CN100413607C - Harmless treatment process for waste chromium slag - Google Patents
Harmless treatment process for waste chromium slag Download PDFInfo
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- CN100413607C CN100413607C CNB200610010604XA CN200610010604A CN100413607C CN 100413607 C CN100413607 C CN 100413607C CN B200610010604X A CNB200610010604X A CN B200610010604XA CN 200610010604 A CN200610010604 A CN 200610010604A CN 100413607 C CN100413607 C CN 100413607C
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Abstract
The present invention relates to a harmless treatment technological method for waste chromium slag, which comprises the following technological process processes: after 40 to 45% of waste chromium slag, 10 to 15% of pulverized coal ash, 10 to 15% of zinc kiln slag and 28 to 30% of red mud are uniformly mixed, the mixture of the waste chromium slag, the pulverized coal ash, the zinc kiln slag and the red mud is crushed to 50 to 80 meshes; the mixture is conveyed into a sintering furnace, and the reducing and sintering reification treatment of the high temperature of 1000 to 1100 DEG C is carried out; after sintered mixed materials are cooled for 2 to 3 hours, the mixed materials are soaked for 20 to 26 hours by water, and then slag materials are filtered by filtering cloth; filtering liquid uses FeSO4 as a reducing agent, the adding amount of the reducing agent is 14 to 16 times of content of Cr<6+> in the waste chromium slag, and the reduction reaction of the filtering liquid is carried out under the condition of the pH value of 8 to 8.5; waste gas generated in a sintering process is conveyed to a washing tower and is washed, and generated water vapor is completely discharged. The present invention overcomes the disadvantage that the existing comprehensive utilization of the waste chromium slag does not carry out a harmless treatment, and the present invention neutralizes and reduces harmful elements in the waste chromium slag and also effectively avoids the environmental pollution of the harmful elements in the comprehensive utilization of the waste chromium slag.
Description
Technical field:
The invention belongs to the innoxious process for treating field of useless chromium slag.
Background technology:
The chromium slag is the waste residue of discharging during sodium dichromate, crome metal are produced, and contains the oxide of magnesium, calcium, silicon, iron, aluminium in the chromium slag and the chrome green that does not react, and also contains water-soluble chromic acid sodium and solubility in acid calcium chromate.Useless chromium slag mainly is that be deposited in as trade waste need not on some vacant lands at present, product that has and technology also will be given up the chromium slag as the raw material of industry, as be used to make calcium magnesium phosphate, cast stone, cement additire or glass and make toner etc., but these all are based on not useless chromium slag were carried out utilizing under the situation of harmless treatment.
Harmful components in the useless chromium slag mainly are sexavalence ions such as water-soluble chromic acid sodium, solubility in acid calcium chromate; In the open the useless chromium slag of Dui Fanging after dash being drenched by rainwater for a long time a large amount of hexavalent chromium with the molten infiltration of the rainwater face of land, to underground water, rivers, the lake produces pollutes, also endanger farmland and aquatic organism, hexavalent chromium is very big to the murder by poisoning of health of human body, its compound has very strong oxidisability, alimentary canal to human body, respiratory tract, skin, mucous membrane and internal organ all have harm, the people of long-term contact hexavalent chromium compound can cause chromium poisoning, and cause headache tired, become thin, apocleisis, the liver kidney also can suffer damage, chromium compound also has carcinogenesis, especially lung cancer; And be utilized as some raw materials of industry without the useless chromium slag of harmless treatment, because the existence of its chemical characteristic can cause secondary pollution to environment.
Summary of the invention:
What purpose of the present invention provided in order to overcome the use defective that above-mentioned existing useless chromium slag exists just that a kind of useless chromium is innoxious, resource, technological process do not have that " three wastes " produce is the useless chromium slag innocent treatment method that remarkable environmental-protection function is arranged.
The objective of the invention is to realize by following technological process.
It has following technological process: will give up chromium slag and flyash, zinc kiln slag, red mud are by useless chromium slag 40～45%, flyash 10～15%, zinc kiln slag 10～15%, red mud 28～30% (all is weight percentage, the proportioning total amount is 100%) be crushed to 50～80 orders after evenly mixing and send in the sintering furnace materialization again and handle through 1000～1100 ℃ of high temperature reduction sintering, compound behind sintering water after cooling off 2～3 hours soaks and with filter cloth slag charge was leached in 20～26 hours again, and filtrate is used FeSO
4As reducing agent, FeSO
4Addition be Cr in the useless chromium slag
6+14～16 times of content add FeSO
4It is to make filtrate through reduction Cr under 8～8.5 the condition at pH value that filtrate is transferred in the back
6+The back produces sediment and supernatant; The waste gas that compound produces in sintering process is delivered to scrubbing tower, makes the soot particle precipitation after the washing, and the water vapour that washing produces is drained; The present invention also reduces filtrate Cr
6+The supernatant that the back produces returns in blowback materialization treatment process or the scrubbing tower.
The primary harmfulness of useless chromium slag is its strong basicity, the present invention mixes trade waste flyash, zinc kiln slag, the red mud of acidity through the reduction sintering and carries out materialization processing and neutralization reaction with useless chromium slag, make the calcium ions and magnesium ions in the useless chromium slag be neutralized into harmless salts substances---slag, slag is the immersion by water again, soluble calcium ions and magnesium ions is comprised contain Cr
6+One of solable matter dissolve into filtrate, produce calcium magnesium phosphate, cast stone, cement additire and be used for sintering deposit ironmaking etc. with regard to making slag after leaching become the neutral raw material of industry, can be used as like this; Useless chromium slag is handled through the materialization of reduction sintering, also makes most hexavalent chromium be reduced into stable chromic salt---slag, and its harmfulness is excluded; The a small amount of hexavalent chromium that contains in slag enters filtrate by the immersion treatment of water, and the hexavalent chromium in the filter residue is eliminated substantially.And the hexavalent chromium in the filtrate is again by adding FeSO in filtrate
4Make reducing agent, the sediment of the chromic salt of its generation is separated, become a kind of harmless valuable raw material of industry; Remove the supernatant behind the chromic salts, also can be by return the blowback materialization processing stage or the waste gas washing stage recycle, reducing production costs, and make whole process flow accomplish real " the no three wastes ".
At the waste gas that useless chromium slag is carried out producing in the materialization processing procedure mainly is CO
2, the present invention introduces waste gas and carries out spray washing in the scrubbing tower, makes CO
2Generate precipitation of calcium carbonate with the supernatant reverse circulation washing of meta-alkalescence, thereby with CO
2Gas is removed, and the sediment that generates can be used as the production auxiliary materials of common brick and is used; The water vapour that the washing back produces is by the blower fan suction evacuation.
Useless chromium slag after the inventive method is handled, its Cr VI evil and other harmfulnesses are excluded, but safety and environmental protection enter the raw material of industry and utilize the field, and the supernatant that produces in the innoxious process returns and recycles, and has not only reduced cost but also do not have discharging of waste liquid; The inventive method cost is low, and the disposal amount is big, and is very wide to the comprehensive utilization prospect of useless chromium slag.
Further set forth content of the present invention below in conjunction with drawings and Examples.
Description of drawings:
Fig. 1 is the inventive method process chart;
Fig. 2 is for returning supernatant the process chart that recycles on Fig. 1 basis.
The specific embodiment:
Embodiment one: as Fig. 1, with useless chromium slag of 430kg and 150kg flyash, the 120kg zinc kiln slag, it is thin to be crushed to 80 orders with ball mill after the 300kg red mud evenly mixes, send into the sintering furnace materialization and handle, adopt 1050 ℃ of high temperature sinterings to come out of the stove after 3 hours and cooled off 2 hours, clinker is crushed to the thin water of 50 orders it was soaked 24 hours, with filter cloth slag charge is leached, filtrate is used FeSO again
4As reducing agent, FeSO
4Adding carry out reduction reaction for 15 times of the hexavalent chromium measured in the filtrate in a large number, add FeSO
4The back transfers filtrate to make hexavalent chromium in the filtrate be reduced into the harmless sediment of chromic salt under pH value is 8 condition; The waste gas that produces in sintering process is sucked sends into spray washing in the scrubbing tower, and the sediment that the washing back generates is removed, and the water vapour that washing produces is by the blower fan suction evacuation.
Embodiment two: see figure two, with useless chromium slag of 450kg and 100kg flyash, the 150kg zinc kiln slag, it is thin to be crushed to 50 orders with ball mill after the 300kg red mud evenly mixes, send into the sintering furnace materialization and handle, adopt 1000 ℃ of high temperature sinterings to come out of the stove after 4 hours and cooled off 3 hours, clinker is crushed to the thin water of 50 orders it was soaked 22 hours, with filter cloth slag charge is leached, filtrate is used FeSO again
4As reducing agent, FeSO
4Adding in a large number carry out reduction reaction for 14 times of the hexavalent chromium measured in the useless chromium slag, add FeSO
4The back transfers filtrate to make hexavalent chromium in the filtrate be reduced into the harmless sediment of chromic salt under pH value is 8.2 condition; The waste gas that produces in sintering process is sucked sends into spray washing in the scrubbing tower, and the sediment that the washing back generates is removed, and the water vapour that washing produces is by the blower fan suction evacuation.Filtrate being reduced removed Cr
6+After supernatant be collected the processing stage of returning the blowback materialization by pipeline or the waste gas washing stage recycles.
Embodiment three: see figure two, with useless chromium slag of 400kg and 150kg flyash, the 150kg zinc kiln slag, it is thin to be crushed to 60 orders with ball mill after the 300kg red mud evenly mixes, sending into the sintering furnace materialization handles to the cooling 3 hours of coming out of the stove after 4 hours of 1100 ℃ of high temperature sinterings, clinker is crushed to the thin water of 50 orders it was soaked 20 hours, with filter cloth slag charge is leached again, and filtrate is used FeSO
4As reducing agent, FeSO
4Adding in a large number carry out reduction reaction for 16 times of the hexavalent chromium measured in the useless chromium slag, add FeSO
4The back transfers filtrate to make hexavalent chromium in the filtrate be reduced into the harmless sediment of chromic salt under pH value is 8.5 condition; The waste gas that produces in sintering process is sucked sends into spray washing in the scrubbing tower, and the sediment that the washing back generates is removed, and the water vapour that washing produces is by the blower fan suction evacuation.Filtrate being reduced removed Cr
6+After supernatant be collected the processing stage of returning the blowback materialization by pipeline or the waste gas washing stage recycles.
Claims (2)
1. harmless treatment process for waste chromium slag, it is characterized in that, it has following technological process: will give up chromium slag and flyash, zinc kiln slag, red mud are by useless chromium slag 40～45%, flyash 10～15%, zinc kiln slag 10～15%, red mud 28～30% (all is weight percentage, the proportioning total amount is 100%) be crushed to 50～80 orders after evenly mixing and send in the sintering furnace materialization again and handle through 1000～1100 ℃ of high temperature reduction sintering, compound behind sintering water after cooling off 2～3 hours soaks and with filter cloth slag charge was leached in 20～26 hours again, and filtrate is used FeSO
4As reducing agent, FeSO
4Addition be Cr in the useless chromium slag
6+14～16 times of content add FeSO
4It is to make filtrate through reduction Cr under 8～8.5 the condition at pH value that filtrate is transferred in the back
6+The back produces sediment and supernatant; The waste gas that compound produces in sintering process is delivered to the scrubbing tower washing, makes the soot particle precipitation after the washing, and the water vapour that washing produces is drained.
2. harmless treatment process for waste chromium slag according to claim 1 is characterized in that filtrate is reduced Cr
6+The supernatant that the back produces returns in blowback materialization treatment process or the scrubbing tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610010604XA CN100413607C (en) | 2006-01-05 | 2006-01-05 | Harmless treatment process for waste chromium slag |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610010604XA CN100413607C (en) | 2006-01-05 | 2006-01-05 | Harmless treatment process for waste chromium slag |
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| CN1799716A CN1799716A (en) | 2006-07-12 |
| CN100413607C true CN100413607C (en) | 2008-08-27 |
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| CNB200610010604XA Expired - Fee Related CN100413607C (en) | 2006-01-05 | 2006-01-05 | Harmless treatment process for waste chromium slag |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103934256B (en) * | 2014-04-21 | 2019-06-04 | 江苏维尔利环保科技股份有限公司 | Chromium slag and wet method detoxifcation method containing chromium pollutant |
| ES2836197T3 (en) * | 2016-03-15 | 2021-06-24 | Fluorchemie Gmbh Frankfurt | Composition containing modified red mud, poor in chromate, as well as a process for its production |
| CN106673682B (en) * | 2016-12-30 | 2020-03-20 | 钢研晟华工程技术有限公司 | Method for producing ferroalloy and refractory material by using solid wastes |
| CN110052473A (en) * | 2019-04-16 | 2019-07-26 | 北京净界新宇环保科技有限公司 | A kind of heavy metal chromium pollution processing method |
| CN114349477B (en) * | 2022-01-12 | 2023-08-25 | 湖南国发控股有限公司 | High chromium slag detoxification formula and synergistic lightweight aggregate production process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562510A (en) * | 2004-04-06 | 2005-01-12 | 济南裕兴化工有限责任公司 | Method for harnessing chromium dregs |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562510A (en) * | 2004-04-06 | 2005-01-12 | 济南裕兴化工有限责任公司 | Method for harnessing chromium dregs |
Non-Patent Citations (6)
| Title |
|---|
| 去除铬渣毒性的研究. 方荣利，金成昌.重庆环境科学，第20卷第1期. 1998 |
| 去除铬渣毒性的研究. 方荣利，金成昌.重庆环境科学，第20卷第1期. 1998 * |
| 粉煤灰电石渣用作金属废渣和酸性铬污泥的稳定/固化剂的试验研究. 李新国，许增贵.环境保护科学，第28卷第111期. 2002 |
| 粉煤灰电石渣用作金属废渣和酸性铬污泥的稳定/固化剂的试验研究. 李新国，许增贵.环境保护科学，第28卷第111期. 2002 * |
| 铬渣的利用研究. 方荣利，金成昌.矿产综合利用，第5期. 1997 |
| 铬渣的利用研究. 方荣利，金成昌.矿产综合利用，第5期. 1997 * |
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