CN1059370A - Chromium residue detoxifying, smelting contain the method for chromium pig iron - Google Patents
Chromium residue detoxifying, smelting contain the method for chromium pig iron Download PDFInfo
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- CN1059370A CN1059370A CN90107448A CN90107448A CN1059370A CN 1059370 A CN1059370 A CN 1059370A CN 90107448 A CN90107448 A CN 90107448A CN 90107448 A CN90107448 A CN 90107448A CN 1059370 A CN1059370 A CN 1059370A
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- chromium
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- slag
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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
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Abstract
A kind of chromium residue detoxifying, smelting contain the method for chromium pig iron, be that the chromium slag is mixed by certain proportioning with iron-bearing material, solid fuel, auxiliary material, through the agglomerating plant sinter molding is that chromium slag agglomerate enters blast-furnace smelting with iron-smelting raw material again, generates to contain chromium pig iron.Adopt this technology, Cr in the chromium slag
+ 6The reduction ratio height, detoxifcation is thorough, and it is big to handle the chromium quantity of slag.Because this technology can be regulated charge composition, the pig iron of different chrome contents can be produced again, the series product that contain chromium pig iron can be developed.Tangible economic benefit and social benefit are arranged, and its environmental benefit is particularly remarkable.
Description
The present invention relates to the blast-furnace smelting detoxification chromium slag and produce the technology that contains chromium pig iron.
The chromium slag is to produce a kind of industrial residue of discharging in sodium dichromate (sodium dichromate 99) process, because of wherein containing a small amount of water-soluble sexavalent chrome (Cr
+ 6), in the process of storing up because of this part Cr of drip washing of rainwater
+ 6Can enter in the surface water or the water that permeates the ground, cause Cr
+ 6To the severe contamination at water source, the growth and the human beings'health of harm animal and plant are a kind of serious source of pollution.In order to eliminate the severe contamination of chromium slag, all did many researchs for many years both at home and abroad.In the prior art as the brickmaking of chromium slag, the system cast stone, the system slag wool, because of reduction and detoxication not thorough, Cr
+ 6Go up to continue to pollute; The application of refining fused(calcium magnesium)phosphate products obtained therefrom has limitation; Chromium slag system glass colorant, system rust-inhibiting paint raw material, because of the treatment capacity of slag too little; Chromic slag wet method reduction and detoxication and dry method reduction and detoxication then because of reason such as economy is uneconomical, make the pollution problem of chromium slag never obtain basic solution.And for example doing methods such as chromium slag refining fused(calcium magnesium)phosphate and high-temperature fusion detoxifcation aspect the blast-furnace technique using yet, but containing oxidation state chromium in the resulting phosphate fertilizer of preceding a kind of method, and using restrictedly, and chromium resource does not obtain recycling; High-temperature fusion detoxifcation coproduction potash fertilizer technology, because of the quantity of slag after the fusion too big, coke ratio is too high, be difficult to economically reach a standard, and gained pig iron amount is very little, blast furnace operating inconvenience, and chrome content is subjected to the restriction of contained chromium in the chromium slag, iron ratio in the pig iron, bad control, can not smelt the pig iron of multiple different chrome contents, product application is restricted.Abroad also adopt buried mostly and build the antiseepage field and stack or solidify the pollution problem that sealing treatment is not also fundamentally eliminated the chromium slag the processing of chromium slag.
The objective of the invention is both fundamentally to eliminate of the pollution of chromium slag, chromium wherein can be got utilization environment.
The present invention is achieved in that a chromium slag behind crushing and screening, presses certain proportioning with solid fuel, iron-bearing material and auxiliary material.After mixing, be chromium slag agglomerate through the agglomerating plant sinter molding.In sintering process, make the Cr in the chromium slag
+ 6Be reduced to Cr more than 85%
+ 3Agglomerate is crushed to certain particle size behind naturally cooling, being mixed with the iron-smelting raw material of routine or chromite enters blast-furnace smelting, generates to contain chromium pig iron.
In sintering process, earlier with various raw material crushing screenings, then according to different requirements to all iron content of chromium slag agglomerate, and higher Cr
+ 6Reduction ratio (＞85%) and knot ore deposit rate (＞70%), with chromium slag and iron-bearing material in 100～60: 0～40 ratio (weight percent) is mixed, and described iron-bearing material is iron scale (being the iron scale that the surface forms during the heating of steel embryo in the rolling process) or powdered iron ore; According to solid-fuelled calorific value, determine that the fuel quantity that adds is: (chromium slag+iron-bearing material): solid fuel=90～86: 10～14(weight percent), described solid fuel is breeze or coal dust; According to CaO, MgO, SiO in the chromium slag
2Content, calculate to determine add the amount of auxiliary material so that the dual alkalinity of chromium slag agglomerate is 1.5～3, described auxiliary material is silicon-containing material-silica, yellow sand and calcic raw material-Wingdale, fluorite etc.
In smelting process, be to change the chromium slag agglomerate amount of allocating into or increase low-grade chromite or the two combination according to containing the different requirements that contain chromium in the chromium pig iron, adopting, the content that contains chromium in the chromium pig iron by different proportioning controls, in addition, in order to help the reduction of chromium, must be according to FeOCr in the furnace charge
2O
3, CaOCr
2O
3, MgOCr
2O
3Content determine to add the amount of auxiliary material-silica, fluorite so that the slag basicity of slag is controlled to be 0.8～1.5.Smelting temperature is observed and is controlled with the silicon content in the pig iron, makes the silicon content in the pig iron be controlled to be 2.5～3%.
Cardinal principle of the present invention is: contain a large amount of CaO, MgO and SiO in the chromium slag
2, the flux that need use when it forms to the blast furnace refining pig iron is similar, has self-fluxing nature or half self-fluxing nature, also has a certain amount of Fe in the chromium slag
2O
3With the small additions of chromium compound, thereby can be used as the flux of blast furnace ironmaking again, but powdery chromium slag can not be directly into blast furnace, thereby must first sinter molding, its agglomerating ultimate principle is identical with iron ore sintering, and that different is Cr
+ 6Be reduced to Cr
+ 3Must in certain acidic conditions and high temperature and CO reducing atmosphere, carry out, after chromium slag agglomerate enters blast furnace, under the smelting condition of blast furnace, not only the oxide compound of iron is reduced into metallic iron, and other metal oxide such as cupric oxide, manganese oxide etc. also are being reduced in various degree, and oxidation state chromium is under high temperature and certain potential of hydrogen condition, also can be reduced to chromium metal, and along with chromium pig iron is closed all-contains in the final formation of the carburetion of Fe, Cr.So entered Cr in the process recycled water that the pig iron is discharged, waste gas and the blast-furnace slag in said process owing to most oxidation state chromium are reduced into to chromium metal
+ 6With total chrome content be micro-, all can be lower than national specified discharge standard, blast-furnace slag is used to make cement and also can pollute after shrend, thereby the chromium slag is detoxified completely.Concrete reaction is as follows:
In the sintering:
Cr under the situation that has CaO, MgO, FeO etc. to exist
2O
3There is the following reaction that mineralizes:
(MeO represents materials such as MgO, CaO, FeO)
SiO is being arranged
2Following reaction is arranged under the situation Deng existence:
In the smelting:
Technical process of the present invention such as accompanying drawing.
Adopt this technology, the chromium slag is total chromium metallization reduction ratio height after sintering, smelting, generally can reach as high as 94% more than 90%, and detoxifcation is thorough, and the processing chromium quantity of slag is big.Again because this technology can be regulated charge composition, can produce the pig iron of different chrome contents, chrome content can be broken through the restriction of ferrochrome ratio in the chromium slag in the pig iron, thereby can develop the series product that contain chromium pig iron, tangible economic benefit and social benefit are arranged, and its environmental benefit is particularly remarkable.
Embodiments of the invention below are described in detail in detail:
Sintering embodiment 1, behind raw material crushing screenings such as chromium slag, breeze (or coal dust), silica, making chromium slag particle degree is that 1～5 millimeter, breeze granularity are that auxiliary material granularities such as 1～3 millimeter, silica are 1～2 millimeter, add the iron scale mixing and stirring again after, carry out sintering at " blow on the level land " pit furnace.Its proportioning is: the chromium slag: iron scale=80: 20, (chromium slag+iron scale): breeze=90: 10, the amount of silica are according to CaO, MgO SiO in the chromium slag
2The content and the requirement of dual alkalinity calculate and decide, in this example, agglomerate, dual alkalinity (CaO/SiO
2) be 2.95, agglomerate all iron content (TFe) is: 21.53%, knot ore deposit rate is: 72%, Cr in the chromium slag
+ 6Be reduced to Cr
+ 3Reduction ratio be: 79.06%.
Sintering embodiment 2, raw material is prepared identical with example 1, and different is: proportioning is: the chromium slag: powdered iron ore=65: 35.
(chromium slag+powdered iron ore): breeze=88: 12,
Agglomerate dual alkalinity (CaO/SiO
2) be: 2.15,
Agglomerate all iron content (TFe) is: 15.32%,
Knot ore deposit rate is: 73.50%.
Cr in the chromium slag
+ 6Be reduced to Cr
+ 3Reduction ratio be: 87.12%.
Sintering embodiment 3, raw material is prepared identical with example 1, and different is:
Proportioning is: chromium slag: silica: powdered iron ore=50: 10: 40
(chromium slag+silica+powdered iron ore): coal dust=86: 14
Agglomerate dual alkalinity (CaO/SiO
2) be: 1.51
Agglomerate all iron content (TFe) is: 10.87%
Knot ore deposit rate is: 75.40%
Cr in the chromium slag
+ 6Be reduced to Cr
+ 3Reduction ratio be: 92.36%.
Sintering embodiment 3, raw material is prepared identical with example 1, and different is that this sintering is to carry out on the mechanize Greenawalt type sintering machine.
Proportioning: chromium slag: silica=85: 15
(chromium slag+silica): breeze=88: 12
Agglomerate dual alkalinity (CaO/SiO
2) be: 1.98
Agglomerate all iron content (TFe) is: 5.28%
Knot ore deposit rate is: 74.80%
Cr in the chromium slag
+ 6Be reduced to Cr
+ 3Reduction ratio be: 89.28%.
The sintering temperature of above sintering example is 1100 ℃～1200 ℃.
Smelting process: behind the chromium slag sintering, so cool off through head, crushing and screening to 10～40 millimeter warehouse entry is stand-by, and smelting process is at 30m
3Carry out on the blast furnace.Outside the feed stock for blast furnace dechromisation slag agglomerate of blast furnace, coke, iron ore, chrome ore, Wingdale, fluorite, silica etc. are arranged still, its proportioning need satisfy different chrome contents and basicity of slag (CaO/SiO in the pig iron
2) 0.8～1.5 requirement.The si content of Control for Kiln Temperature in the pig iron is 2.5～3%.
Smelt embodiment 1:
Charge composition (every batch of furnace charge of kg/):
Measured result:
Smelt embodiment 2,
Charge composition (every batch of furnace charge of kg/):
| Coke | Iron ore | Chromium slag agglomerate | Silica | Fluorite | Basicity of slag (calculating) |
| 340 | 120 | 400 | 20 | 30 | 1.15 |
| Chrome content in the pig iron (calculating) | |||||
| 7.12％ | |||||
Measured result:
| Basicity of slag | Chrome content in the pig iron | Chromium recovery ratio | Si content in the pig iron |
| 1.06 | 7.62％ | 94.65％ | 2.52％ |
| Total chrome in the slag | Cr in the slag +6Content | ||
| 0.25％ | ＜1ppm | ||
Smelt embodiment 3,
Charge composition (every batch of furnace charge of kg/):
| Coke | Iron ore | Chrome ore | Chromium slag agglomerate | Silica | Fluorite |
| 340 | 100 | 50 | 350 | 20 | 30 |
| Basicity of slag (calculating) | Chrome content in the pig iron (calculating) |
| 0.9 | 11％ |
Measured result:
| Basicity of slag | Chrome content in the pig iron | Chromium recovery ratio | Si content in the pig iron |
| 0.85 | 11.31％ | 94.62％ | 2.96％ |
| Total chrome in the slag | Cr in the slag +6Content | ||
| 0.36％ | ＜1ppm | ||
Claims (4)
1, the method for a kind of chromium residue detoxifying, the smelting iron content pig iron, it is characterized in that mixing by certain proportioning in chromium slag and iron-bearing material, solid fuel, auxiliary material, is chromium slag agglomerate through the agglomerating plant sinter molding, enter blast-furnace smelting with iron-smelting raw material again, generation contains chromium pig iron.
2, method according to claim 1, basis contains the different requirements that contain chromium in the chromium pig iron in it is characterized in that smelting, can adopt change chromium slag agglomerate to go into the stove proportional quantity or increase low-grade chromite or the two combination, contain the content of chromium in the chromium pig iron by different proportionings controls.
3, according to claim 1 or 2 described methods, it is characterized in that in the smelting process, the amount of control auxiliary material-silica, fluorite, making the slag basicity of slag is 0.8～1.5.
4, by claim 1 or 2 described methods, the various proportioning raw materials that it is characterized in that the sintering stage are to determine like this:
Difference according to all iron content of chromium slag agglomerate requires and higher Cr
+ 6Reduction ratio (＞85%) and knot ore deposit rate (＞70%) be the chromium slag then: iron-bearing material (iron scale or powdered iron ore)=100～60: 0～40(weight percent);
Determine then (chromium slag+iron-bearing material): solid fuel (breeze or coal dust)=90～86: 10～14(weight percent) according to solid-fuelled calorific value;
According to CaO, MgO, SiO in the chromium slag
2Content, the supplementary product kind that determine to add: the class and the amount of silicon-containing material (silica, yellow sand), calcic raw material (Wingdale, fluorite), the dual alkalinity that makes chromium slag agglomerate is 1.5～3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90107448A CN1059370A (en) | 1990-08-31 | 1990-08-31 | Chromium residue detoxifying, smelting contain the method for chromium pig iron |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90107448A CN1059370A (en) | 1990-08-31 | 1990-08-31 | Chromium residue detoxifying, smelting contain the method for chromium pig iron |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1059370A true CN1059370A (en) | 1992-03-11 |
Family
ID=4880553
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90107448A Pending CN1059370A (en) | 1990-08-31 | 1990-08-31 | Chromium residue detoxifying, smelting contain the method for chromium pig iron |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705317B (en) * | 2009-09-14 | 2011-06-29 | 重庆瑞帆再生资源开发有限公司 | Harmless process method for chrome slag by utilizing metallurgy sintering and blast furnace |
| CN101503743B (en) * | 2008-10-26 | 2012-07-04 | 闫晓峰 | Production process for producing special purpose cast iron by blast furnace and electric furnace duplex weak oxidation process |
| CN102557137A (en) * | 2012-03-15 | 2012-07-11 | 甘肃锦世化工有限责任公司 | Method for producing sodium chromate and co-producing chrome-containing cast iron by three-stage process through un-calcium roasting |
| CN103103346A (en) * | 2013-01-08 | 2013-05-15 | 内蒙古包钢钢联股份有限公司 | Recycling method for calcium-free chromium slag sintered building block |
| CN103122407A (en) * | 2013-03-14 | 2013-05-29 | 赖红君 | Direct blast furnace innocent treatment method of chromic slag pressure block |
| CN101875987B (en) * | 2009-12-02 | 2013-06-05 | 吐鲁番沈宏金属工业有限责任公司 | Method for smelting low chromium pig iron by utilizing chromium slag |
| EP2602066A2 (en) | 2011-12-08 | 2013-06-12 | Makita Corporation | Electric power tool |
| CN103361484A (en) * | 2012-03-26 | 2013-10-23 | 云南曲靖越钢集团有限公司 | Harmless treatment method of chromium slag generated by preparation of chromium salt employing little calcium roasting method, and application of method |
| CN104017927A (en) * | 2014-06-03 | 2014-09-03 | 中信锦州金属股份有限公司 | Method of smelting chromium-containing pig iron by utilization of chromium slag |
| CN104131123A (en) * | 2014-07-28 | 2014-11-05 | 张兴林 | Chromium slag harmless treatment method utilizing chromium slag sintering ironmaking |
| CN104674014A (en) * | 2015-02-09 | 2015-06-03 | 河北钢铁股份有限公司承德分公司 | Clean reutilization method of chromium residue |
| TWI487799B (en) * | 2010-03-29 | 2015-06-11 | Nisshin Steel Co Ltd | Method of treating chrome-containing molten metal and slag |
| CN105861833A (en) * | 2016-06-08 | 2016-08-17 | 江苏省冶金设计院有限公司 | Method for combined treatment of copper slags and chromium slags |
| CN106086429A (en) * | 2016-06-08 | 2016-11-09 | 江苏省冶金设计院有限公司 | A kind of Combined Treatment chromium slag and the method for copper ashes |
| CN106500106A (en) * | 2016-09-19 | 2017-03-15 | 中信锦州金属股份有限公司 | A kind of method detoxified to leached-out chromium residue by utilization sintering technology |
| CN101906500B (en) * | 2010-02-05 | 2017-06-09 | 甘肃锦世化工有限责任公司 | It is a kind of to comprehensively utilize the method that non-calcium chromium slags are directly produced chromium-base alloy steel |
| CN109500046A (en) * | 2018-09-21 | 2019-03-22 | 浙江金泰莱环保科技有限公司 | Chromium strengthens cured method in one kind waste containing chromium |
| CN110431243A (en) * | 2017-03-21 | 2019-11-08 | 朗盛德国有限责任公司 | The method for preparing the particle of iron content and chromium |
| CN110935711A (en) * | 2019-11-13 | 2020-03-31 | 武汉钢铁有限公司 | Method for recycling steel multi-component waste |
| CN111675549A (en) * | 2020-06-22 | 2020-09-18 | 山东洛尔环保科技有限公司 | Resource utilization method of hexavalent chromium contaminated soil |
| CN114150148A (en) * | 2021-12-10 | 2022-03-08 | 四川鑫鼎新材料有限公司 | Method for extracting chromium-containing alloy from iron-chromium solid tailings to manufacture stainless steel product |
-
1990
- 1990-08-31 CN CN90107448A patent/CN1059370A/en active Pending
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503743B (en) * | 2008-10-26 | 2012-07-04 | 闫晓峰 | Production process for producing special purpose cast iron by blast furnace and electric furnace duplex weak oxidation process |
| CN101705317B (en) * | 2009-09-14 | 2011-06-29 | 重庆瑞帆再生资源开发有限公司 | Harmless process method for chrome slag by utilizing metallurgy sintering and blast furnace |
| CN101875987B (en) * | 2009-12-02 | 2013-06-05 | 吐鲁番沈宏金属工业有限责任公司 | Method for smelting low chromium pig iron by utilizing chromium slag |
| CN101906500B (en) * | 2010-02-05 | 2017-06-09 | 甘肃锦世化工有限责任公司 | It is a kind of to comprehensively utilize the method that non-calcium chromium slags are directly produced chromium-base alloy steel |
| TWI487799B (en) * | 2010-03-29 | 2015-06-11 | Nisshin Steel Co Ltd | Method of treating chrome-containing molten metal and slag |
| EP2602066A2 (en) | 2011-12-08 | 2013-06-12 | Makita Corporation | Electric power tool |
| CN102557137A (en) * | 2012-03-15 | 2012-07-11 | 甘肃锦世化工有限责任公司 | Method for producing sodium chromate and co-producing chrome-containing cast iron by three-stage process through un-calcium roasting |
| CN102557137B (en) * | 2012-03-15 | 2014-11-12 | 内蒙古黄河铬盐股份有限公司 | Method for producing sodium chromate and co-producing chrome-containing cast iron by three-stage process through un-calcium roasting |
| CN103361484A (en) * | 2012-03-26 | 2013-10-23 | 云南曲靖越钢集团有限公司 | Harmless treatment method of chromium slag generated by preparation of chromium salt employing little calcium roasting method, and application of method |
| CN103103346A (en) * | 2013-01-08 | 2013-05-15 | 内蒙古包钢钢联股份有限公司 | Recycling method for calcium-free chromium slag sintered building block |
| CN103122407A (en) * | 2013-03-14 | 2013-05-29 | 赖红君 | Direct blast furnace innocent treatment method of chromic slag pressure block |
| CN103122407B (en) * | 2013-03-14 | 2014-08-06 | 赖红君 | Direct blast furnace innocent treatment method of chromic slag pressure block |
| CN104017927B (en) * | 2014-06-03 | 2015-11-25 | 中信锦州金属股份有限公司 | A kind of chromium slag melting that utilizes is containing the method for chromium pig iron |
| CN104017927A (en) * | 2014-06-03 | 2014-09-03 | 中信锦州金属股份有限公司 | Method of smelting chromium-containing pig iron by utilization of chromium slag |
| CN104131123A (en) * | 2014-07-28 | 2014-11-05 | 张兴林 | Chromium slag harmless treatment method utilizing chromium slag sintering ironmaking |
| CN104674014B (en) * | 2015-02-09 | 2017-07-07 | 河北钢铁股份有限公司承德分公司 | A kind of method of chromium slag resource clean utilization |
| CN104674014A (en) * | 2015-02-09 | 2015-06-03 | 河北钢铁股份有限公司承德分公司 | Clean reutilization method of chromium residue |
| CN106086429A (en) * | 2016-06-08 | 2016-11-09 | 江苏省冶金设计院有限公司 | A kind of Combined Treatment chromium slag and the method for copper ashes |
| CN105861833A (en) * | 2016-06-08 | 2016-08-17 | 江苏省冶金设计院有限公司 | Method for combined treatment of copper slags and chromium slags |
| CN106500106A (en) * | 2016-09-19 | 2017-03-15 | 中信锦州金属股份有限公司 | A kind of method detoxified to leached-out chromium residue by utilization sintering technology |
| CN106500106B (en) * | 2016-09-19 | 2019-06-07 | 中信锦州金属股份有限公司 | A method of detoxified using sintering technology leached-out chromium residue |
| CN110431243A (en) * | 2017-03-21 | 2019-11-08 | 朗盛德国有限责任公司 | The method for preparing the particle of iron content and chromium |
| CN109500046A (en) * | 2018-09-21 | 2019-03-22 | 浙江金泰莱环保科技有限公司 | Chromium strengthens cured method in one kind waste containing chromium |
| CN110935711A (en) * | 2019-11-13 | 2020-03-31 | 武汉钢铁有限公司 | Method for recycling steel multi-component waste |
| CN110935711B (en) * | 2019-11-13 | 2022-01-18 | 武汉钢铁有限公司 | Method for recycling steel multi-component waste |
| CN111675549A (en) * | 2020-06-22 | 2020-09-18 | 山东洛尔环保科技有限公司 | Resource utilization method of hexavalent chromium contaminated soil |
| CN111675549B (en) * | 2020-06-22 | 2023-03-10 | 山东洛尔环保科技有限公司 | Resource utilization method of hexavalent chromium contaminated soil |
| CN114150148A (en) * | 2021-12-10 | 2022-03-08 | 四川鑫鼎新材料有限公司 | Method for extracting chromium-containing alloy from iron-chromium solid tailings to manufacture stainless steel product |
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