CN1225562C - Method of producing titanium enriched material using titanium mineral - Google Patents

Abstract

The invention discloses a method for producing titanium-rich material by using titanium ore resources. The invention can effectively recycle and utilize various valuable elements in vanadium-titanium magnetite surface ores, surface ores and weathered ores. The technical scheme of the present invention is: the vanadium-titanium magnetite is subjected to pre-selection, throwing tailings or weathered ore washing, and then undergoes magnetization roasting stage grinding, so that the gangue minerals are separated to obtain ilmenite concentrate, or the ilmenite concentrate and vanadium-titanium Iron concentrate is mixed in a certain proportion, then mixed with binder and carbonaceous reducing agent, and then pelletized for pre-reduction or directly into the furnace. High-titanium slag, semi-steel and alloy produced by smelting in electric blast furnace or submerged arc furnace The molten iron is blown with vanadium and chromium by the dual method, and the obtained steel slag containing vanadium and chromium is separated by wet extraction, and the high titanium slag enters the pyrometallurgical beneficiation process of titanium slag to produce artificial rutile and glass-ceramics. The artificial rutile titanium-rich material and coal finely ground are mixed in a certain proportion and then added with a binder to make carbon-containing titanium particles. After roasting and cooling in the roaster, they are sieved and classified into carbon-containing rutile with particle size of +0.3mm～-1.4mm Titanium-rich material.

Description

Method for producing titanium-rich material by using titanium ore

technical field

The present invention belongs to titanium ore (vanadium-titanium magnetite, titanium sand ore) metal mineral dressing and smelting method, especially from rock ore type vanadium-titanium magnetite surface ore, surface ore and weathered ore to manufacture iron and steel products, extract sulfuric acid method High-grade acid-soluble titanium-rich materials used in titanium dioxide factories, carbon-containing rutile titanium-rich materials and vanadium-chromium products used in chloride-process titanium dioxide factories, and comprehensive utilization of other valuable elements.

Background technique

In nature, titanium resources are usually in the form of oxides and other metal oxides, especially iron oxides, forming solid solutions (rutile), or independent minerals (vanadium-titanium magnetite, titanium placer, etc.). Titanium ore referred to in the present invention refers to titanium ore deposits (primary vanadium-titanium magnetite and titanium placer) with industrial value, that is, cut-off grade primary ore (vanadium-titanium magnetite) TiO ₂ ≥ 5% to 6%, titanium sand Titanium deposits with ore (ilmenite) minerals ≥ 10kg/ ^m3 . The titanium in the primary vanadium-titanium _magnetite exists in the two purpose minerals of titano-magnetite and ilmenite _. ·TiO ₂ ) is a guest crystal mineral and the main crystal mineral magnetite (FeO·Fe ₂ O ₃ ) exists in the same quality, and iron and titanium cannot be separated by mechanical and physical beneficiation methods. This kind of vanadium-titanium-magnetite has huge reserves, and low-grade ore with TFe<23%, external ore and weathered ore, which account for 70% of the geological reserve, will be discarded as mining waste during mining and utilization. In fact, these mining waste rocks are identified as iron and vanadium resources, together with the rich ore and medium ore in the table, and it is mainly confirmed as titanium resources. Vanadium-titanium magnetite is used as a titanium ore resource for the production of titanium dioxide, titanium metal and other titanium series products. Usually the primary vanadium-titanium magnetite first enters the iron concentrator, and the strong magnetic titano-magnetite and weak magnetic ilmenite, sulfide and silicate minerals are separated into vanadium-containing ilmenite concentrate through magnetic separation. This iron concentrate enters the blast furnace-converter oxygen furnace iron and steel smelting process (such as my country's Panzhihua Iron and Steel (Group) Company, Russia's Tyusov Metallurgical Plant, etc.) as ironmaking raw materials, or iron direct reduction process to produce iron and steel products. Because it contains ~0.3% V ₂ O ₅ , it has high economic value, and vanadium slag can be produced in the steelmaking process, which is an important raw material for vanadium products. However, there are still 2% to 6% granular ilmenite in the vanadium-titanium-iron concentrate separated by the iron beneficiation plant. In addition, titanium and iron are isomorphic in titano-magnetite, and the beneficiation method cannot be separated. One of the main reasons why some vanadium-titanium ferroconcentrate iron is low in titanium and high in TiO ₂ >12%, which causes great difficulties in the subsequent iron and steel smelting process. In view of the fact that the titanium content of vanadium-titanium magnetite concentrate accounts for a large proportion of the total titanium content of the original ore, taking Panzhihua Lanjian mining area as an example, its share exceeds 50% to 60%. For Panzhihua Iron and Steel Co., Ltd., which is the raw material for ironmaking, the absolute amount of titanium dioxide that enters the blast furnace smelting along with the mining of iron ore can be as high as 600,000 to 700,000 tons of TiO ₂ per year, but this vanadium-titanium ferroconcentrate contains titanium Low grade, coupled with the requirements of the iron and steel smelting process, especially the blast furnace-converter process, acidic solvents and alkaline solvents need to be added to the blast furnace ingredients, so that the titanium dioxide content of the produced titanium slag does not exceed 25%, and the blast furnace smelting can go smoothly. As a result, there is no industrialized method to extract titanium products from titanium slag and a large number of methods to utilize this titanium slag, resulting in the accumulation of about 3.5 million tons of this titanium slag every year, forming a huge environmental pressure.

Due to the vanadium-containing ilmenite concentrate that enters the direct reduction process, the titanium slag produced usually contains less than 60% TiO ₂ , and it is difficult to enter the existing process of manufacturing artificial rutile, so low-grade titanium resources such as vanadium ilmenite concentrate have not been used so far The method of successfully extracting carbon-containing artificial rutile titanium-rich materials as raw materials is used in the production of chloride-process rutile titanium dioxide, sponge titanium, titanium materials, etc. in the chloride-process titanium dioxide factory.

The iron dressing plant adopts one-stage grinding and one-time magnetic separation to recover titanium magnetite in titanium ore, and the tailings of the iron dressing plant are used as the raw ore of the titanium dressing plant, and the gravity separation-electric separation process is used to recover +0.074mm granular ilmenite, and the strong magnetic One by one flotation process recovery - 0.075mm granular ilmenite, production of TiO ₂ 47% titanium concentrate, titanium (TiO ₂ ) recovery rate of 20% in the titanium beneficiation plant, calculated from mining to titanium concentrate, the current titanium recovery rate is 3.95% . Low-grade titanium concentrate (TiO ₂ 43%~53%) is used in sulfuric acid titanium dioxide factory to produce sulfuric acid titanium dioxide. The discharge of "three wastes" is extremely large and the environmental pollution is extremely serious. To produce one ton of titanium dioxide, 2.5-4t of green vitriol (titanium sulfate 7 hydrate), 7-11t of 20% waste sulfuric acid, 100-250t of acidic waste water, 15000-20000m3 ^of acidic dusty waste gas, and 0.2-0.3t of waste residue ( on a dry basis). Producing one ton of titanium dioxide requires about 4 tons of sulfuric acid. Except for the production of ferrous sulfate, part of the sulfuric acid is consumed, and the rest of the sulfuric acid is turned into waste water, waste gas, and waste residue. Such a large amount of waste discharge is almost non-existent for other chemical products. Due to the "three wastes" treatment, the sulfuric acid titanium dioxide factory urgently needs to use high-grade acid-soluble titanium-rich materials as raw materials. At home and abroad, acid-soluble titanium-rich materials are produced by electric smelting of rock ore (primary ore) or titanium sand ore. The grade of titanium dioxide is only 41%-72% TiO ₂ . So far, no acid-soluble titanium-rich material with high-grade TiO ₂ 75%-92% has been produced. .

When mining vanadium-titanium magnetite, the low-grade ore, off-surface ore and weathered ore, which account for about 70% of the geological reserves, are discarded as mining waste rocks. There are more than 10 million tons of titanium ore resources in Panxi area as mining waste rocks every year. reject.

Contents of the invention

Purpose of the present invention: the one, be reduced to TFe22%～30% by TFe34%～40% by TFe34%～40% at present by TFe34%～40%, reduce raw ore and select iron grade TFe10%, three purpose minerals (titanium magnetite, granular titanium Iron ore and sulfide) mixed dressing and smelting; second, the recovery rate of titanium is increased from the current 3.95% to 70% (calculated from mining to ilmenite concentrate), and the recovery rate of iron is increased from the current 56.99% to 70% (from mining Calculated to molten iron), vanadium recovery rate increased from the current 26.83% to 70% (calculated from mining to vanadium slag); the third is to save resources, protect resources, rationally develop and comprehensively utilize vanadium and titanium resources, and treat the current waste rock as mining The discarded low-grade ore, off-surface ore, and weathered ore, which account for 70% of the geological reserves of vanadium-titanium ore, are all recycled; the fourth is to produce 75% to 92% of TiO ₂ acid-soluble titanium-rich materials suitable for use in sulfuric acid titanium dioxide factories; Fifth, the production of TiO ₂ >92%-96% is suitable for the use of low-calcium magnesium carbon-containing rutile titanium-rich materials used in chloride-process titanium dioxide factories; sixth, the development and utilization of Panxi vanadium-titanium magnetite by Panzhihua Iron and Steel Company is mainly iron , produce 50 tons of iron to produce one ton of titanium dioxide by-product, the ratio of titanium to iron is 1/50, and Panzhihua Jinti High-tech Co., Ltd. utilizes the method of the present invention to mainly develop and utilize Panxi vanadium-titanium magnetite, comprehensively balanced recovery Iron, vanadium, chromium and other valuable elements, the ratio of titanium to iron is 1/3, one ton of titanium dioxide is produced, and 3 tons of iron are produced by-product. Panxi vanadium-titanium magnetite (vanadium-titanium ore) is essentially titanium ore.

The present invention is realized through the following technical scheme: the vanadium-titanium magnetite (or titanium placer ore) is pre-selected and discarded or weathered ore is washed and then subjected to magnetization and roasting stage grinding, so that the gangue minerals are separated to obtain ilmenite concentrate ( or titanium sand concentrate), or this ilmenite concentrate (or titanium sand concentrate) and vanadium-titanium iron concentrate (or titanium concentrate) are mixed in a certain proportion and then added with binder (bentonite, etc.) and carbonaceous reduction After the agent is mixed, the pellets are pre-reduced or directly put into the furnace, and the high-titanium slag (melted titanium slag) and semi-steel (alloy molten iron) with TiO ₂ >68% are produced in the electric blast furnace or submerged arc furnace. Double blowing of vanadium and chromium, the obtained steel slag containing vanadium and chromium is extracted and separated from vanadium and chromium by wet method, high titanium slag (dissolved titanium slag) is isolated from air and cooled, and after crushing, grinding and gravity separation, the grade of titanium dioxide is increased to TiO ₂ 75% ~92%, acid-soluble titanium-rich material crushed to a fineness of 0.045mm-0.075mam by Raymond mill, high-titanium slag (melted titanium slag) enters the pyrometallurgical beneficiation process of titanium slag, and artificial rutile titanium-rich material is produced (TiO ₂ >92%~96%) and glass-ceramics. In order to improve the chlorination rate of rutile titanium-rich material in the chlorination fluidized bed furnace (fluidized bed), the utilization rate of titanium and to prevent the chlorination molten salt from clogging the hole network of the chlorination fluidized bed, coal is infiltrated into the rutile titanium-rich material, and added The binder (wood pulp, etc.) is mixed and granulated, and after roasting, the air is isolated or cooled by inert gas, and then sieved into carbon-containing rutile and titanium-rich materials with a particle size of +0.3mm to 1.4mm.

Method of the present invention comprises following processing step:

①-70～0mm titanium ore pre-selection tailings production process: -70～0mm titanium ore is roughed by pre-screening machine (1), electromagnetic roller (2), and electromagnetic roller (3) sweeps and discards tailings ₁ ; pre-selection The ore is pre-screened and inspected by the screening machine (4), +10mm ore enters the fine crusher (5), -10~0mm ore is demagnetized and then enters the first stage of grinding machine (6) for grinding; the ore discharged from the mill passes through the spiral classifying screen ( 7) Classification, +3mm ore returns to the mill for regrinding, -3~0mm ore enters the first gravity separation or weak magnetic separation process;

②+70mm weathered ore washing production process: weathered ore is screened (8), +70mm ore block is crushed to -70~0mm by stone crusher (9), and ore is washed by ore washing machine (10); +10mm The ore enters the fine crusher (5), and the -10mm ore enters the first stage grinding machine (6); the ore discharged from the mill is classified by the spiral classifying screen (7), and the +3mm ore is returned to the mill (6) for regrinding, -3～ 0mm ore enters the first gravity separation or weak magnetic separation process;

③Produce ilmenite concentrate or titanium sand concentrate according to the process flow of "grinding-gravity separation-weak magnetic separation-magnetization roasting-grinding-gravity separation-strong magnetic separation" in the magnetization roasting stage: -70mm titanium ore is pre-selected and discarded Or after the weathered ore is washed, the -10mm ore goes through a stage of grinding (6); the ore discharged from the mill is graded by the spiral classifying screen (7), the +3mm ore is returned to the mill (6) for regrinding, and the -3mm ore enters Gravity concentrator (11) roughing, discarding tailings ₂ to get rough concentrate ₁ , medium ore roughed by weak magnetic separator (12) to get rough concentrate ₂ ; weak magnetic tailings demagnetization, filtering and drying (13 ) into fluidized fluidized furnace or rotary kiln or slope type roaster for magnetization roasting (14); magnetization roasting coarse concentrate and coarse concentrate ₁ and coarse concentrate ₂ enter the second-stage mill (15) for fine grinding, and the second-stage mill discharges ore Classification by demagnetizing spiral classifying screen or hydrocyclone (16); +0.15mm ore is returned to mill (15) for regrinding, and -0.15mm minerals that have been dissociated from monomers are subjected to gravity concentrator (17) for the second time Gravity separation roughing, get concentrated ore ₃ and tailings ₃ ; Gravity separation ore gets concentrated ore ₄ through a field-strength magnetic separator (18) roughing, and field-strength magnetic separation tailings demagnetization passes secondary field strength Magnetic separator (19) sweeps and discards tailings ₄ to obtain concentrate ₅ ; concentrate ₃ , concentrate ₄ and concentrate ₅ are mixed to obtain ilmenite concentrate or titanium sand concentrate;

④Produce ilmenite concentrate or titanium sand concentrate according to the process of magnetization roasting stage "grinding-weak magnetic separation-strong magnetic separation-magnetization roasting-grinding-weak magnetic separation-strong magnetic separation": -70mm titanium ore After the pre-selected tailings or weathered ore washing, the -10mm ore is subjected to one-stage grinding (6), the ore discharged from the mill is graded by the spiral classifying screen (7), and the +3mm ore is returned to the grinding machine (6) for regrinding;- The 3-0mm ore enters the weak magnetic separator (12) for rough separation to obtain coarse concentrate ₁ and coarse concentrate ₂ , and the coarse concentrate ₂ is demagnetized and enters the first high-field strong magnetic separator (18) to discard tailings ₂ to obtain Coarse concentrate ₃ ; Coarse concentrate ₃ is filtered and dried (13) and enters fluidized fluidized furnace or rotary kiln or slope type roaster magnetized roasting (14); Magnetized roasted coarse concentrate and coarse concentrate ₁ enter the second stage mill (15) to fine Grinding, the second-stage mill discharges ore and is classified by a spiral classifying screen or a hydrocyclone (16); +0.15mm ore is returned to the second-stage ore mill (15) for regrinding, and -0.15mm ore is passed through a weak magnetic separator (12 ) to obtain concentrate ₄ , the tailings of the weak magnetic separation enter the second high-field magnetic separator (19) through demagnetization to obtain concentrate ₅ , and the tailings of the secondary high-field magnetic separator (19) enter the second high-field magnetic separator (19) through demagnetization. The three-time field strong magnetic separator (20) discards tailings ₃ to obtain concentrate ₆ ; concentrate ₄ , concentrate ₅ and concentrate ₆ are mixed to obtain ilmenite concentrate or titanium sand concentrate;

⑤High titanium slag or melted titanium slag produced by electric furnace smelting of ilmenite concentrate or titanium sand concentrate produced in the magnetization roasting stage: ilmenite concentrate or titanium sand concentrate, or the ilmenite concentrate, titanium sand concentrate Mix with vanadium-titanium iron ore concentrate or titanium concentrate in a certain proportion, add binder and carbonaceous reducing agent after mixing (22), make pellets (23), enter the rotary kiln (24) for pre-reduction or directly enter Furnace, smelting in electric blast furnace or submerged arc furnace (25) to produce alloy molten iron and TiO ₂ >68% high titanium slag or molten titanium slag; Vanadium and chromium are extracted and separated by conventional metallurgy; high-titanium slag or molten titanium slag enters the gravity beneficiation process to produce high-grade acid-soluble titanium-rich materials after being isolated from the air; high-titanium slag, molten titanium slag enters the pyrometallurgical beneficiation process to produce rutile Titanium-rich material;

⑥ High-grade titanium slag or melted titanium slag gravity beneficiation to produce high-grade acid-soluble titanium-rich material: high-titanium slag or melted titanium slag is sent to the cooling furnace (26) where air is removed by vacuum pump (27) or inert gas is input After cooling, carry out crushing (28), ore grinding (29), gravity beneficiation (30), tailings are processed into glass-ceramics; medium ore is returned to electric furnace smelting (25), and gravity beneficiation concentrate is TiO ₂ 75%～92% The acid-soluble titanium-rich material is ground into an acid-soluble titanium-rich material with a fineness of 0.045 mm to 0.075 mm by Raymond mill (31);

⑦High-titanium slag or molten titanium slag or acid-soluble titanium-rich material pyrometallurgical beneficiation to produce rutile titanium-rich material: high-titanium slag or molten titanium slag or acid-soluble titanium-rich material that has not been finely ground by Raymond mill (31) Enter heat preservation crystallization oxidation furnace (32), blow oxygen with electric arc heating or oxygen-fuel spray gun or oxygen, air DC plasma generator to heat preservation oxidation furnace (32) heating and blow oxygen, add silica, fluoride additive simultaneously, to high titanium Deep oxidation of slag or acid-soluble titanium-rich material, so that the low-valent titanium oxide in the solid solution titanium-containing mineral black titanite mainly based on Ti ₃ O ₅ in high-titanium slag or titanium-rich material is oxidized into octahedron The structure of rutile TiO ₂ , calcium and magnesium and other impurities are excluded and enter the silicate glass to form rutile titanium-rich material. The rutile titanium-rich material makes the rutile grains grow in the slow cooler (33) After cooling, through crushing (34), ore grinding (35) and gravity separation (36), the tailings are discarded to obtain TiO ₂ >92% to 96% low-calcium magnesium artificial rutile titanium-rich material, and the middle ore is returned to the heat preservation oxidation furnace (32 ) to smelt and oxidize again to increase the recovery rate of titanium, and process the tailings into glass-ceramics;

⑧. TiO ₂ produced by pyrometallurgical beneficiation > 92% ~ 96% low-calcium magnesium artificial rutile titanium-rich material to produce carbon-containing rutile titanium-rich material: rutile titanium-rich material and coal with fixed carbon C > 60% are passed through the mill (37 ), (38) finely grind to -0.045mm and mix with binder ingredients (39), C/TiO ₂ >20%～30%, binder 0.3%～0.6%, granulate (40); carbon Titanium grains are roasted in 900 DEG C～950 DEG C roasting furnaces for 20 minutes (41); Then, carbon-containing titanium grains are sent into a cooler (43) with a vacuum pump (42) to evacuate air or inert gas to prevent carbon-containing titanium After the particles are oxidized and cooled, they are classified by double-layer spiral classifying sieves or two single-layer spiral classifiers (44), and the carbon-containing titanium particles of -0.3 mm and +1.4 mm are returned to the mill (37) for regrinding and recycling. A carbon-containing rutile titanium-rich material with a particle size of +0.3mm～-1.4mm is obtained.

The present invention has produced the following beneficial effects: one, the resource utilization efficiency is high, the currently selected iron grade of vanadium-titanium ore is reduced from TFe34% to 40% to TFe22% to 30%, and the raw ore selected iron grade TFe10% is reduced; the other is titanium The recovery rate is increased from the current 3.95% to 70% (calculated from mining to ilmenite concentrate), the recovery rate of iron is increased from 56.99% to 70% (calculated from mining to molten iron), and the recovery rate of vanadium is increased from the current 26.83 % is increased to 70% (calculated from mining to vanadium slag); the third is to save resources, protect resources, rationally develop and comprehensively utilize resources, and can effectively recycle vanadium-titanium magnetite surface ore, surface ore and weathered ore (or titanium all kinds of valuable elements in placer), and the utilization rate of titanium ore resources has been increased from the current 30% to 100%; the fourth is to produce TiO ₂ 75%-92% acid-soluble titanium-rich materials suitable for use in sulfuric acid titanium dioxide factories Fifth, the production of TiO ₂ >92% to 96% is suitable for the use of low-calcium magnesium carbon-containing rutile titanium-rich materials used by chloride-process titanium dioxide factories; sixth, Panzhihua Iron and Steel Company is currently developing and utilizing Panxi vanadium-titanium magnetite with iron as its Mainly, only one ton of titanium dioxide is produced by producing 50 tons of iron, and the ratio of titanium to iron is 1/50. Panzhihua Jinti High-tech Co., Ltd. implements this patent to develop and utilize Panxi vanadium-titanium magnetite, which is mainly titanium, and comprehensively balances the recovery of iron , vanadium, chromium and other valuable elements, the ratio of titanium to iron is 1/3, one ton of titanium dioxide is produced, and 3 tons of iron are produced by-product. Panxi vanadium-titanium magnetite (vanadium-titanium ore) is essentially titanium ore.

Description of drawings

Fig. 1 is a process flow diagram of the present invention;

Fig. 2 is the process flow chart of the pre-selected tail throwing process of the present invention;

Fig. 3 is the weathered ore washing process flow chart of the present invention;

Fig. 4 is another process flow chart of the present invention.

Detailed ways

The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

As shown in Figures 1 and 4, -70mm titanium ore (vanadium-titanium magnetite, titanium placer) is pre-selected and washed by tailings or weathered ore, and -10mm ore is washed by magnetization and roasting to separate gangue minerals. Obtain ilmenite concentrate (or titanium sand concentrate), or this ilmenite concentrate (or titanium sand concentrate) and vanadium-titanium iron concentrate (or titanium concentrate) are mixed in a certain proportion and then added with binder (bentonite etc.) mixed with carbonaceous reducing agent, pelletized for pre-reduction or directly into the furnace, smelted in electric blast furnace or submerged arc furnace to produce TiO ₂ >68% high-titanium slag (melted titanium slag) and semi-steel (alloy molten iron), the alloy molten iron is blown with vanadium and chromium by double-link method, and the obtained steel slag containing vanadium and chromium is extracted and separated from vanadium and chromium by wet method. Increase TiO ₂ 75% to 92%, use Raymond mill to pulverize acid-soluble titanium-rich materials with a fineness of 0.045mm to 0.075mm, high titanium slag (melted titanium slag) enters the pyrometallurgical beneficiation process of titanium slag, production Artificial rutile titanium-rich materials (TiO ₂ >92%-96%) and glass-ceramics were produced. In order to improve the chlorination rate of rutile titanium-rich material in the chlorination fluidized bed furnace (fluidized bed), the utilization rate of titanium and to prevent the chlorination molten salt from clogging the hole network of the chlorination fluidized bed, coal is infiltrated into the rutile titanium-rich material, and added The binder (wood pulp, etc.) is mixed and granulated. After roasting, isolate the air or pass in an inert gas to cool it, and sieve it into carbon-containing rutile and titanium-rich materials with a particle size of +0.3mm～-1.4mm.

As shown in Figure 2, the ore pre-selection tailings production process, the process is: -70mm titanium ore (vanadium-titanium magnetite, titanium placer) is pre-screened (1), roughed by electromagnetic rollers (2), The electromagnetic roller (3) sweeps and discards the tailings ₁ , the pre-selected ore is pre-screened and inspected by the screening machine (4), the +10mm ore enters the fine crusher (5) for fine crushing, and the -10~0mm ore enters the first-stage grinding machine after demagnetization (6) Grinding, the ore discharged from the mill is classified by the demagnetizing spiral grading screen (7), the +3mm ore returns to the mill for regrinding, and the -3~0mm ore enters the first re-election or weak magnetic separation process.

As shown in Figure 3, the weathered ore washing production process is as follows: the weathered ore passes through the screen (8), the +70mm ore block is crushed to -70 ~ 0mm by the stone crusher (9), and the ore washing machine ( 10), +10mm ore enters the fine crusher (5) for fine crushing, -10~0mm ore enters the first stage grinding machine (6) for grinding, and the ore discharged from the mill is classified by the demagnetizing spiral classifying screen (7), +3mm ore Return to the first section of the mill (6) for regrinding, and the -3-0mm ore enters the first gravity separation or weak magnetic separation process.

As shown in Figure 1, in the magnetization roasting stage, the grinding process of "grinding-gravity separation-weak magnetic separation-magnetization roasting-grinding-gravity separation-strong magnetic separation" produces ilmenite concentrate (or titanium placer). The process is : -70mm titanium ore (vanadium-titanium magnetite, titanium sand ore) is pre-selected and washed, and the -10mm ore is subjected to one-stage grinding (6), and the ore is discharged through the demagnetizing spiral classifying screen (7 ) classification, the ore greater than 3mm returns to the mill (6) for regrinding, the ore less than 3mm enters the gravity separator (11) for rough separation, and the tailings ₂ are discarded to obtain the coarse concentrate ₁ , and the middle ore is passed through the weak magnetic separator (12 ) roughing to obtain coarse concentrate ₂ , tailings demagnetized by weak magnetic separation, filtered and dried (13), then enter the fluidized fluidized furnace (or rotary kiln or slope type roaster) for magnetization roasting (14), and magnetize roast the coarse concentrate and coarse concentrate _1. Coarse ore ₂ enters the secondary mill (15) for fine grinding, and the ore discharged from the secondary mill is classified by the demagnetizing spiral sub-machine screen (or hydrocyclone) (16), and the +0.15mm ore returns to the mill (15 ) re-grinding, -0.15mm monomer dissociated minerals (purpose minerals and gangue minerals) are subjected to gravity concentrator (17) for the second re-election roughing to obtain concentrate ₃ and tailings ₃ , and re-centre Through the rough separation of the high-field magnetic separator (18) to obtain the concentrate ₄ , the demagnetization of the tailings by the high-field magnetic separator (19) sweeps and discards the tailings ₄ to obtain the concentrate ₅ , Concentrate ₃ , Concentrate ₄ and Concentrate ₅ are mixed to obtain ilmenite concentrate (or titanium sand concentrate).

As shown in Figure 4, in the magnetization roasting stage, the grinding process of "grinding-weak magnetic separation-strong magnetic separation-magnetization roasting-grinding-weak magnetic separation-strong magnetic separation" produces ilmenite concentrate (or titanium placer) , the process is: -70mm titanium ore (vanadium-titanium magnetite, titanium placer) is pre-selected, thrown tailings or weathered ore washing, and -10mm ore is subjected to a stage of grinding (6), and the ore discharge of the mill is passed through the demagnetization spiral Grading sieve (7) for classification, +3mm ore returns to ore mill (6) for regrinding, -3~0mm ore enters weak magnetic separator (12) for rough separation to obtain coarse concentrate ₁ and coarse concentrate ₂ , coarse concentrate ₂ Demagnetization enters the first high-strength magnetic separator (18) and discards the tailings ₂ to obtain the coarse concentrate ₃ , and the coarse concentrate ₃ is filtered and dried (13) and enters the fluidized bed furnace (or rotary kiln or slope type roaster) for magnetization roasting ( 14), the magnetized roasted coarse concentrate and the coarse concentrate ₁ enter the second stage mill (15) for fine grinding, and the second stage mill discharges ore and is classified by the demagnetizing spiral classifying screen (or hydrocyclone) (16), The +0.15mm ore is returned to the second-stage grinding machine (15) for regrinding, the -0.15mm ore is passed through the weak magnetic separator (12) to obtain concentrate ₄ , and the tailings of the weak magnetic separation are demagnetized and enter the second high-strength magnetic separation Machine (19) gets concentrated ore ₅ , and the tailings of secondary field strong magnetic separator (19) enters the third time of field strong magnetic separator (20) through demagnetization and gets rid of tailings ₃ to get concentrated ore ₆ , and concentrated ore _4. Concentrate ₅ and concentrate ₆ are mixed to obtain ilmenite concentrate (or titanium sand concentrate).

As shown in Figures 1 and 4, the ilmenite concentrate (or titanium sand ore) produced in the magnetization roasting stage is smelted in an electric furnace to produce high-titanium slag (melted titanium slag). The process is: ilmenite concentrate (or titanium sand) ore), or this ilmenite concentrate (or titanium placer) and vanadium-titanium iron concentrate (or titanium concentrate) are mixed in a certain proportion and added with binder (bentonite, etc.) and carbonaceous reducing agent after mixing ( 22), make pellets (23), enter the rotary kiln (24) for pre-reduction or directly enter the furnace, and produce semi-steel (alloy molten iron) and high-titanium slag (melted titanium slag) in the electric blast furnace or submerged arc furnace (25). ) (TiO ₂ ＞68%), the alloyed molten iron is blown with vanadium and chromium by the dual method, and the obtained steel slag containing vanadium and chromium is extracted and separated by hydrometallurgy, and the high titanium slag (melted titanium slag) enters the gravity after being isolated from the air and cooled. The beneficiation process produces high-grade acid-soluble titanium-rich materials, or high-titanium slag (melted titanium slag) enters the pyrometallurgical beneficiation process to produce rutile titanium-rich materials.

As shown in Figures 1 and 4, the high-grade acid-soluble titanium-rich material is produced by utilizing high-titanium slag (melted titanium slag), and the process is: the high-titanium slag (melted titanium slag) is sent into the vacuum pump (27) to take out the air Or after cooling in the cooling furnace (26) of input inert gas, carry out crushing (28), ore grinding (29), gravity separation (30), tailings are processed into glass-ceramics, medium ore is returned to electric furnace smelting (25), TiO ₂ 75%-92% acid-acid-soluble titanium-rich material is ground by a Raymond mill (31) into an acid-soluble titanium-rich material with a fineness of 0.045mm-0.075mm, which is the most ideal raw material for the production of sulfuric acid process titanium white.

As shown in Figures 1 and 4, using high-titanium slag (melted titanium slag) or acid-soluble titanium-rich material pyrometallurgical beneficiation to produce rutile titanium-rich material, the process is: high titanium slag (melted titanium slag) or untreated The acid-soluble titanium-rich material finely ground by Raymond mill (31) enters the thermal insulation crystallization oxidation furnace (32), blows oxygen with electric arc heating or uses oxygen-fuel spray gun or oxygen (air) DC plasma generator to thermal insulation oxidation furnace (32) Heating and blowing oxygen, adding silica and fluoride additives at the same time, deeply oxidizes high-titanium slag or acid-soluble titanium-rich material, so that the main titanium-containing mineral black titanite (Ti ₃ 0 ₅ based The low-valent titanium oxide in the solid solution) is oxidized into octahedral rutile (TiO ₂ ), impurities such as calcium and magnesium are excluded, and enter the silicate glass to form rutile titanium-rich material. The petrochemical titanium-rich material grows and cools in the slow cooler (33), then crushes (34), ore grinding (35) and gravity separation (36) to discharge the tailings, and obtains TiO ₂ >92%-96 % low-calcium-magnesium artificial rutile titanium-rich material, the middle ore returns to the heat preservation oxidation furnace (32) for smelting and oxidation again to improve the recovery rate of titanium, and the tailings are processed into glass-ceramics. As shown in Figures 1 and 4, the carbon-containing rutile titanium-rich material is produced by using low-calcium-magnesium artificial rutile titanium-rich material (TiO ₂ >92%~96%). The process is: rutile titanium-rich material (TiO ₂ >92%~ 98%) and coal (fixed carbon C > 60%) are finely ground to -0.045mm (-325 order) and binder (wood pulp etc.) batching (39) mixing through mill (37), (38) ( C/TiO ₂ >20%～30%, binder 0.3%～0.6%), granulate (40), carbon-containing titanium particles are roasted in a 900°C-950°C roasting furnace for 20 minutes (41), and then The carbon-titanium particles are sent into a cooler (43) with a vacuum pump (42) to remove air or an inert gas to prevent oxidation and cooling of the carbon-containing titanium particles, and then pass through double-layer spiral classifiers or two single-layer spiral classifiers (44 ) classification, -0.3mm particle size and +1.4mm particle size carbon-containing titanium particles are returned to the mill (37) for regrinding (37) for recycling, and the carbon-containing rutile titanium-rich material of +0.3mm～-1.4mm particle size is used as production Chloride rutile titanium dioxide is the most ideal raw material.

Claims (1)

1, a kind of method of utilizing titanium ore to produce rich titanium material comprises the steps:

1.-and 70～0mm titanium ore tailings discarding by preconcentration technological process of production :-70～0mm titanium ore is roughly selected through prescreening machine (1), electromagnetism roller (2), and electromagnetism roller (3) is scanned and dumped mine tailing ₁The preliminary election ore reaches test sieve extension set (4) through in advance, and+10mm ore advances fine crusher (5), and-10～0mm ore enters primary grinding machine (6) ore grinding after taking off magnetic; The grinding machine ore discharge is through spiral grading sieve (7) classification, and+3mm ore returns grinding machine and regrinds, and-3～0mm ore enters gravity treatment for the first time or the low intensity magnetic separation technical process of taking the lead;

2.+and the 70mm weathered ore washup technological process of production: the weathered ore warp is every sieve (8), and+70mm nugget is crushed to-70～0mm through stoning machine (9), through log washer (10) washup; + 10mm ore enters fine crusher (5), and-10mm ore enters first section ore mill (6); The grinding machine ore discharge is through spiral grading sieve (7) classification, and+3mm ore returns grinding machine (6) and regrinds, and-3～0mm ore enters gravity treatment for the first time or the low intensity magnetic separation technical process of taking the lead;

3. produce concentrated ilmenite or titanium sand concentrate by magnetizing roasting stage grinding and stage separation " ore grinding-gravity treatment-low intensity magnetic separation-magnetizing roasting-ore grinding-gravity treatment-high intensity magnetic separation " technical process :-70mm titanium ore is after tailings discarding by preconcentration or weathered ore washup, and the ore of-10mm is through primary grinding (6); The grinding machine ore discharge is through spiral grading sieve (7) classification, and the ore of+3mm returns grinding machine (6) and regrinds, and the ore of-3mm enters gravity concentrator (11) and roughly selects, and dumps mine tailing ₂Get rough concentrate ₁, chats through low intensity magnetic separation machine (12) roughly select rough concentrate ₂The low intensity magnetic separation mine tailing enters fluidizing furnace or rotary kiln or ramp type stoving oven magnetizing roasting (14) after taking off magnetic, filtration drying (13); Magnetizing roasting rough concentrate and rough concentrate ₁, rough concentrate ₂Enter two sections grinding machines (15) fine grinding, two sections grinding machine ore discharges are through taking off magnetic spiral grading sieve or hydrocyclone (16) classification; + 0.15mm ore returns grinding machine (15) and regrinds, and-0.15mm the mineral of monomer dissociation carries out the gravity treatment second time through gravity concentrator (17) and roughly selects, concentrate ₃And mine tailing ₃The gravity treatment chats through a midfield intensity magnetic separator (18) roughly select concentrate ₄, midfield high intensity magnetic separation mine tailing takes off magnetic compass secondary midfield intensity magnetic separator (19) and scans and dump mine tailing ₄Get concentrate ₅Concentrate ₃, concentrate ₄And concentrate ₅Mix concentrated ilmenite or titanium sand concentrate;

4. produce concentrated ilmenite or titanium sand concentrate by magnetizing roasting stage grinding and stage separation " ore grinding-low intensity magnetic separation-high intensity magnetic separation-magnetizing roasting-ore grinding-low intensity magnetic separation-high intensity magnetic separation " technical process :-70mm titanium ore is after tailings discarding by preconcentration or weathered ore washup, the ore of-10mm is through primary grinding (6), the grinding machine ore discharge is through spiral grading sieve (7) classification, and+3mm ore returns ore mill (6) and regrinds;-3～0mm ore enter low intensity magnetic separation machine (12) roughly select rough concentrate ₁And rough concentrate ₂, rough concentrate ₂Take off magnetic and enter for the first time that midfield intensity magnetic separator (18) dumps mine tailing ₂Get rough concentrate ₃Rough concentrate ₃Filtration drying (13) enters fluidizing furnace or rotary kiln or ramp type stoving oven magnetizing roasting (14); Magnetizing roasting rough concentrate and rough concentrate ₁Enter second section grinding machine (15) fine grinding, second section grinding machine ore discharge is through spiral grading sieve or hydrocyclone (16) classification; + 0.15mm returns in the ore deposit secondary grinding machine (15) and regrinds, and-0.15mm ore gets concentrate through low intensity magnetic separation machine (12) ₄, the low intensity magnetic separation mine tailing through take off magnetic enter for the second time midfield intensity magnetic separator (19) concentrate ₅, secondary midfield intensity magnetic separator (19) mine tailing enters for the third time through taking off magnetic that midfield intensity magnetic separator (20) dumps mine tailing ₃Get concentrate ₆Concentrate ₄, concentrate ₅And concentrate ₆Mix concentrated ilmenite or titanium sand concentrate;

5. the concentrated ilmenite of magnetizing roasting stage grinding and stage separation production or titanium sand concentrate electrosmelting are produced titanium slag or the molten titanium slag that divides: concentrated ilmenite or titanium sand concentrate, perhaps this concentrated ilmenite, titanium sand concentrate and sefstromite concentrate or ilmenite concentrate mix back (22) behind binding agent and the carbonaceous reducing agent mixing by a certain percentage, make pelletizing (23), advance rotary kiln (24) prereduction or, smelt production alloy hot metal and TiO at the hot stove of electric blast furnace or ore deposit (25) directly into stove ₂＞68% titanium slag or the molten titanium slag that divides; Alloy hot metal blows vanadium chromium through duplex practice, and the slag that gained contains vanadium chromium separates vanadium chromium with hydrometallurgical extraction; And titanium slag or molten branch titanium slag secluding air enter the rich titanium material of gravity concentration process production higher-grade solubility in acid after cooling off; Titanium slag, molten divide titanium slag or enter the pyrometallurgy ore dressing process produce the rich titanium material of rutile;

6. titanium slag or molten divide titanium slag gravity concentration production higher-grade solubility in acid rich titanium material: titanium slag or molten divide titanium slag send into vacuum pump (27) take out cool off in the cool furnace (26) of air or input inert gas after, carry out fragmentation (28), ore grinding (29), gravity concentration (30), mine tailing is processed into devitrified glass; Chats returns electrosmelting (25), and the gravity concentration concentrate is TiO ₂The rich titanium material of 75%～92% solubility in acid is worn into the rich titanium material of solubility in acid that fineness is 0.045mm～0.075mm through Raymond mill (31);

7. titanium slag or molten divide titanium slag or the rich titanium material of solubility in acid pyrometallurgy ore dressing to produce the rich titanium material of rutile: titanium slag or moltenly divide titanium slag or enter insulation crystallization oxidized still (32) without the rich titanium material of the solubility in acid of Raymond mill (31) fine grinding, with the electric-arc heating oxygen blast or with oxygen one Fuel lance or oxygen, air direct current plasma producer to insulation oxidized still (32) heating oxygen blast, add silica, fluoride additive simultaneously, the rich titanium material of titanium slag or solubility in acid is carried out deep oxidation, make in titanium slag or the rich titanium material mainly with Ti ₃O ₅Be oxidized to the rutile TiO of octahedral structure for the titanium suboxide in the Solid solution titaniferous ore anosovite of base ₂, impurity such as calcium magnesium are left out, and enter in the silicate glass body, form the rich titanium material of rutilization, and the rich titanium material of this rutilization makes the cooling of rutile grain growth in annealer (33) after broken (34), and ore grinding (35) and gravity treatment (36) dump mine tailing, get TiO ₂The rich titanium material of＞92%～96% low calcium and magnesium artificial rutile, chats returns the melting oxidation once more of insulation oxidized still (32), and to improve the rate of recovery of titanium, mine tailing is processed into devitrified glass;

8., the TiO of pyrometallurgy ore dressing production ₂The rich titanium material of＞92%～96% low calcium and magnesium artificial rutile is produced the rich titanium material of carbon containing rutile: the coal of rich titanium material of rutile and fixed carbon C＞60% arrives-0.045mm and binder formulation (39) mixing C/TiO through grinding machine (37), (38) fine grinding ₂＞20%～30%, binding agent 0.3%～0.6%, granulation (40); The roasting 20 minutes (41) in 900 ℃～950 ℃ stoving ovens of carbon containing titanium grain; Then carbon containing titanium grain is sent into vacuum pump (42) take out air or have prevent carbon containing titanium grain oxidation cooling in the water cooler (43) of inert gas after, through double-layer spiral sizing screen or two individual layer screw classifiers (44) classification,-0.3mm grade and+1.4mm grade carbon containing titanium grain returns grinding machine (37) recycle of regrinding ,+0.3mm～-the rich titanium material of carbon containing rutile of 1.4mm grade.

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