Yibin Tianyuan Haifeng Hetai Co., Ltd. was founded in 2016. It is a wholly-owned subsidiary of Yibin Tianyuan Group Co., Ltd. and an important platform for the development of the titanium chemical industry.

Technology Source Company Profile

Yibin Tianyuan Haifeng Hetai Co., Ltd. was founded in 2016. It is a wholly-owned subsidiary of Yibin Tianyuan Group Co., Ltd. and is an important platform for the development of the titanium chemical industry. The company is positioned to build a "chlorine-titanium" integrated industrial model, making full use of Tianyuan Group's green environmental protection industrial chain innovation model and mature chlor-alkali production platform, and adopting the world's most advanced chlorination production process to plan for the short term. To achieve the goal of 400,000 tons and 1 million tons in the long term, we are committed to becoming the leader in China's chloride titanium dioxide industry. The company has now built a chloride titanium dioxide project with an annual output of 50,000 tons.

Technical background knowledge points:

1. Internationally, except for DuPont's chloride-based titanium dioxide factory in the United States, which uses TiO2 titanium ore with a grade of about 60% as raw material, the rest use chloride-rich titanium materials as raw materials.

2, titanium chloride-rich materials generally refer to three types: natural rutile, artificial rutile or titanium chloride slag (including UGS slag).

3. Although my country is a country rich in titanium resources, natural rutile suitable for the production of sponge titanium and chloride titanium dioxide, and high-quality titanium ore suitable for processing into chloride-rich titanium materials are in short supply. The TiO2 grade in the titanium slag from the reduction smelting of titanium concentrates in

4, Panxi and Chengde areas can only reach 70-77%, while the content of MgO+CaO is as high as 7-10% and cannot be used for boiling chlorination.

5. Although there are weathered placer resources in Yunnan, the weathering is not complete, and the content of CaO, MgO, SiO2 and other impurities in the mine is also high.

6. Guangxi and Guangdong have some high-quality sand ore resources that can meet the index requirements for the production of chlorinated titanium-rich materials, but the output is too small.

7. There is a small amount of natural rutile in Hainan, but mining is prohibited due to tourism development.

8. There are more than 60 titanium slag manufacturers in my country, mainly concentrated in Sichuan, Yunnan, Hebei, Liaoning, Inner Mongolia and other provinces and regions, with an annual production capacity of about 1.5 million tons. Although there are many titanium slag production companies in my country, there are few large-scale companies. There are only 2 to 3 companies with an annual output of more than 100,000 tons.

9. In 2019, the annual output of titanium slag nationwide was approximately 800,000 tons, of which the output of chlorinated slag was only 200,000 to 300,000 tons, which is far from meeting the needs of the development of my country's chloride-based titanium dioxide and sponge titanium industries.

10. Currently, the companies that can supply large quantities of titanium chloride materials in the world are mainly Rio Tinto Group and Eluka Company. Among them, Rio Tinto Group supplies UGS slag and RTCS slag. Eluka mainly supplies artificial rutile and natural rutile.

11. Due to the high impurity content and low quality of domestic titanium concentrate, imported high-quality titanium concentrate must be used to produce qualified titanium chloride slag. The supply channels for high-quality titanium concentrate are also limited by Rio Tinto Group and Japan. Multinational groups such as Mitsui Group and British Bass Company have monopolies, and their supply quantity, price and other factors are not controlled by the domestic market.

12. In order to use domestic resources, we have developed technological routes such as hydrochloric acid method, rust method, and selective chlorination method, and established four pilot test bases across the country. The results show that these processes have long processes and high product impurity content. , production costs are not up to standard, and environmental protection pressure is high, etc., the industrial promotion has not been realized in the end.

Previously tried technology

1, the invention patent of CN1225526C discloses a method of using titanium ore resources to produce titanium-rich materials. The technical solution is: vanadium Titanium magnetite is pre-selected and tailed or washed with weathered ore and then magnetized, roasted and ground to separate the gangue minerals to obtain ilmenite concentrate, or this titanium concentrate and vanadium titanium magnetite in a certain proportion Mix and add binder and carbon reducing agent to form pellets and perform pre-reduction or directly put them into the furnace. They are smelted in an electric blast furnace or submerged arc furnace to produce high titanium slag and semi-steel. The alloy molten iron is blown with vanadium and chromium by the double method, and the resulting Steel slag is extracted and separated from vanadium and chromium by wet extraction, while high titanium slag enters the pyrometallurgical beneficiation process of titanium slag to produce artificial rutile and glass-ceramics. Artificial rutile titanium-rich material and coal powder are ground and mixed according to a certain proportion and then added with a binder to make carbon-containing particles. After roasting and cooling, the carbon-containing rutile titanium-rich material with a particle size of +0.3mm~-1.4mm is screened.This technology can produce low-calcium-magnesium-rich titanium materials with coarse particles and a grade of 92 to 96%. However, there are problems such as complex production process, long process, low titanium yield, high energy consumption, and high cost. The invention patents of

2 and CN106011501A disclose a method for preparing titanium-rich materials from Panzhihua ilmenite. This method first oxidizes Panzhihua ilmenite concentrate at high temperature in the air, and then reduces it through H2/CO mixed gas. The reduced titanium iron Mineral materials are rusted and separated in NH4Cl solution.

The specific steps are as follows: a. Screen the Panzhihua ilmenite concentrate, put it into the muffle furnace and oxidize it in the air at high temperature, and then cool it naturally after insulation; b. Put the oxidized and bonded Panzhihua ilmenite concentrate After the particles are crushed, they are put into a boiling furnace for reduction, heated in an N2 atmosphere and then introduced into a mixed gas of H2 and CO for reduction and roasting to obtain reduced ilmenite; c. Perform rust separation on the reduced ilmenite; After screening, the titanium-rich material and iron oxidation products were obtained. The particle size of the titanium-rich material was +48um, the TiO2 content was 74.31%, and the recovery rate reached 98.9%. This method is simple in process and easy to operate, can efficiently reduce ilmenite, improve the reduction metallization rate of ilmenite, and is beneficial to the recycling of iron. However, this method is difficult to remove calcium, magnesium, and silicon impurities in Panzhihua titanium concentrate, resulting in low grade titanium-rich materials, high calcium and magnesium impurities, , and difficulty in meeting the raw material index requirements for boiling chlorination.

3, CN104944466A invention patent discloses a production method for preparing titanium-rich materials by wet method, including obtaining acidic titanium liquid, obtaining reduced titanium, and preparing titanium-rich materials. The process steps of the production method are: adding concentrated sulfuric acid or hydrochloric acid or Add the mixture of sulfuric acid and hydrochloric acid and ilmenite into the premixing tank, then add it to the acidolysis pot, add the initiator liquid to obtain the acidolysis product; dilute it to obtain an acidic titanium liquid; mix the ilmenite concentrate and pulverized coal It is calcined in the rotary kiln and magnetically separated to obtain reduced titanium; the acidic titanium is filtered to obtain a high-purity acidic titanium liquid; the step-reduced titanium is added to the high-purity acidic titanium liquid for reduction; when trivalent titanium appears in the titanium liquid When titanium is removed, the reduction ends; solid-liquid separation occurs; the solid phase is dried to obtain titanium-rich material. This invention can produce a titanium-rich material that meets the needs of the chlorination method, which can save a lot of energy consumption in electric furnace melting and provide a new development model for the production of titanium dioxide by the sulfuric acid method. However, this invention has high requirements for the quality of titanium concentrate. The lower the requirements for calcium, magnesium and silicon impurity elements in the ore, the better. It is difficult for domestic titanium concentrate to meet the requirements. The invention patents of

4 and CN100336924C disclose a method for preparing primary titanium-rich materials from high calcium magnesium titanium concentrate. The titanium concentrate with a grade of 45-50% is ground to a particle size of less than 0.074mm, and 8-8% of the weight of the titanium concentrate is added. Made of 20% water, 3-5% binder sodium silicate, 10-20% coke, 1-5% sodium sulfate, 1-3% iron powder, 3-5% potassium chloride Composite pellets with a diameter of 10 to 15 mm are subjected to microwave drying, microwave heating reduction, and mineral processing and separation, and finally 60 to 70% primary titanium-rich materials are obtained. Since ilmenite is a strong absorber, microwave heating heats up quickly, which is beneficial to improving production efficiency. Using composite additives, the reduction temperature is reduced to 80-120°C. The primary titanium-rich material has good acid solubility in calcium and magnesium impurities, and the primary titanium-rich material has good acid solubility in calcium and magnesium impurities. Material quality is high. However, the technical process route is complex, the dosage of chemical additives is large, and the product grade is low. It cannot be used directly in the chloride titanium dioxide production device and requires further subsequent deep processing, which will lead to an increase in production costs. At the same time, the microwave equipment is complex and expensive. , there are few reports on the industrial application of large-scale microwave equipment. The patent applications of

5 and CN110093504A provide a method for preparing titanium-rich materials using high-calcium magnesium titanium concentrate, which includes the following steps: 1) Mix the high-calcium magnesium titanium concentrate and coal powder, conduct ball milling, and then add the mixture to the mixture. Add binders, additives and water to the powder, and obtain mixed pellets after mixing, pelletizing, and drying; 2) Spread the pellets evenly on the grate machine, and perform pre-dehydration and preheating treatments respectively; 3) Send the pretreated pellets into the first rotary kiln for a primary reaction; 4) Send the pellets after the primary reaction into the second rotary kiln for a secondary reaction. The reaction atmosphere is a mixture of hydrogen and nitrogen Atmosphere; 5) Send the pellets after the secondary reaction to the cooling chamber for cooling, and then crush and magnetically separate.The method adopted in the present invention respectively realizes the high-temperature environment and atmosphere environment required for the preparation of TiCxOyNz by reduction and nitridation of high-calcium magnesia ilmenite, greatly improves the production efficiency of TiCxOyNz, reduces production costs, and at the same time provides ideal raw materials for the low-temperature chlorination process. However, the process route of this technology is long and complex, the equipment is complex, and the final crushing and magnetic separation processes lead to a reduction in titanium element yield. The invention patents of

6 and CN1552628A disclose a method for preparing artificial rutile from high calcium magnesium vanadium titanium magnetite. First, the titanium concentrate is subjected to weak oxidation treatment , then magnetic separation is performed, and then it is added to the spherical cooking Hydrochloric acid is used for pressure leaching in the device. After the reaction is completed, the solid and liquid are separated, dried, calcined, and magnetically separated to granulate the fine-grained product. Finally, high-quality artificial rutile suitable for the chlorination process is obtained. The mother liquor in the production process is treated by spray calcination. , the iron oxide is recycled, and the HCl acid mist generated is returned for use. The process flow of this invention is relatively complete and can produce products that meet the requirements of boiling chlorination. However, it has problems such as long process flow, complex equipment, high powdering rate, and difficulty in granulating fine materials. The invention patents of

7 and CN101177297A disclose a method for preparing high-quality artificial rutile from high-calcium magnesia ore. The process steps are: ball milling activation, hydrochloric acid normal pressure leaching, solid-liquid separation, washing and drying, calcination, and fine granulation. grain. This method activates the ilmenite concentrate through mechanical energy, improves the leaching performance of the ilmenite concentrate, and finally obtains a higher-grade artificial rutile product, and reduces energy consumption to a certain extent. However, this process has problems such as high product powdering rate, difficulty in granulation, and unresolved mother liquor treatment. The invention patents of

8 and CN101412536A disclose a method for preparing artificial rutile from high calcium magnesium vanadium titanium magnetite. This method uses Panxi vanadium titanium magnetite as raw material. First, it is fluidized and oxidized and roasted at a certain temperature, and then the oxidized and roasted material is fluidized and reduced and roasted, and then the modified material is treated with a certain concentration of Fluidized hydrochloric acid leaching, and finally solid-liquid separation, drying and calcination to obtain the product. The biggest highlight of this method is the introduction of fluidization technology, which reduces the material reaction time and the powdering rate of the product to a certain extent. However, this method is difficult to avoid the powdering problem, has high requirements on titanium particle size, complex fluidization equipment, and high operational requirements.

9. At present, Canadian QIT Company is the only company that can successfully use high-calcium, magnesium, and silicon raw materials to produce high-grade titanium-rich materials (UGS slag) for boiling chlorination, and has achieved industrial production. The company’s technology will be introduced separately later. Its general route is to oxidize titanium slag (TiO282.55%, CaO0.47%, MgO5.56%) with a particle size range of less than 75 to 850 μm in a fluidized bed at 950°C to 1200°C for 45 minutes, and then Reduction with mixed gas (containing 85% CO and 15% H2) for 1 hour at 700°C to 800°C. The reduced titanium slag is subjected to pressurized acid leaching at 145°C to wash the acid leaching product and then pass it through with a concentration of 5% to 10% NaOH solution is alkaline leached at a leaching temperature of 50°C to 100°C, and then the leached product is calcined at 600°C to 800°C to obtain a high-grade titanium-rich material with about 95% TiO2. The patents of

10 and CN109499744A disclose a method for preparing chlorinated titanium-rich material using high calcium magnesium silicon titanium concentrate, which includes the following steps: (1) ball milling the titanium concentrate, then slurrying, and then adding flotation reagents. Positive flotation to obtain low-silicon titanium concentrate; (2) Mix the obtained low-silicon titanium concentrate with hydrochloric acid for acid leaching, filtration, washing and drying to obtain fine-grained titanium-rich material; (3) Combine step (2) ) The fine-grained titanium-rich material obtained is heated, melted, cooled, and then crushed to obtain chloride titanium-rich material. The patents of

11 and CN110629045A provide a method for preparing titanium-rich materials for boiling chlorination from low-grade titanium slag. The method includes the following steps: (1) drying and screening titanium slag; (2) subjecting titanium concentrate to high-temperature strong oxidation reaction at 950-1000°C; (3) then oxidizing the titanium concentrate at 800-850°C Carry out a weak reduction reaction; (4) Add hydrochloric acid and perform pressure leaching under heating and rotating conditions; (5) Solid-liquid separation, washing and drying to obtain the finished titanium-rich material. The above-mentioned patents can produce high-grade titanium chloride materials with qualified calcium and magnesium indicators, but the process route is long, the equipment is complex, the by-product mother liquor is difficult to process, and the cost is high, making it difficult to promote.

Key points of this technology

Process route of this technology

1. Ball mill the Panxi titanium concentrate, and then float it 4 times with a flotation agent to separate into low silicon titanium concentrate (43%) and high silicon titanium concentrate (55 %)

2. The calcium and magnesium content in low-silicon titanium concentrate is high, so it is diluted with Vietnamese titanium concentrate, and then reduced with an electric furnace.

3. When making titanium chloride slag, about 40% of domestic raw materials can be used. In fact, it is 40 %*40%. The remaining options have to be dealt with separately.

Thoughts

Domestic efforts have been made for decades to make good use of domestically produced titanium ore. In fact, the effect is very poor, so we still have to import titanium concentrate from abroad. The essential problem is that we are walking in the dead end of chlorination. In addition to carefully digesting QIT technology, the leaders of the industry can consider whether we should not struggle in this dead end. Metal thermal reduction and electrolysis are the steps for domestic titanium ores. route.

Let’s take a look at the effect of the original Panxi titanium concentrate composition after 4 times of flotation. Isn’t it a collapse? Neither magnesium nor calcium can reduce the mineral level of Vietnam , and titanium cannot improve it much. The reason for so much effort is just to be able to mix some domestic materials for use. This technology is still a new technology announced in August 2021. It is said that the newly built 50,000 tons of production capacity can lead the domestic chloride titanium dioxide industry, right? It is said that this domestic industry is too backward.

Silicon oxide 2.58% dropped to 0.66% (Vietnam mine 0.92%)

Calcium oxide 2.27% dropped to 0.23% (Vietnam mine 0.04%)

Magnesium oxide 3.75% dropped to 1.75% (Vietnam mine 0.63%)

Titanium oxide 46.5% rose to 48.2% (Vietnam ore 54.6%)

Let’s look at the composition of the high titanium slag produced after blending Vietnam’s titanium concentrate. It is simply too collapsed.

Example 1

Example 2

Example 3