CN103074484B - Method for comprehensively treating phosphorus-containing oolitic hematite and red mud - Google Patents

Method for comprehensively treating phosphorus-containing oolitic hematite and red mud Download PDF

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CN103074484B
CN103074484B CN201310015662.1A CN201310015662A CN103074484B CN 103074484 B CN103074484 B CN 103074484B CN 201310015662 A CN201310015662 A CN 201310015662A CN 103074484 B CN103074484 B CN 103074484B
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red mud
oolitic hematite
coal
phosphorous
integrated conduct
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CN103074484A (en
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王成彦
尹飞
揭晓武
何发钰
陈永强
阮书锋
杨卜
杨永强
居中军
李强
王军
张永禄
邢鹏
郜伟
柳杨
王振文
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Beijing General Research Institute of Mining and Metallurgy
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Abstract

The invention discloses a method for comprehensively treating phosphorus-containing oolitic hematite and red mud, which is characterized by comprising the following steps: after mixing crude ore of the oolitic hematite, the red mud and coal according to a certain proportion, grinding and uniformly mixing; carrying out ore crushing and metallized reduction roasting; after slowly cooling the roasted product to a temperature of 400 to 750 DEG C, carrying out water quenching and shock cooling and carrying out ball milling on the water-quenched roasted product; carrying out magnetic separation on the ball-milled ore pulp to obtain similar sponge iron powder and tailings; and melting the similar sponge iron powder to obtain high-quality molten iron with phosphorus content of less than 0.01%. The method disclosed by the invention has a short flow, is continuous, is energy-saving, has high productivity, has high resource utilization rate and is environmental-friendly; the problems of high stacking construction cost of the red mud, high maintenance cost and the like can be solved; and the product can be used as a high-quality raw material for steelmaking and has high output.

Description

The integrated conduct method of a kind of phosphorous oolitic hematite and red mud
Technical field
An integrated conduct method for phosphorous oolitic hematite and red mud, a method for molten iron is prepared in the rear metallization of the waste material red mud batching reducing roasting-magnetic separation-molten point that relates to a kind of phosphorous oolitic hematite raw ore and alumina industry output.
Background technology
Oolitic hematite disseminated grain size is superfine, and often with spathic iron ore, chamosite and phosphorus ore containing symbiosis or parcel mutually, be one of iron ore type of generally acknowledged the most difficult choosing both at home and abroad at present.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 iron ore deposit reserves is oolitic hematite.Oolitic hematite often forms large-scale mine, for example Lorraine iron ore of France, Clinton's iron ore of the U.S. and a surname of northern China dragon formula iron ore, southern Ningxiang formula iron ore, this type of resource foreign matter of phosphor, aluminium, silicon equal size are high, and development difficulty is very large, not yet obtains at present effective exploitation utilization.
At present, the conventional treatment process of phosphorous oolitic hematite is mainly physical concentration, flotation and reduction roasting magnetic separation etc., 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 is the Patent Application Publication of " a kind of processing method with directly producing spongy iron from high-phosphor oolitic hematite " adds the dephosphorizing agent sodium carbonate that accounts for high-phosphor oolitic hematite weight 20~30%, taking coal as reductive agent at 900~1000 DEG C reducing roasting 30~40min, then reclaim metallic iron wherein by low intensity magnetic separation method, this flow process can obtain more than 90%, the product of phosphorus content~0.08%.But this technique need add 20~30% sodium carbonate, additive cost is high, and with adding of a large amount of sodium carbonate, calcining fusing point reduces greatly, and roasting process easily causes body of heater bonding wall built-up, and can make impurity Na in concentrate 2o content is high.
Red mud, is that bauxite refines the waste producing in alumina process, because it is gained the name for crimson look mud.Along with the development of aluminium industry, approximately 6,000 ten thousand tons of red muds of the annual output in the whole world at present, the red mud quantity discharged of China is more than 4,500,000 tons every year.Most of alumina producers are that red mud is piled up or impouring deep-sea in the world.In red mud, contain the metals such as a large amount of iron, aluminium, sodium, calcium, 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 comprehensive regulation of red mud and the efficient recovery of metals resources thereof become the focus of people's growing interest.Before the main or outer row of processing of red mud, adopt high intensity magnetic separation, Extraction parts iron ore concentrate, mine tailing is directly stored up.
Summary of the invention
The object of the invention is the deficiency existing 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 object of the invention is to be achieved through the following technical solutions.
An integrated conduct method for 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 to mix, fragmentation; The ingredients by weight ratio of its mix process is: phosphorus oolitic hematite 60%~95%, and red mud 5%~40%, and be 15%~30% coal of phosphorus oolitic hematite and red mud gross weight;
(2) broken material of step (1) is carried out to reducing roasting; In its reducing roasting process, reducing roasting equipment adopts the one in rotary kiln, rotary hearth furnace, multiple hearth furnace, and thermal source is coal gas or coal, and combustion-supporting gas is air, and high-temperature zone temperature is 950~1150 DEG C, and the high-temperature zone residence time is 0.5~3h, controls out kiln gas CO/CO 2be 3.5~4.5;
(3) calcining of reducing roasting carries out shrend, ball milling;
(4) after ball milling, carry out magnetic separation and obtain iron powder and mine tailing;
(5) iron powder step (4) being obtained obtains molten iron molten dividing.
The integrated conduct method of a kind of phosphorous oolitic hematite of the present invention and red mud, is characterized in that coal that mix process is allocated into is one or more in brown coal, bituminous coal, 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 described broken pelletization of step (1), and particle size after cracking exceedes 90% for being less than 5mm.
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 that step (2) gained calcining is cooling through sealing cooling cylinder, to shrend chilling after 400~750 DEG C, calcining ball milling, grinding particle size accounts for 85~95% for being 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 to magnetic separation, enter 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 point process that it is characterized in that described step (5) is that iron powder employing electric furnace that step (4) is obtained melts point, add 0.1%~2% slag former, 1550~1650 DEG C 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 phosphorous oolitic hematite 2high Deng acidic oxide or compounds content, be acid ore deposit, and CaO, Al in red mud 2o 3, Na 2cO 3high in basic oxide or compounds content, be alkaline ore deposit, the reaction that after its batching, metallization reducing roasting process exists 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
With allocating into compared with the ferruginization such as sodium carbonate, Sodium sulfate anhydrous.min(99) sinter process of traditional washing process and exploitation recently, method flow of the present invention is short, serialization, energy-conservation, production capacity is large, resource utilization is high, environmentally friendly; Raw ore, without fine grinding, is directly crushed to-5mm; Allocate alkaline scrap material red mud into, do not add other additive, cost is low, also can solve the problem 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 red mud 2o 3exist, with the SiO in oolitic hematite 2in conjunction with, the generation of fayalite can be effectively suppressed, and calcining Melting point elevation can be made, 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 is high and iron recovery is high; Melt the phosphorous high-quality molten iron that is less than 0.01% of point output, can be used as the high quality raw material of steel-making, product value is high.Effectively comprehensive treating process red mud, the overstocked problem of storing up of alleviation or releasing aluminium industry waste material, has huge realistic meaning and social benefit.
Method of the present invention, mixes rear granulation by phosphorous oolitic hematite raw ore, red mud, reductive agent, and the pellet reducing roasting of metallizing in reduction furnace, makes the Fe in oolitic hematite and red mud 2o 3be reduced into Fe, and impurity forms the compound without magnetic, calcining, through mill ore magnetic selection, obtains concentrate class iron sponge powder and the mine tailing of iron content >90%.The molten point further removing impurities of concentrate, obtains the phosphorous high-quality molten iron that is less than 0.01%.Mine tailing can be used for manufacturing cement, does not produce secondary pollution.
Brief description of the drawings
Fig. 1 process flow sheet of the present invention.
Embodiment
An integrated conduct method for phosphorous oolitic hematite and red mud, handling object is phosphorous oolitic hematite raw ore and Bayer process red mud, its treatment step comprises successively:
(1) oolitic hematite raw ore, red mud, coal are carried out after batch mixing broken;
(2) particle of step (1) is metallized reducing roasting;
(3) calcining shrend chilling behind slow cooling to 400~750 DEG C, shrend calcining ball milling;
(4) after ball milling, carry out magnetic separation and obtain iron powder and mine tailing;
(5) iron powder step (4) being obtained obtains the phosphorous high-quality molten iron that is less than 0.01% molten dividing.
The integrated conduct method of a kind of phosphorous oolitic hematite and red mud, the blending process of the step (1) described in it, 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, hard coal.
An integrated conduct method for phosphorous oolitic hematite and red mud, the broken pelletization after batch mixing, particle size after cracking exceedes 90% for being 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 the one in rotary kiln, rotary hearth furnace, multiple hearth furnace, thermal source is coal gas or coal, combustion-supporting gas is air, high-temperature zone temperature is 950~1150 DEG C, 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 that step (2) gained calcining is cooling through sealing cooling cylinder, to shrend chilling after 400~750 DEG C, calcining ball milling, grinding particle size accounts for 85~95% for being 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 to magnetic separation, enter 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.
An integrated conduct method for phosphorous oolitic hematite and red mud,, the molten point process of 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 DEG C of temperature controls, time 1~3h, obtains the phosphorous high-quality molten iron that is less than 0.01%; Described slag former is SiO 2, CaO, CaCO 3in one or more.
Embodiment 1
Join ore deposit: oolitic hematite (TFe 43%, P 0.9%, Al 2o 37%, SiO 222%) 48 parts, red mud (TFe 24%, CaO 14%, Al 2o 313%, SiO 29%, Na 4%) 30 parts, 22 parts, bituminous coal, is crushed to after mixing and is less than 5mm and accounts for 96%,
Roasting: particle metallization reducing roasting, control 1000 DEG C of temperature, CO/CO in inner flue gas of the stove 2=3.8, residence time 2h, the shrend after heat exchange cooling cylinder is cooled to 500 DEG C of output calcining.
Ball milling magnetic separation: shrend calcining is milled to and is less than 0.074mm and accounts for 94%, sizes mixing to pulp density 20% after ball milling, and magnetic separation under 1500 oersteds, obtains concentrate class iron sponge powder (TFe 90%, P 0.13%, Al 2o 31.8%, SiO 23.0%), wherein iron elimination factor 92%, phosphorus decreasing ratio 90%.
Molten point: class iron sponge powder carries out high temperature melting and divides, control 1550 DEG C of temperature, constant temperature time 2h, obtains high-quality molten iron (P 0.004%).
Embodiment bis-
Join ore deposit: oolitic hematite (TFe 43%, P 0.9%, Al 2o 37%, SiO 222%) 64 parts, red mud (TFe 24%, CaO 14%, Al 2o 313%, SiO 29%, Na 4%) 16 parts, 20 parts, hard coal, is crushed to after mixing and is less than 5mm and accounts for 95%,
Roasting: particle metallization reducing roasting, control 1150 DEG C of temperature, CO/CO in inner flue gas of the stove 2=4.0, residence time 0.5h, the shrend after heat exchange cooling cylinder is cooled to 600 DEG C of output calcining.
Ball milling magnetic separation: shrend calcining is milled to and is less than 0.074mm and accounts for 95%, sizes mixing to pulp density 20% after ball milling, and magnetic separation under 1000 oersteds, obtains concentrate class iron sponge powder (TFe 93%, P 0.14%, Al 2o 31.3%, SiO 22.8%), wherein iron elimination factor 93%, phosphorus decreasing ratio 91%.
Molten point: class iron sponge powder carries out high temperature melting and divides, control 1600 DEG C of temperature, constant temperature time 1.5h, obtains high-quality molten iron (P 0.005%).

Claims (7)

1. an integrated conduct method for 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 to mix, fragmentation; The ingredients by weight ratio of its mix process is: phosphorus oolitic hematite 60%~95%, and red mud 5%~40%, and be 15%~30% coal of phosphorus oolitic hematite and red mud gross weight;
(2) broken material of step (1) is carried out to reducing roasting; In its reducing roasting process, reducing roasting equipment adopts the one in rotary kiln, rotary hearth furnace, multiple hearth furnace, and thermal source is coal gas or coal, and combustion-supporting gas is air, and high-temperature zone temperature is 950~1150 DEG C, and the high-temperature zone residence time is 0.5~3h, controls out kiln gas CO/CO 2be 3.5~4.5;
(3) calcining of reducing roasting carries out shrend, ball milling;
(4) after ball milling, carry out magnetic separation and obtain iron powder and mine tailing;
(5) iron powder step (4) being obtained obtains molten iron molten dividing.
2. the integrated conduct method of a kind of phosphorous oolitic hematite according to claim 1 and red mud, is characterized in that coal that mix process is allocated into is one or more in brown coal, bituminous coal, hard coal.
3. the integrated conduct method of a kind of phosphorous oolitic hematite according to claim 1 and red mud, is characterized in that the described broken pelletization of step (1), and particle size after cracking exceedes 90% for being less than 5mm.
4. 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 that step (2) gained calcining is cooling through sealing cooling cylinder, to shrend chilling after 400~750 DEG C, calcining ball milling, grinding particle size accounts for 85~95% for being less than 0.074mm.
5. 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 to magnetic separation, enter 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.
6. the integrated conduct method of a kind of phosphorous oolitic hematite according to claim 1 and red mud, the molten point process that it is characterized in that described step (5) is that iron powder employing electric furnace that step (4) is obtained melts point, add 0.1%~2% slag former, 1550~1650 DEG C of temperature controls, time 1~3h, obtains molten iron.
7. 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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CN103276193B (en) * 2013-06-21 2015-07-08 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
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
CN104988322B (en) * 2015-08-04 2018-01-02 江苏省冶金设计院有限公司 The integrated conduct method of red mud and slag
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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