Progress in boring manganese ore beneficiation technology in China

Our rich manganese ore reserves, ranking the highest in the world. However, rich ore (manganese grade >30%) is rare, accounting for only 5.4% of the country's total reserves. The ore contains high impurities and many associated components, of which P/Mn>0.005, manganese ore reserves of Mn/Fe<3 account for 46% of the total reserves. Most of this type of ore is a native manganese carbonate ore, and the ore structure is fine and extremely difficult to select. Its typical mines are Hunan Huayuan high- phosphorus manganese ore and Guizhou Zunyi high- iron manganese mine.

Since the 1980s, under the direct leadership of the Ministry of Metallurgy and organizations, through the efforts of the scientific and technical personnel, so that the type of hard rock mineral beneficiation technology breakthrough progress.

I. Process mineralogy research

In recent years, the main objective of the research on the process mineralogy of high-phosphorus and high-iron manganese carbonate ore is to clarify the quantitative characteristics of manganese carbonate ore in order to determine the beneficiation method and process of Taili, and to predict the ore dressing index and the sorting effect of ore. Judgment.

(1) Composition of manganese minerals and their process characteristics

The main manganese-bearing minerals in the ore are manganese phosphate minerals. Other manganese-containing minerals are only a few. The current cultivation can only be considered as gangue minerals, such as Ruihuihui right. Manganese carbonate minerals mainly appear as carbonate minerals of the same type of Ca, Mg, Fe and Mn. There are binary, ternary and quaternary isomorphic series of rhodochrosite in the Huayan manganese ore. Zunyi well copper ores QUATERNION manganese carbonate minerals containing different Mn, Fe, Ca, Mg element (Table 1).

Table 1 Contents of Mn, Fe, Ca, and Mg in manganese-containing carbonate minerals (%)

The results of this study not only determine the name of the mineral, but more importantly, determine the content of each component in the mineral, which has important use value for mineral processing research.

(2) The existence state and process characteristics of the true assignment

Li Qiang, from Beijing University of Science and Technology, proposed that phosphorus in the deposited carbonate ore mainly exists in the state of apatite and collophosphorus. Its source has three aspects. One is derived from terrigenous debris, the other is phosphorus-containing minerals that are produced with manganese carbonate, and the third is phosphorus-containing minerals. It is also suggested that there are different types of phosphorus-containing minerals in different mines, such as apatite in Huayu manganese ore; Zhuhaishan manganese ore in Xiushan in Sichuan is mainly composed of phosphate rock; Tiantaishan manganese ore in Chang'an and Changyang ancient city manganese ore are Apatite and collophanite coexist.

The distribution characteristics of phosphorus in the calyx type manganese carbonate ore were quantitatively studied by the selective soaking-sieving analysis method. This method has a universal significance in determining the distribution characteristics of phosphorus in the ore in which manganese is present in the carbonate state.

(3) Occurrence state of iron and its process characteristics

The Kunming Institute of Metallurgy has conducted in-depth research on the process mineralogy of Zunyi high-iron manganese carbonate ore. It has been found that iron has three occurrence states in the deposited manganese carbonate ore: it exists in the assimilation state in the Taiwan manganese carbonate. Iron sulfide (pyrite, pyrite) and iron silicate (chlorite). For example, the 850 level of ore has a manganese content of 18.44%, an iron content of 9.51%, and Mn/Fe=1.94. The distribution rates of iron in the above three occurrence states are 32.70%, 29.34%, and 37.96%, respectively. According to the results of this study, strong magnetic separation can effectively remove iron from sulfides and silicates, but to remove iron from carbonates, flotation must be used.

(4) The influence of ore structure and structure on mineral processing

Most of the minerals deposited in manganese carbonate ore are fine particles and cryptocrystals. It is necessary to grind very fine (generally <10μm) to achieve monomer dissociation. It is difficult to obtain high quality products by mechanical beneficiation methods. However, the manganese minerals are unevenly distributed in the ore. The ore is pre-selected or the final concentrate is obtained by selecting the medium-grain strong magnetic separation method of the Fulian organism. However, the grain size of manganese minerals in Zunyi high-iron manganese ore is relatively coarse, and it is feasible to use mechanical beneficiation to enrich manganese.

(5) Prediction of ideal indicators for ore sorting

Tang Xinming et al. of Changsha Research Institute of Mining and Metallurgy proposed to use statistical methods to predict the ideal index of ore selection. Li Qiang, et al., of Beijing University of Science and Technology, proposed to use the ore specific magnetization coefficient method to predict the ideal index of ore. These methods are new methods that have never been mentioned before, and have important guiding significance for mineral processing research.

(6) Research on physical properties

According to the characteristics of ore embedding, Beijing University of Science and Technology proposed to study the magnetic properties and density of rhodochrosite by indirect method. Changsha Institute of Mining and Metallurgy and Xiangtan Manganese Mine also proposed the equation of relationship between magnetic properties and density of ore-type manganese ore and manganese content of ore. The ore magnetism and density are linear with the ore manganese content, and the effects of mineral components on magnetism have also been studied in detail. This research not only has important academic value but also has important use value.

In the past 10 years, the results of manganese ore dressing technology research have been numerous, and 10 research reports and papers have been presented. According to incomplete statistics, six papers have been published at major international conferences.

Second, the selection process

The beneficiation of high-phosphorus and high-iron fine-grained manganese carbonate ore has been the main research topic of manganese ore research. A large number of experimental research work has been carried out by various research units on the process characteristics of refractory manganese ore, and great progress has been made. The strong magnetic industrial test of Xiangtan manganese ore, the industrial test of the three series of transformation of Zunyi manganese ore dressing workshop, the industrial test of the first mining stone of Huayu manganese mine, the technical appraisal of the Ministry of Metallurgical Industry, and the establishment of a batch of manganese ore dressing industrial production plant. However, the processing capacity of the concentrator is very small, no more than 100,000 tons, and the process is simple and the technical indicators are not ideal. In 1985, the high-phosphorus and commercial iron-poor manganese ore beneficiation technology was listed as the “seventh five-year” research project. After the efforts of various test units, the manganese-rich phosphorus reduction of Hunan Huayuan high-phosphorus manganese ore and the manganese-rich iron reduction of Zunyi high-iron manganese ore were tested. Has been completed.

(1) Study on manganese-rich phosphorus reduction in high-phosphorus manganese ore

Huayu manganese ore is a shale -carbonate deposit deposited in a large offshore semi-closed basin. It is a type of fine-grained high-phosphorus low-iron and manganese-poor ore. The ore includes Sichuan Xiushan Manganese Mine and Guizhou Songjiao Manganese Mine. More than 100 million tons. Since 1980, Beijing University of Science and Technology and other units have carried out a large number of experimental research work on manganese-rich phosphorus reduction in Huayan manganese mine, and in 1983 passed the technical review of the Ministry of Metallurgy.

Responsible by the Maanshan Mine Research Institute, the Beijing University of Science and Technology, Changsha Black Metallurgy Mine Design and Research Institute participated in the strong magnetic separation - black manganese ore continuous expansion test, was completed in June 1990. The speed of each test in the past 10 years is as follows:

1, medium (coarse) grain magnetic separation

The Beijing University of Science and Technology and the Maanshan Mine Research Institute have used a variety of magnetic separation equipment and different magnetic separation processes to select the manganese ore, which can increase the manganese grade by 6-10%. The main test results are shown in Table 2.

Table 2 (coarse) grain magnetic separation process and indicators

The test results listed in Table 2 show that the strong magnetic separation effect is very good.

The Changsha Research Institute of Mining and Metallurgy and other units carried out industrial tests on the ore of the first section of Huayan Manganese Mine (from the north to the 18 exploration line from the south to the 14 exploration line and above 738m above sea level). After the ore was broken to 6~0mm, it was induced by CGDE-210. The roller type strong magnetic separator was firstly selected. The concentrate was dehydrated by spiral classifier and the manganese content was 25.12%, the phosphorus content was 0.162%, the P/Mn=0.0064, the recovery rate was 83.33%, the raw ore contained 19.55% manganese, and the phosphorus content was 0.179%. After sintering, the concentrate contains 36.72% manganese, 0.217% phosphorus, and P/Mn=0.0059, which meets the third-grade manganese standard. The test results show that the indicators are better, the process is simple, and it has been adopted for design. The ore dressing plant was officially put into operation in May 1987, which is a welcome step for the development and utilization of manganese carbonate ore.

2, black manganese ore method to reduce phosphorus

The Beijing University of Science and Technology, the Laboratory of the Guangdong Geological Bureau, the Experimental Propagation of the Hunan Geological Bureau, and the Maanshan Mine Research Institute have all used the manganese ore method to reduce the phosphorus content in the strong magnetic separation concentrate, and all have achieved ideal indicators.

In 1990, he was responsible for the Maanshan Mine Research Institute, and the Beijing University of Science and Technology and the Changsha Black Metallurgical Mine Design and Research Institute participated in the continuous expansion test of the manganese ore method in the ore of the Huayuan Manganese Mine. Good results can be obtained by boiling roasting of calyx manganese ore magnetic separation concentrate. There are two kinds of calcined ore, namely coarse concentrate and fine grain mine. The two types of calcined sand are continuously leached with dilute acid to reduce phosphorus, and the two kinds of manganese concentrate products obtained after leaching are mixed as a first-class manganese concentrate. The index is: manganese grade 40.15%, phosphorus grade 0.144%, P/Mn=0.0036, total manganese recovery is 82.71%, concentrate yield 42.01%. Comprehensively exceed the requirements of the "seventh five-year" research indicators (first grade manganese grade ≥ 40%, manganese yield ≥ 20%, P / Mn = 0.003-0.004; secondary manganese grade ≥ 35%, manganese yield 55-60%, P /Mn = 0.004 - 0.005).

(II) New test for manganese-rich iron reduction in Zunyi manganese ore

In 1990, the Maanshan Mine Research Institute was responsible for the continuous expansion of the magnetic-floating-heavy combined process of the Beijing University of Science and Technology and the Changsha Black Metallurgical Mine Design and Research Institute. The scale of the test was 57 kg/h of raw ore, and the equipment was continuously operated for 72 hours. The final index: first grade manganese concentrate yield 13.50%, manganese containing 32.44%, ferromanganese ratio 7.541; secondary manganese concentrate yield 18.14%, manganese containing 30.37%, ferromanganese ratio 5.32; tertiary manganese concentrate yield 14.92%, The manganese content is 27.56%, the ferromanganese ratio is 3.5l; the total manganese recovery rate is 76.38%.

According to the comprehensive manganese concentrate yield of 100%, the yields of the first, second and third grade manganese concentrates are 20%, 60% and 20%, respectively. The calculation results are shown in Table 3.

Table 3 Calculation results of concentrate distribution indicators at all levels

The indicators in Table 3 meet or exceed the national “seventh five-year” research requirements (first grade manganese concentrate yield 20%, secondary manganese concentrate yield 60%, tertiary manganese concentrate yield 20%, integrated manganese concentrate The manganese recovery rate is 75%).

The expansion of the test process mainly uses stage grinding, strong magnetic-flotation, and flotation of mines, supplemented by re-election of pyrite in the strong magnetic tailings. This process structure is simplified and reasonable compared to existing production processes.

With the stage grinding process, one third of the tailings can be thrown away, reducing the amount of grinding in the second stage and saving energy. The collector has good collection performance and strong selectivity, and the concentrate foam product is easy to dehydrate and can be used at normal temperature.

Third, the study of new separation methods

In recent years, in order to expand the utilization of manganese ore resources and improve the selection criteria, Beijing University of Science and Technology, Changsha Research Institute of Mining and Metallurgy, Central South University of Technology, Northeast Institute of Technology, Wuhan University of Technology and other graduate schools have applied a series of new beneficiation methods to manganese ore dressing. In the field, great progress has been made.

Beijing University of Science and Technology uses a new process of controlled dispersion-shear flocculation flotation to separate the fine-grained magnesite and apatite monomer minerals, and effectively removes the apatite impurities from the mixed ore. Using water glass and HY-85 mixed dispersant, the manganese grade can be obtained from the rhodochrosite less than 6.9μm and the apatite mixed mine of less than 7.8μm (P=0.277%) in the sodium oleate system, and the manganese recovery is 39.35%. The rate is 66.02% manganese concentrate, and the concentrate contains 0.133.

Both Beijing University of Science and Technology and Changsha Research Institute of Mining and Metallurgy use high-gradient magnetic separation technology to test manganese-rich phosphorus reduction in Huayan manganese ore. Beijing University of Science and Technology used a high-gradient magnetic separation device to dephosphorize the fine-grained manganese ore (-10μm accounted for 90%). Under the appropriate pH condition, a high-efficiency dispersant L _{433 was added} . After a strong agitation, the slurry was present. Good dispersion. After a coarse-pure high-gradient magnetic separation, a concentrate containing 27.50% manganese and 0.137% phosphorus can be obtained from a test compound containing 23.60% manganese and 0.0169% phosphorus, wherein P/Mn is 0.00498, which is burned. Standard for post-secondary metallurgical manganese.

Changsha Research Institute of Mining and Metallurgy used high gradient magnetic separation treatment for Huayan manganese ore. The manganese ore grade of the original ore is 18.30%, and the phosphorus grade is 0.201%. After treatment, the manganese content of the concentrate is 26.50%, the phosphorus grade is 0.122%, the manganese grade after burning is up to 40%, P/Mn=0.0047, and the manganese recovery rate is 57.78%. It is shown that high gradient magnetic separation is effective.

Wuhan Iron and Steel Institute applied the magnetic seed sorting method to the fine-grained manganese ore for the first time. The manganese grade was 22.86% of the rhodochrosite and quartz 1:1 mixed for alkali sorting, which could increase the manganese grade of the concentrate to 41.12. %, the recovery rate was 98.32%.

Central South University of Technology uses a new process of high vibration gradient and pellet leaching to reduce the sorghum manganese ore. The pellet leaching process obtained better dephosphorization effect, and the Northeast Institute of Technology used flocculation flotation process to treat the sassafras manganese ore and achieved certain effects.

The above research results provide a large amount of technical reserve data, which laid a solid foundation for the development of manganese ore beneficiation technology and created favorable conditions.

Fourth, theoretical research

In recent years, the theoretical research of manganese ore beneficiation has been paid attention to and developed rapidly. In particular, colleges and universities have done a lot of work on the theoretical study of manganese ore dressing. According to incomplete statistics, more than 10 postgraduate students have carried out new processes and theoretical research on manganese ore dressing, and obtained a number of research results with high academic value, which have certain guiding significance for manganese ore beneficiation research and production.

Beijing University of Science and Technology has studied the mechanism of action of fatty acid collectors in the flotation of rhodochrosite, especially the conclusions of the ratio of the various chemicals in the mixed collectors and the results of sorting. Has important reference value.

The microscopic mechanism of the separation of fine-grained manganese ore and siderite minerals from Beijing University of Science and Technology. The study on the microscopic mechanism of the separation of fine-grained manganese ore and chlorite suspensions by Wuhan Iron and Steel University is the rhodochrosite- The separation of chlorite, rhodochrosite and siderite provides a theoretical basis.

A more detailed study was carried out on the characteristics of rhodochrosite and the problems in actual flotation. For example, the role of modifiers such as water glass in the sodium oleate-magm manganese ore flotation system has obtained some theoretical and practical references. At the same time, the role of the flocculating and flocculating dispersing agent, flocculation and collector in the fine-grained manganese ore was studied in detail.

Wuhan Iron and Steel Institute studied the effect of pH on flocculation and sedimentation behavior of fine-grained manganese carbonate concentrate, and proposed the concentration and dehydration process of Zunyi manganese concentrate. Whether it is natural sedimentation or high-molecular flocculation, it is closely related to the isoelectric point of rhodochrosite. The optimum pH value can be adjusted to the natural pulp pH value without adjustment.

V. Some views

Significant progress in refractory manganese ore dressing technology will greatly promote the development of China's manganese industry production.

(1) The mature mineral processing technology should be planned to be applied to manganese ore production as soon as possible, to build a new plant or to renovate an existing concentrator. For example, a stage grinding and a magnetic-floating-heavy combined process for treating Zunyi high-iron manganese ore can be obtained. The second and third grade manganese concentrates have a total manganese recovery rate of 76.38%. This result should be applied to production as soon as possible.

(2) Pay attention to arranging new developments or applying high-efficiency new equipment to the manganese ore beneficiation field as soon as possible. For example, the pulsation high gradient magnetic separator has many advantages, and the test of manganese ore beneficiation should be arranged.

(3) Organizing and arranging the production of effective pharmaceuticals for manganese ore dressing and strengthening the development of new effective pharmaceuticals.

(4) Continue to support and encourage new methods and theoretical research on manganese ore beneficiation, and its research results will certainly promote the faster development of manganese ore beneficiation technology.

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