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Application of New Pharmacy in the Separation of Fluorite and Calcite, Barite and Quartz Flotation
Application of New Pharmacy in the Separation of Fluorite and Calcite , Barite and Quartz Flotation
Che Liping
Abstract: The regularity of new collector H602 and inhibitor S602 in the flotation separation of fluorite and calcite, barite and quartz was studied. The optimal flotation separation conditions were determined and the effect of the agent was discussed. mechanism.
Key words: H602 collector; S602 inhibitor; fluorite; calcite; barite; quartz; flotation separation
Fluorite is currently the main source of industrial fluorine in the world. China's fluorite resources are abundant, ranking first in the world. In nature, the natural fluorite-rich mineral resources that can be directly exploited and utilized are less. Therefore, domestic and foreign fluorite ore must be selected to obtain high-quality commercial fluorite suitable for direct use or deep processing, that is, the grade is greater than 98%. Fluorite concentrate.
Industrial fluorite deposit mainly silicates, metal carbonates and multiple symbiotic fluorite deposits. High silicate content fluorite deposit calcium fluoride, fluorite minerals are closely associated calcite and a small amount of quartz, pyrite and other minerals, sorting easier; carbonates of calcium fluoride content than fluorite deposit Low, minerals closely associated with fluorite are minerals such as calcite, barite, quartz, etc., which are difficult to select; polymetallic symbiotic fluorite deposits contain less calcium fluoride, and minerals closely related to fluorite have calcite and recrystallized , quartz, sericite, chlorite, kaolin minerals, sorting difficult. With the exploitation and utilization of fluorite deposits, the silicate fluorite deposits are reduced, and the selection of fluorite minerals tends to be complicated and difficult to select. The chemical composition of fluorite is CaF 2 , which is closely associated with minerals such as calcite, barite and quartz in the deposit, and the associated minerals such as calcite, barite and quartz are very similar to the fluorite minerals (such as minerals). Floating, density, specific magnetic susceptibility, dielectric constant, etc., therefore, the separation of fluorite and associated minerals is more complicated and difficult.
In this study, new collectors and inhibitors of fluorite were used, and according to the characteristics of minerals and pharmaceuticals, appropriate adjusting agents were selected, and an effective pharmaceutical system was combined to realize fluorite and calcite and barite. Separation of associated minerals such as quartz.
1 sample
The sample of this study is a typical carbonate fluorite deposit, which is formed by the interaction of fluorine-containing hydrothermal intrusion lime cracks with limestone. The shape of the ore body is complex and diverse, most of which are vein-like and lenticular, with a small amount of disseminated or regular plate. The main mineral fluorite is dense block, breccia or disseminated. The symbiotic minerals are mainly calcite, barite, quartz and a small amount of minerals such as mica and amphibole.
A sample taken from a domestic ore heap before the mineral fluorite crushing plant, sample distribution, containing about 65% CaF 2. The surface of the nugget of the sample is weathered, the pulverization is serious, the oxidation is partial, the amount of slime is more, and the crushing and grinding are easier. The grinding fineness of this study is about -74 μm, which accounts for about 80%, and the fluorite mineral monomer dissociation degree is 98%.
The mineral properties of fluorite, calcite, barite and quartz are shown in Table 1. As can be seen from Table 1, the four minerals are non-conducting, non-magnetic or weakly magnetic polar minerals. It is difficult to separate effectively by conventional single re-election, magnetic separation and electrostatic separation. However, due to the difference in their crystal structure, effective fluorite collectors and associated mineral inhibitors are used, and appropriate The combination of pharmacy can achieve the separation of fluorite and associated minerals such as calcite, barite and quartz, and obtain high-grade fluorite concentrate.
Table 1 Mineral properties of fluorite, calcite, barite, quartz
Mineral name
Molecular formula
Crystal system
hardness
density
Specific magnetic susceptibility (×10 -6 )
Dielectric constant
fluorite
Calcite
Barite
quartz
CaF 2
CaCO 3
BaSO 4
SiO 2
Isometric
Tripartite
Oblique square
Tripartite
4
3
3 to 3.5
7
3.18
2.7 to 2.9
4.3 to 4.7
2.65
-0.46~-1.54
-0.08~-1.25
-0.44~-0.25
-1.03~-0.14
2.52~8.5
5.10 to 9.5
5.22~8.0
4.50～8.0
2 The main process factors affect the flotation separation
According to the characteristics of the sample and the nature of the mineral, as well as the mechanism of action of the flotation agent, the new agent H602 is used as a collector for fluorite, and S602 is used as an inhibitor of associated minerals such as calcite, barite, quartz, etc. As a modifier of pulp, several chemicals were rationally combined and combined, and the sample was subjected to the separation test of preferential flotation fluorite minerals. The new agent was studied in the flotation separation of fluorite and calcite, barite, quartz and other minerals. Regularity, the effects of various main process factors on the floatability of minerals were investigated. The test results are shown in Figures 1 to 6.
Fig.1 Effect of pulp pH on mineral floatability
1—fluorite; 2—calcite;
3—barite; 4—quartz; the same below
The experimental results show that the optimum pH range for the flotation separation of fluorite and calcite, barite, quartz and other minerals is 10.5～11.5. In alkaline pulp, S602 strongly inhibits minerals such as calcite, barite and quartz. When the amount of S602 is too large, fluorite is also inhibited; H602 can selectively float fluorite, and if it is excessive, it loses selectivity.
Figure 2 Effect of S602 dosage on mineral floatability
[next]
The matching of combined alkaline substances affects the flotation effect of fluorite. When the preparation ratio is reasonable, the activation of fluorite is related. The ratio of the amount of combined basic substances to the amount of S602 inhibitor is also an important factor. When appropriate, it can play the role of dispersing the slime, which is conducive to flotation separation; the slurry temperature and the slurry concentration have different effects on the flotation separation. When the pulp temperature is lower than 16 °C and the slurry concentration is lower than 15% or higher At 45%, the sorting effect was significantly reduced.
Figure 3 Effect of H602 dosage on mineral floatability
Figure 4 Effect of the ratio of combined basics on the floatability of minerals
Figure 5 Effect of slurry temperature on mineral floatability
Figure 6 Effect of slurry concentration on mineral floatability
3 test results analysis
3.1 New drug test results
The experimental research shows that the dosage of various flotation reagents is appropriately adjusted to determine the optimal flotation separation conditions. The pH value of the slurry is 10.5, the slurry temperature is 30 °C, the slurry concentration is 40%, and the selection is 30%. The amount of combined alkaline is 3.603kg/t, the dosage of S602 is 3.025kg/t, and the dosage of H602 is 0.988kg/t. After one rough selection and five times selection, the grade of fluorite can be obtained >98%, recovery rate The average results of the stability test of >69% and fluorite concentrates with high impurity content are listed in Table 2.
Table 2 H602 collector stability test average result /%
Mineral name
Yield
grade
Recovery rate
Fluorite concentrate
Middle mine 1
Middle mine 2
Middle mine 3
Middle mine 4
Middle mine 5
Flotation tailings
Flotation to mine
46.64
3.22
6.58
3.07
7.60
9.21
23.68
100.0
98.19
80.08
75.63
71.02
59.38
50.92
5.12
65.95
69.45
3.91
7.55
3.31
6.84
7.11
1.83
100.0
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3.2 Comparison of new drug combination and oleic acid combination test results
Oleic acid is a commonly used collector in fluorite flotation. The flotation effect is better, but there are a series of problems such as high flotation temperature, large consumption of chemicals, high price and increased production cost. All research and production units are actively seeking and developing new collectors to replace oleic acid. In response to this problem, we have successfully developed a new collector H602.
The combination of the oleic acid flotation fluorite test is sodium carbonate + water glass + baking gum + oleic acid, the pulp temperature is 50 ° C, other conditions are the same as the test conditions in Table 2, after a rough selection, five times selection The selection index (average results of stability test) is shown in Table 3. The dosage (kg/t) of the drug is 4.229 sodium carbonate, 4.430 water glass, 0.036 baking rubber, and 0.685 oleic acid.
Table 3 Average results of oleic acid collector stability test /%
Mineral name
Yield
grade
Recovery rate
Fluorite concentrate
Middle mine 1
Middle mine 2
Middle mine 3
Middle mine 4
Middle mine 5
Flotation tailings
Flotation to mine
33.97
3.38
5.15
5.88
9.56
16.18
28.88
100.0
96.75
83.27
82.86
81.42
80.10
64.25
9.04
65.14
50.46
4.31
6.56
7.35
11.76
15.97
3.59
100.0
The results in Table 4 are the results of the use of different collectors, the same regulators, and the same process conditions (same as Table 2). The test results show that the new collector H602 is more suitable for the drug system combined with it. Under the same conditions, the selection effect of H602 is more significant.
Table 4 Comparison results of H602 and oleic acid collectors /%
Product name
Yield
grade
Recovery rate
Remarks
Fluorite concentrate
Flotation mine
Flotation tailings
Flotation to mine
45.76
30.43
23.80
100.0
98.80
61.91
5.64
65.39
69.14
28.81
2.05
100.0
H602
Collector
Fluorite concentrate
Flotation mine
Flotation tailings
Flotation to mine
22.06
56.21
21.73
100.0
93.46
76.07
10.79
65.72
31.38
65.06
3.56
100.0
Oleic acid
Collector
In the fluorite flotation separation test, H602 has obvious advantages over oleic acid. For example, H602 adopts low-temperature flotation, and the flotation agent consumes less. The agent also has a low synthesis cost, and the price is relative to oil. The characteristics of low acid, these features can reduce energy consumption and reduce production costs.
4 discussion
The minerals such as fluorite, calcite and barite are all easy-float minerals. The lattice energy can be between 417 and 519, and the floatability is basically the same. The metal ions of these three minerals are all divalent ions with similar chemical properties. The pH value of the pulp required for flotation is alkaline. Therefore, the flotation separation of fluorite with calcite and barite minerals is particularly difficult. It can only rely on the special properties of the agent and the synergistic effect of the agent and multiple selection operations. Complete flotation separation. The floatability of quartz is slightly worse, its lattice energy is about 5190, and other characteristics are also different. Therefore, the flotation separation of fluorite and quartz is easier to carry out, and the rough selection operation can discard most of the quartz into the tailings. However, minerals such as silicon-containing mica and fine quartz are mixed in the floating minerals and a small amount of slime enters the selection, which makes the selected enrichment relatively low. The fluorite concentrate has high impurity content, relying on the action of the agent and multiple fines. Select, can achieve effective separation [1] .
H602 is a mixed fatty acid collector with simple synthesis process, low production cost, simple preparation and operation, and remarkable screening effect. Compared with commonly used fatty acid collectors, its hydrophobic properties and mineral-selective properties and collectors can have significant advantages.
The mechanism of action of H602 on fluorite. After the cations of fluorite in the solution are hydrolyzed into Ca 2+ and CaOH + hydroxyl complexes in solution, they are re-adsorbed on the surface of the mineral. The effect of H602 on the surface of fluorite is mainly through the hydroxyl group. - COO - The functional group is formed by chemisorption of a metal chelate and a hydroxy complex to form a chelate. The stable form of the formed chelate is affected by the pH of the medium and the amount of collector, see Figures 1 and 3. Tests have shown that minerals are slightly soluble and contribute to the adsorption of the collector. If the slurry mixing time is extended or the slurry temperature is increased, the selection index can be improved.
S602 is a reactive silicic acid colloid inhibitor, and its adhesion ability is 1.30 to 1.63 times higher than that of water glass, and the selection type of inhibition is greatly improved (Fig. 7). S602 inhibits the associated minerals of fluorite. It is believed that in the process of mineral flotation, H 2 SiO 4 + in the active colloidal colloidal solution adsorbs on the mineral surface, making the associated minerals hydrophilic and inhibited [2] . The presence of active silicic colloid inhibitors does not inhibit the adsorption of H602 collector on the surface of fluorite. S602 can selectively float the target mineral fluorite while selectively inhibiting the associated mineral floatation. The selectivity of this inhibitor selection is affected by the amount of S602, see Figure 7.
Figure 7 The amount of water glass and active silicate colloid
Effect of recovery rate of pure mineral flotation on hematite
1—water glass; 2—active silicate colloid
5 conclusions
H602 is an effective fluorite collector with good selection index. It forms a relatively stable chelate with the surface of the fluorite, making it float. H602 is cheap and practical. S602 is a colloidal inhibitor with better selectivity and has a stronger ability to inhibit associated minerals.
In alkaline medium, the combination of basic alkali + S602 + H602 is the main pharmaceutical factor for the separation of fluorite and associated minerals such as calcite, barite and quartz.
H602 is a fatty acid collector, so it is not only an effective collector for fluorite minerals, but also widely used in the flotation of non-ferrous metals, ferrous metals, rare metals and other minerals.
references
1 Zhu Jianguang et al. Flotation Pharmacy. Beijing: Metallurgical Industry Press, 293
2 Mei Guangjun et al. Non-ferrous metals (mineralization part), 2000 (2): 32