CN113318865B - Flotation reagent for high-calcium magnesium vanadium titano-magnetite and method for preparing chlorinated titanium-rich material from high-calcium magnesium vanadium titano-magnetite - Google Patents
Flotation reagent for high-calcium magnesium vanadium titano-magnetite and method for preparing chlorinated titanium-rich material from high-calcium magnesium vanadium titano-magnetite Download PDFInfo
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Abstract
The invention discloses a high-calcium magnesium vanadium titano-magnetite flotation reagent which comprises a composite reagent, a collecting agent, a regulator and an inhibitor, wherein the composite reagent is composed of synthetic dodecylamine, tall acid and mixed amine. Also discloses a method for preparing a chlorinated titanium-rich material from the high-calcium magnesium vanadium titano-magnetite, which comprises the step of carrying out flotation by using the flotation reagent for the high-calcium magnesium vanadium titano-magnetite. The advantages are that: 1) the flotation reagent for the high-calcium magnesium vanadium titano-magnetite provided by the invention can greatly reduce the impurity content in the Panxi titanium concentrate, and lays a foundation for post-smelting high-titanium slag meeting the chlorination index requirement. 2) By blending outsourcing titanium concentrate with the granularity of 200-500 meshes with the titanium concentrate, the incrustation phenomenon in the smelting process can be prevented, the slag turning risk is reduced, and the comprehensive yield of titanium elements is improved. 3) Solves the problem that the Panxi titanium concentrate is difficult to be used for producing the chlorinated titanium-rich material, and has the advantages of short flow, low cost and the like.
Description
Technical Field
The invention relates to a titanium dioxide production technology, in particular to a titanium dioxide production technology by a chlorination process.
Background
In recent years, with the increasingly strict environmental protection policy of China, the production of sulfuric acid method titanium dioxide with high pollution in the titanium industry is limited. The production technology of titanium dioxide by a chloride process, which has less environmental influence and higher technical content, is encouraged by national industrial policies. According to statistics, the capacity of titanium dioxide produced by chlorination process in China has increased to about 40 ten thousand tons per year by 2019. Compared with the sulfuric acid method titanium dioxide production technology, the chlorination method has the advantages of short flow, high automation degree, good product quality, environmental friendliness and the like, but also has the problem of strict requirement on raw material indexes, and the chlorination method titanium dioxide factory internationally except for the indigenous part of the Dupont America adopts TiO 2 The titanium ore with the grade of about 60 percent is used as the raw material, and the rest is the chloridized rich titanium material. The titanium-rich chloride material generally refers to three types of natural rutile, artificial rutile or titanium chloride slag (including UGS slag).
At present, the serious shortage of high-quality chlorination raw material supply in China directly affects the development prospects of the chlorination-process titanium dioxide industry and the titanium sponge industry in China, and is mainly caused by the following reasons:
1. although China is a big titanium resource country, the method is suitable for producing natural rutile from titanium sponge and titanium dioxide by chlorination process, and is suitable for processing into high-quality titanium ore resource shortage of chlorinated titanium-rich material. According to the introduction of related data, more than 95 percent of titanium resources in China belong to primary vanadium titano-magnetite (mainly distributed in Panxi and Chengde areas), and TiO in the ore belongs to primary vanadium titano-magnetite 2 Low grade, CaO, MgO, SiO 2 Reducing and smelting TiO in the titanium slag with high content of equal impurities 2 The grade can only reach 70-77%, and the content of MgO + CaO reaches 7-10%, so that the catalyst cannot be used for boiling chlorination. In China Yunnan region, although the weathering placer resources exist, the weathering is not complete, and CaO, MgO and SiO in the placer resources 2 The content of the impurities is also high, the distribution of ore deposit is scattered, the mining scale is small, and in addition, the 'depletion' problem caused by over mining is caused, and the quantity and the quality of the impurities are difficult to support the development of the high-end titanium industry in China. Guangxi and Guangdong have part of placer resources with excellent quality, can meet the index requirements of producing the titanium-rich chloride material, but have too small yield. There is a small amount of natural rutile in the Hainan area, but exploitation is prohibited due to the development of the tourist industry.
2. At present, more than 60 titanium slag production enterprises exist in China, the titanium slag production enterprises are mainly concentrated in provinces such as Sichuan, Yunnan, Hebei, Liaoning and inner Mongolia, and the annual capacity is about 150 million tons. Although China has more titanium slag production enterprises, the large-scale enterprises are few, the annual output is only 2-3 enterprises with more than 10 ten thousand tons, and the difference is larger compared with the difference from abroad. In recent years, due to the shortage of domestic power resources and high-quality titanium concentrate supply and the like, production of some enterprises is stopped or reduced. The annual output of titanium slag in the nation in 2019 is about 80 ten thousand tons, wherein the annual output of chloride slag is only 20-30 ten thousand tons, the requirement of industrial development of titanium dioxide and titanium sponge by the chlorination process in China cannot be met, and the shortage part needs to be supplemented by imported natural rutile, artificial rutile, UGS slag or chloride slag.
3. A large foreign multinational company controls the supply channel of the chlorinated titanium-rich materials in China, and at present, enterprises which can supply a large amount of chlorinated titanium-rich materials worldwide are mainly a force group and an Ailuca company, wherein the force group supplies UGS slag and RTCS slag. Elafin is mainly supplied with synthetic rutile and natural rutile. Because the two enterprises establish long-term cooperation with other national titanium dioxide enterprises, the chlorinated titanium-rich materials sold to China market are limited in quantity and high in price, and the requirements of the development of the China titanium industry are difficult to meet.
4. Because the domestic titanium concentrate has higher impurity content and lower quality, the titanium chloride slag with qualified indexes can be produced only by adopting imported high-quality titanium concentrate, and the supply channel of the high-quality titanium concentrate is monopolized by international groups such as the development group, the Japan triple well group, the British Bess company and the like, and the supply quantity, the price and other factors are not controlled by the domestic market.
In view of the above reasons, the development of domestic raw materials to prepare titanium-rich chloride materials is the key to the healthy and sustainable development of titanium dioxide and titanium sponge in the chlorination process in China. The national has long recognized the importance of the supply and production technology of the domestic titanium-rich chloride material, the ministry of chemical industry organizes many colleges and scientific research institutions in China as early as the period of 'seventy five' and 'eighty five', the research, development and attack of the technology for producing the titanium-rich chloride material based on domestic raw materials are developed, the technical routes of hydrochloric acid method, corrosion method, selective chlorination method and the like are successively adopted, four pilot test bases are established in China, and the results show that the processes have the problems of long flow, high product impurity content, low production cost, high environmental protection pressure and the like, and the industrial popularization (industrialization) is not finally realized.
In recent years, with the rapid development of the titanium industry in China, the technology for producing the chlorinated titanium-rich material based on the domestic titanium resource is more prominent and important. A large number of domestic enterprises and research and development institutions have made intensive research and certain achievements for the purpose.
The invention patent with publication number CN1225562C discloses a method for producing titanium-rich material by using titanium ore resources, which adopts the technical scheme that: vanadium titano-magnetite is carried out by pre-selecting, discarding tailings or washing weathered ores, then carrying out magnetizing roasting and grinding separation, separating gangue minerals to obtain ilmenite concentrate, or mixing the ilmenite concentrate and the vanadium titano-magnetite according to a certain proportion, adding binder and carbon reducer to pelletize, carrying out pre-reduction or directly feeding into a furnace, smelting in an electric blast furnace or a submerged arc furnace to produce high titanium slag and semisteel, blowing vanadium and chromium from alloy molten iron by a duplex method, extracting and separating vanadium and chromium from the obtained steel slag by a wet method, and feeding the high titanium slag into a pyrometallurgical beneficiation process of the titanium slag to produce artificial rutile and microcrystalline glass. Grinding the artificial rutile titanium-rich material and the coal powder, mixing according to a certain proportion, adding a binder to prepare carbon-containing particles, roasting, cooling and screening to obtain the carbon-containing rutile titanium-rich material with the particle size of +0.3mm to-1.4 mm. The technology can obtain the low-calcium-magnesium titanium-rich material with coarse particles and 92-96% of grade, but has the problems of complex production process, long flow, low titanium yield, high energy consumption, high cost and the like.
The invention patent with publication number CN106011501A discloses a method for preparing titanium-rich material from Panzhihua ilmenite, which comprises the steps of firstly, preparing Panzhihua titanium concentrate in a titanium-rich materialHigh-temperature oxidation in air, then passing through H 2 Reduction of the/CO gas mixture, reduction of the ilmenite material in NH 4 Rust corrosion separation in the Cl solution comprises the following specific steps: a. screening the Panzhihua ilmenite concentrate, putting the Panzhihua ilmenite concentrate into a muffle furnace for high-temperature oxidation in air, and naturally cooling the Panzhihua ilmenite concentrate after heat preservation; b. crushing the oxidized and bonded Panzhihua ilmenite concentrate particles, putting the crushed Panzhihua ilmenite concentrate particles into a fluidized bed furnace for reduction, and adding N into the fluidized bed furnace for reduction 2 Heating in the atmosphere and introducing H 2 Reducing and roasting with CO mixed gas to obtain reduced ilmenite; c. carrying out corrosion separation on the reduced ilmenite; screening the rusted product to obtain a titanium-rich material and an iron oxidation product, wherein the particle size of the titanium-rich material is +48um, and the particle size of the TiO is +48um 2 The content is 74.31%, and the recovery rate reaches 98.9%. The method has simple process and convenient operation, can efficiently reduce the ilmenite, improves the reduction metallization rate of the ilmenite, and is beneficial to recycling of iron. However, the method is difficult to remove calcium, magnesium and silicon impurities in the Panzhihua titanium concentrate, so that the grade of the titanium-rich material is not high, the calcium and magnesium impurities are high, and the index requirements of the boiling chlorination raw material are difficult to meet.
The invention patent with publication number CN104944466A discloses a production method for preparing a titanium-rich material by a wet method, which comprises the steps of obtaining acidic titanium solution, obtaining reduced titanium and preparing the titanium-rich material, wherein the production method comprises the following process steps: adding concentrated sulfuric acid or hydrochloric acid or a mixed solution of sulfuric acid and hydrochloric acid and ilmenite into a premixing tank, adding into an acidolysis pot, and adding a trigger solution to obtain an acidolysis product; diluting to obtain acidic titanium solution; mixing the titanium concentrate and pulverized coal, calcining in a rotary kiln, and taking out of the rotary kiln for magnetic separation to obtain reduced titanium; filtering the acidic titanium to obtain acidic titanium liquid with high purity; adding the reduced titanium in the step into high-purity acidic titanium liquid for reduction; when trivalent titanium appears in the titanium solution, the reduction is finished; solid-liquid separation; and drying the solid phase to obtain the titanium-rich material. The method can produce a titanium-rich material meeting the requirement of a chlorination process, can save the consumption of a large amount of energy in electric furnace melting, and can provide a new development mode for the production of titanium white by a sulfuric acid process. However, the invention has higher requirements on the quality of the titanium concentrate, the lower the requirements on impurity elements of calcium, magnesium and silicon in the ore, the better, the titanium concentrate produced in China is difficult to meet, and simultaneously, the invention also needs to be matched with a corresponding titanium dioxide device by a sulfuric acid method, and the application range of the invention is greatly limited.
The invention with publication number CN100336924C discloses a method for preparing a primary titanium-rich material from high-calcium magnesium titanium concentrate, which comprises the steps of grinding 45-50% of titanium concentrate to a granularity of less than 0.074mm, adding 8-20% of water, 3-5% of binder sodium silicate, 10-20% of coke, 1-5% of sodium sulfate, 1-3% of iron powder and 3-5% of potassium chloride based on the weight of the titanium concentrate to prepare a composite pellet with the diameter of 10-15 mm, and finally preparing 60-70% of the primary titanium-rich material through microwave drying, microwave heating reduction and mineral separation. The ilmenite belongs to a strong wave absorbing body, so that the microwave heating temperature rise speed is high, the production efficiency is favorably improved, the reduction temperature is reduced to 80-120 ℃ by adopting the composite additive, the acid solubility of calcium and magnesium impurities of the primary titanium-rich material is good, and the grade of the primary titanium-rich material is high. However, the technical process route is complex, the chemical additive dosage is large, the product grade is low, the titanium dioxide can not be directly used on a titanium dioxide production device by a chlorination method, and subsequent deep processing is needed, so that the production cost is increased, and meanwhile, microwave equipment is complex and expensive, and the industrial application of large-scale microwave equipment is rarely reported.
Patent application with publication number CN110093504A provides a method for preparing titanium-rich material by using high-calcium magnesium titanium concentrate, which comprises the following steps: 1) mixing the high-calcium magnesium titanium concentrate and the coal powder, then carrying out ball milling, then adding a binder, an additive and water into the mixed powder, and carrying out uniform mixing, pelletizing and drying to obtain mixed pellets; 2) uniformly spreading the pellets on a chain grate, and respectively carrying out pre-dehydration and preheating treatment; 3) feeding the pretreated pellets into a first rotary kiln for primary reaction; 4) conveying the pellets subjected to the primary reaction into a second rotary kiln for secondary reaction, wherein the reaction atmosphere is a mixed atmosphere of hydrogen and nitrogen; 5) and sending the pellets after the secondary reaction into a cooling chamber for cooling, and then crushing and magnetically separating. The method adopted by the invention respectively realizes the high-temperature environment and the atmosphere environment required by the preparation of the TiCxOyNz by reducing and nitriding the high-calcium-magnesium ilmenite, greatly improves the production efficiency of the TiCxOyNz, reduces the production cost and provides ideal raw materials for a low-temperature chlorination process. However, the technical process is long and complicated, the device and equipment are complicated, and the final crushing and magnetic separation process results in the reduction of the yield of the titanium element.
At present, a plurality of domestic scholars research and discover: the hydrochloric acid can effectively remove iron and most of CaO, MgO and Al in the titanium concentrate 2 O 3 MnO and the like, thereby obtaining TiO-containing 2 The synthetic rutile is 88-96% of high-grade synthetic rutile, is particularly suitable for processing various complex titanium concentrates, and makes the production process of the synthetic rutile by the hydrochloric acid method become a hotspot of the research on the production technology of the chlorinated titanium-rich material at present. For example, the invention patent with publication number CN1552628A discloses a method for preparing artificial rutile from high-calcium magnesium vanadium titano-magnetite, which comprises the steps of carrying out weak oxidation treatment on titanium concentrate, carrying out magnetic separation, adding the titanium concentrate into a spherical digester, carrying out pressure leaching by using hydrochloric acid, carrying out solid-liquid separation after the reaction is finished, drying, calcining, carrying out magnetic separation, granulating a fine-grained product, and finally obtaining the high-quality artificial rutile suitable for a chlorination process, wherein mother liquor in the production process is treated by a spray calcination method, iron oxide in the mother liquor is recycled, and generated HCl acid mist is returned for use. The invention has more complete process flow, can obtain products meeting the boiling chlorination requirement, but has the problems of long process flow, complex equipment, high pulverization rate, difficult fine material granulation and the like. Also, for example, patent publication No. CN101177297A discloses a method for preparing high-quality synthetic rutile from high-calcium magnesium rock ore, which comprises the following steps: ball milling activation, hydrochloric acid atmospheric pressure leaching, solid-liquid separation, washing and drying, calcining and fine particle granulation. The method activates the titanium concentrate through mechanical energy, improves the leaching performance of the titanium concentrate, finally obtains the synthetic rutile product with higher grade, and reduces energy consumption to a certain extent. However, the process has the problems of high product pulverization rate, difficult granulation, unsolved mother liquor treatment and the like. In addition, the invention patent with the publication number of CN101412536A discloses a method for preparing artificial rutile from high-calcium magnesium vanadium titano-magnetite. The method comprises the steps of taking Panxi vanadium titano-magnetite as a raw material, firstly carrying out fluidized oxidation roasting on the Panxi vanadium titano-magnetite at a certain temperature, then carrying out fluidized reduction roasting on the material after oxidation roasting, then carrying out fluidized leaching on the modified material by hydrochloric acid with a certain concentration, and finally carrying out solid-liquid separation, drying and roasting to obtain the product. The methodThe biggest highlight of the method is the introduction of fluidization technology, which reduces the reaction time of materials and the pulverization rate of products to a certain extent. But the method is difficult to avoid the problem of pulverization, and has the defects of high requirement on the particle size of the titanium ore, complex fluidization equipment, high operation requirement and the like.
From the world, at present, the Canada QIT company is the only company which can successfully utilize high-calcium, magnesium and silicon raw materials to produce high-grade rich titanium materials (UGS slag) for boiling chlorination and realize industrial production, but the process technology is strictly kept secret from the outside. U.S. Pat. No. 5830420 to QIT company discloses that titanium slag (TiO) with a particle size range of less than 75-850 μm 2 82.55%, CaO0.47%, MgO5.56%), oxidizing at 950-1200 deg.C for 45min in fluidized bed, and mixing with gas (containing 85% CO and 15% H) at 700-800 deg.C 2 ) Reducing for 1h, carrying out pressure acid leaching on the reduced titanium slag at 145 ℃, washing the acid leaching product, carrying out alkali leaching at the leaching temperature of 50-100 ℃ by using 5-10% NaOH solution, and calcining the leaching product at 600-800 ℃ to obtain TiO 2 About 95 percent of high-grade titanium-rich material.
By using UGS slag production technology of QIT company as reference, researchers in China put forward a technical route for producing chlorinated rich materials based on Panzhihua titanium concentrate as a raw material, for example, a patent with publication number CN109499744A discloses a method for preparing chlorinated rich titanium materials by using high-calcium magnesium silicon titanium concentrate, which comprises the following steps: (1) ball-milling the titanium concentrate, then carrying out size mixing, and then adding a flotation reagent for direct flotation to obtain low-silicon titanium concentrate; (2) mixing the obtained low-silicon titanium concentrate with hydrochloric acid, and performing acid leaching, filtering, washing and drying to obtain a fine-grained titanium-rich material; (3) and (3) heating and melting the fine-fraction titanium-rich material obtained in the step (2), cooling, and crushing to obtain the titanium-rich chloride material. The invention optimizes and improves the existing production process of titanium concentrate containing high calcium, magnesium and silicon in Panxi province, and removes a large amount of impurities such as calcium, titanium, silicon, calcium, silicon-aluminum compound and the like through flotation, wherein SiO is 2 The removal rate reaches more than 60 percent, and Si O is avoided 2 Form a "glass phase" solid solution with CaO which is difficult to react with hydrochloric acidThe acid leaching effect is responded, and the acid leaching efficiency and the quality of the leached titanium-rich material are greatly improved. The patent with the publication number of CN110629045A provides a method for preparing a titanium-rich material for boiling chlorination from low-grade titanium slag. The method comprises the following steps: (1) drying and screening the titanium slag; (2) carrying out high-temperature strong oxidation reaction on the titanium concentrate at 950-1000 ℃; (3) then carrying out weak reduction reaction at 800-850 ℃; (4) adding hydrochloric acid, and leaching under heating and rotating conditions; (5) and (4) carrying out solid-liquid separation, washing and drying to obtain a titanium-rich material finished product. The above patents can obtain the titanium-rich chloride material with high grade and qualified calcium and magnesium indexes, but the process route is longer, the equipment is complex, the byproduct mother liquor is difficult to treat, and the cost is higher, so the popularization is difficult.
The above patents can basically obtain high-grade titanium-rich raw materials, but due to the problems of technology, cost or environmental protection, except the industrial application of the patent CN104944466A of the Bailey company, other industrial production is rarely reported.
Disclosure of Invention
The invention provides a flotation agent for high-calcium magnesium vanadium titano-magnetite, which aims to reduce the cost of preparing chloridizable titanium-rich materials from Panxi titanium concentrate.
The technical scheme adopted by the invention is as follows: the high-calcium magnesium vanadium titano-magnetite flotation reagent comprises a composite reagent, a collecting agent, a regulator and an inhibitor, wherein the composite reagent consists of synthetic dodecylamine, tall acid and mixed amine.
As a further improvement of the invention, the composite medicament is composed of synthetic dodecylamine, talmic acid and mixed amine according to the mass ratio of 80: 5-15.
As a further improvement of the invention, the collector is diesel; the regulator is H 2 SO 4 (ii) a The inhibitor is composed of water glass and malonic acid according to the mass ratio of 1: 1-3.
As a further improvement of the invention, the mass ratio of the composite medicament, the collecting agent, the regulator and the inhibitor is 10: 10-30: 1-5: 1-15.
The invention also discloses a method for preparing the chlorinated titanium-rich material from the high-calcium magnesium vanadium titano-magnetite, which comprises the step of carrying out flotation by using the flotation reagent for the high-calcium magnesium vanadium titano-magnetite.
The method for preparing the chlorinated titanium-rich material from the high-calcium magnesium vanadium titano-magnetite can be specifically implemented according to the following steps:
s1, ball-milling the high-calcium magnesium vanadium titano-magnetite to fully dissociate ilmenite and gangue, and then adjusting the concentration of the ground ore pulp according to the mass ratio of ore water of 1: 4-8;
s2, adding the high-calcium magnesium vanadium titano-magnetite flotation reagent into the ore pulp to carry out flotation for 2-4 times to obtain titanium concentrate;
s3, blending the titanium concentrate and outsourcing titanium concentrate according to a certain proportion, then adding anthracite as a reducing agent, and carrying out electric smelting to obtain high-titanium slag;
s4, crushing and screening the high titanium slag obtained by smelting to obtain the titanium slag.
As a further improvement of the method, the blending mass ratio of the titanium concentrate to the outsourcing titanium concentrate is 1: 1.5-2.
As a further improvement of the invention, the granularity of the purchased titanium concentrate is 200-500 meshes, and the purchased titanium concentrate with the granularity is blended with the titanium concentrate, so that the incrustation phenomenon in the smelting process can be prevented, the slag turning risk is reduced, and the comprehensive yield of titanium elements is improved.
As a further improvement of the invention, in the step S4, the titanium-rich chloride material with the particle size of 60-160 meshes being more than 80% by mass is obtained through crushing and screening.
The invention also discloses a chlorinated titanium-rich material, which is prepared by the method for preparing the chlorinated titanium-rich material from the high-calcium magnesium vanadium titano-magnetite.
The high-calcium magnesium vanadium titano-magnetite of the invention refers to SiO in percentage by mass 2 More than or equal to 2.5 percent of vanadium titano-magnetite, and more than or equal to 5.0 percent of CaO + MgO, such as Panxi vanadium titano-magnetite.
The invention has the beneficial effects that: 1) the flotation reagent for the high-calcium magnesium vanadium titano-magnetite provided by the invention can greatly reduce the impurity content in the Panxi titanium concentrate, and lays a foundation for post-smelting high-titanium slag meeting the chlorination index requirement. 2) By blending outsourcing titanium concentrate with the granularity of 200-500 meshes with the titanium concentrate, the incrustation phenomenon in the smelting process can be prevented, the slag turning risk is reduced, and the comprehensive yield of titanium elements is improved. 3) The method solves the problem that the Panxi titanium concentrate is difficult to be used for producing the chlorinated titanium-rich material, and has the advantages of short flow, low cost and the like; the invention has strong adaptability of raw materials, wide sources and stable supply, can stand domestic high-calcium magnesium vanadium titano-magnetite, and has lower comprehensive cost than overseas imported ores; the invention does not relate to a new process, new equipment and a new material, has smaller technical risk and is easy for industrialized popularization.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
The first embodiment is as follows:
the chlorinated titanium-rich material is produced according to the following method:
(1) for a certain Panxi high silicon calcium magnesium titanium concentrate (TiO) 2 ：46.51％、SiO 2 : 2.58%, CaO: 2.27%, MgO: 3.75 percent) of the ore pulp, fully dissociating the ilmenite and the gangue, and then adjusting the concentration of the ground ore pulp according to the ratio of the mass ratio of the ore water to the ore water of 1: 6;
(2) adding a high-calcium magnesium vanadium titano-magnetite flotation reagent into the ore pulp to carry out flotation for 4 times to obtain concentrated titanium concentrate; the high-calcium magnesium vanadium titano-magnetite flotation reagent is prepared from a composite reagent, diesel oil and H 2 SO 4 The inhibitor is composed of synthetic dodecylamine, talmic acid and mixed amine according to the mass ratio of 10:30:3:12, wherein the composite medicament is composed of synthetic dodecylamine, talmic acid and mixed amine according to the mass ratio of 80:10: 10; the inhibitor consists of water glass and malonic acid according to the mass ratio of 1:1. Titanium concentrate (TiO) obtained by flotation 2 ：48.19％、SiO 2 : 0.66%, CaO: 0.23%, MgO: 1.75%) yield of 43.5% and the high-silicon titanium concentrate yield obtained was 55.67% (TiO) 2 : 44.38%), with a titanium loss of less than 2%.
(3) Blending the titanium concentrate and outsourcing Vietnam A ore with the granularity of 250-300 meshes according to the mass ratio of 1:2, wherein the Vietnam A ore comprises the following components:
| item | TiO 2 | TFe | SiO 2 | CaO | MgO | Al 2 O 3 | P 2 O 5 | S | Others |
| Vietnam A ore w/%) | 54.63 | 29.28 | 0.92 | 0.04 | 0.63 | 0.78 | 0.07 | ≤0.01 | —— |
The titanium slag product with the following components is finally obtained by carrying out carbon thermal reduction on the mixed titanium concentrate and a measured amount of anthracite as a reducing agent in an electric furnace:
| item | TiO 2 | TFe | SiO 2 | CaO | MgO | Al 2 O 3 | Others |
| Titanium slag w/%) | 90.57 | 3.17 | 1.72 | 0.16 | 1.63 | 1.18 | —— |
(4) The titanium slag is crushed to finally obtain the high-titanium slag with the components, wherein the particle size of the high-titanium slag ranges from 60 meshes to 160 meshes, and the mass percent of the particles is 80.37%, and the high-titanium slag can completely meet the index requirements of titanium dioxide raw materials in a chlorination process.
Example two:
the chlorinated titanium-rich material is produced according to the following method:
(1) for a certain Panxi high silicon calcium magnesium titanium concentrate (TiO) 2 ：46.51％、SiO 2 : 2.58%, CaO: 2.27%, MgO: 3.75 percent) of the ore pulp, fully dissociating the ilmenite and the gangue, and then adjusting the concentration of the ground ore pulp according to the ratio of the mass ratio of the ore water to the ore water of 1: 6;
(2) adding a high-calcium magnesium vanadium titano-magnetite flotation reagent into the ore pulp to carry out flotation for 4 times to obtain a titanium concentrate; the high-calcium magnesium vanadium titano-magnetite flotation reagent is prepared from a composite reagent, diesel oil and H 2 SO 4 The inhibitor is composed of synthetic dodecylamine, talmic acid and mixed amine according to the mass ratio of 10:20:5:13, wherein the composite medicament is composed of synthetic dodecylamine, talmic acid and mixed amine according to the mass ratio of 80:10: 10; the inhibitor consists of water glass and malonic acid according to the mass ratio of 1: 2. Titanium concentrate (TiO) obtained by flotation 2 ：48.19％、SiO 2 : 0.66%, CaO: 0.23%, MgO: 1.75%) yield of 43.5% and the high-silicon titanium concentrate yield obtained was 55.67% (TiO) 2 : 44.38%), with a titanium loss of less than 2%.
(3) Blending the titanium concentrate and outsourcing Vietnam A ore with the granularity of 250-300 meshes according to the mass ratio of 2: 3, wherein the Vietnam A ore comprises the following components:
| item | TiO 2 | TFe | SiO 2 | CaO | MgO | Al 2 O 3 | P 2 O 5 | S | Others |
| Vietnam a ore w/%) | 54.63 | 29.28 | 0.92 | 0.04 | 0.63 | 0.78 | 0.07 | ≤0.01 | —— |
The titanium slag product with the following components is finally obtained by carrying out carbon thermal reduction on the mixed titanium concentrate and a measured amount of anthracite as a reducing agent in an electric furnace:
| item | TiO 2 | TFe | SiO 2 | CaO | MgO | Al 2 O 3 | Others |
| W/% of titanium slag | 89.57 | 3.66 | 2.11 | 0.21 | 1.98 | 1.56 | —— |
(4) The titanium slag is crushed to finally obtain the high titanium slag with the components, wherein the mass percentage of the particles with the granularity of 60-160 meshes is 81.23%, and the high titanium slag can meet the index requirements of titanium dioxide raw materials in a chlorination process.
Example three:
the chlorinated titanium-rich material is produced according to the following method:
(1) for a certain Panxi high silicon calcium magnesium titanium concentrate (TiO) 2 ：46.51％、SiO 2 : 2.58%, CaO: 2.27%, MgO: 3.75 percent) of the ore pulp, fully dissociating the ilmenite and the gangue, and then adjusting the concentration of the ground ore pulp according to the ratio of the mass ratio of the ore water to the ore water of 1: 6;
(2) adding a high-calcium magnesium vanadium titano-magnetite flotation reagent into the ore pulp to carry out flotation for 4 times to obtain concentrated titanium concentrate; the flotation reagent for the high-calcium magnesium vanadium titano-magnetite consists of a composite reagent,diesel oil, H 2 SO 4 The inhibitor consists of synthetic laurylamine, talmic acid and mixed amine according to a mass ratio of 10:16:3:10, wherein the compound medicament consists of the synthetic laurylamine, the talmic acid and the mixed amine according to a mass ratio of 80:10: 10; the inhibitor consists of water glass and malonic acid according to the mass ratio of 1: 1.3. Titanium concentrate (TiO) obtained by flotation 2 ：48.19％、SiO 2 : 0.66%, CaO: 0.23%, MgO: 1.75%) yield of 43.5% and the high-silicon titanium concentrate yield obtained was 55.67% (TiO) 2 : 44.38%), with a titanium loss of less than 2%.
(3) Blending the titanium concentrate and outsourcing Vietnam A ore with the granularity of 250-300 meshes according to the mass ratio of 3: 2, wherein the Vietnam A ore comprises the following components:
| item | TiO 2 | TFe | SiO 2 | CaO | MgO | Al 2 O 3 | P 2 O 5 | S | Others |
| Vietnam a ore w/%) | 54.63 | 29.28 | 0.92 | 0.04 | 0.63 | 0.78 | 0.07 | ≤0.01 | —— |
The titanium slag product with the following components is finally obtained by carrying out carbon thermal reduction on the mixed titanium concentrate and a measured amount of anthracite as a reducing agent in an electric furnace:
| item | TiO 2 | TFe | SiO 2 | CaO | MgO | Al 2 O 3 | Others |
| W/% of titanium slag | 87.57 | 4.14 | 2.38 | 0.32 | 2.21 | 1.89 | —— |
As can be seen from the above table, the indexes of the titanium slag components cannot meet the index requirements of titanium dioxide raw materials in the chlorination process.
The above examples illustrate that the blending proportion of the decontaminated Panxi titanium concentrate into the Vietnam A ore can reach 40%, and the concentrate can replace expensive imported titanium concentrate with limited quantity to a certain extent.
Comparative example one:
this comparative example is a control experiment of example one, carried out following exactly the same procedures and conditions as example one, except that outsourcing Vietnam A ore was crushed to a particle size of < 120 mesh in step (3). The mixed titanium concentrate is mixed with a certain amount of anthracite coal as a reducing agent to carry out carbon thermal reduction in an electric furnace, so that a severe crusting phenomenon occurs, and a titanium slag product with the following components is finally obtained:
| item | TiO 2 | TFe | SiO 2 | CaO | MgO | Al 2 O 3 | Others |
| Titanium slag w/%) | 86.97 | 4.69 | 2.41 | 0.19 | 1.97 | 1.87 | —— |
As can be seen from the first example and the first comparative example, the external titanium concentrate with the granularity of 250-300 meshes is mixed with the titanium concentrate of the invention, so that the incrustation phenomenon in the smelting process can be prevented, and the yield of titanium elements is improved.
Claims (6)
1. The method for preparing the chlorinated titanium-rich material from the high-calcium magnesium vanadium titano-magnetite is characterized by comprising the following steps:
s1, carrying out ball milling on the high-calcium magnesium vanadium titano-magnetite to fully dissociate ilmenite and gangue, and then adjusting the concentration of the milled ore pulp according to the ratio of the mass ratio of ore to water of 1: 4-8;
s2, adding a high-calcium magnesium vanadium titano-magnetite flotation reagent into the ore pulp to perform flotation for 2-4 times to obtain concentrated ilmenite; the high-calcium magnesium vanadium titano-magnetite flotation reagent comprises a composite reagent, a collecting agent, a regulator and an inhibitor, wherein the composite reagent consists of synthetic dodecylamine, tall acid and mixed amine;
s3, blending the titanium concentrate and the purchased titanium concentrate according to a certain proportion, then blending anthracite as a reducing agent, and carrying out electrometallurgy smelting to obtain high-titanium slag; the blending mass ratio of the titanium concentrate to the outsourcing titanium concentrate is 1: 1.5-2; the granularity of the outsourcing titanium concentrate is 200-500 meshes;
s4, crushing and screening the high titanium slag obtained by smelting to obtain the titanium slag.
2. The method for preparing the chlorinated titanium-rich material from the high-calcium magnesium vanadium titanomagnetite according to claim 1, characterized in that: the composite agent is composed of synthetic dodecylamine, talmic acid and mixed amine according to a mass ratio of 80: 5-15.
3. The method for preparing the chlorinated titanium-rich material from the high-calcium magnesium vanadium titanomagnetite according to claim 2, characterized in that: the collecting agent is diesel oil; the regulator is H 2 SO 4 (ii) a The inhibitor is composed of water glass and malonic acid according to the mass ratio of 1: 1-3.
4. The method for preparing the chlorinated titanium-rich material from the high-calcium magnesium vanadium titanomagnetite according to claim 3, characterized in that: the mass ratio of the composite reagent to the collecting agent to the regulating agent to the inhibiting agent is 10: 10-30: 1-5: 1-15.
5. The method for preparing the chlorinated titanium-rich material from the high-calcium magnesium vanadium titano-magnetite according to claim 1, characterized in that: and step S4, crushing and screening to obtain the chlorinated titanium-rich material with the particle size of 60-160 meshes, wherein the mass percent of the particles is more than 80%.
6. The titanium-rich chloride material prepared by the method for preparing the titanium-rich chloride material from the high-calcium magnesium vanadium titano-magnetite as claimed in any one of claims 1 to 5.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU4104778A (en) * | 1978-10-25 | 1980-05-01 | Companhia Vale Do Rio Doce | Process for beneficiation of titanium ores |
| CN102399998A (en) * | 2011-11-18 | 2012-04-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for reducing and smelting titania slag by utilizing vanadium-titanium-iron ore concentrates in molten state |
| CN102417944A (en) * | 2011-11-18 | 2012-04-18 | 攀钢集团研究院有限公司 | Method for utilizing vanadium-titanium-secondary iron concentrate to smelt acid-soluble titanium slag by way of smelting reduction |
| CN109338124A (en) * | 2018-11-23 | 2019-02-15 | 宜宾天原集团股份有限公司 | A method of chlorination rich-titanium material is prepared using high silicon-calcium-magnesium ilmenite concentrate |
| CN109468424A (en) * | 2018-11-23 | 2019-03-15 | 宜宾天原集团股份有限公司 | A method of high titanium slag is prepared using low grade natural rutile |
| CN110629044A (en) * | 2019-10-29 | 2019-12-31 | 攀钢集团钛业有限责任公司 | Method for directly smelting titanium slag from fine-fraction titanium concentrate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU472288B2 (en) * | 1971-04-29 | 1973-10-18 | Wendell E. Dunn, Inc | A process for beneficiating titaniferous ores |
| JPH0688149A (en) * | 1992-09-08 | 1994-03-29 | Ishihara Sangyo Kaisha Ltd | Method for refining titanium-containing material |
| CN101649392B (en) * | 2009-09-23 | 2011-04-13 | 攀钢集团攀枝花钢铁研究院有限公司 | Pelletizing method of ilmenite concentrates and pellet binder |
| CN103451419B (en) * | 2013-08-23 | 2015-06-03 | 重钢西昌矿业有限公司 | Method for recovering iron, vanadium and titanium from schreyerite through shaft furnace reduction and electric furnace smelting and separating deep reduction |
| CN103952532B (en) * | 2014-04-23 | 2016-01-20 | 鞍钢集团矿业公司 | Utilize the method that alkali soaks, v-ti magnetite concentrate is selected in classification again |
-
2021
- 2021-05-17 CN CN202110532589.XA patent/CN113318865B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU4104778A (en) * | 1978-10-25 | 1980-05-01 | Companhia Vale Do Rio Doce | Process for beneficiation of titanium ores |
| CN102399998A (en) * | 2011-11-18 | 2012-04-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for reducing and smelting titania slag by utilizing vanadium-titanium-iron ore concentrates in molten state |
| CN102417944A (en) * | 2011-11-18 | 2012-04-18 | 攀钢集团研究院有限公司 | Method for utilizing vanadium-titanium-secondary iron concentrate to smelt acid-soluble titanium slag by way of smelting reduction |
| CN109338124A (en) * | 2018-11-23 | 2019-02-15 | 宜宾天原集团股份有限公司 | A method of chlorination rich-titanium material is prepared using high silicon-calcium-magnesium ilmenite concentrate |
| CN109468424A (en) * | 2018-11-23 | 2019-03-15 | 宜宾天原集团股份有限公司 | A method of high titanium slag is prepared using low grade natural rutile |
| CN110629044A (en) * | 2019-10-29 | 2019-12-31 | 攀钢集团钛业有限责任公司 | Method for directly smelting titanium slag from fine-fraction titanium concentrate |
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