CN102936650B - Method for comprehensively utilizing red mud and high-phosphorus iron ore - Google Patents
Method for comprehensively utilizing red mud and high-phosphorus iron ore Download PDFInfo
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- CN102936650B CN102936650B CN201210497818.XA CN201210497818A CN102936650B CN 102936650 B CN102936650 B CN 102936650B CN 201210497818 A CN201210497818 A CN 201210497818A CN 102936650 B CN102936650 B CN 102936650B
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- red mud
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- phosphorus iron
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Abstract
The invention relates to a method for comprehensively utilizing red mud and high-phosphorus iron ore, and specifically relates to a red mud and high-phosphorus iron ore solid dephosphorization and iron extraction technology. The method comprises the following preparation steps of: a, evenly mixing powdered high-phosphorus iron ore, powdered red mud and pulverized coal according to the proportion of 100: (1-100): (1-100), b, heating the mixed material obtained in the step a in a temperature range of 100-900 DEG C and preserving the temperature for 10-300min, c, after the material obtained in the step b is cooled, soaking the material by water for 10-120min and then filtering the liquid, and d, carrying out magnetic separation on the solid filtered in the step c, wherein the magnetic part is hematite or magnet or iron ore concentrate and the phosphorus content is less than 0.3wt%. According to the method, the red mud can be effectively utilized to reduce the pollution to the environment, and at the same time, the phosphorus content of the high-phosphorus iron ore can be decreased for recycling. The method is simple in process, low in production cost and beneficial to industrial popularization.
Description
Technical field
The invention belongs to the energy and metallurgical metal field, relate in particular to the method for comprehensive utilization of metallurgy of aluminium red mud and high ferrophosphorus, be specially the solid-state dephosphorus iron extraction technology of red mud and high-phosphorus iron ore.
Background technology
Red mud is with alkali, from bauxite, to extract the solid residue obtaining after aluminum oxide, be in aluminum oxide production process to one of principal element of environment, the main ingredient of red mud has SiO
2, CaO, Fe
2o
3, Al
2o
3, Na
2o, TiO
2and certain rare earth element and micro-radioelement.1.0～1.7 tons of red muds of the about output of one ton of aluminum oxide of general every production.According to incomplete estimation, approximately 6,000 ten thousand tons of red muds are discharged in the whole world every year.China is the world the 4th large alumina producing state, and accumulation red mud storage is up to 4,100 ten thousand tons.A large amount of red muds is outdoor to be stored up, and occupies farmland and massif, stirs up a cloud of dust, and causes environment and topsoil, and the pH of red mud is very high, and its pH of leaching solution is about 12.1～13.0.Alkali lye in red mud infiltrates with rainwater the pollution that underground water source is caused on stratum.The utilization ratio of red mud is only 4% left and right at present, also not yet finds up to now the effective way of utilizing in a large number red mud.
The red mud pilling enormous amount that the metallurgy of aluminium produces, in red mud, the extraction of iron is mainly to iron red mud magnetic separation at present, sub-elects iron ore concentrate utilization; Direct-reduction is carried iron due to needs high-temperature operation, apparatus and process complicated condition, still can not meet industrial requirements, and red mud has been obtained practical application effect as civil material, but it is few to process red mud amount.
The main methods of red mud has: utilize red mud produce cement (Ren Dongmei, Mao Yanan. the comprehensive utilization of red mud [J]. non-ferrous metals industry, 2002, [5]: 57-58); Iron in carbon reduction red mud, magnetic separation absorption method (Liao Chunfa, ginger state equality, the technique from recovering iron from red mud, Chinese Mining Industry, the 16th volume second phase .2007 February); CN101275182 under hot conditions by the SiO in red mud
2and Fe
2o
3the ferro-silicon being reduced into, Al
2o
3generate calcium aluminate, Na with CaO
2o and K
2o at high temperature volatilizees, through the cooling precipitation of refining, and broken apart calcium aluminate material and the ferro-silicon of obtaining; CN101463426 discloses a kind of comprehensive treating process red mud method that comprises chloridizing roasting, slag disposal, is settled out the steps such as mishmetal slag, dry dirt and circulation fluid disposal.
High-phosphorus iron ore in North America, all there are huge reserves in the areas such as the Yangtze valley of Northern Europe, Australia, Saudi Arabia and China.At China's reserves that only oolitic high phosphorus iron ore of western Hubei Province is verified, just up to 4,000,000,000 tons, approximately 74.5 hundred million tons of total reservess, are still not yet effectively utilized at present.China's iron ore deposit is widely distributed, and genetic type is various, and lean ore is many, and rich ore is few, and in ferruginous deposits, symbiosis component is many.In 1834 place's iron ores of finding out at oneself, total proven reserve are 531.4 hundred million tons, and retained reserve is 501.2 hundred million tons, and wherein the retained reserve of high-phosphorus iron ore is 74.5 hundred million tons, accounts for 14.86% of the total retained reserve of national iron ore.The high-phosphorus iron ore of China is mainly distributed in the areas such as the Inner Mongol in Yunnan, Sichuan, Hubei, Hunan, Anhui, Jiangsu and the North China of the Yangtze valley, it distributes extensively, reserves are large, but its mineral composition is complicated, phosphorus ore thing disseminated grain size is tiny, between phosphorus ore thing and iron mineral, relation is complicated, connecting forces is large, belongs to refractory ore.For a long time, owing to not developing desirable method for reducing phosphorus, make domestic existing people measure iron ore deposit can not to be effectively used, cause some mine to stop exploitation because of phosphorous height.
Phosphorus in high-phosphorus iron ore is mainly with phosphatic rock or francolite form and other mineral paragenesis, contaminate the grain edges in Iron Oxide Minerals, embedding is distributed in quartz or carbonate minerals, a small amount of tax is stored in the lattice of iron mineral, and phosphorite crystal is mainly column, needle-like, collection crystalline substance or the embedding of shot shape and is distributed in iron mineral and gangue, granularity is less, not easily separated, belongs to refractory mineral.Cannot be in ore dressing process dephosphorization, therefore, cannot be fully used at present.
Blast furnace does not possess dephosphorizing capacity substantially, if so high phosphorus content is all put into hot metal pretreatment and steelmaking process, must bring heavy economical load to steelmaking process, and the generation of simultaneously a large amount of foamy slags also must bring very large technique trouble to steelmaking process.Therefore, if can be before entering blast furnace dephosphorization, not only can save pre-treatment cost, can also avoid the trouble of steelmaking process.
Before entering blast furnace, reduce the phosphorus content in ore, rely on existing Technology to be still difficult to solve.The existing study route of high-phosphorus iron ore mainly contains acidleach dephosphorization, alkali soaks dephosphorization, reduction and gaseous dephosphorization etc.Prior art still haves much room for improvement at aspects such as cost, environmental protection.
Patent of invention CN101862701A and CN102513203A provide a kind of high phosphorus-sulfur siderite reverse flotation dephosphorization, scan dephosphorization, make high phosphorus-sulfur siderite resource obtain rationally utilizing the method for high phosphorus-sulfur siderite resource recycling.
The method also red mud and high-phosphorus hematite not being fully utilized simultaneously at present.
Summary of the invention
The present invention will solve red mud simultaneously cannot utilize the phosphorus problem of falling to the pollution problem of environment and high-phosphorus iron ore, and the present invention, by red mud+high-phosphorus iron ore solid state reduction transformation technology, reaches the object of " treatment of wastes with processes of wastes against one another ".
For addressing the above problem, the present invention adopts following technical scheme.
A method for red mud and high-phosphorus iron ore comprehensive utilization, comprises following preparation process:
A, powdery high-phosphorus iron ore, powdery red mud, coal dust are mixed according to the part by weight of 100:1～100:1～100;
B, by the mixing material of step a heating and thermal insulation 10min～300min in the temperature range of 100 ℃～900 ℃;
C, after step b material cooled, to filter out liquid after water soaking 10～120min;
D, the solid that step c is leached carry out magnetic separation separation, and magnetic part is rhombohedral iron ore or magnetite or iron ore concentrate.
Preferred version is that the part by weight of the high-phosphorus iron ore of powdery described in step a, powdery red mud, coal dust is 1:1:1.
Preferred version is, described in step c, for the water soaking, is recirculated water.
Preferred version is that the liquid filtering described in step c can be used for the preparation of phosphate fertilizer.
Preferred version is, in steps d, after magnetic resolution, non-magnetic part can be used for metal recovery, and described metal is aluminium, titanium, rare dissipated metal, rare rare earth metal etc.
Red mud of the present invention is the red mud that metallurgy of aluminium process produces.
Present disclosure high-phosphorus iron ore main component: TFe is that 35-60wt%, P content are 0.4-1.8wt%.
Preferred version is that, in the magnetic part Bessemer ore that the separation of magnetic separation described in steps d obtains, the content of phosphorus is less than 0.3wt%
Principle of the present invention is to utilize the method for the solid-state ore deposit of low temperature inversion of phases, use alkaline red mud the soluble phosphate transfection in high-phosphorus iron ore to be turned to the phosphoric acid salt of solubility, simultaneously, coal dust is magnetite or iron ore concentrate by the iron oxide reduction in high-phosphorus iron ore and red mud, by solid-liquid separation, phosphate transfection is moved on in the aqueous solution again, reach the object of dephosphorization, the solid part staying can, by magnetic separation effect, be isolated low-phosphorous magnetite or iron ore concentrate wherein.
The invention has the beneficial effects as follows, by red mud and high-phosphorus iron ore solid state reduction ore deposit phase-inversion technologies, can not enter the high-phosphorus iron ore of blast furnace ironmaking and a large amount of waste red mud comprehensive utilizations that aluminium metallurgy produces, unavailable resource is effectively utilized, the waste of stacking is in a large number become to resource recycling, reach the object of " treatment of wastes with processes of wastes against one another ".Use this invention can effectively utilize red mud, thereby reduce its pollution to environment; And the phosphorus content that can reduce high-phosphorus iron ore simultaneously, makes its resource utilization.Technique of the present invention is simple, and low production cost is conducive to industrialization promotion.
Embodiment
Embodiment 1
The method of a kind of red mud of the present invention and high-phosphorus iron ore comprehensive utilization comprises following preparation process:
A, 1kg high-phosphorus iron ore, 10g red mud and 10g coal dust are mixed, wherein the main component of red mud is: SiO2 is that 12wt%, CaO are 3.5wt%, Fe
2o
3for 38wt%, Al
2o
3for 18wt%, Na
2o is 9 wt %, TiO
2for 1.5wt%; High-phosphorus iron ore main component: TFe is 50wt%, Al
2o
3for 5wt%, P are 1.28wt%;
B, the mixing material described in step a is heated to 100 ℃, insulation 10min;
C, after step b reaction finishes, be down to room temperature, to filter out liquid after water soaking 10min, it reclaimed to the preparation for phosphate fertilizer;
D, the solid that step c is leached, carry out magnetic separation, obtains rhombohedral iron ore; The nonmagnetic portion obtaining is aluminium, silicon, titanium and other valuable metal salt mixture in high-phosphorus iron ore and red mud, can carry out to this part the recycling of aluminium, titanium, rare dissipated metal, rare rare earth metal etc.
Test by analysis, the product obtaining is rhombohedral iron ore, its P content is 0.3wt%.
Embodiment 2
The method of a kind of red mud of the present invention and high-phosphorus iron ore comprehensive utilization comprises following preparation process:
A, the coal dust of 1kg high-phosphorus iron ore, 500g red mud and 100g is mixed, wherein the main component of red mud is: SiO2 is that 12wt%, CaO are 3.5wt%, Fe
2o
3for 38wt%, Al
2o
3for 18wt%, Na
2o is 9 wt %, TiO
2for 1.5wt%; High-phosphorus iron ore main component: TFe is 50wt%, Al
2o
3for 5wt%, P are 1.28wt%;
B, the mixing material described in step a is heated to 500 ℃, insulation 300min;
C, after step b reaction finishes, be down to room temperature, filter out liquid after soaking 60min with recirculated water;
D, the solid that step c is leached, carry out magnetic separation separation, obtains magnetite; Aluminium in high-phosphorus iron ore and red mud, titanium, rare dissipated metal, rare rare earth metal enter nonmagnetic portion and are recycled.
Test by analysis, obtaining product is magnetite, phosphorous in iron: 0.15%.
Embodiment 3
The method of a kind of red mud of the present invention and high-phosphorus iron ore comprehensive utilization comprises following preparation process:
A, the high-phosphorus iron ore of 500g, 500g red mud and 500g coal dust are mixed, wherein the main component of red mud is: SiO2 is that 12wt%, CaO are 3.5wt%, Fe
2o
3for 38wt%, Al
2o
3for 18wt%, Na
2o is 9 wt %, TiO
2for 1.5wt%; High-phosphorus iron ore main component: TFe is 50wt%, Al
2o
3for 5wt%, P are 1.28wt%;
B, the mixing material described in step a is heated to 900 ℃, insulation 120min;
C, after finishing, step b reaction is down to room temperature, to filter out liquid after water soaking 120min;
D, the solid that step c is leached, carry out magnetic separation separation, obtains iron ore concentrate; Aluminium in high-phosphorus iron ore and red mud, titanium etc. enter nonmagnetic portion and are recycled.
Test by analysis, obtaining product is iron ore concentrate, its phosphorus content is 0.08wt%.
Claims (7)
1. the method that red mud and high-phosphorus iron ore fully utilize, is characterized in that: comprise following preparation process:
A, powdery high-phosphorus iron ore, powdery red mud, coal dust are mixed according to the part by weight of 1:1:1;
B, by the mixing material of step a heating and thermal insulation 10min～300min in the temperature range of 100 ℃～500 ℃;
C, after step b material cooled, to filter out liquid after water soaking 10～120min;
D, the solid that step c is leached carry out magnetic separation separation, and magnetic part is rhombohedral iron ore or magnetite or iron ore concentrate.
2. the method for a kind of red mud according to claim 1 and high-phosphorus iron ore comprehensive utilization, is characterized in that: the liquid filtering described in step c can be used for the preparation of phosphate fertilizer.
3. the method that a kind of red mud according to claim 1 and high-phosphorus iron ore fully utilize, it is characterized in that: in steps d after magnetic resolution, the nonmagnetic part obtaining can be used for metal recovery, and described metal is aluminium, titanium, rare dissipated metal, rare rare earth metal.
4. the method for a kind of red mud according to claim 1 and high-phosphorus iron ore comprehensive utilization, is characterized in that: described red mud is the red mud producing in metallurgy of aluminium process.
5. the method for a kind of red mud according to claim 1 and high-phosphorus iron ore comprehensive utilization, is characterized in that: high-phosphorus iron ore main component TFe content is that 35-60wt%, P content are 0.4-1.8wt%.
6. the method for a kind of red mud according to claim 1 and high-phosphorus iron ore comprehensive utilization, is characterized in that: in the magnetic part Bessemer ore that the separation of magnetic separation described in steps d obtains, the content of phosphorus is less than 0.3wt%.
7. the method for a kind of red mud according to claim 1 and high-phosphorus iron ore comprehensive utilization, is characterized in that: described in step c, for the water soaking, be recirculated water.
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| CN104120207B (en) * | 2014-08-09 | 2016-04-06 | 武钢集团昆明钢铁股份有限公司 | One joins the raw ferriferous method in ore deposit with tin tail iron ore concentrate and the poor assorted ore deposit of high harmful element |
| CN105087938B (en) * | 2015-08-04 | 2018-07-13 | 江苏省冶金设计院有限公司 | The method and system of valuable metal is recycled from red mud |
| CN106622671A (en) * | 2016-12-27 | 2017-05-10 | 中蓝连海设计研究院 | Direct flotation desiliconization and acid leaching magnesium removal combination treatment technology for phosphate ores |
| CN107084932A (en) * | 2017-05-22 | 2017-08-22 | 中南冶金地质研究所 | The method of separating and assaying of phosphorus in a kind of Armco magnetic iron of Ningxiang-type iron ore |
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