Jamesonite ore (formula Pb 4 FeSb 6 S l4) is mainly produced in the territory of the manufacturers Nandan, five other mining Wei, which is containing more valuable metals such as lead, antimony, zinc, Polymetallic sulphide deposits such as indium and silver , among which the resources of strontium are second to none in China and the world. Most of the current smelting processes of the brittle sulphur lead bismuth ore concentrate are reduced and smelted by sintering desulfurization-blast furnace. The process has low sulfur dioxide pollution and low comprehensive recycling level, especially the valuable metals such as zinc and antimony in the mine are not recovered at all. And so on.
In order to change the defects of the traditional smelting process, a new process for smelting the brittle sulphur lead bismuth ore concentrate was studied. By adding "alkali" solid "sulfur" method, all the sulfur in the ore is brought into the smelting slag during smelting, and the lead-bismuth alloy is produced at the same time; and the alkali is recovered from the smelting slag in the form of sodium sulfide and sodium hydroxide. The recovered alkali is used to manufacture sodium pyroantimonate product; after the smelting slag recovers the alkali therein, it finally forms high zinc slag, which is enriched with metals such as zinc, iron , bismuth, antimony and lead, and zinc and iron therein. Most of the elements are in the form of sulfides and can be separated by flotation. The new process has the advantages of no sulfur dioxide production, high comprehensive recovery level and good technical and economic indicators; it has good economic and social benefits.
This paper mainly studies the comprehensive recycling of alkaline smelting slag produced by the melting part of the new process. In addition to the main component sodium sulfide, the alkaline smelting slag produced by the smelting section (hereinafter referred to as "alkaline slag") is substantially enriched in lead sulphur lead bismuth ore concentrate (hereinafter referred to as "clay mine"). All ingredients except silver. Therefore, the comprehensive recycling of alkali slag is also an important factor related to the success of the whole process. In this study, the all-wet process was used for the recovery of alkali residue. First, the sodium sulfide and other soluble salts in the alkali residue are introduced into the solution (sodium sulfide solution) by water immersion, so that the soluble matter and the insoluble matter in the alkali slag are separated, and the insoluble matter all enters the alkali slag leaching residue, wherein It is enriched with elements such as zinc, copper , iron and indium, and also contains elements such as lead, antimony and silver. According to the composition and properties of the slag leaching residue, it can be positioned as a zinc ore containing various metal components. mineral processing plant into the zinc concentrate to be recovered which have valuable components. Then, the recovered sodium sulfide solution is used to leach the barium in the brittle ore to prepare sodium pyroantimonate.
First, raw materials and process
Raw materials: alkali residue, concentrate. The alkali slag is produced by the industrial test of this research. The raw material components are shown in Table 1.
Table 1 Raw material composition (mass fraction) /%
raw material | Pb | Sb | Ag 1) | Zn | In 1) | Cu |
Brittle mine | 26.25 | 22.48 | 780 | 5.10 | 160 | 0.28 |
Alkali residue | 2.37 | 1.14 | 125 | 7.62 | 180 | 0.45 |
raw material | As | S | Na 2 S | Fe | CaO | SiO 2 |
Brittle mine | 0.2 | 22.46 | - | 7.45 | 1.82 | 3.24 |
Alkali residue | 0.18 | 35.2 | 52 | 11.31 | 3.62 | 4.70 |
1) The unit is g/t.
Process flow: The process of alkali residue treatment is shown in Figure 1.
Figure 1 Alkali slag treatment process
Second, experimental equipment and methods
The main experimental equipment: beaker (4000 mL), electric stirrer (200W), glass thermometer (0 ~ 100 °C), vacuum pump, Buchner funnel (φ150), suction filter bottle (2000ml), electric furnace (1kW) and so on.
Experimental method: Firstly, the leaching experiment was carried out on sodium sulfide in the alkali residue, and the alkali residue was crushed before the experiment, and sieved through 40 mesh (0.36 mm) for use. This experiment mainly investigates the influence of various kinetic conditions (temperature, time, liquid-solid ratio, etc.) on the leaching rate of sodium sulfide when the alkali residue is leached; the sodium sulfide slurry is vacuum filtered, the filter residue is washed with a little hot water; all the filtrate (sodium sulfide) The solution was combined for the next dipping experiment; then the production process of sodium pyroantimonate was prepared by air oxidation method. The concentrate and the oxygen powder were respectively subjected to leaching of cesium and sodium citrate test.
3. Thermodynamic analysis of sodium sulphate leaching from strontium sulfide
The main reaction of leaching cesium in sodium sulfide solution is a heterogeneous reaction involving two phases of liquid and solid. Sb, S, Na 3 fractions contained in the leaching system may be more complex form complex ions in water. Through the thermodynamic analysis of the Sb-S-H 2 O system and the Sb-Na-S-H 2 O system, the corresponding laws can be found to make the leaching process under the most favorable conditions.
For the Sb-S-H 2 O system, it is a complex complex system in the solution of its basic negative potential region, except for the presence of a single ligand mononuclear complex (SbS 2 - , SbS 3 3 - In addition to SbS 4 3 - ), there are also multiple ligand complexes (Sb 2 S 4 2 - , Sb 2 S 5 4 - , Sb 2 S 6 6 - ) and partial oxo ligands and all The complex ion of the oxo ligand, such as SbSO - , SbSO 2 - , the latter such as SbO + , SbO 2 - , SbO 3 3 - , SbO 3 - , SbO 4 3 - . As the ligand, S 2 - also has a plurality of variable ions (S 2 2 - , S 2 O 3 2 - , SO 4 2 - , SO 3 2 - ) and variant ions (HS - ).
According to the principle of simultaneous balance and the principle of electrical neutrality, some people used the computer to solve the exponential equation, and calculated the potential-pH value of the Sb-S-H 2 O system, and plotted the potential-pH diagram at normal temperature, as shown in Figure 2 ( C(Sb) and C(S) respectively represent the total concentration of Sb and S in the solution at equilibrium).
Figure 2 Sb-S-H 2 O system φ-pH diagram
c(Sb)=1mol/L; c(S)=2mol/L
It can be seen from Fig. 2 that on the solid-liquid equilibrium line, as the pH increases, the potential moves negatively, and the complex ions containing ruthenium in the solution are separated by a complex ion (SbS 2 - ) with a small coordination number. The main (pH<13.6) transitions to complex ions with large coordination number (SbS 3 3 - , Sb 2 S 6 6 - ) (pH=13.6～14.2); at the same time, the number of oxygen sulfur atoms replaced by ruthenium anions Increasing, for example, at pH > 14.2, mainly SbO 3 3 - .
Calculations show that the dissolution of Sb 2 S 3 in sodium sulfide solution mainly occurs as follows:
It can be seen from Fig. 2 that the stable region of the solution, especially the simple coordination complex ion stable region, is narrow; that is, as the potential increases, the number of oxo ligands increases, so that it eventually becomes all oxo. SbO 4 3 - or SbO 3 - and SbO 3 3 - or SbO 2 - plasma, and oxygen-substituted S 2 - is oxidized to S 2 O 3 2 - or the like. This fully demonstrates that the leachate is easily oxidized to form various sodium salts (Na 2 S 2 O 3 , Na 2 SO 3 , Na 2 SO 4 ) and the like.
It can also be seen from Fig. 2 that as the ratio of C(Sb)/c(S) decreases, the solid phase and the Sb 2 S 3 solid phase stable region shrink, and the solution stable region expands. When C(Sb)/c(S)=1/2, the Sb 2 S 3 solid phase stable region is large; when C(Sb)/c(S)=1/3, the Sb 2 S 3 solid phase The stable zone is reduced to a narrow strip. The calculations show that when c(Sb)/c(S) ≤ 1/4, the Sb 2 S 3 solid phase stable region in the figure disappears. This indicates that the suitable leaching conditions for the strontium sulfide concentrate are c(Sb)/c(S) ≤ 1/4.
For the Sb-Na-S-H 2 O system, the alkaline leaching process actually has Na+ participation, making the system relationship more complicated. In the negative potential region of c(Sb)=0.5mol/L, c(S)=2mol/L, in addition to the equilibrium relationship of Sb-S-H 2 O system, there is Sb-Na at 25 °C. -S-H 2 O alkaline negatively charged region in which the solution is in equilibrium with Na 3 SbO 4 crystals, solution and NaSbS 2 crystals, and solid Sb and solid NaSbS 2 . As shown in Figure 3.
Figure 3 Sb-S-Na-H 2 O system ψ-pH diagram
It can be seen from Fig. 3 that Na 3 SbO 4 and NaSbS 2 have a wide stable region, that is, the actually present large solution stable region is covered by the two solid phase regions, and therefore, Na 3 SbO 3 in an alkaline solution. The preparation of Na 3 SbO 4 crystals is very easy to carry out.
Fourth, the results and discussion
(1) Leaching of sodium sulfide in alkali residue
1. Effect of degree on leaching of sodium sulfide
The effect of temperature on sodium sulphide leaching is shown in Figure 4. In the experimental temperature range, the leaching rate of sodium sulfide increases almost linearly with increasing temperature. However, when the temperature exceeds 90 ° C, the leaching rate of sodium sulfide tends to decrease slightly; it may be because the temperature increases, increasing the degree of oxidation of sodium sulfide in the solution. Therefore, the optimum leaching temperature is selected to be 90 °C.
Figure 4 Effect of temperature on sodium sulphide leaching
2. Comparison of the effect of sodium sulphide leaching
The effect of liquid-solid ratio on the leaching rate of sodium sulfide is shown in Fig. 5. When the liquid-solid ratio is too small (less than 3), the concentration of sodium sulfide in the solution is too high, and at the same time, since the solid content of the system is too high, the surface diffusion of the solid-liquid surface is affected, and the leaching rate of sodium sulfide is not high. When the liquid-solid ratio is too large (greater than 5), the amount of sodium sulfide is increased due to the excessive system. At the same time, according to the previous theoretical analysis, the concentration of sodium sulfide should be controlled at 110-130g/L when leaching. Therefore, a suitable liquid to solid ratio of 4:1 is selected.
Figure 5 Effect of liquid-solid ratio on sodium sulphide leaching
3, the impact of sodium sulphide leaching time on vulcanization
The leaching rate of sodium also has a large effect, as shown in Figure 6. In theory, sodium sulphide is very soluble in water and its dissolution rate should be fast. However, it can be seen from Fig. 6 that the dissolution time needs to be 80 min or more, probably because the alkali residue contains other insoluble substances, and the components in the alkali residue are closely combined with each other to form a solid solution, so that the sodium sulfide dissolves slowly. In fact, if the alkali slag particles are ground fine enough, the dissolution time can be greatly shortened. In the industry, if the molten alkali slag can be directly leached, the leaching effect may be much better. The best leaching time for this study was 90 min.
Figure 6 Effect of time on sodium sulphide leaching
The sodium sulfide solution after leaching is very alkaline, the slurry particles are very fine, and the filtration tends to cause diafiltration, so that the obtained sodium sulfide filtrate becomes a black suspension, and it is necessary to stand still for more than 12 hours to become clear. In order to solve this problem, the filter cloth materials for filtration were compared and selected. Finally, it is considered that the polypropylene fiber reinforced filter cloth is most suitable for the filtration of sodium sulfide pulp.
(2) Sodium leaching comprehensive verification experiment
According to the above single factor experiment, comprehensive experimental verification was carried out on sodium sulphide leaching (see Table 2 for the results). Fixation conditions: liquid-solid ratio is 4:1, temperature is 90 ° C, time is 90 min. It is known from Table 2 that the leaching rate of sodium sulfide is about 92% under optimal leaching conditions; the obtained sodium sulfide solution contains about 110 g/L of sodium sulfide. The composition of the solution is exactly in accordance with the conditions for leaching the sodium pyroantimonate product.
Table 2 Parallel verification experiment results
Serial number | Input | output | Sodium sulfide leaching rate /% | Slag rate /% | ||||
Alkali residue /g | Sodium sulfide /g | filtrate /mL | Sodium sulfide /(g·L -1 ) | Sodium sulfide /g | Leaching residue /g | |||
1 | 600 | 312 | 2548 | 112.9 | 287.7 | 301.2 | 92.2 | 50.2 |
2 | 600 | 312 | 2548 | 114.5 | 290.5 | 291.6 | 93.1 | 48.6 |
3 | 600 | 312 | 2562 | 111.8 | 286.4 | 307.8 | 91.8 | 51.3 |
4 | 600 | 312 | 2539 | 114.1 | 289.8 | 293.4 | 92.9 | 48.9 |
5 | 600 | 312 | 2553 | 111.9 | 285.8 | 306 | 91.6 | 51 |
average | 600 | 92.3 | 50 | |||||
(3) Alkali slag leaching slag composition and composition
The alkali slag leaching rate is 50% relative to the alkali slag. Alkali slag leaching slag is almost all of the zinc, iron, silicon, calcium and other elements in the brittle sulphur lead bismuth ore concentrate, and also contains valuable elements such as lead, antimony, silver and indium. The alkali residue leaching slag composition is shown in Table 3. It can be seen that the total content of lead and zinc is about 20%.
Table 3 Alkali residue leaching slag composition (mass fraction) /%
Pb | Sb | Ag 1) | Zn | In 1) | S | Na 2 S | Fe | CaO | SiO 2 |
4.68 | 0.75 | 260 | 15.31 | 350 | 24.80 | 2.68 | 22.52 | 4.86 | 6.35 |
1) The unit is g/t.
By comparing the slag components in the alkali slag leaching slag and the alkali slag, it can be seen that a considerable portion of the cerium in the alkali slag is leached into the human sodium sulfide solution, and the leaching rate is 67%; the actual test for strontium in the sodium sulfide solution The content is 1.6 to 1.9 g/L, and this data is basically consistent with the calculated data.
The phase analysis of zinc and iron in the leaching residue of alkali residue shows that zinc and iron are basically present in the slag in the form of sulfide. Therefore, zinc should be present in the form of monomeric zinc sulfide in the alkali residue leaching slag, which provides a basis for further chemical separation of the slag, since the sulfide mineral of zinc is easily separated and enriched by chemical beneficiation.
V. Preparation of sodium pyroantimonate
The system for extracting strontium from brittle ore by using alkali sulfide to obtain sodium pyroantimonate product has been used by relevant manufacturers. The most typical process is air oxidation method, and the technical conditions are relatively mature.
Due to the complexity of the sodium sulfide solution obtained in this study, in addition to Na 2 S, Na 2 CO 3 , NaAsO 3 , NaOH, Na 2 SO 3 , Na 2 SO 4 may be contained. Therefore, referring to the actual production operating conditions, this experiment mainly investigates the difference between the properties of the alkali-smelting system obtained by water leaching of the alkali slag obtained from the smelting part of the present study and the conventional alkali-sulphide system; mainly the leaching effect on the hydrazine from the system. The consumption of sodium sulfide and the quality of sodium pyroantimonate products have been demonstrated in detail.
(1) Effect of leaching of brittle sulfur lead bismuth ore concentrate by sodium sulfide solution
The leaching was carried out under the given conditions by adding 2000 mL of sodium sulfide solution per 500 g of concentrate. After the leaching was completed, all the filtration was carried out. The filter residue was washed with a small amount of hot water, dried, and weighed (lead residue).
Fixation conditions for leaching: temperature 90 ° C, time 90 min, liquid to solid ratio of 4:1. The experimental results are shown in Table 4.
Table 4 Brittle ore leaching effect
Experiment number | Input | output | 锑 leaching rate /% | Na 2 S consumption ratio | Lead slag rate /% | |||||
Brittle mine / g | Contains Sb/g | Alkali residue leachate / mL | Containing Na 2 S/(g·L -1 ) | Leachate/mL | Sb/(g·L -1 ) | Lead slag / g | ||||
1 | 500 | 101.4 | 1850 | 54.3 | 356 | 89.4 | 2.02 | 71.2 | ||
2 | 500 | 104.0 | 1880 | 53.8 | 357 | 90.0 | 2.06 | 71.4 | ||
3 | 500 | 112.4 | 2000 | 106.3 | 1760 | 59.4 | 343 | 93.0 | 2.03 | 68.6 |
4 | 500 | 121.5 | 1820 | 56.6 | 346.5 | 91.6 | 2.36 | 69.3 | ||
5 | 500 | 109.6 | 1690 | 61.5 | 347.5 | 92.5 | 2.11 | 69.5 | ||
average | 91.3 | 2.12 | 70 | |||||||
It is known from Table 4 that when the alkaline slag leaching solution is used to leach the brittle ore, the leaching rate of strontium is about 91.3% on average (according to the input concentrate), and the sulphide is consumed by 2.12t of sulphide per leaching of metal, and does not consume caustic soda. The conventional sodium sulfide system consumes 25 kg of Na 2 S 2.0 t (pure amount) NaOH per ton. This fully demonstrates that it is completely feasible to use the sodium sulfide solution obtained in this study to leach the bismuth in the brittle sulphur lead bismuth ore. The leaching effect is no less than that of the industrial sodium sulphide system. At the same time, from the leaching effect, the vulcanization obtained in this study The sodium solution contains enough sodium hydroxide to meet the needs of leaching.
(2) Lead slag composition
The composition of the lead slag after the leaching of the brittle sulphur lead bismuth ore concentrate is shown in Table 5. In addition to antimony, arsenic and sulfur, other elements in the concentrate basically enter the lead slag, which is in line with the previous theoretical analysis. Sodium sulfide solution has good selectivity for leaching of bismuth, except for arsenic. The impurity element is not substantially leached into the human leachate.
Table 5 Lead slag composition (mass fraction) /%
Pb | Sb | Zn | Sn | In 1) | Ag 1) | Fe | Cu | As | SiO 2 | CaO | S |
37.79 | 2.83 | 7.29 | 0.42 | 220 | 1114 | 10.64 | 0.40 | 0.11 | 4.52 | 2.41 | 20.54 |
1) The unit is g/t.
(3) Quality of sodium pyroantimonate product
The sodium pyroantimonate sample was prepared by directly adding hydrogen peroxide obtained by the leaching solution obtained in 5.1, and the results are shown in Table 6. The quality of the obtained sodium pyroantimonate completely meets the electronic industrial grade quality standard (ZBG12019-89). This is sufficient to demonstrate that the sulfide base produced in this research process can be used to extract brittle ore or oxygen powder to produce a qualified sodium pyroantimonate product.
Table 6 Experimental quality of sodium pyroantimonate sample
sample | chemical composition/% | colour | Fineness / μm | |||||||
ΣSb | Sb 2 O 3 | Na 2 O | Fe 2 O 3 | CuO | Cr 2 O 3 | V 2 O 5 | PbO | |||
1 | 49.20 | 0.21 | 12.50 | 0.015 | 0.0005 | 0.0005 | 0.001 | 0.02 | silver gray | -150 |
2 | 49.38 | 0.18 | 12.63 | 0.012 | 0.0003 | 0.005 | 0.0005 | 0.02 | white | -150 |
Conclusion
(1) A process flow for comprehensive utilization of alkaline smelting slag of brittle sulfur lead bismuth ore is proposed. The sodium sulfide is used for leaching the brittle ore to prepare the sodium pyroantimonate product; the metal elements other than cerium are substantially enriched in the alkali slag leaching slag, and the high indium, high lead and zinc smelting can be produced by further flotation. mine.
(2) The optimum conditions for leaching sodium sulfide from alkali residue are: liquid-solid ratio of 4:1, temperature of 90 ° C, time of 90 min; under this condition, the leaching rate of sodium sulfide can reach 92%; the obtained sodium sulfide solution contains Sodium sulfide is about 110g/L, and the composition of the solution is just in line with the conditions for leaching the sodium pyroantimonate product.
(3) The elements such as zinc and iron in the alkali slag leaching residue are basically present in the slag in the form of sulfides, which is advantageous for obtaining zinc concentrate by flotation; about 67% of the bismuth in the alkali slag is leached into the sodium sulfide. Solution.
(4) Using the alkali slag leachate (sodium sulfide solution) to leach the brittle sulfur lead bismuth ore concentrate, the leaching rate of bismuth is more than 91%, and the sulphide consumption of the metal sulphide is 2.12t per leaching, and does not consume caustic soda. It is completely feasible to use the sodium sulfide solution obtained in this study to leach the bismuth in the brittle sulfur lead bismuth ore. The leaching effect is no less than that of the industrial sodium sulfide system. At the same time, from the leaching effect, the sodium sulfide solution obtained in the present study contains Sufficient sodium hydroxide is sufficient to meet the needs of leaching.
(5) The quality of the sodium pyroantimonate product obtained can meet the quality standard requirements of sodium pyroantimonate for the electronics industry.
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