CN101275182A - Comprehensive utilization method for red mud - Google Patents
Comprehensive utilization method for red mud Download PDFInfo
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- CN101275182A CN101275182A CNA2008100475556A CN200810047555A CN101275182A CN 101275182 A CN101275182 A CN 101275182A CN A2008100475556 A CNA2008100475556 A CN A2008100475556A CN 200810047555 A CN200810047555 A CN 200810047555A CN 101275182 A CN101275182 A CN 101275182A
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Abstract
The invention belongs to the technical field of comprehensive utilization of red mud. The technical proposal of the invention is that: adding coke, anthracite which is 7-75% of mass of red mud, calcium compound which is 0-16% or aluminiferous compounds which is 0-645% into the red mud, placing in an electrical furnace after mixing; melting to deoxidize at the temperature ranging from 1400 to 1800 DEG C, and keeping temperature for 0.5 to 4 hours, crushing the red mud for separation after naturally cooling. The main chemical ingredients of the red mud is that: SiO<2> is 10-23wt%, Fe<2>O<3> is 7-40wt%, Al<2>O<3> is 6-20wt%, CaO is 3-45 wt%, Mgo is 0.5-3 wt%, K<2>O is 0.1-0.4 wt%, Na<2>O is 2-11 wt%, TiO<2> is 1-6 wt%, cauterized loss is 8-12wt%. Under high temperature, SiO<2> and Fe<2>O<3> in the red mud of the invention are deoxidized into ferro-silicon alloy, Al<2>O<3> and CaO are generated to calcium aluminate, Na<2>O and K<2>O are volatilized at high temperature to be refined, cooled and deposited to obtain the calcium aluminate material and ferro-silicon alloy by crushing separation, so the invention has the characteristics of wide application range and high additional value.
Description
Technical field
The invention belongs to the technical field of red mud comprehensive utilization.Be specifically related to a kind of method of utilizing electric smelting reduction red mud to prepare Antaciron and calcium aluminate material.
Background technology
Red mud is the solid, powdery discarded object of discharging in the aluminium oxide metallurgy industry production process, 1.0～1.7 tons of red muds of the about output of one ton of aluminium oxide of general every production.According to incomplete estimation, about 6,000 ten thousand tons of the annual discharging in whole world red mud.China is the world the 4th big alumina producing state, and accumulation red mud volume of cargo in storage is up to 4,100 ten thousand tons.A large amount of red muds are stored up in the open, occupy farmland and massif, stir up a cloud of dust, and cause environment and topsoil, and the PH of red mud is very high, and its leach liquor is about 12.1～13.0.Alkali lye in the red mud infiltrates the pollution that underground water source is caused on the stratum with rainwater.But the utilization rate of red mud only is about 15% at present, also not yet finds up to now the effective diameter that utilizes in a large number red mud.
In recent years, the comprehensive utilization of red mud has caused both domestic and externally generally to be paid attention to, and the research that relevant red mud is used comprises: with red mud do rubber and plastics filler, with red mud as pavior, prepare unburned red-mud coal ash brick, make alkali slag-red mud cement, red mud be applied to the research of cement concrete.Wherein most studies all is to be difficult to invested in plantization because utilization is few, efficient is not high or Financial cost is high.As:
Utilize red mud produce the research of cement (Ren Dongmei, Mao Yanan. the comprehensive utilization of red mud [J]. non-ferrous metals industry, 2002, [5]: 57-58), because red mud alkalinity height, the red mud proportioning is subjected to cement to contain the alkali index to restrict, make red mud be subjected to considerable restraint as the application of producing cement raw material, the comprehensive utilization ratio of red mud is 35%～50% only, and utilization ratio is lower.
Iron in the charcoal reduction red mud, the method that reclaims through magnetic separation process (Liao Chunfa, ginger state equality. from the technical study of recovering iron from red mud. Chinese Mining Industry. the 2nd phase .2007 February of the 16th volume), but because a large amount of SiO in the red mud
2, Al
2O
3, the materials such as CaO do not take full advantage of, and cost is higher, and utilization rate is low, is difficult to realize the utilization of the Comprehensive of red mud.
Summary of the invention
Task of the present invention provides and a kind ofly has wide range of applications, utilization ratio is higher, added value is high, the simple red mud comprehensive utilization method of technology.
For finishing above-mentioned task, the technical solution used in the present invention is: 0～16% calcium containing compound of 7～75% coke of red mud quality or hard coal, red mud quality or 0～645% aluminum contained compound are added in the red mud; Mix being placed in the electric furnace, melting and reducing under 1400～1800 ℃ of conditions is incubated 0.5～4 hour then, and is broken apart behind the naturally cooling.
The main chemical compositions of red mud is: SiO
2Be 10～23wt%, Fe
2O
3Be 7～40wt%, Al
2O
3Be that 6～20wt%, CaO are that 3～45wt%wt, MgO are 0.5～3wt%, K
2O is 0.1～0.5wt%, Na
2O is 2.0～11wt%, TiO
2Be 1～6wt%, burning mistake is 8～12wt%.
Wherein: calcium containing compound or be lime stone or for calcium hydroxide; Aluminum contained compound or be alumina or for grog; Electric furnace or be electric arc furnaces or for induction furnace.
Owing to adopt technique scheme, the present invention reduces red mud by high-temperature fusion.Under hot conditions, the SiO in the red mud
2And Fe
2O
3The Antaciron that is reduced into, Al
2O
3Generate calcium aluminate, Na with CaO
2O and K
2O at high temperature volatilizees, through refining cooling precipitation, broken apart Antaciron and the calcium aluminate material of obtaining.Prepared calcium aluminate material both can be used as the calcium aluminate refractory materials, can be used as the pre-melted slag in the Iron And Steel Industry again, and ferro-silicon can be as the reductor and the alloying constituent of steel-making, applied range, and the added value height has reached the high-efficiency comprehensive utilization of red mud.So the present invention have have wide range of applications, utilization ratio is higher, added value is high, the technology characteristic of simple.
Embodiment
Below in conjunction with embodiment, only the invention will be further described, rather than limiting the scope of the invention.
Embodiment 1
A kind of method of comprehensive utilization of red mud.Earlier the coke of 9～11wt% of red mud quality is mixed being placed in the electric arc furnaces with red mud, make the mixture melting under 1400～1500 ℃ of conditions, be incubated 0.5～1 hour, the upper strata is calcium aluminate material, and lower floor is Antaciron; Broken after naturally cooling off, separation obtains calcium aluminate and Antaciron piece then.The main phase of the calcium aluminate material of gained is CA
2And CA
6
Red mud in the present embodiment is Bayer process red mud, and its main chemical compositions is: SiO
2Be 18～20wt%, Fe
2O
3Be 35～40wt%, Al
2O
3Be that 18～20wt%, CaO are that 3～4wt%, MgO are 0.5～1wt%, K
2O is 0.1～0.3wt%, Na
2O is 6～11wt%, TiO
2Be that 1.5～2wt%, igloss amount are 9～12wt%.
Embodiment 2
A kind of method of comprehensive utilization of red mud.Earlier 4～6% Wingdales of 7～10% coke of red mud quality and red mud quality are mixed being placed in the electric arc furnace with red mud, CaO is 53.34wt% in the Wingdale; Make the mixture fusion then under 1500～1550 ℃ of conditions, be incubated 1～1.5 hour, the upper strata is a calcium aluminate material, and lower floor is a ferro-silicon; After broken behind the naturally cooling, separate, obtain calcium aluminate and ferro-silicon piece.The main phase of the calcium aluminate material of gained is CA
2
Red mud composition in the present embodiment is Bayer process red mud, and its main chemical compositions is: SiO
2Be 10～15wt%, Fe
2O
3Be 30～36%wt, Al
2O
3Be that 15～20wt%, CaO are that 3～10wt%, MgO are 0.5～1wt%, K
2O is 0.1～0.3wt%, Na
2O is 6～10wt%, TiO
2Be that 1.5～2wt%, igloss amount are 9～12wt%.
Embodiment 3
A kind of method of comprehensive utilization of red mud.Earlier the Wingdale of 6～14wt% of the hard coal of 7～11wt% of red mud quality and red mud quality is mixed being placed in the electric arc furnace with red mud, CaO is 53.34% in the Wingdale.Make the mixture melting and reducing then under 1500～1550 ℃ of conditions, be incubated 1～1.5 hour, the upper strata is calcium aluminate material, and lower floor is Antaciron; Finally by naturally rear broken, the separation of cooling, obtain calcium aluminate and Antaciron piece.The main thing of the calcium aluminate material of gained is CA mutually
2And CA.
Red mud composition in the present embodiment is Bayer process red mud, and its main chemical compositions is: SiO
2Be 11～15wt%, Fe
2O
3Be 35～38%wt, Al
2O
3Be that 18～20wt%, CaO are that 3～4wt%, MgO are 1～2wt%, K
2O is 0.1～0.3wt%, Na
2O is 6～11wt%, TiO
2Be that 1.5～2wt%, igloss amount are 9～12wt%.
Embodiment 4
A kind of method of comprehensive utilization of red mud.Earlier the Wingdale of 14～16wt% of the coke of 9～10wt% of red mud quality and red mud quality is mixed being placed in the electric arc furnace with red mud, CaO is 53.34wt% in the Wingdale; Make the mixture fusion then under 1550～1650 ℃ of conditions, be incubated 1.5～2 hours, the upper strata is a calcium aluminate material, and lower floor is a ferro-silicon; After broken behind the naturally cooling, separate, obtain calcium aluminate and ferro-silicon piece.The main phase of the calcium aluminate material of gained is CA, a small amount of CA
2
Red mud composition in the present embodiment is Bayer process red mud, and its main chemical compositions is: SiO
2Be 18～20wt%, Fe
2O
3Be 18～30wt%, Al
2O
3Be that 18～20wt%, CaO are that 3～4wt%, MgO are 0.5～1wt%, K
2O is 0.1～0.3wt%, Na
2O is 6～10wt%, TiO
2Be that 1.5～2wt%, igloss amount are 9～12wt%.
Embodiment 5
A kind of method of comprehensive utilization of red mud.Earlier 21～25wt% high grade bauxite of the hard coal of 10～13wt% of red mud quality and red mud quality is mixed with red mud and be placed in the electric arc furnace; Make the mixture fusion then under 1650～1750 ℃ of conditions, be incubated 2～3 hours, the upper strata is a calcium aluminate, and lower floor is a ferro-silicon; After broken behind the naturally cooling, separate, obtain calcium aluminate and ferro-silicon piece.The main phase of the calcium aluminate material of gained is CA
6With a small amount of CA
2
Red mud composition in the present embodiment is Bayer process red mud, and its main chemical compositions is: SiO
2Be 18～20wt%, Fe
2O
3Be 35～38wt%, Al
2O
3Be that 9～16wt%, CaO are that 3～4wt%, MgO are 0.5～1wt%, K
2O is 0.1～0.3wt%, Na
2O is 6～10wt%, TiO
2Be that 1.5～2wt%, igloss amount are 9～12wt%.
Embodiment 6
A kind of method of comprehensive utilization of red mud: the secondary alumina of 25～30wt% of the coke of 11～14wt% of red mud quality and red mud quality is mixed being placed in the electric arc furnace earlier with red mud; Make the mixture fusion then under 1650～1750 ℃ of conditions, be incubated 2～3 hours, the upper strata is a calcium aluminate, and lower floor is a ferro-silicon; After broken behind the naturally cooling, separate, obtain calcium aluminate and ferro-silicon piece.The main phase of the calcium aluminate material of gained is CA
6With a small amount of CA
2
Red mud composition in the present embodiment is Bayer process red mud, and its main chemical compositions is: SiO
2Be 18～20wt%, Fe
2O
3Be 35～38wt%, Al
2O
3Be that 18～20wt%, CaO are that 4～8wt%, MgO are 0.5～1wt%, K
2O is 0.1～0.3wt%, Na
2O is 6～10wt%, TiO
2Be that 1.5～2wt%, igloss amount are 9～12wt%.
Embodiment 7
A kind of method of comprehensive utilization of red mud.Earlier three grades of alumina of 30～35wt% of the hard coal of 12～17wt% of red mud quality and red mud quality are mixed with red mud and be placed in the induction furnace; Make the mixture fusion then under 1650～1750 ℃ of conditions, be incubated 2～3 hours, the upper strata is a calcium aluminate, and lower floor is a ferro-silicon; After broken behind the naturally cooling, separate, obtain calcium aluminate and ferro-silicon piece.The main phase of the calcium aluminate material of gained is CA
6With a small amount of CA
2
Red mud composition in the present embodiment is Bayer process red mud, and its main chemical compositions is: SiO
2Be 18～20wt%, Fe
2O
3Be 35～38wt%, Al
2O
3Be 18～20wt%,, CaO is that 5～7wt%, MgO are 0.5～1wt%, K
2O is 0.11～0.3wt%, Na
2O is 6～10wt%, TiO
2Be that 1.5～2wt%, igloss amount are 9～12wt%.
Embodiment 8
A kind of method of comprehensive utilization of red mud.Earlier the clay of 32～81wt% of the coke of 17～23wt% of red mud quality and red mud quality is mixed with red mud and be placed in the electric arc furnaces; The chemical composition of clay is SiO
2Be 53.67wt%, Fe
2O
3Be 0.33wt%, Al
2O
3Be 31.32wt%, CaO is 1.80wt%.
Make the mixture melting then under 1650～1750 ℃ of conditions, be incubated 2～3 hours, the upper strata is calcium aluminate, and lower floor is Antaciron; Finally by naturally rear broken, the separation of cooling, obtain calcium aluminate and Antaciron piece.The main phase of the calcium aluminate material of gained is CA
2And CA
6
Red mud composition in the present embodiment is Bayer process red mud, and its main chemical compositions is: SiO
2Be 18～20wt%, Fe
2O
3Be 35～38wt%, Al
2O
3Be that 18～20wt%, CaO are that 3～4wt%, MgO are 0.5～1wt%, K
2O is 0.1～0.3wt%, Na
2O is 6～10wt%, TiO
2Be that 1.5～2wt%, igloss amount are 9～12wt%.
Embodiment 9
A kind of method of comprehensive utilization of red mud.Earlier the high grade bauxite of 81～180wt% of the coke of 8～12wt% of red mud quality and red mud quality is mixed with red mud and be placed in the induction furnace; Make the mixture fusion then under 1750～1800 ℃ of conditions, be incubated 3～4 hours, the upper strata is a calcium aluminate, and lower floor is a ferro-silicon; After broken behind the naturally cooling, separate, obtain calcium aluminate and ferro-silicon piece.The main phase of the calcium aluminate material of gained is CA and CA
2
Red mud composition in the present embodiment is red mud from sintering process, and its main chemical compositions is: SiO
2Be 14～16wt%, Fe
2O
3Be 15～20wt%, Al
2O
3Be that 6～8wt%, CaO are that 40～45wt%, MgO are 1.5～3wt%, K
2O is 0.2～0.5wt%, Na
2O is 2～3wt%, TiO
2Be that 1.5～3wt%, igloss amount are 9～10wt%.
Embodiment 10
A kind of method of comprehensive utilization of red mud.Earlier three grades of alumina of 110～260wt% of the hard coal of 14～30wt% of red mud quality and red mud quality are mixed with red mud and be placed in the induction furnace; Make the mixture fusion then under 1750～1800 ℃ of conditions, be incubated 3～4 hours, the upper strata is a calcium aluminate, and lower floor is a ferro-silicon; After broken behind the naturally cooling, separate, obtain calcium aluminate and ferro-silicon piece.The main thing of the calcium aluminate material of gained is CA, CA mutually
2And CA6.
Red mud composition in the present embodiment is red mud from sintering process, and its main chemical compositions is: SiO
2Be 14～16wt%, Fe
2O
3Be 18～20wt%, Al
2O
3Be that 6～8wt%, CaO are that 10～30wt%, MgO are 1.5～3wt%, K
2O is 0.2～0.5wt%, Na
2O is 2～3wt%, TiO
2Be that 1.5～3wt%, igloss amount are 9～10wt%.
Embodiment 11
A kind of method of comprehensive utilization of red mud.Earlier 260～645wt% clay of the anthracite of 30～75wt% of red mud quality and red mud quality is mixed and be placed in the induction furnace; The main chemical compositions of clay is SiO
2Be 53.67wt%, Fe
2O
3Be 0.33wt%, Al
2O
3Be 31.32wt%, CaO is 1.80wt%.Make the mixture melting then under 1750～1800 ℃ of conditions, be incubated 3.5～4 hours, the upper strata is calcium aluminate, and lower floor is Antaciron; Finally by naturally rear broken, the separation of cooling, obtain calcium aluminate and Antaciron piece.The main phase of the calcium aluminate material of gained is CA and CA
2
Red mud composition in the present embodiment is red mud from sintering process, and its main chemical compositions is: SiO
2Be 14～16wt%, Fe
2O
3Be 18～20wt%, Al
2O
3Be that 6～8wt%, CaO are that 15～40wt%, MgO are 1.5～3wt%, K
2O is 0.2～0.5wt%, Na
2O is 2～3wt%, TiO
2Be that 1.5～3wt%, igloss amount are 9～10wt%.
Embodiment 12:
A kind of method of comprehensive utilization of red mud.Earlier 90～92wt% high grade bauxite of the coke of 7～9wt% of red mud quality and red mud quality is mixed with red mud and be placed in the electric arc furnace; Make the mixture fusion then under 1750～1800 ℃ of conditions, be incubated 3～4 hours, the upper strata is a calcium aluminate, and lower floor is a ferro-silicon; After broken behind the naturally cooling, separate, obtain calcium aluminate and ferro-silicon piece.The main phase of the calcium aluminate material of gained is CA, and a small amount of CA
2
Red mud composition in the present embodiment is the combination method red mud, and its main chemical compositions is: SiO
2Be 16～23wt%, Fe
2O
3Be 7～16wt%, Al
2O
3Be that 8～10wt%, CaO are that 42～45wt%, MgO are 0.5～1wt%, K
2O is 0.1～0.3wt%, Na
2O is 3～6wt%, TiO
2Be that 3～6wt%, igloss amount are 8～10wt%.
This specific embodiment under hot conditions, the SiO in the red mud
2And Fe
2O
3The Antaciron that is reduced into, Al
2O
3Generate calcium aluminate system, Na with CaO
2O and K
2O at high temperature volatilizees, and obtains Antaciron and calcium aluminate based material through concise precipitation refrigerated separation.The calcium aluminate based material both can be used as the calcium aluminate refractory materials, can be used as the pre-melted slag in the Iron And Steel Industry again, and ferro-silicon can be as the reductor and the alloying constituent of steel-making, applied range, and the added value height has reached the high-efficiency comprehensive utilization of red mud.
Claims (4)
1, a kind of method of comprehensive utilization of red mud is characterized in that 0～16% calcium containing compound of 7～75% coke of red mud quality or hard coal, red mud quality or 0～645% aluminum contained compound are added in the red mud; Mix being placed in the electric furnace, melting and reducing under 1400～1800 ℃ of conditions is incubated 0.5～4 hour then, and is broken apart behind the naturally cooling;
The main chemical compositions of red mud is: SiO
2Be 10～23wt%, Fe
2O
3Be 7～40wt%, Al
2O
3Be that 6～20wt%, CaO are that 3～45wt%, MgO are 0.5～3wt%, K
2O is 0.1～0.5wt%, Na
2O is 2～11wt%, TiO
2Be 1～6wt%, burning mistake is 8～12wt%.
2, the method for comprehensive utilization of red mud according to claim 1 is characterized in that described calcium containing compound or for Wingdale or for calcium hydroxide.
3, the method for comprehensive utilization of red mud according to claim 1 is characterized in that described aluminum contained compound or for alumina or for chamotte.
4, the method for comprehensive utilization of red mud according to claim 1 is characterized in that described electric furnace or for electric arc furnace or for induction furnace.
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| CN101429582B (en) * | 2008-12-04 | 2010-06-16 | 武汉科技大学 | Method for producing ferro-silicon alloy and calcium aluminate material with red mud and aluminum ash |
| CN101984080A (en) * | 2010-11-29 | 2011-03-09 | 董亚飞 | Process and device for separating iron and aluminum silica slag from red mud and removing alkali metal |
| CN102174664A (en) * | 2010-11-24 | 2011-09-07 | 胡长春 | Comprehensive utilization method of red mud coal-base rotary kiln method |
| CN102787210A (en) * | 2012-06-28 | 2012-11-21 | 辽宁中汇环保科技有限公司 | Calcareous premelted composite deoxidation and desulfurization agent for low-cost steel-making and method for preparing same |
| CN103898331A (en) * | 2014-03-28 | 2014-07-02 | 中国铝业股份有限公司 | Method for comprehensive recovery of tantalum and niobium from red mud |
| CN105358486A (en) * | 2013-07-05 | 2016-02-24 | 奥图泰(芬兰)公司 | Process and plant for purifying red mud |
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| CN102174664A (en) * | 2010-11-24 | 2011-09-07 | 胡长春 | Comprehensive utilization method of red mud coal-base rotary kiln method |
| CN101984080A (en) * | 2010-11-29 | 2011-03-09 | 董亚飞 | Process and device for separating iron and aluminum silica slag from red mud and removing alkali metal |
| CN101984080B (en) * | 2010-11-29 | 2012-05-23 | 董亚飞 | Process and device for separating iron and aluminum silica slag from red mud and removing alkali metal |
| CN102787210A (en) * | 2012-06-28 | 2012-11-21 | 辽宁中汇环保科技有限公司 | Calcareous premelted composite deoxidation and desulfurization agent for low-cost steel-making and method for preparing same |
| CN105358486A (en) * | 2013-07-05 | 2016-02-24 | 奥图泰(芬兰)公司 | Process and plant for purifying red mud |
| CN105358486B (en) * | 2013-07-05 | 2018-02-09 | 奥图泰(芬兰)公司 | Method and apparatus for purifying red soil |
| CN103898331A (en) * | 2014-03-28 | 2014-07-02 | 中国铝业股份有限公司 | Method for comprehensive recovery of tantalum and niobium from red mud |
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| CN106699132B (en) * | 2016-11-23 | 2020-06-23 | 贵州省过程工业技术研究中心 | Method for producing heat-insulating material by utilizing red mud |
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