Our extensive distribution of vanadium titanium magnetic iron ore deposits, abundant reserves, reserves and production ranks third in the country's iron ore, has proven reserves of 9.83 billion t, prospective reserves of 300 million tons, mainly distributed in Sichuan Panzhihua - Xichang area, Hebei Chengde area, Shaanxi Hanzhong area, Hubei Fuyang, Fuyang area, Guangdong Xingning and Shanxi Daixian. Among them, Panzhihua-Xichang area is the main metallogenic belt of China's vanadium-titanium magnetite. It is also one of the important production areas of similar deposits in the world. It is about 300km long from north to south. It has 7 large and extra-large deposits, and medium-sized deposits. Where. The chemical composition of the ore and mineral processing products are shown in Table 1 and Table 2.
Table 1 Chemical composition of Sichuan Panzhihua vanadium-titanium magnetite
Chemical composition percentage (%)
Fe 30.55
TiO 2 10.42
V 2 O 5 0.30
Co 0.017
Ni 0.014
S 0.64
P 0.013
Table 2 Chemical composition of ore dressing products of Panzhihua vanadium-titanium magnetite in Sichuan (%)
Iron-vanadium concentrate, titanium concentrate, sulphur- cobalt concentrate, Fe 51.56 31.56 49.01
TiO 2 12.73 47.53 1.62
V 2 O 5 0.564 0.68 0.282
Co 0.020 0.016 0.258
Ni 0.013 0.006 0.192
Al 2 O 3 4.69 1.16 1.40
SiO 2 4.64 2.78 5.42
CaO 1.57 1.20 1.69
MgO 3.91 4.48 2.16
S 0.53 0.25 36.61
P 0.004 0.01 0.019
Scandium ore mainly titaniferous augite, magnetite, ilmenite and titanium, the distribution function of the mineral content of the product is changed before two minerals, scandium occurrence therein to form isomorphism. Augite in titanium, Sc 3+ to aliovalently isomorphous replacement under Fe 2+ and Mg 2+, relying on electricity balance Fe 3+, Al 3+ Si 4+ alternative implementation. The permutation relation is
Sc 3+ + Al 3+ →(Fe 2+ ,Mg 2+ )+ Si 4+
The isomorphic relationship of ç±» in ilmenite is
Sc 3+ +(Fe 3+ + Al 3+ )→(Fe 2+ ,Mg 2+ )+ Ti 4+
The occurrence of bismuth in titanomagnetite is mainly related to the ilmenite and ilmenite spatter.
The most abundant of the minerals in the ore dressings is the electrowinning tailings, which contain 77 ppm of Sc 2 O 3 , followed by iron concentrates and re-selected tailings with 63 ppm and 51.4 ppm of Sc 2 O 3 , respectively. A general method for extracting rhodium from these raw materials is outlined below.
1) Electroporation tailings and re-election of tailings é’ª are mainly rich in titanium ordinary pyroxene. There are two main methods for the recovery of pyroxene in China:
Acid treatment - decomposition with sulfuric acid, heating and stirring for 4 ~ 5h, until the SO 2 steam is completely eliminated; or with hydrochloric acid (HCl + NaF) decomposition, temperature 80 ~ 100 ° C, treatment 4 ~ 5h.
Alkaline treatment - the minerals are melted together with NaHSO4 and NaOH for 1 h at a temperature of 500-600 °C. The hydrate obtained by the alkali fusion method is filtered and precipitated to remove alkali, and then dissolved by heating in hydrochloric acid. The hydrate is precipitated from the solution with ammonia, filtered and calcined to form an oxide.
2) Titanium concentrate é’ª In the smelting process of titanium concentrate electric furnace, it is mainly enriched in high-titanium slag. When high-titanium slag is further subjected to high-temperature chlorination in a boiling furnace to produce titanium tetrachloride, most of the strontium is chlorinated to ScCl 3 . Volatilized into the dust, cooled and collected by the dust collector, the Sc 2 O 3 content can reach 736ppm. [next]
3) The grade of antimony in iron concentrate iron concentrate is Sc 2 O 3 20ppm. The trend of niobium in sintering and steel making process is mainly concentrated in ironmaking blast furnace slag, which can be considered for recovery. The Soviet Union began research in this area in the 1950s, using the alkali-carbonate method to recover strontium from blast furnace slag. That is, the slag is decomposed with sulfuric acid, then the hydroxide is precipitated by alkalization, and the cerium concentrate is prepared by treatment with carbonate. Finally, the thiosulfate is extracted and the oxalate is precipitated, and the oxalate is calcined to obtain Sc 2 O. 3 .
In the 1980s, with the skyrocketing price of the world market, the domestic research and development boom was initiated. The extraction mainly focused on titanium-containing raw materials - sulfuric acid waste liquid for producing titanium dioxide, chlorinated soot during titanium production, and selection. Titanium tailings. Domestic production unit in Shanghai Dongsheng titanium dioxide plant, Guangxi Guangxi Bureau of Mines, Hunan Institute of rare earth metal material, Ganzhou cobalt smelter, such as titanium dioxide plant in Guangzhou. After entering the 1990s, due to the large sale of its past inventory and domestic over-production in the former Soviet Union countries, the world market was oversupplied, and the price of sputum was greatly reduced, directly affecting the production of cockroaches. The research and production status of extracting rhodium from titanium-containing raw materials are described below.
(1) Extraction of lanthanum from titanium white waste acid When sulfuric acid is used to produce titanium white powder from ilmenite, the amount of ruthenium contained in the hydrolyzed acidic waste liquid accounts for about 80% of the total content of ilmenite. Most of the cerium oxide produced in China comes from titanium dioxide factory. Shanghai Dongsheng Titanium Dioxide Factory and Shanghai Yuelong Chemical Plant and Guangzhou Titanium Dioxide Factory have established a cerium oxide production line. Hangzhou Sulfuric Acid Plant put into operation a set of industrial equipment with an annual output of 30kg of cerium oxide, forming a three-stage enthalpy process route of “continuous extraction—12-stage countercurrent washing titanium-chemical refiningâ€, and the product content is stable at 98~99%. Shanghai Chemical Yuelong using P204-TBP- initial kerosene synergistic extraction Scandium, NaOH stripping, hydrochloric acid was dissolved, and then by 55-62% TBP (or P350) extraction resin scandium extraction chromatography for purification, and finally purified by oxalic acid, The yield of Sc 2 O 3 with a purity greater than 99.9% is obtained, and the yield of the whole method is greater than 70%.
In the former Soviet Union 0.4MP 2 0 4 scandium extraction mother liquor from the titanium dioxide, O / A = 1/100 when almost fully with titanium, scandium, iron, calcium and separation of impurities, the solid NaF stripping scandium, then 3% H 2 SO 4 is dissolved, and the yield of the test enthalpy is 85 to 90%. Yang Jian et al. used P204-TBP to extract bismuth from titanium dioxide mother liquor, first adding inhibitors, inhibiting the extraction of iron and titanium by P 2 0 4 , and then extracting the organic phase with mixed acid and sulfuric acid to make TiO 2 in the organic phase. The content was reduced to 0.1 mg/l and the Fe content was reduced to 0.5 mg/l. Feng Yanlin et al. extracted P507-N7301-kerosene extractant with an extraction rate of over 95%, and the purity of the second oxalic acid precipitated Sc 2 O 3 product was over 99%. Nie Li et al. used two sections to extract, the first stage was extracted with P507-sterol-kerosene, the second stage was extracted with P5709-TBP-kerosene, and the hydrazine was concentrated more than 50 times. Liu Huizhong first used N1923 to selectively extract ruthenium, and then added TBP extract to further remove impurities. The two stages were concentrated more than 50 times. After oxalic acid purification, the purity of Sc 2 O 3 was 99%, and the recovery rate was 84%. In addition, the ion exchange method and the emulsion liquid membrane method have also been used for titanium white waste liquid lifting.
(2) scandium arc melting for a high slag from ilmenite dust extraction chloride, Sc 2 O 3 because the same generation and niobium, uranium, vanadium oxide having a high heat, it is very stable and will not be restored And stay in the high titanium slag. When the high-titanium slag is subjected to high-temperature chlorination to produce TiCl 4 , cerium is enriched in chlorinated soot. Fushun aluminum plant fifty-one branch plant production line production scandium oxide 20 ~ 30kg. Ke Jiajun et al [14] found that the content of strontium in chlorinated soot can reach 0.03~0.12%, the main form is ScCl 3 ; and the process of hydrometallurgical extraction of Sc 2 O 3 , including water immersion, TBP kerosene solution extraction, The unit operation of oxalic acid precipitation purification and burning has been carried out in small and expanded tests to obtain a Sc 2 O 3 product with a purity of 99.5%. From chlorinated soot to products, the recovery rate of hydrazine is 60%. Xie Lina uses a low concentration of alkylphosphine ( phosphoric acid) (P507, P204) to extract hydrazine directly from the leaching solution with a large amount of Fe 3+ in a small ratio. Using ethanol as a back stripping agent, the ruthenium can be stripped at room temperature; and the zirconium separation coefficient is 0.4S/Zr=1893 by using zirconium with 0.4% HF. Yang Zhifa et al. used P5709-N235-kerosene extraction ruthenium and 5M HCl 60 °C stripping to completely separate Sc 3+ from Fe 3+ , Fe 2+ , Ti 3+ , Al 3+ , Mn 2+ , Ca 2+ , etc . It solves the problems of separation of Sc 3+ /Fe 3+ and slow phase separation. Hejin Lin et al mention when smoke from scandium chloride, extraction and separation using P204 Fe, Mn, NaOH stripping scandium enriched 83-fold; dissolved chemically purified using hydrochloric acid, concentrated hydrochloric acid and extracted TBP- separating scandium and RE Dowex50W-X8 exchange resin钪, the purity of Sc is >99.5%, and the yield is >56%. Sun Benliang et al. used an organic polybasic weak acid precipitant to precipitate hydrazine in the leaching solution of chlorinated soot hydrochloric acid. After two precipitations and two acid hydrolysiss, the removal rate of iron and manganese in the leaching solution was over 99.8%, and the precipitation rate of hydrazine was up to 100%; then P204 + modifier + sulfonated kerosene as extractant, O / A = 1 / 20, extraction of cesium at room temperature, DSc up to 139, the separation coefficient of bismuth and iron, manganese reached 9270 and 10700 respectively; 5% After NaOH stripping, the stripping rate was 99.6%. Lin Weiming et al. used benzylic acid to extract hydrazine, and the yield of hydrazine was 98.3%.
(3) Extraction of strontium from selected titanium tailings Panzhihua has completed a concentrating plant with a designed scale of 13.5 million t/a, with an annual output of 5.883 million tons of iron concentrates and an annual output of 745.53 million tons of tailings, which is in urgent need of comprehensive utilization. Zhang Zonghua tested the original ore of the iron ore plant at the time of the “Eighth Five-Year Plan†for the comprehensive evaluation of the Panzhihua vanadium-titanium magnetite. The iron ore in the iron ore plant was 27.00 g/t. Calculated according to the design scale, 364.25 tons of 钪 is recovered from the treated ore every year, and its value is 24.425 billion yuan. They scandium containing 63g / t Titanium tailings as raw materials, processing additives or pretreatment magnetic electric separation process can be divided into selected titanaugite tailings, feldspar, containing scandium, respectively 114g / t 121g/t; leaching with leaching solution with hydrochloric acid, the leaching rate can reach 93.64%; the leaching rate can be up to 97.90% by alkali fusion and hydrolysis of hydrochloric acid; the extraction rate can reach 98.90% by TBP extraction; The stripping rate is 98.00%; and then refined with oxalic acid to obtain a Sc 2 O 3 product with a grade of 99.95%, the market price is 36,000 yuan / kg. Due to the relatively high price and small market capacity, no factory has been built yet.
summary:
In summary, the cerium in the titanium white mother liquor is in an ionic state, and the extraction process is simple, so the early production of cerium oxide is mostly used as a raw material; however, the content of cerium is low (10-25 ppm), and is restricted by the production of titanium dioxide. (The annual output of 1000t titanium dioxide can recover dozens of kilograms of cerium oxide). The ruthenium in chlorinated soot exists in the form of ScCl 3 , and the recovery is not difficult. The question is whether the chlorinated soot is sufficient; if the cerium oxide content is 500 ppm on average, at least 50 kg of cerium oxide product should be treated. 100t chlorinated soot, the amount of treatment is quite large. In the titanium tailings, the strontium is mainly present in the pyroxite of (Ca, Mg, Al, Ti)Si 2 O 6 silicate structure. The decomposition of tailings is difficult, and it is often subjected to acidification or alkalization (~1000 °C). Melting; however, the output of tailings is very large, and the absolute amount of strontium produced is considerable, providing sufficient raw materials for the production of strontium; however, the treatment of tailings must also take into account the comprehensive utilization of other resources.
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