision crushing process of Cr VI in the chromium slag fully contacts with barium ions and reaction rapidly, therefore its chromic content of material that comes out through ball mill is up to standard fully, and it is better to remove the toxic effect fruit; Pulverizing, wet-milling, stripping, reaction all realize in same equipment, have shortened the time of chromic immersion, stripping, reaction, have also reduced operation, shorten flow process, reduced the equipment input, reduced power consumption, reduce treatment cost, and can reach detoxifying effect better.
As improvement, technical process comprises sieves the screen cloth of the material behind the above-mentioned ball-milling reaction by 120-300 order/inch, material by screen cloth enters and concentrates thickening apparatus and carry out material and concentrate thickening, material after the concentrated thickening is sent in the quality control regulating reservoir, in the quality control regulating reservoir, stir the sulfate that adds requirement according to the total content that concentrates the material barium ions, make the reaction of barium ions and sulfate generate water-fast barium sulfate precipitate.Material after above-mentioned the concentrating is reacted with sulfate in quality control conditioned reaction pond, generate insoluble sulfate precipitation, thereby reach the purpose of control solubility barium, make in the chromium slag after the processing and still contain the insoluble brium carbonate of part, can effectively control the Cr VI that contained trivalent chromium may be become by the air eremacausis under field conditions (factors) in the filter residue.
As improvement, technical process comprises that the thick slag of staying on the screen cloth after above-mentioned technology sieved sends back to mix grinding reaction in the ball mill again, guarantees that the chromium slag reaches except that the toxic effect fruit.
As improvement, technical process comprises the material in the quality control regulating reservoir carries out Separation of Solid and Liquid after qualified after testing.The former chromium slag moisture content that drops into is 18%～25%, and handling back chromium slag moisture content is 30%～35%.
As improvement, technical process comprises the overfall discharge of clear liquid above the pond after the material sedimentation that concentrates in the thickening apparatus concentrates, and flows to millpond for recycling; It is recycling that the filtrate of carrying out Separation of Solid and Liquid after the material in the quality control regulating reservoir is qualified is after testing returned millpond.Supernatant liquor after concentrating flows out from the overflow launder of pond face, and row supplies recycling to millpond; The underflow material is discharged from the bottom, pond, makes concentration basin can realize the streamlined operation of charging simultaneously, discharging simultaneously, has reduced the sedimentation time, has improved output, and the equipment automatization height manually significantly reduces, and has reduced treatment cost.Material behind the concentration response is carried out Separation of Solid and Liquid, the filtrate cycle utilization.Process water balance is still needed and is wanted supplementing water, realizes in the technological process that industrial water is recycling, so whole explained hereafter realizes the factory effluent zero-emission.
As improvement, filter residue after the Separation of Solid and Liquid and cement, lime, sandstone are mixed for subgrade stability soil, and comprehensive utilization chromium slag makes in the subgrade stability soil chromic content well below state specified standards.
As the common improvement of such scheme, concentrated thickening apparatus is a width of cloth streaming concentrator.
As improvement, the rare material water ratio behind ball mill mix grinding reaction and the screen filtration is 80---85%, enter the thickening of width of cloth streaming concentrator after, be condensed into moisture content and be the dense material below 50%.
As improvement, sulfate is calcium sulfate or ferrous sulfate.
The present invention has the handling process weak point, technology is simple, effective except that poison, and industrially scalable is big, the advantage that the production line automaticity is high.
Description of drawings
Fig. 1 is a process chart of the present invention.
The specific embodiment
Embodiment 1
The elder generation water become solution, brium carbonate dissolved dilution to become suspension the barium chloride dissolved dilution, with moisture content be that 25% chromium slag enters mix grinding in the ball mill simultaneously.The chromium slag enters ball mill by batcher, belt conveyor.Chromium slag and solution, suspension run foul of each other with the iron ball of ball mill in ball mill and make the chromium ground-slag broken during mix grinding, Cr VI in the chromium slag is constantly stripping and fully contact and reaction rapidly with barium ions in the solution in the collision crushing process, carrying out the limit pulverizes, the limit ball milling, the limit stripping generates water-fast barium chromate.
Material behind the ball-milling reaction is all sieved by the classifying screen of 300 order/inches, and the material by classifying screen moisture content 85% enters width of cloth streaming concentrator to carry out material and concentrates thickening, and the material that concentrates after the thickening is that moisture content is 50% slurry.Staying thick slag on the classifying screen after sieving sends back to and carries out above-mentioned mix grinding reaction in the ball mill again.Slurry after the concentrated thickening is discharged from the bottom, pond, be sent to quality control with mortar pump and regulate in the stirring pool, and carry out sample analysis, add an amount of calcium sulfate according to the content that contains solubility barium in the slurry, with in and in the underflow material excessive solubility barium, control the content of barium in the slag with this.Concentrate the overfall discharge of supernatant liquor above the pond after the interior material sedimentation of thickening apparatus concentrates, flow to millpond for recycling.
With quality control regulate in the stirring pool material after testing indexs such as Cr VI, total chromium, barium qualified after, enter the solid-liquid separating machine Separation of Solid and Liquid.In operating process, the water in the millpond enters solid-liquid separating machine by filter cloth simultaneously, as filter cloth choking phenomenon is arranged, and by the filter cloth wash water, carries out filter cloth regeneration.It is recycling that filtrate after the Separation of Solid and Liquid is returned millpond, and moisture content is that 35% filter residue and cement, lime, sandstone are mixed for subgrade stability soil.Wherein there is the brium carbonate of part indissoluble still to retain in the chromium slag, with the Cr VI of possible oxidized generation in the control filter residue.
Embodiment 2
As different from Example 1, first water becomes solution, brium carbonate dissolved dilution to become suspension the barium chloride dissolved dilution, with moisture content be that 21% chromium slag enters mix grinding in the ball mill simultaneously.Material behind the ball-milling reaction all sieves by the classifying screen of 200 order/inches, is 83% by the material water ratio behind the classifying screen, and the material water ratio after the concentrated thickening is 48% slurry.Slurry in stirring pool is regulated in quality control adds an amount of ferrous sulfate.The moisture content of the filter residue after handling is 33%.
Embodiment 3
As different from Example 1, first water becomes solution, brium carbonate dissolved dilution to become suspension the barium chloride dissolved dilution, with moisture content be that 18% chromium slag enters mix grinding in the ball mill simultaneously.Material behind the ball-milling reaction all sieves by the classifying screen of 120 order/inches, is 80% by the material water ratio behind the classifying screen, and the material water ratio after the concentrated thickening is 45% slurry.The moisture content of the filter residue after handling is 30%.
Beneficial effect
Make in the test at subgrade stability soil embodiment 1,2,3, press filter residue 71kg, river sand 50kg, lime 6.5kg, cement 10.5kg, be pressed into the square that thickness is 30cm after the mixing and stirring, after 7 days, test its compression strength 〉=5Mpa, compactness CBR 〉=96%, stablize and contain Cr VI 0.1～0.25mg/kg among the scholar, be significantly less than the standard of the 0.5mg/kg of national regulation.Detect no change through trimestral tracking.
Claims (9)
1. technics for expelling poison for chromic slag, it is characterized in that technical process comprises: water becomes solution, brium carbonate dissolved dilution to become suspension the barium chloride dissolved dilution, put into the ball mill mix grinding simultaneously with the chromium slag, during mix grinding that the chromium ground-slag is broken, Cr VI in the chromium slag is constantly stripping in crushing process, with barium ions reaction in the solution, generate water-fast barium chromate.
2. a kind of technics for expelling poison for chromic slag as claimed in claim 1, it is characterized in that technical process comprises sieves the screen cloth of the material behind the above-mentioned ball-milling reaction by 120-300 order/inch, material by screen cloth enters and concentrates thickening apparatus and carry out material and concentrate thickening, material after the concentrated thickening is sent in the quality control regulating reservoir, in the quality control regulating reservoir, stir the sulfate that adds requirement according to the total content that concentrates the material barium ions, make the reaction of barium ions and sulfate generate water-fast barium sulfate precipitate.
3. a kind of technics for expelling poison for chromic slag as claimed in claim 2 is characterized in that technical process comprises that the thick slag of staying on the screen cloth after above-mentioned technology sieved sends back to mix grinding reaction in the ball mill again.
4. a kind of technics for expelling poison for chromic slag as claimed in claim 3, it is characterized in that technical process comprises the material in the quality control regulating reservoir carries out Separation of Solid and Liquid after qualified after testing.
5. a kind of technics for expelling poison for chromic slag as claimed in claim 4 is characterized in that technical process comprises the overfall discharge of clear liquid above the pond after the material sedimentation that concentrates in the thickening apparatus concentrates, and flows to millpond for recycling; It is recycling that the filtrate of carrying out Separation of Solid and Liquid after the material in the quality control regulating reservoir is qualified is after testing returned millpond.
6. a kind of technics for expelling poison for chromic slag as claimed in claim 5 is characterized in that filter residue and cement, lime, the sandstone after the Separation of Solid and Liquid is mixed for subgrade stability soil.
7. as any described a kind of technics for expelling poison for chromic slag of claim 2 to 6, it is characterized in that concentrating thickening apparatus is width of cloth streaming concentrator.
8. a kind of technics for expelling poison for chromic slag as claimed in claim 7 is characterized in that the rare material water ratio behind ball mill mix grinding reaction and the screen filtration is 80-85%, enter the thickening of width of cloth streaming concentrator after, be condensed into moisture content and be the dense material below 50%.
9. a kind of technics for expelling poison for chromic slag as claimed in claim 8 is characterized in that sulfate is calcium sulfate or ferrous sulfate.
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| CN2007100288150A CN101112647B (en) | 2007-06-26 | 2007-06-26 | Technics for expelling poison for chromic slag |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249330A (en) * | 2011-04-28 | 2011-11-23 | 武汉纺织大学 | Method for industrially eliminating toxic ingredients in chromium slag |
| CN103121802A (en) * | 2011-11-18 | 2013-05-29 | 中国科学院过程工程研究所 | Method for preparing magnesium-oxy-chloride cement by utilizing chromium slag produced through salt sub-melting technology |
| CN107890621A (en) * | 2017-10-18 | 2018-04-10 | 华南理工大学 | A kind of method for innocent treatment containing the poisonous solid waste of Cr VI |
| CN109266362A (en) * | 2018-11-09 | 2019-01-25 | 西南科技大学城市学院 | A kind of modifying agent and its application |
| CN111437561A (en) * | 2020-04-08 | 2020-07-24 | 北京高能时代环境技术股份有限公司 | Chromium slag wet detoxification method based on mechanochemical strengthening |
| CN113633920A (en) * | 2021-09-15 | 2021-11-12 | 中国恩菲工程技术有限公司 | Chromium slag detoxification method |
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| CN1044567C (en) * | 1989-07-05 | 1999-08-11 | 广州市珠峰研究所 | Comprehensive utilization and eliminating poison of chromium cinder |
| CN1057508C (en) * | 1997-12-26 | 2000-10-18 | 广州铬渣处理新技术工程公司 | Method for extracting chromium from chroming waste water and waste slag |
| CN1060816C (en) * | 1998-05-29 | 2001-01-17 | 广州铬渣处理新技术工程公司 | Method for comprehensive uses by dissolving chromium residue to eliminate toxicity |
| CN1369361A (en) * | 2001-02-16 | 2002-09-18 | 李新 | Process for reclaiming waste dregs of sodium bichromate and using it to make bricks |
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2007
- 2007-06-26 CN CN2007100288150A patent/CN101112647B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1044567C (en) * | 1989-07-05 | 1999-08-11 | 广州市珠峰研究所 | Comprehensive utilization and eliminating poison of chromium cinder |
| CN1057508C (en) * | 1997-12-26 | 2000-10-18 | 广州铬渣处理新技术工程公司 | Method for extracting chromium from chroming waste water and waste slag |
| CN1060816C (en) * | 1998-05-29 | 2001-01-17 | 广州铬渣处理新技术工程公司 | Method for comprehensive uses by dissolving chromium residue to eliminate toxicity |
| CN1369361A (en) * | 2001-02-16 | 2002-09-18 | 李新 | Process for reclaiming waste dregs of sodium bichromate and using it to make bricks |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249330A (en) * | 2011-04-28 | 2011-11-23 | 武汉纺织大学 | Method for industrially eliminating toxic ingredients in chromium slag |
| CN103121802A (en) * | 2011-11-18 | 2013-05-29 | 中国科学院过程工程研究所 | Method for preparing magnesium-oxy-chloride cement by utilizing chromium slag produced through salt sub-melting technology |
| CN103121802B (en) * | 2011-11-18 | 2014-11-05 | 中国科学院过程工程研究所 | Method for preparing magnesium-oxy-chloride cement by utilizing chromium slag produced through salt sub-melting technology |
| CN107890621A (en) * | 2017-10-18 | 2018-04-10 | 华南理工大学 | A kind of method for innocent treatment containing the poisonous solid waste of Cr VI |
| CN107890621B (en) * | 2017-10-18 | 2020-02-18 | 华南理工大学 | Harmless treatment method for toxic solid waste containing hexavalent chromium |
| CN109266362A (en) * | 2018-11-09 | 2019-01-25 | 西南科技大学城市学院 | A kind of modifying agent and its application |
| CN109266362B (en) * | 2018-11-09 | 2021-03-23 | 西南科技大学城市学院 | Modifying agent and application thereof |
| CN111437561A (en) * | 2020-04-08 | 2020-07-24 | 北京高能时代环境技术股份有限公司 | Chromium slag wet detoxification method based on mechanochemical strengthening |
| CN113633920A (en) * | 2021-09-15 | 2021-11-12 | 中国恩菲工程技术有限公司 | Chromium slag detoxification method |
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| CN101112647B (en) | 2010-10-27 |
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Denomination of invention: Technics for expelling poison for chromic slag Effective date of registration: 20121112 Granted publication date: 20101027 Pledgee: Societe Generale Bank, Limited by Share Ltd, Guangzhou branch Pledgor: Guangzhou Pude Environmental Protection Facility Co., Ltd. Registration number: 2012440000001 |
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Effective date of registration: 20130520 Address after: 510600 Guangzhou, Yuexiu District, Temple Road, the right of the new layer on the ground floor, No. third, No. 90, No. 168 Patentee after: Guangzhou Xinzhicheng Environmental Protection Technology Machinery Equipment Co., Ltd. Address before: 510600, room 111-115, 1112 Xin Xin Road, Yuexiu District temple, Guangdong, Guangzhou Patentee before: Guangzhou Pude Environmental Protection Facility Co., Ltd. |
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