CN103074484A - Comprehensive treatment method of oolitic hematite containing phosphorus and red mud - Google Patents
Comprehensive treatment method of oolitic hematite containing phosphorus and red mud Download PDFInfo
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- CN103074484A CN103074484A CN2013100156621A CN201310015662A CN103074484A CN 103074484 A CN103074484 A CN 103074484A CN 2013100156621 A CN2013100156621 A CN 2013100156621A CN 201310015662 A CN201310015662 A CN 201310015662A CN 103074484 A CN103074484 A CN 103074484A
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- red mud
- oolitic hematite
- phosphorous
- coal
- integrated conduct
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Abstract
The invention discloses a comprehensive treatment method of oolitic hematite containing phosphorus and red mud, which is characterized by comprising the following steps: mixing raw ore of oolitic hematite, red mud and coal according to a certain proportion, crushing and uniformly mixing; carrying out metallization reduction roasting on crushed ore; slowly cooling the calcine to 400-750 ℃, then quenching with water, and carrying out ball milling on the water-quenched calcine; magnetically separating the ball-milling ore pulp to obtain sponge-like iron powder and tailings; and melting and separating the sponge-like iron powder to obtain high-quality molten iron containing less than 0.01 percent of phosphorus. The method has the advantages of short flow, continuity, energy conservation, high capacity, high resource utilization rate and environmental friendliness; the problems of high stacking construction cost, high maintenance cost and the like of the red mud can be solved, and the product can be used as a high-quality raw material for steelmaking and has high product output value.
Description
Technical field
The integrated conduct method of a kind of phosphorous oolitic hematite and red mud, the rear metallization of the waste material red mud batching reducing roasting-magnetic separation-molten minute that relates to a kind of phosphorous oolitic hematite raw ore and alumina industry output prepares the method for molten iron.
Background technology
The oolitic hematite disseminated grain size is superfine, and often with spathic iron ore, chamosite and phosphorus ore containing symbiosis or mutual parcel, be present domestic and international one of iron ore type of generally acknowledged the most difficult choosing.Domestic oolitic hematite, limonite resource reserve are very large, and two kinds of resources have been added up 6,000,000,000 tons, and wherein 1/9 of the iron ore deposit reserves is oolitic hematite.Oolitic hematite often forms large-scale mine, for example a surname of Clinton's iron ore of Lorraine iron ore, the U.S. of France and northern China dragon formula iron ore, southern Ningxiang formula iron ore, this type of resource foreign matter of phosphor, aluminium, silicon equal size height, development difficulty is very large, not yet obtains at present the effective exploitation utilization.
At present, the conventional treatment process of phosphorous oolitic hematite is mainly physical concentration, flotation and reduction roasting magnetic separation etc., the process dephosphorization rate is low, simultaneously the impurity such as effective elimination aluminium silicon, iron concentrate grade is low, iron recovery is low, cost is high, larger to environmental hazard.
The employing of recent development is added dephosphorizing agent to phosphorous oolitic hematite reducing roasting-magnetic separation technology, application number is 200910079152.4, denomination of invention for the Patent Application Publication of " a kind of processing method with directly producing spongy iron from high-phosphor oolitic hematite " adding account for the dephosphorizing agent yellow soda ash of high-phosphor oolitic hematite weight 20～30%, take coal as reductive agent at 900～1000 ℃ of lower reducing roasting 30～40min, then with low intensity magnetic separation method recovery metallic iron wherein, this flow process can obtain more than 90%, the product of phosphorus content～0.08%.But this technique need add 20～30% yellow soda ash, and the additive cost is high, and with the adding of a large amount of yellow soda ash, the calcining fusing point reduces greatly, and roasting process easily causes body of heater bonding wall built-up, and can make impurity Na in the concentrate
2O content is high.
Red mud is that bauxite refines the waste that produces in the alumina process, because it is gained the name for crimson look mud.Along with the development of aluminium industry, present about 6,000 ten thousand tons of red muds of the annual output in the whole world, be more than 4,500,000 tons red mud quantity discharged every year of China.Most of alumina producers are that red mud is piled up or the impouring deep-sea in the world.Contain the metals such as a large amount of iron, aluminium, sodium, calcium in the red mud, storing up of red mud not only takies a large amount of soils and farmland, expends more stockyard construction and maintenance cost, causes serious water pollution, and wasted a large amount of metals resources.Therefore, the efficient recovery of the comprehensive regulation of red mud and metals resources thereof becomes the focus of people's growing interest.The processing of red mud mainly still effluxes front employing high intensity magnetic separation, the Extraction parts iron ore concentrate, and mine tailing is directly stored up.
Summary of the invention
The objective of the invention is the deficiency that exists for above-mentioned existing Technology, provide that a kind of technique is simple, cost is low, can realize the comprehensive phosphorous oolitic hematite of producing of industrialization and the integrated conduct method of red mud.
The objective of the invention is to be achieved through the following technical solutions.
The integrated conduct method of a kind of phosphorous oolitic hematite and red mud is characterized in that described treatment step comprises successively:
(1) oolitic hematite raw ore, red mud, coal are carried out mix, fragmentation;
(2) broken material with step (1) carries out reducing roasting;
(3) calcining of reducing roasting carries out shrend, ball milling;
(4) carry out magnetic separation behind the ball milling and obtain iron powder and mine tailing;
(5) iron powder that step (4) is obtained obtained molten iron in molten minute.
The integrated conduct method of a kind of phosphorous oolitic hematite of the present invention and red mud, the ingredients by weight ratio that it is characterized in that the mix process of described step (1) is: phosphorus oolitic hematite 60%～95%, red mud 5%～40%, and be 15%～30% coal of phosphorus oolitic hematite and red mud gross weight.
The integrated conduct method of a kind of phosphorous oolitic hematite of the present invention and red mud is characterized in that coal that the mix process is allocated into is one or more in brown coal, bituminous coal, the hard coal.
The integrated conduct method of a kind of phosphorous oolitic hematite of the present invention and red mud is characterized in that the broken pelletization of described step (1), and particle size after cracking is to surpass 90% less than 5mm.
The integrated conduct method of a kind of phosphorous oolitic hematite of the present invention and red mud, it is characterized in that in the reducing roasting process of described step (2), reducing roasting equipment adopts a kind of in rotary kiln, rotary hearth furnace, the multiple hearth furnace, thermal source is coal gas or coal, combustion-supporting gas is air, the high-temperature zone temperature is 950～1150 ℃, and the high-temperature zone residence time is 0.5～3h, controls out kiln gas CO/CO
2Be 3.5～4.5.
The integrated conduct method of a kind of phosphorous oolitic hematite of the present invention and red mud, the shrend mechanical milling process that it is characterized in that described step (3) is through the cooling of sealing cooling cylinder with step (2) gained calcining, shrend chilling after 400～750 ℃, the calcining ball milling, grinding particle size is for to account for 85～95% less than 0.074mm.
The integrated conduct method of a kind of phosphorous oolitic hematite of the present invention and red mud, the magnetic separation sepn process that it is characterized in that described (4) is that step (3) ball milling ore pulp is carried out magnetic separation, advance ore deposit pulp solids mass concentration and be controlled at 15～25%, magneticstrength is controlled at 800～1500 oersteds, obtains concentrate iron powder and mine tailing.
The integrated conduct method of a kind of phosphorous oolitic hematite of the present invention and red mud, the molten minute process that it is characterized in that described step (5) is that the iron powder employing electric furnace that step (4) obtains is melted minute, add 0.1%～2% slag former, 1550～1650 ℃ of temperature controls, time 1～3h obtains molten iron.
The integrated conduct method of a kind of phosphorous oolitic hematite of the present invention and red mud is characterized in that described slag former is SiO
2, CaO, CaCO
3In one or more.
The integrated conduct method of a kind of phosphorous oolitic hematite of the present invention and red mud, main chemical reactions is as follows:
Batching is according to SiO in the phosphorous oolitic hematite
2High Deng acidic oxide or compounds content, be acid ore deposit, and CaO, Al in the red mud
2O
3, Na
2CO
3High in basic oxide or compounds content, be alkaline ore deposit, the reaction that the metallization reducing roasting process exists after its batching mainly contains:
2C+O
2?=2CO
Fe
2O
3+CO=2FeO+CO
2
FeO+CO=?Fe+CO
2
Fe
2O
3+3CO?=2Fe+3CO
2
Fe
2O
3+?2C?=2Fe+3CO
CaO+SiO
2?=?CaO·SiO
2
Al
2O
3+?SiO
2=?Al
2O
3·SiO
2
Na
2CO
3+SiO
2=Na
2O·SiO
2+CO
2
4SiO
2+Al
2O
3+?Na
2CO
3=Na
2O·Al
2O
3·4SiO
2+CO
2
CaO+?Al
2O
3?=?CaO·Al
2O
3
Ca
3(PO
4)
2+5C+3SiO
2=P
2(g)+5CO+3CaO·SiO
2
Compare with the ferruginization sinter processs such as yellow soda ash, Sodium sulfate anhydrous.min(99) of allocating into of traditional washing process and recently exploitation, method flow weak point of the present invention, serialization, energy-conservation, production capacity is large, resource utilization is high, environmentally friendly; Raw ore need not fine grinding, directly be crushed to-5mm gets final product; Allocate the alkaline scrap material red mud into, do not add other additive, cost is low, also can solve the problems such as cost of erection and maintenance cost height of storing up of red mud; With the roasting of red mud batching, because of a large amount of Al in the red mud
2O
3Exist, with the SiO in the oolitic hematite
2In conjunction with, the generation of energy establishment fayalite, and can make the calcining Melting point elevation, prevent the bonding wall built-up of roasting process; The magnetic separation separation efficiency of the impurity such as iron and phosphorus, aluminium, silicon is high, and phosphorus, aluminium, silicon decreasing ratio height and iron recovery are high; Molten minute output is phosphorous less than 0.01% high-quality molten iron, can be used as the high quality raw material of steel-making, and product value is high.The overstocked problem of storing up of aluminium industry waste material is alleviated or removed to effective comprehensive treating process red mud, and huge realistic meaning and social benefit are arranged.
Method of the present invention will be granulated behind phosphorous oolitic hematite raw ore, red mud, the reductive agent mixing, and the pellet reducing roasting of metallizing in reduction furnace makes the Fe in oolitic hematite and the red mud
2O
3Be reduced into Fe, and impurity forms the compound without magnetic, calcining obtains iron content through mill ore magnetic selection〉90% concentrate class iron sponge powder and mine tailing.Molten minute further removing impurities of concentrate obtains phosphorous less than 0.01% high-quality molten iron.Mine tailing can be used for making cement, does not produce secondary pollution.
Description of drawings
Fig. 1 process flow sheet of the present invention.
Embodiment
The integrated conduct method of a kind of phosphorous oolitic hematite and red mud is processed liking phosphorous oolitic hematite raw ore and Bayer process red mud, and its treatment step comprises successively:
(1) oolitic hematite raw ore, red mud, coal are carried out behind the batch mixing broken;
(2) particle of step (1) is metallized reducing roasting;
(3) calcining shrend chilling behind slow cooling to 400～750 ℃, shrend calcining ball milling;
(4) carry out magnetic separation behind the ball milling and obtain iron powder and mine tailing;
(5) iron powder that step (4) is obtained obtained phosphorous less than 0.01% high-quality molten iron in molten minute.
The integrated conduct method of a kind of phosphorous oolitic hematite and red mud, the blending process of its described step (1), phosphorous oolitic hematite 60～95%, red mud 5～40%, and accounting for the coal of total ore deposit weight 15～30%, the coal of allocating into is one or more in brown coal, bituminous coal, the hard coal.
The integrated conduct method of a kind of phosphorous oolitic hematite and red mud, the broken pelletization behind the batch mixing, particle size after cracking is to surpass 90% less than 5mm.
The integrated conduct method of a kind of phosphorous oolitic hematite and red mud, in the metallization reducing roasting process of described step (2), reducing roasting equipment adopts a kind of in rotary kiln, rotary hearth furnace, the multiple hearth furnace, thermal source is coal gas or coal, combustion-supporting gas is air, the high-temperature zone temperature is 950～1150 ℃, and the high-temperature zone residence time is 0.5～3h, controls out kiln gas CO/CO
2Be 3.5～4.5.
The integrated conduct method of a kind of phosphorous oolitic hematite and red mud, the calcining shrend mechanical milling process of described step (3) is through the cooling of sealing cooling cylinder with step (2) gained calcining, shrend chilling after 400～750 ℃, the calcining ball milling, grinding particle size is for to account for 85～95% less than 0.074mm.
The integrated conduct method of a kind of phosphorous oolitic hematite and red mud, the magnetic separation sepn process of described step (4) is that step (3) ball milling ore pulp is carried out magnetic separation, advance ore deposit pulp solids mass concentration and be controlled at 15～25%, magneticstrength is controlled at 800～1500 oersteds, obtains concentrate iron powder and mine tailing.
The integrated conduct method of a kind of phosphorous oolitic hematite and red mud,, the molten minute process of the electric furnace of described step (5) is molten the dividing of iron powder that step (4) is obtained, add 0.1～2% slag former, 1550～1650 ℃ of temperature controls, time 1～3h obtains phosphorous less than 0.01% high-quality molten iron; Described slag former is SiO
2, CaO, CaCO
3In one or more.
Embodiment 1
Join the ore deposit: (TFe 43%, and P 0.9%, Al for oolitic hematite
2O
37%, SiO
222%) 48 parts, (TFe 24%, and CaO 14%, Al for red mud
2O
313%, SiO
29%, Na 4%) 30 parts, 22 parts in bituminous coal is crushed to less than 5mm behind the mixing and accounts for 96%,
Roasting: particle metallization reducing roasting, 1000 ℃ of control temperature, CO/CO in the inner flue gas of the stove
2=3.8, residence time 2h, the shrend after the heat exchange cooling cylinder is cooled to 500 ℃ of output calcining.
The ball milling magnetic separation: shrend calcining ball milling is sized mixing behind the ball milling to pulp density 20% to accounting for 94% less than 0.074mm, magnetic separation under 1500 oersteds, and (TFe 90%, and P 0.13%, Al to obtain concentrate class iron sponge powder
2O
31.8%, SiO
23.0%), wherein the iron elimination factor 92%, phosphorus decreasing ratio 90%.
Molten minute: the class iron sponge powder carried out high temperature melting and divides, 1550 ℃ of control temperature, and constant temperature time 2h obtains high-quality molten iron (P 0.004%).
Embodiment two
Join the ore deposit: (TFe 43%, and P 0.9%, Al for oolitic hematite
2O
37%, SiO
222%) 64 parts, (TFe 24%, and CaO 14%, Al for red mud
2O
313%, SiO
29%, Na 4%) 16 parts, 20 parts in hard coal is crushed to less than 5mm behind the mixing and accounts for 95%,
Roasting: particle metallization reducing roasting, 1150 ℃ of control temperature, CO/CO in the inner flue gas of the stove
2=4.0, residence time 0.5h, the shrend after the heat exchange cooling cylinder is cooled to 600 ℃ of output calcining.
The ball milling magnetic separation: shrend calcining ball milling is sized mixing behind the ball milling to pulp density 20% to accounting for 95% less than 0.074mm, magnetic separation under 1000 oersteds, and (TFe 93%, and P 0.14%, Al to obtain concentrate class iron sponge powder
2O
31.3%, SiO
22.8%), wherein the iron elimination factor 93%, phosphorus decreasing ratio 91%.
Molten minute: the class iron sponge powder carried out high temperature melting and divides, 1600 ℃ of control temperature, and constant temperature time 1.5h obtains high-quality molten iron (P 0.005%).
Claims (9)
1. the integrated conduct method of a phosphorous oolitic hematite and red mud is characterized in that described treatment step comprises successively:
(1) oolitic hematite raw ore, red mud, coal are carried out mix, fragmentation;
(2) broken material with step (1) carries out reducing roasting;
(3) calcining of reducing roasting carries out shrend, ball milling;
(4) carry out magnetic separation behind the ball milling and obtain iron powder and mine tailing;
(5) iron powder that step (4) is obtained obtained molten iron in molten minute.
2. the integrated conduct method of a kind of phosphorous oolitic hematite according to claim 1 and red mud, the ingredients by weight ratio that it is characterized in that the mix process of described step (1) is: phosphorus oolitic hematite 60%～95%, red mud 5%～40%, and be 15%～30% coal of phosphorus oolitic hematite and red mud gross weight.
3. the integrated conduct method of a kind of phosphorous oolitic hematite according to claim 1 and red mud is characterized in that coal that the mix process is allocated into is one or more in brown coal, bituminous coal, the hard coal.
4. the integrated conduct method of a kind of phosphorous oolitic hematite according to claim 1 and red mud is characterized in that the broken pelletization of described step (1), and particle size after cracking is to surpass 90% less than 5mm.
5. the integrated conduct method of a kind of phosphorous oolitic hematite according to claim 1 and red mud, it is characterized in that in the reducing roasting process of described step (2), reducing roasting equipment adopts a kind of in rotary kiln, rotary hearth furnace, the multiple hearth furnace, thermal source is coal gas or coal, combustion-supporting gas is air, the high-temperature zone temperature is 950～1150 ℃, and the high-temperature zone residence time is 0.5～3h, controls out kiln gas CO/CO
2Be 3.5～4.5.
6. the integrated conduct method of a kind of phosphorous oolitic hematite according to claim 1 and red mud, the shrend mechanical milling process that it is characterized in that described step (3) is through the cooling of sealing cooling cylinder with step (2) gained calcining, shrend chilling after 400～750 ℃, the calcining ball milling, grinding particle size is for to account for 85～95% less than 0.074mm.
7. the integrated conduct method of a kind of phosphorous oolitic hematite according to claim 1 and red mud, the magnetic separation sepn process that it is characterized in that described (4) is that step (3) ball milling ore pulp is carried out magnetic separation, advance ore deposit pulp solids mass concentration and be controlled at 15～25%, magneticstrength is controlled at 800～1500 oersteds, obtains concentrate iron powder and mine tailing.
8. the integrated conduct method of a kind of phosphorous oolitic hematite according to claim 1 and red mud, the molten minute process that it is characterized in that described step (5) is that the iron powder employing electric furnace that step (4) obtains is melted minute, add 0.1%～2% slag former, 1550～1650 ℃ of temperature controls, time 1～3h obtains molten iron.
9. the integrated conduct method of a kind of phosphorous oolitic hematite according to claim 1 and red mud is characterized in that described slag former is SiO
2, CaO, CaCO
3In one or more.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103276193A (en) * | 2013-06-21 | 2013-09-04 | 山东鲁铭高温材料科技有限公司 | Method and device for preparing powdered iron through magnetizing low-iron red mud |
| CN104988322A (en) * | 2015-08-04 | 2015-10-21 | 江苏省冶金设计院有限公司 | Comprehensive processing method of red mud and acetylene sludge |
| CN105177277A (en) * | 2015-08-04 | 2015-12-23 | 江苏省冶金设计院有限公司 | Comprehensive treatment method of red mud and laterite-nickel ore |
| CN106636520A (en) * | 2016-12-06 | 2017-05-10 | 江苏省冶金设计院有限公司 | System and method for preparing metallized pellet |
| CN108004421A (en) * | 2017-11-10 | 2018-05-08 | 广西生富锑业科技股份有限公司 | A kind of stibnite oxygen enriched molten bath melting processing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103276193A (en) * | 2013-06-21 | 2013-09-04 | 山东鲁铭高温材料科技有限公司 | Method and device for preparing powdered iron through magnetizing low-iron red mud |
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| CN108004421A (en) * | 2017-11-10 | 2018-05-08 | 广西生富锑业科技股份有限公司 | A kind of stibnite oxygen enriched molten bath melting processing method |
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