I. Resource distribution of ilmenite

Advances in Research on titanium iron ore flotation ilmenite (FeTiO 3) theoretical content of TiO 2 52.63% titanium dioxide and titanium extraction is the main mineral. Ilmenite is a trigonal system, often has a plate-like crystals, or granular aggregates in blocks, steel or gray iron black, metallic luster, hardness of 5-6 Mohs, a specific gravity of 4.7 to 4.78, with weak magnetism [1] .

In nature, ilmenite is found as an associated mineral in igneous and metamorphic rocks, and can also form sand minerals [2] . Mainly distributed in Canada, Norway, South Africa, Australia, the United States, India, China, the former Soviet Union, Sri Lanka, Brazil, Finland and other countries [3] . Well-known mines include Lake Ellad in Quebec, Canada, and the Telles mine in Norway. The famous waterfront sand mines are located in Trang Wankol, India, the Maclntyre mine in New York, the east coast of Australia and the Otanmaki mine in Finland [4] .

Statistics and reports on the world's titanium resource reserves are diverse, and the data from different sources are very different. The main reason for the difference is the difference in mineral types included in the statistics. Therefore, statistics on the world's titanium resources are only of reference value and not very accurate and complete statistics. According to published data from authoritative institutions such as the USGS, the world's titanium ore geological reserves total 5·10 8 t~12·10 8 t (calculated as TiO 2 ) [5] , of which ilmenite accounts for about 80%, rutile (including sharp Titanium ore) accounts for about 20%. The statistical resource reserves are mainly sand resources, and the rock mines only include ilmenite ore with high grades in Canada and Norway. Titanium magnetite is not counted, because the ilmenite and magnetite are tightly combined, and titanium minerals with higher titanium content cannot be selected.

China's ilmenite resources are very rich [6] , spread over 20 provinces and regions, both rock and mineral, and sand mines, of which rock and minerals account for the majority. The rock deposits are mainly distributed in the Panxi area of ​​Sichuan and the Chengde area of ​​Hebei. For example, in the Panzhihua iron ore mine in Sichuan, China, ilmenite is distributed between the magnetite particles or in the cracking, and forms a large deposit. Sand mines are mainly distributed along the coasts of Guangdong, Guangxi and Hainan. In addition, there is an inland sand mine between the two, distributed in the Fumin area of ​​Yunnan.

2. Progress in research on ilmenite flotation

(1) Research status of ilmenite flotation reagent

Before the ilmenite flotation, the sulfide minerals are first sorted by flotation, and then the ilmenite is floated. Sulfide flotation using conventional flotation reagent system, i.e., xanthate as collector, No. 2 oil as foaming agent, a pH adjusting agent is sulfuric acid, and some also plant selected from copper sulfide flotation sulfuric acid as activator [7] .

There are many researches on ilmenite flotation agents, but the main research content is the choice of collectors. Ilmenite common collector of fatty acids, mostly oleic acid and salts thereof abroad, such as tall oil soap or oil trap collector mixed with the coal. In recent years, a large amount of research work has been carried out on hydrocarbon-based phosphonic acid collectors and hydroxamic acid collectors [8] . However, the combination of two or more agents is often superior to any one of them. This is the synergistic effect of the agents. In recent years, the use of mixed agents for flotation of ilmenite has become the most important research direction. .

1. Research on combined collectors

Zhu Jianguang of Central South University [9] used A, B, C three kinds of collectors to form a new MOS collector, which can produce synergistic effect. After the successful MOS flotation Panzhihua fine ilmenite industrial test in May 1997, 1997 Since June of this year, the plant's micro-particle recycling process has been put into production. From the production situation in the past year, the production index has exceeded the industrial test index (concentration grade 47.01%), and the fine-grained titanium concentrate grade reached 48%~ 49%, the recovery rate is 61%. Now it has been expanded into two production series from one production series. The fine-grained titanium concentrate produced in these two series has stable quality, TiO 2 ≥47.50%, S≤0.18%, after small flotation test, industrial test and more than four years. Industrial production practices have proven that MOS is a good collector for fine-grained ilmenite [10] .

For recycling Superfine Ilmenite beneficiation this problem, Panzhihua Iron and Steel Mining Company Design and Research Institute [11] and Panzhihua Iron and Titanium Company after three years of laboratory research work, developed a new type of collector R-2, and plant in Panzhihua titanium micro-fine particles of titanium concentrate production line testing industrial test, achieved better results, in the case where TiO 2 ore grade of 21% ilmenite TiO 2 grade of 47.5% or more, The recovery rate of flotation is nearly 70%, and the cost of titanium concentrate is less than 50 yuan/ton, which is more than 50% lower than the cost of the original MOS collector.

Changsha Institute of Mining and Metallurgy Xie Jianguo [12] and others made a new type of collector ROB, which is prepared by mixing organic hydroxy citrate and kerosene as main raw materials through pretreatment, reaction, refining and emulsification. An anionic collector containing a polar group such as a hydroxyl group and a carboxyl group. Using ROB as a collector, a fine-grained ilmenite flotation industrial test was carried out at the Panzhihua ilmenite ore dressing plant to obtain a good indicator of concentrate TiO 2 grade 48%, recovery rate 75%, and the May 2000 production line. Compared with the production index of the second series of MoS as the collector, the concentrate series increased by 0.65% and the recovery rate increased by 7.3% [10] . The cost per ton of titanium concentrate flotation reagent was reduced to 40.54 yuan, and the economic benefit was remarkable.

The RST collector [13] is made by using Tal oil as a basic raw material and after a moderate oxidation, with a certain amount of additives. Use RST as a collector to float the fine-grained fine mud of the Panzhihua ilmenite ore dressing plant. After feeding with 19.75% FiO 2 , first flotation desulfurization, H 2 SO 4 as pH adjuster, oxalic acid as inhibitor, then RST as collector, flotation after flotation, after a rough selection, Four selected closed-circuit processes yielded a titanium concentrate containing 48.28% Tio with a recovery rate of 79.9% [9] , which is good compared to the MOS collector used in production and the styrene phosphonic acid used in the laboratory. Capture performance and price advantages.

Ma Zhongchen [14] studied the collection performance of the new collector H717. Compared with the R-2 and diesel combination collectors at the ilmenite ore dressing plant, the titanium concentrate obtained with H717 at the same dosage. The TiO 2 grade and recovery rate are higher than the on-site collector, and in the case of reduced dosage (20% reduction compared with the amount of on-site collector), the obtained beneficiation index is still better than the on-site pharmaceutical index. The experimental study of ilmenite samples proves that the new collector H717 is a collector of flotation ilmenite with strong harvesting ability and good selectivity. The results of flotation test show that the collector has good collection ability and good selectivity for ilmenite ore sorting. The test procedure uses a rough selection, a single sweep, and a secondary selection process. When H717 and diesel are used as collectors, the feedstock containing 29.92% TiO 2 can be obtained with 45.00% TiO 2 with a recovery of 53.23%. Titanium concentrate [15] . If the collector is used instead of the collector of ilmenite in the field, the cost of the ore dressing can be reduced, and better economic and technical indicators can be obtained.

Xie Zejun [16] studied the beneficiation performance of the new collector XT. After a large number of pharmaceutical tests, three agents A, B and C were selected. A drug has strong ability to capture and has certain selectivity; B has better selectivity but poor harvesting ability; C agent has better selectivity and better harvesting ability, and has anti-selection resistance. The role of drug removal. According to the principle of synergistic effect, the XT new floating titanium collector was synthesized by experiment to find the best ratio. After more than one year of laboratory exploration and production in the Panzhihua Titanium Plant, the industrial test of XT's new floating titanium collector has strong performance and good selectivity. When the grade of TiO 2 is 17.80%, the grade of concentrate TiO 2 is 47.42%, and the recovery rate of work is 73.28%, which exceeds the MOS production index.

He Hu [17] and others studied the effect of ZY collectors on the sorting of coarse-grained ilmenite. The test samples were selected by the Panzhihua Iron and Steel Co., Ltd., and the iron ore of the Yankou Township Concentrator in Miyi County. The flotation agent is a ZY collector and sulfuric acid, because the ZY collector is synthesized by using by-products of oleochemicals and petrochemicals as the main raw materials, so the price is low, and some mixed ilmenites with better selectivity are collected. Compared with R-2 collectors and ROB collectors, ZY collectors have low selectivity for ilmenite and cannot be used to select fine-grained ilmenite. The flotation of coarse-grained ilmenite has a very important meaning, which can reduce the selectivity of collectors. At the meeting of the concentrator, the ZY collector was used instead of the original collector, and the grinding operation was cancelled. The production results show that the concentrate TiO 2 grade is 47% to 47.5%, and the flotation recovery rate is about 70%. ZY has been used in the plant for more than one year. The production index is stable. The dosage of the agent is more than MOS, which is 3000~3500g/t, and the cost of the medicament is reduced by 15%. The annual production is 8 months, which can save 600,000 yuan [10] ] .

Zhong Zhiyong and Yu Dewen [1/8] studied the application of R-3 collector in the flotation of coarse titanium concentrate of Heshan Iron and Steel Mine in Chenggang, and the open circuit test results show that the obtained titanium concentrate The grade of TiO 2 is 48.33%, the recovery rate of flotation open circuit is 63.36%, and the dosage of collector is 1500g/t.

The compounded fatty acid soap was used as a collector [6] and Pb(NO 3 ) 2 as an activator to achieve good separation of ilmenite and gangue minerals without adding any inhibitor. In the Dressing Works - fine flotation results: ore grade of 21.96% TiO 2, TiO 2 concentrate grade of 47.82%. The flotation recovery rate is 63.25%. The cost of ilmenite flotation agents is significantly reduced due to the absence of inhibitors.

2, the study of conditioning agents

Panzhihua Iron and Steel (Group) Mining Company Design and Research Institute [19] conducted a series of experimental studies on the flotation of fine-grained ilmenite in Panzhihua, using F968 as collector, SSB and oxalic acid as regulators. Studies have shown that SSB and oxalic acid are regulators that can effectively inhibit gangue minerals while maintaining the pH of the pulp in a weakly acidic or near-neutral range. The final indicator obtained is better than the field test technical indicators.

The primary fine-grained ilmenite inhibits flotation, which makes the collector consume more, which is unfavorable for reducing the cost of ore dressing. Yu Dewen [20] research shows that H 2 SO 4 and Pb 2 + ions have a good activation effect on ilmenite, with H 2 SO 4 as the pH adjuster and Pb 2 + ion as the ilmenite activator. The fatty acid soap is a collector and achieves good separation of ilmenite and gangue minerals without adding any inhibitor.

(II) Research status of ilmenite flotation process

The comprehensive TiO 2 grade of fine-grained ilmenite flotation tailings in Panzhihua Iron and Steel Co., Ltd. is about 12%, that is, about 24% of ilmenite is contained in tailings for recycling. Yu Dewen [21] adopts strong The magnetic grinding-flotation process can recover 46.34% of TiO 2 grade and 3.21% of titanium concentrate from the floating titanium tailings of Panzhihua Iron and Steel Co., Ltd., and the recovery rate of strong magnetic separation operation is 62.53%. The rate is 28.52%, the recovery rate of flotation open circuit is 20.04%, and the concentrate yield is 11.25%. Because the tailings contain more hematite and limonite, it has a greater impact on the re-selected titanium concentrate grade. Therefore, tailings re-grinding can improve the flotation of ilmenite and the choice of flotation reagents. Sex.

Wu Caibin from East China Jiaotong University and Duan Xixiang from Kunming University of Science and Technology [22] , based on the characteristics of fine grain size and fine grade yield of titanium and iron minerals in a certain ore, starting from saving capital investment costs and optimizing the beneficiation process, adopting the structure Simple, easy-to-use spiral chute tailing and shaker recovery principle of ilmenite. The main process flow is spiral chute rough selection and tailing. The chute coarse concentrate is magnetically removed by iron and shaker is sorted to enrich coarse titanium. Concentrate, coarse titanium concentrate re-grinding and re-selection, obtained a good technical and economic indicators.

Goushushan [23] for the iron ore tailings of Chenggang Heishan Iron Mine, the mineral composition is complex, the mineral inlay size is fine, etc., respectively, the full-scale strong magnetic separation - spiral beneficiation - electrification process and coarse grain using strong magnetic Selection - coarse concentrate re-grinding - spiral beneficiation - electrification, fine grain using flotation classification into the selection process. The obtained results show that the TiO 2 grade of the full-scale process titanium concentrate is 46.84%, and the recovery rate is 40.59%; while the titanium concentrate TiO 2 grade in the coarse-grained process is 47.26%, the recovery rate is 41.06%, in addition to titanium metal. The fine-grained product with a volume of 31.38% enters the flotation operation to recover fine-grained ilmenite.

Zhang Tian [24] and so on further explored the selection criteria of Huili Baicao Titanium Plant. According to the characteristics of ore properties, the whole-grain re-election, coarse-grain grading re-election and re-election re-grinding flotation were carried out. Titanium test study of multiple processes. Through comparison, a reasonable production process is proposed, and the method of selecting one by weight can greatly improve the titanium selection index. To find a way out to produce qualified titanium concentrates from a large number of re-selected mines.

Desliming and concentrating of fine-grained ilmenite is one of the key technologies for the fine-grain recovery of Panzhihua titanium resources. Li Maolin [25] of Changsha Research Institute of Mining and Metallurgy and other research conducted various kinds of CSI-100 high-efficiency desliming and concentration cyclone. The conditional test determines the reasonable geometric parameters and classification process parameters of the cyclone, and successfully solves the technical problem of fine particle de-sludge concentration.

Third, the conclusion

1. In recent years, many scientific research workers have done a lot of research on ilmenite flotation, and have made good progress, and achieved remarkable economic benefits in production. The most important one is to study new ilmenite. The selection of collectors, especially fine-grained ilmenite, has increasingly attracted the attention of mineral processing workers. For example, the new combination collectors MOS, R-2, ROB, RST and ZY are all fine-grained titanium. A good collector for iron ore.

2, the use of different combinations of collectors, can improve their collection of minerals, get better indicators than the use of drugs alone, and the cost of pharmaceuticals can be significantly reduced. Flotation is the most effective method for recovering fine-grained ilmenite. Therefore, strengthening the development of new combined flotation reagents will be one of the future development directions of ilmenite flotation research.

3. Due to the variety of pesticides required for the recovery of fine-grained ilmenite, the large amount of the process and the long process flow, the production cost of the fine-grained ilmenite is relatively high, so it should be further studied in the process of the agent and the improved flotation process. In order to reduce production costs, resources can be fully utilized to achieve sustainable development.

references

[1] Datang Database. 20042 Mo Wei, Deng Guozhu, et al. Titanium Metallurgy [M]. Beijing: Metallurgical Industry Press, 1998.133

[3] Hao Bin. Current status and prospects of China's titanium industry [J] Vanadium and Titanium. 1996, (5): 67

[4] Xu Xiangyang. Study on Panzhihua Fine-Grained Ilmenite Flotation Combined Collector[D]. Master's Thesis of Changsha Research Institute of Mining and Metallurgy, 2000(8)

[5] Deng Guozhu. The status of world titanium resources and their development and utilization [J] Progress in Titanium Industry, 2002 (5): 9-12

[6] Yang Jia, Li Kui, et al. Status and development of comprehensive utilization of ilmenite resources [J]Materials Report. 2003(8), 17(8)

[7] Dai Xinyu. Progress in primary ilmenite ore dressing technology [J]. China Mining, 2002, (2): 40-42

[8] Zhu Junshi. Vanadium-titanium magnetite beneficiation [M]. Beijing: Metallurgical Industry Press, 1996, 237

[9] Zhu Jianguang, et al. Preparation of ilmenite collector using the best point of synergy effect[J]. Nonferrous Metals (Selection Part), 2002(4): 39-41

[10] Zhu Jianguang. Progress of Flotation Reagents in 2002[J]. Foreign Metal Ore Dressing, 2003(2): 4-10

[11] Yuan Guohong, et al. Experimental study on the selection of fine-grained ilmenite from Panzhihua by R2 collector [J] Metal Mine, 2001(9): 37-39

[12] Xie Jianguo, Zhang Yusheng, et al. Experimental study on flocculating fine-grained ilmenite by ROB with new collector[J] Mining and Metallurgical Engineering, 2002(6): 47-54

[13] Xie Jianguo, Chen Ranghuai, et al. New flotation agent RST flotation fine-grained strontium iron ore [J] Nonferrous Metals, 2002(2): 58-74

[14] Ma Zhongchen.Experimental study on the selection of ilmenite by H717 collector[J]Color Mining and Metallurgy,2003(8):18-22

[15] Zhu Jianguang. Advance of Flotation Reagents in 2003 [J] Wenwai Metal Ore Dressing 2004(2): 4-11

[16] Xie Zejun. Industrial Test of XT New Floating Titanium Collector[J]. Minerals Comprehensive Utilization, 2004(8): 22-24

[17] He Hu. Experimental Study on Separation of Coarse Grade Ilmenite by ZY Collector[J]. 金属矿,2002(6):23-25

[18] Zhong Zhiyong, et al. Flotation test of coarse titanium concentrate in Heishan Iron Mine of Chenggang [J]. Hebei Metallurgy, 2003 (11): 18-26

[19] Experimental study on the enrichment of Panzhihua fine grain and ilmenite by Dai Xinzi 17968 collector[J].Metal Mine,2000(11):40-43

[20] Yu Dewen, Zhong Zhiyong, Non-inhibited activated flotation of primary fine-grained ilmenite [J] Mining Express, 2000(7): 16-1821 Yu Dewen's experimental study on recovery of ilmenite from titanium flotation tailings. Mining Express [ J] 2003 (1): 40-42

[22] Wu Caibin, Duan Xixiang, et al. Experimental study on the selectivity of weathered ilmenite [J]. Metal Mines. 2002(12): 44-46

[23] Wang Guangrui. Experimental study on process characteristics and ore dressing process of Heishan ilmenite[J] Chenggang Technology, 2002(3): 1-4

[24] Zhang Tian, ​​et al. Optimization experiment of titanium process selection in Huili Baicao Titanium Plant [M]. Panzhihua Science and Technology, 2002, (2): 30-33

[25] Li Maolin, et al. Study on the concentration and classification of fine-grained ore concentrate [J] Metal Mine. 2000(10): 39-41

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