Li Shaoyuan, Zhang Gaomin
(High Long Gold Mining Ltd., Guangxi Tianlin 533312)
CLC number: TD923 Document code: A Article ID: 1671-9492 (2004) 03-0047-03
Fluorite is a strategic mineral [1] , which plays a big role in the economic development of a country. It is widely distributed all over the world, and it has been used as one of the most advantageous mineral products for export earning in China for a long time. Wide range, can be used in metallurgy, chemical, ceramics, cement, glass and other industries. Fluorite ore types silicate, carbonates, barite and fluorite and symbiotic and symbiotic polymetallic fluorite, color is very rich, reselection processing methods, magnetic separation to obtain metallurgical grade fluorspar Concentrate, and acid-grade fluorite concentrate is mainly obtained by flotation; its flotation collector is mainly composed of fatty acids, followed by hydrocarbyl sulfate, alkyl sulfonate, tal oil [1 ], P-733 reported to have good soap selective collector role fluorite carbonate [2], the main inhibitor is sodium silicate, phosphate lesser extent, tannic acid [2], roasted Glue, starch, dextrin, lignosulfonate, etc. [3] .
For silicate fluorite ore, which is mainly composed of quartz and has a low content of carbonate minerals, it can be easily realized by using oleic acid as a collector, sodium carbonate as a regulator, and water glass as an inhibitor of gangue. Separation of fluorite and gangue to obtain high quality acid grade fluorite concentrate [2]. For carbonate fluorite ore containing more calcite , it is necessary to achieve the separation of fluorite and obtain high-quality acid-grade fluorite concentrate, which is economically feasible but very difficult. Because both the calcite and fluorite minerals contain the same Ca 2+ in the crystal lattice, the behavior of the collector and inhibitor on the surface of the two minerals is similar, and it is difficult to separate the calcite from the fluorite ore [1] ] . Therefore, the company wants to obtain acid-grade high-quality fluorite concentrate from carbonate fluorite ore with a calcite content of about 16%. How to realize the separation of calcite and fluorite is particularly important. Therefore, under the entrustment of the company, in the absence of the same type of fluorite ore dressing materials, and the technology is relatively confidential, a lot of experimental work has been carried out on the carbonate fluorite ore to seek for carbonate gangue minerals such as calcite. Inhibitors of effective inhibition and their mineral processing agents.
1. Ore properties
1.1 The chemical composition of the ore
The main chemical composition analysis results of the ore are shown in Table 1.
Table 1 Analysis results of main chemical components of ore /%
chemical composition content | CaF 2 65.78 | CaO 11.12 | SiO 2 14.50 | MgO 0.40 | Al 2 O 3 0.50 | C 1.29 |
chemical composition content | Fe 0.18 | Cu <0.005 | Pb <0.001 | Zn <0.001 | S 0.0072 |
It can be seen from Table 1 that the content of CaF 2 is more than 65%, which belongs to fluorite rich ore. Secondly, SiO 2 and CaO are the main gangue minerals. The content of other elements is very low and there is no recovery value. Therefore, fluorite is the only one of the mine. Recycling ingredients.
1.2 Mineral composition of ore
The ore mineral composition is shown in Table 2.
Table 2 Mineral composition of ore /%
Non-metallic mineral | Metal mineral | ||
Mineral name | content | Mineral name | content |
fluorite Calcite, dolomite quartz Other minerals | 65.78 18.09 14.5 1.63 | Hematite, limonite Pyrite Yellow copper ore Galena Sphalerite | 0.34 Trace Trace Trace Trace |
It is known from the mineral composition that the composition of the ore is simple and the useful mineral is fluorite. The gangue mineral is mainly calcite and dolomite, and the content is as high as 18%, followed by quartz, which belongs to carbonate fluorite ore.
1.3 The structure of the ore
Observed by the naked eye and combined with mineral phase analysis, it can be seen that fluorite crystals are better, the crystal grain size is coarse, the particle size varies widely, and the structure is more complicated. The fluorite is closely combined with carbonate minerals and quartz, and some fluorite is formed in the early stage. In calcite, there are calcite and quartz inclusions in the fluorite, and the later formed carbonate minerals and quartz along the fluorite crack joints are widely replaced and filled. It can be seen from the ore structure that the three main minerals in the ore are intertwined and symbiotic, making the boundary between fluorite and gangue minerals very complicated, and the hardness of calcite is smaller than that of fluorite, which is easily overgrinded in grinding and deteriorates. Flotation operation, when the grinding fineness is not enough, is not conducive to the single dissociation of fluorite and calcite, making the sorting of fluorite and calcite very difficult. [next]
2. Beneficiation test
2.1 The formulation of the beneficiation process
Due to the company's technical and economic conditions, geographical location (inconvenient transportation, lack of various materials, especially in the region without mineral processing pharmacy) and on-site process conditions (a section of crushing a grinding, a rough selection, a sweeping, five times fine In order to minimize the input, reduce or even change the process, the main consideration is to start with the mineral processing pharmacy system; and because of the high content of calcite in the ore, it is impossible to achieve the silicate-based pharmaceutical system. Separation, so the test is mainly based on a combination of inhibitors and inhibitors that have an effective inhibitory effect on collectors and calcite that selectively capture fluorite and calcite, and which are less inhibitory to fluorite.
2.2 Material preparation
The test sample was taken by the company's inspector. After being crushed to -2mm, the sample was mixed and sampled, and analyzed. The analysis results showed that the CaF 2 content was 71.2%, the CaCO 3 content was 16.8%, and the SiO 2 content. It is 10.4%; half of the sample is used as a backup sample, and half is used for testing.
2.3 Exploratory test of inhibitors
According to the current status of the production site process and the manufacturer's fineness requirements for the product, first determine the ore grinding fineness -74μm is 80%, the collector oleic acid dosage is 200g/t, Na 2 CO 3 is the pulp conditioning agent, and maintain the pulp. The pH is 9-10, and its inhibitors are water glass, hexametaphosphate, tannic acid [3] , pyrophoric acid, dextrin, baking gum [3] , sodium carboxymethyl cellulose (CMC) [4] ] and adjuvants Al 3+ and Fe 2+.
From the test results, it is difficult to separate fluorite and calcite by using one of the above inhibitors alone; when using flotation, water glass or a small amount of Al 3+ or Fe 2+ is added , the foam is sticky, and it is produced when selected. Flocs, serious inclusions, difficult to defoam, can not be separated; use sodium hexametaphosphate, tannic acid, coke flavor acid acid foam, refreshing, easy to defoam, no flocculation, less inclusion, can get qualified fine Mine, but its inhibition is very strong, a large number of fluorite are suppressed, difficult to control, and the recovery rate is not high; using dextrin, baking gum, CMC has a certain selective inhibition, but the foam is still a little sticky, The separation was not good; therefore, a combination of the above two or more inhibitors was used, and it was found that the combination of water glass, dextrin and Al 3+ was better, but the index was still not satisfactory. Finally, acidified water glass and inhibitor Y (an organic polymer compound, soluble in water) and additive A (an inorganic compound, non-toxic, soluble in water) were used together, and good test results were obtained.
2.4 grinding fineness condition test
300g of test sample and 500ml of water were separately ground in the XMQ240×90 cone ball mill for testing. The grinding time was different. The amount of oleic acid of the collector was 200g/t. Na 2 CO 3 was used as the pulp conditioner to maintain the slurry. pH 9～10, the inhibitor is acidified water glass combined with Y and additive A, wherein the acidified water glass is water glass: concentrated sulfuric acid: water=10:10:100; after one rough selection, five times selected products fluorite essence mine. The grinding fineness test results are shown in Table 3.
Table 3 Grinding fineness test results /%
Grinding fineness -74μm | 58 | 63.5 | 75 | 83 | 87 | 91 | 98 |
CaCO 3 content Fluorite recovery | 2.1 66 | 1.5 76.4 | 1.12 74.6 | 0.84 78 | 1.34 80.2 | 1.94 85.66 | 2.56 86 |
It can be seen from the test results that the fineness of grinding is 75%~87%-74μm. Under the condition of grinding energy consumption, the grinding fineness is selected to be -74μm83%.
2.5 collector type and dosage condition test
The oleic acid, sodium alkyl sulfate [1] , P-733 soap [2] were compared in the field. The oleic acid foam was relatively solid and easy to defoam during flotation, while the foam was very rich when using sodium alkyl sulfate and P-733 soap. However, the foam is not real, it is not easy to defoam, the foam transportation is more difficult, and the company's stock of a large amount of oleic acid, oleic acid recovery rate is relatively high, and the harvesting power is strong. In order to meet the actual production conditions of the company, it was decided to use oleic acid as the collector of fluorite ore, and the condition was tested. The amount of oleic acid was variable during the test, and other conditions were unchanged. The test results are shown in Table 4.
Table 4 oleic acid dosage test results
Oleic acid dosage / (kg · t -1 ) | 0.400 | 0.300 | 0.240 | 0.180 | 0.135 | 0.090 |
CaCO 3 content /% CaF 2 content /% Fluorite recovery rate /% | 4.34 95.2 92 | 2.65 96.8 87 | 0.99 98.3 76.15 | 0.91 98.5 70 | 0.60 98.7 60 | 0.57 99.0 48 |
It can be seen from the results in Table 4 that the recovery rate of fluorite increases rapidly with the increase of the amount of oleic acid, and the content of CaCO 3 also increases, the main grade of the concentrate decreases, and the product is unqualified. The collector was then selected to be 240 g/t.
2.6 inhibitor dosage test
In this test, the grinding fineness is -74μm, which is 83%, the crude ore slurry pH is maintained at 9-10, and the oleic acid dosage is 240g/t. After a rough selection and five times selection, the product fluorite concentrate, inhibitor The test results of the compounding dosage are shown in Table 5, wherein M:Y:A represents the mass ratio of acidified water glass, inhibitor Y and additive A.
Table 5 Inhibitor ratio test results
M:Y:A/(kg·t -1 ) | 0.4:0.8:0.05 | 0.5:0.5:0.05 | 0.5:0.3:.05 | 0.5:0.2:0.05 |
CaCO 3 content /% CaF 2 content /% Fluorite recovery rate /% | 0.44 98.8 54 | 0.6 98.7 65.3 | 0.72 98.5 76.45 | 1.49 97.8 82.15 |
It can be seen from Table 5 that the effect is better when the dosage ratio of the preparation is 0.5:0.3:0.05. Acidity is compared with water glass acidity test. Concentrated sulfuric acid (analytical grade) is used for acidification, and the ratio of H:S:O represents the volume ratio of water glass: concentrated sulfuric acid:water in acidified water glass. The test results are shown in Table 6.
Table 6 Water glass acidification test results
H:S:O | 1:1:10 | 1:0.5:10 | 4:1:40 | 10:1.5:100 |
CaCO 3 content /% CaF 2 content /% Fluorite recovery rate /% | 0.76 98.6 77.1 | 0.8 98.8 82.43 | 0.79 98.76 85.66 | 1.54 97.5 89.3 |
From the results in Table 6, it can be seen that the acidification degree of the acidified water glass is 4:1:40. The effect is better, and the ratio of the acidified water glass does not form a gel, and always remains in a solution state, when it is acidified to 1:1:10. Or when 1:05:10, the silicic acid gel is easily formed and cannot flow, and when the degree of acidification is too low, the selective inhibition effect is poor. Therefore, the acidification degree of the acidified water glass is 4:1:40, which is convenient for production and application, and the selective inhibition is also strong. At the same time, it is very important to add a small amount of combination inhibition at the time of selection. [next]
2.7 comprehensive condition test
Through the above tests, the two sets of parallel verification tests of comprehensive conditions were carried out under the above conditions. The conditions were: grinding fineness -74μm 83%, coarse pulp concentration 25%, pH 9-10, oleic acid dosage 240g/t. The acidification degree of the inhibitor acidified water glass is 4:1:40, and the combined inhibitor dosage is M:Y:A=0.5:0.3:0.05, and the recovery rate of the selected products is 84.56% and 85.7%, respectively; the CaCO 3 content is less than 1.0%, CaF 2 content is greater than 98%.
3, the conclusion
1. The company's ore is carbonate fluorite rich ore, the mineral composition is simple, it is fluorite, calcite, quartz; fluorite is closely related to calcite and quartz, and the flotation of calcite and fluorite is very similar, flotation Separation is very difficult. The general pharmaceutical system cannot be sorted at all, and only a combination of agents and agents with special selective inhibition effects can be sought.
2, due to the complex relationship between fluorite and calcite and quartz mosaic, the ore is rich; so consider fine grinding to facilitate the dissociation of the ore, but at the same time because calcite hardness is lower than fluorite, calcite is very easy to over-grind, The deterioration of subsequent flotation operations and the impact on product quality and mineral processing indicators. Therefore, the fineness of grinding must be controlled.
3. Through a large amount of research work, this experiment selected a combination of special selective inhibitors for the other side of the stone, and achieved good technical and economic indicators, the recovery rate of more than 85%, making full use of mineral resources.
4. The economic benefits are remarkable. The original ore resources can be used from the original unusable, which increases the reserve resources of the concentrator. It can reverse the unfavorable situation of the shortage of resources in the concentrator. For example, the treatment volume is 100t/d, and the recovery rate is 85%. Calculated according to the current price of 600 yuan / t, the annual economic benefit can be more than 2.5 million yuan.
5, the inhibitor is cheap and easy to obtain, easy to add and operate control.
references
[1] A. Yukar, adsorption mechanism of fluorite flotation collector [J], foreign metal ore dressing, 2003, (7): 21-24.
[2] Meng Xianyi, Research on a fluorite ore beneficiation process in India [J], Nonferrous Metals (Mineral Processing), 1999, (3): 13-15.
[3] China Nonferrous Metals Metallurgy Handbook [M], Beijing: Metallurgical Industry Press.
[4] Hu Weibai, Flotation [M], Beijing: Metallurgical Industry Press, 1989.
[5] Zhou Jixue, Li Changgen, Development of mineral processing technology of peridotite in Shizhuyuan tungsten- molybdenum- bismuth fluorite ore [J], Nonferrous Metals (Mineral Processing), 1999, (2): 7-12.
THE TEST RESEARCH FOR PROCSSING FLUORITE ORE
CONTAINING CARBONATE MINERALS
LI Shao-yuan,ZHANG Gao-ming
(Gaolong Gold Mining Limited Company, Tianlin Guangxi 533312, China)
ABSTRACT
According to the difference of mineral property,flotation tests have been done to separate fluorite from carbonate minerals.Through large numbers of test,thedepressant which can depress effective carbonate minerals contained in fluorite ore such as calcite,etc,has been found out.By using This depressant,fluorite can be separated successfully from calcite.The test results show that,high grade fluo rite concentrate which contains CaF2 over 98%and CaCO3 less than 1.0%,can be acquired by using flotation process,and the recovery of CaF2 is more Than 85%.
KEY WORDS: fluorite; calcite; depressant; flotation process
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