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Lithium is widely used in atomic energy, aircraft, missile, aerospace, metallurgy, petroleum, electrical and electronic instries. The lowest instrial grade of lithium in general ore is Li < sub > 2 < / sub > o 0.6% ~ 0.8%, while a bauxite deposit in Henan province contains Li < sub > 2 < / sub > O 0.n% ~ 1.15%. In order to evaluate it accurately, we must find out its occurrence state
although the content of lithium is not low, the particle size of the minerals is mostly less than 0.01mm e to the fine particle size of the minerals, and no lithium minerals can be identified under the microscope, so it is impossible to select various single minerals. Moreover, the atomic number of lithium is n = 3, which can not be detected by electron microprobe, so it is very difficult to find out the occurrence state of lithium by means of rock and mineral identification, and basically find out the occurrence state of lithium in two types of ores by means of occurrence analysis
(1) preparation of large samples according to the grade of the deposit, multiple weighted average ore matching of small samples are taken. L < sub > 1 < / sub > sample is bauxite, l < sub > 2 < / sub > sample is the top and bottom of bauxite (clay ore). The exploration team sent small samples, and the ore composition of two large samples is shown in table 3.17
Table 3.15 sample combination and chemical analysis results of Li < sub > 2 < / sub > O in bauxite
Table 3.16 sample combination and chemical analysis results of Li < sub > 2 < / sub > O in bauxite roof and floor (clay ore)
after small samples are processed to particle size less than 0.075mm, Al < sub > 2 < / sub > o < sub > 3 < / sub >, Fe < sub > 2 < / sub > o < sub > 3 < / sub >, SiO < sub > 2 < / sub >, Fe < sub > 2 < / sub > o < sub > 2 < / sub > o < sub > 3 < / sub >, SiO < sub > 2 < / sub > 2 < / sub > o < sub > 3 < / sub > 3 < / sub >, Fe < sub > 2 < / sub > o Li < sub > 2 < / sub > O, the results are listed in table 3.15 and table 3.16. The samples were prepared according to the mass ratio of small samples, and after fully mixing, Al < sub > 2 < / sub > o < sub > 3 < / sub >, Fe < sub > 2 < / sub > o < sub > 3 < / sub >, SiO < sub > 2 < / sub >, Li < sub > 2 < / sub > o were determined. The results are listed in table 3.17
Table 3.17 analysis results of large sample ore matching (W < sub > b < / sub > /%)
note: it is required that the analysis results of large sample composition are made by the exploration team
it can be seen from the results in table 3.17 that the four analysis results are in good agreement, indicating that the prepared two large samples are very representative
According to the rock and mineral identification data, the ore of the deposit is mainly composed of the following minerals: boehmite, kaolinite, sericite, hydromica, chlorite, limonite, rutile, anatase, sphene, zircon and organic matter, and no independent mineral of lithium is found. The disseminated grain size of minerals is very fine, including boehmite, kaolinite, sericite, hydromica, etc. the particle size is less than 0.01mm, only a few pieces of boehmite particle size is 0.01-0.02MM(3) complete analysis of ore samples
the complete analysis items are selected according to the mineral composition and element combination. The results of complete analysis of two large samples are listed in table 3.18
Table 3.18 total analysis results of large sample (W < sub > b < / sub > /%)
note: since f is the anion in the composition, it should be corrected according to the oxide measurement, and the correction is - 8% for every 19% F
(4) mineral composition analysis according to the mineral assemblage of large samples, the chemical phase analysis of silicon, aluminum, titanium, iron, potassium, carbon and other elements was designed to measure the mineral amount of these minerals. Chemical phase analysis of silicon is used to determine quartz and total silicate silicon, and chemical phase analysis of aluminum is used to determine monohydrate, kaolinite, sericite and hydromica. Rutile, anatase and sphene were determined by chemical phase analysis of titanium. Iron carbonate and limonite were determined by chemical phase analysis of iron. Chemical phase analysis of potassium was used to determine hydromica and sericite. Chemical phase analysis of carbon is used to determine organic carbon and carbonate. According to the characteristic element content of the mineral, the mineral quantity of the mineral can be calculated according to the measured or theoretical mineral composition. If there are chemical phase analysis data of two elements, the one with high accuracy shall prevail. Some elements, such as lithium, manganese, magnesium, etc., which may exist in a mineral in the state of isomorphism, are determined by determining the total amount of each phaseaccording to the results of chemical phase analysis of characteristic elements, the total amount of other elements must be consistent with the content of the element directly measured in the sample
The mineral composition of the two samples is shown in table 3.19 and table 3.20. The distribution of lithium in the table is determined by the method described later. It can be seen from the results in the table that the mineral composition obtained on the basis of full analysis and accurate determination has also obtained more accurate results
Table 3.19 detailed list of mineral composition of L < sub > 1 < / sub > large sample (W < sub > b < / sub > /%)
① minus fluorine correction 0.08
The chemical phase analysis methods of the six elements are as follows:(1) chemical phase analysis of silicon. 0.5g sample was added with 25ml of H < sub > 3 < / sub > Po < sub > 4 < / sub >, and at (25 ± 10) After 12 min, remove and cool to 150 ℃, add 100ml 15g / L tartaric acid and 10ml fluoroboric acid, mix well, filter and wash. The resie is quartz and the filtrate is silicon in silicate
(2) phase analysis of aluminum. According to figure 2.1 analysis process (3) chemical phase analysis of titanium. ① Determination of rutile: 0.5g sample added with 0.05g NaF, 50ml HCl (2 + 1), heated in boiling water bath for 1.5h, filtered and washed. The titanium in the resie is the titanium of rutile. ② Determination of sphene: 0.2g sample was calcined at 750 ℃ for 30min, taken out, cooled and transferred to beaker, then 30 ml 30g / L NH < sub > 4 < / sub > HF < sub > 2 < / sub > &; HNO < sub > 3 < / sub > (1 + 9) was soaked in boiling water bath for 45 min. The titanium in the filtrate, that is, the titanium in the cadmium ore, and the titanium in the resie, that is, the titanium in rutile and ilmenite (4) chemical phase analysis of iron. 0.5g sample plus 100ml 100g / L NH < sub > 4 < / sub > CL & 8259; 5 g / L o-phenanthroline, heated for 1 h, filtered, filtrate colorimetric determination of iron, iron carbonate. Total Fe < sup > 3 + < / sup > (total Fe & ᦇ 8259; Iron carbonate is iron in limonite, which is composed of < inline media object > < imageobject > < imagedata role = 3 "fileref = image / figure_ 0157_ 0185. JPG "> < title > < / Title >< / picdesc > < / imagedata > < / imageobject > < / inlinemediaobject >
Table 3.20 detailed list of mineral composition of L < sub > 2 < / sub > large sample (W < sub > b < / sub > /%)
① minus fluorine correction 0.06
(5) chemical phase analysis of potassium. Take 0.2g sample, add 50ml HCl (8 + 92), heat it in boiling water bath for 20min, filter it (extract it twice continuously in this way, and correct the dissolution rate of potassium in resie for the second time), measure the potassium in hydromica phase in filtrate and sericite phase in resie (6) chemical phase analysis of carbon. First, dissolve the sample with phosphoric acid, determine CO < sub > 2 < / sub > in carbonate by non-aqueous titration, and determine total carbon by non-aqueous titration with combustion method, and calculate organic carbon by subtraction (5) analysis of occurrence state of lithium1. Preliminary study of occurrence mineral of lithium
design two chemical phase analysis processes. The first is the chemical phase analysis process of aluminum, which divides aluminum into four phases: gibbsite phase, chlorite + hydromica phase, kaolinite + sericite phase and monohydrate phase. The other is chemical phase analysis of potassium, which is divided into two phases: hydromica phase and sericite phase. After phase separation, lithium is determined in each phase in order to find out which phase lithium is enriched in and narrow the range of occurrence of lithium. The preliminary analysis results are listed in table 3.21 and table 3.22
Table 3.21 preliminary study on the distribution of lithium by phase analysis of aluminum
Table 3.22 preliminary study on the distribution of lithium by phase analysis of potassium
it can be seen from the analysis results that potassium mainly exists in kaolinite and sericite phases
Analysis of occurrence state of lithium in kaolinite and sericite? In what state? Further investigation is needed (1) the experiment of dissolution conditions of kaolinite and sericite. Using 150g / L KOH ᦇ 8259; Using 150g / L KCl as the selective solvent, kaolinite can be separated from sericite by the thermal alkali decomposition of kaolinite and the same ion effect of potassium ion. When 0.5g sample is added with 50ml of the above solvent and heated for 2.5h, the dissolution rate of kaolinite, sericite and diaspore is 100%, 2% and 1.5% ~ 2.0%, respectively (2) controlled dissolution analysis of kaolinite. 0.5g sample was soaked in 40ml HCl (8 + 92) for 30min to dissolve hydromica. Chlorite and possible gibbsite, filter and discard filtrate. The resie was treated with 150 g / L KOH; 150 g / L KCl was used as control solution. Each time, 50 ml solvent was added, heated and leached for 30 min, and then filtered. After the filtrate was constant volume, Li < sub > 2 < / sub > O (atomic absorption spectrometry), SiO < sub > 2 < / sub > (molybdenum blue colorimetry), Al < sub > 2 < / sub > o < sub > 2 < / sub > (complexometric titration) were determined. Finally, the resie was used for controlling the dissolution of Sericite. The results are shown in table 3.23 and table 3.24. The cumulative leaching rates of Li < sub > 2 < / sub > O, SiO < sub > 2 < / sub > and Al < sub > 2 < / sub > o < sub > 3 < / sub > in the filtrate of five successive leaches in table 3.23 are plotted (see Fig. 3.5), and three basically coincident curves are obtained. The figure 3.5 illustrates that the three systems of SiO < sub > 2 < / sub > · al < sub > 2 < / sub > al < sub > 2 < / sub > o < sub > 3 < / sub > and Li < sub > 2 < / sub > o are leaching from the same mineral, and the five times total value of W (SiO < sub > 2 < / sub > < sub > 2 < / sub > · al < sub > 2 < / sub > 2 < / sub > o < sub > o < sub > 3 < sub > 3 < / sub > 3 < / sub > and Li < sub < sub > 2 < / sub > 2 < / sub > 2 < / sub > o) for five times is w (SiO < sub < sub > 2 < / sub > 2 < / sub > < sub > 2 < / sub > / sub > / sub >) / w (al < sub < sub < sub < sub > 2 < sub < sub > 2 < sub > 2 < sub > 2 < sub > 2 < sub > 2 < sub > 2 < sub > 2 < sub > 2 < sub > 16, It shows that: 1) the SiO < sub > 2 < / sub > and Al < sub > 2 < / sub > o < sub > 3 < / sub > leached in this phase belong to kaolinite phase. ② The distribution of lithium in kaolinite is homogeneous
Table 3.23 l < sub > 1 < / sub > controlled dissolution analysis of kaolinite
note: theoretical value of kaolinite w (SiO < sub > 2 < / sub >) / w (al < sub > 2 < / sub > o < sub > 3 < / sub >) = 1.16
Table 3.24 l < sub > 2 < / sub > kaolinite controlled dissolution analysis
Fig. 3.5 kaolinite masked dissolution analysis curve
(3) sericite controlled dissolution analysis. The resie of kaolinite was leached continuously. First, 30 ml HCl (2 + 8) &; HF (2 + 98) was extracted in boiling water bath for 30 min, twice, and then with 30 ml HCl (2 + 9) &; HF (5 + 95) was soaked in boiling water bath for 40 min, twice. Al < sub > 2 < / sub > o < sub > 3 < / sub > (complexometric titration), K < sub > 2 < / sub > O, Li < sub > 2 < / sub > O (atomic absorption spectrometry) were simultaneously determined in the four leaching solutions. The results and data processing are listed in table 3.25 and table 3.26
Table 3.25 l < sub > 1 < / sub > sericite controlled dissolution analysis
note: theoretical value of Sericite w (al < sub > 2 < / sub > o < sub > 3 < / sub >) / w (k < sub > 2 < / sub > o) /% = 3.26
Table 3.26 l < sub > 2 < / sub > sericite controlled dissolution analysis
the same as the data mapping of kaolinite controlled dissolution analysis, the cumulative leaching rates of Al < sub > 2 < / sub > o < sub > 3 < / sub >, K < sub > 2 < / sub > O and Li < sub > 2 < / sub > O in the order of leaching are plotted, and three curves of basic coincidence are also obtained. The figure 3.6 illustrates that Al < sub > 2 < / sub > o < sub > o < sub > 3 < / sub > 3 < / sub >, K < sub > 2 < / sub > O and Li < sub > 2 < / sub > O and Li < sub > 2 < / sub > o are three systems of Al < sub > 2 < / sub > o < sub > o < sub > o < sub > 3 < sub > 3 < / sub > 3 < / sub >, K < sub > 2 < / sub > sub > O > 3 < / sub >, K < sub > 2 < / sub > 2 < / sub > o) ratio (L < sub > 1 < / sub > < sub > 1 < / sub > 1 < / sub > and l < sub > 2 < / sub > 2 < / sub > all are 3.26 for 3.26) and theoretical w (al < al < sub > 1 < / sub > 1 < / sub > 1 < / sub > 1 < / sub > 1 < / sub > 1 < / sub > 1 < / sub > 1 < / sub > 26, The results show that: (1) the leached al < sub > 2 < / sub > o < sub > 3 < / sub >, K < sub > 2 < / sub > O in this phase belong to sericite phase. ② Lithium is also distributed homogeneously in sericite
Figure 3.6 controlled dissolution analysis curve of Sericitehttp://bt.icefish.org/ Ice fish BT release page
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