Yunnan a multi-metal complex sulfide ore containing polymetallic sulfide ore more metal elements copper, lead, zinc, sulfur and the like. The ability to effectively separate and recover various metal elements is an important prerequisite for the development and construction of ore. To this end, the ore is subjected to a beneficiation process to find an effective and reasonable beneficiation process and process conditions for sorting the ore. Through various flotation processes and process studies, the reasonable process flow and chemical conditions for sorting the ore were determined, and a good selection index was obtained, and cyanide-free flotation was achieved without K 2 Cr 2 0 7 In the case, copper and lead were successfully separated.
First, the nature of the ore
(1) Multi-element analysis of raw ore
The results of multi-element analysis of raw ore are shown in Table 1-2.
Table 1 Multi-element analysis results of raw ore% (1)
element | S | Fe | Mn | SiO 2 | MgO | CaO | Al 2 O 3 |
Quality score | 21.63 | 20.23 | 0.26 | 27.06 | 2.33 | 4.17 | 5.04 |
Table 2 Multi-element analysis results of raw ore% (2)
element | TiO 2 | Au | As | Ag | Cu | Pb | Zn |
Quality score | <0.5 | 0.12 | 0.01 | <1 | 0.45 | 3.18 | 4.21 |
Note: The unit of gold and silver is g/t.
(II) Phase analysis of copper, lead and zinc in ore
The analysis results of copper, lead and zinc phases of raw ore are shown in Table 3, Table 4 and Table 5.
Table 3 Copper phase analysis results%
Chemical phase | Primary copper sulfide | Secondary copper sulfide | Free copper oxide | Combined copper oxide | all bronze |
Quality score Distribution rate | 0.42 89.36 | <0.001 | 0.008 1.70 | 0.042 8.94 | 0.47 100.0 |
Table 4 Lead phase analysis results%
Chemical phase | Galena | Lead bismuth | White mine lead | Lead jarosite and other | Full lead |
Quality score Distribution rate | 3.17 97.53 | <0.001 | 0.06 1.85 | 0.02 0.62 | 3.25 100.0 |
Table 5 % of zinc phase analysis results
Chemical phase | Zinc sulfide | Zinc silicate | Other zinc | All zinc |
Quality score Distribution rate | 3.91 94.44 | 0.08 1.93 | 0.15 3.63 | 4.14 100.0 |
(III) Research on ore mineralogy
Ore X-ray diffraction analysis showed that the main mineral ore pyrite, quartz, dolomite, zinc blende wurtzite, galena, chalcopyrite, plagioclase, pyrrhotite, hematite mining, white mica, chlorite. The mineral composition and content of the ore are shown in Table 6.
Table 6 Composition and content of the sample
Mineral name Molecular formula Quality score | Pyrite FeS 2 33.95 | quartz SiO 2 18.10 | dolomite CaMg(CO 3 ) 2 11.16 | Sphalerite Î’-ZnS 4.65 |
Mineral name Molecular formula Quality score | Wurtzite ZnS 1.53 | Galena PbS 3.81 | Chalcopyrite CuFeS2 1.27 | Plagioclase (Ca,Na)(Si,l) 4 O 8 |
Mineral name Molecular formula Quality score | Pyrrhotite Fe 1-X S 1.37 | Hematite Fe 2 O 3 3.57 | muscovite (K,Na)(Al,Mg,Fe) 2 (Si 31 Al 09 )O 10 (OH) 11.89 | |
Mineral name Molecular formula Quality score | Chlorite (Mg, Fe, Al) 6 (Si, Al) 4 O 10 (OH) 2.48 | Anatase TiO 2 1.03 | other - 1.00 | |
The largest galena plaque in the ore sample can be up to 1 cm in diameter, but generally 0.3 to 0.5 mm, which is irregular. It is often filled with pyrite and pyrrhotite, which is filled with plaque and short veins. The diameter of the particles is 0.003~0.5mm. Galena is generally produced in massive structures and densely disseminated tectonic rocks, and sphalerite and chalcopyrite are embedded in pyrite and pyrrhotite. There are also a small number of pyrite and pyrrhotite intercalated in the quartz gangue, which is vein-like and reticular, producing a sparsely disseminated structure. Some galenas are also coated with pyrite and pyrrhotite.
Sphalerite generally has a particle diameter of 0.001-0.5mm, and is symbiotic with galena, chalcopyrite, continuous, symbiotic with chalcopyrite, and closely intertwined. It is produced in pyrite and pyrrhotite. Shape, mesh vein, knot-like distribution. In the vicinity of sphalerite, sometimes there are many film-like white, colorless calcite , and sometimes it can be produced together with galena spots. Sphalerite is irregularly variegated in the ore of massive structure and pyrite, and there are galena plaques and spot sizes in sphalerite; in the disseminated ore or veined ore In the middle, the sphalerite is often symbiotic with the fine veins of pyrite, and is small plaques and fine veins on the edge of pyrite and pyrrhotite. Galena and chalcopyrite spots appear in large sphalerite plaques, and galena, chalcopyrite veins and short veins appear on some sides.
Chalcopyrite is the main copper mineral in the ore. It is a small-shaped cluster of shaped crystals. It is distributed in the bulk ore with lead-zinc ore, pyrite and pyrrhotite, and the particle size changes greatly. In the veined ore, chalcopyrite and quartz are closely related, and in quartz veins, they are often spotted and spotted in voids and fissures. In calcareous gangue, chalcopyrite is distributed along joints, textures, and textures. The sulfide minerals of copper are in the form of fine veins and veins embedded in pyrite. The thickness of copper and zinc single minerals varies, and some fine particles are less than 0.01 mm. In the chalcopyrite, there is a wrap of the sphalerite particles, and in the edge of the sphalerite and in the granules, chalcopyrite is also intercalated or encapsulated in the form of particles. Their particle size distribution is uneven, but they are generally between 0.003 and 0.02 mm.
Second, mineral processing test research
(1) Experimental study on flotation process
Hybrid flotation process: After the original ore is milled to 75%-74μm, CuSO 4 , butyl xanthate and 730A are added to the crude and sweeping. The copper, lead and zinc mixture is floated by one rough selection, three selections and one sweeping process. Concentrate and medium ore (selected as a blank selection), discarding tailings. Mixing concentrate to 90%-74μm, using activated carbon and Na 2 S to remove the drug, adding Na 2 SO 3 + ZnSO 4 to inhibit zinc minerals, ethyl xanthate as a collector , 730A as a foaming agent, using a rough selection , a sweeping process for the separation of copper, lead minerals and zinc minerals, concentrates and medium mines are copper-lead mixed concentrates, tailings are zinc concentrates; copper-lead mixed concentrates with activated carbon after drug removal, using K 2 Cr 2 0 7 is used as an inhibitor, 730A is used as a foaming agent, and lead-free copper is used for copper and lead separation to obtain copper concentrate and lead concentrate. The test indicators obtained by the open-circuit test of the mixed flotation process are shown in Table 7.
Table 7 Flotation process exploration test indicators
Process | product name | Yield | grade | Recovery rate | ||||
Cu | Pb | Zn | Cu | Pb | Zn | |||
mixing Flotation Process | Copper concentrate Lead concentrate Zinc concentrate Total mine Tailings Feed mine | 0.83 6.45 4.77 16.01 71.94 100.0 | 23.39 0.32 0.87 0.78 0.054 0.42 | 3.18 38.47 1.08 4.62 0.17 3.42 | 46.22 12.61 46.07 5.17 0.43 4.20 | 46.22 4.91 9.88 29.73 9.26 100.0 | 0.77 72.55 1.51 21.63 3.54 100.0 | 1.26 19.37 52.33 19.71 7.34 100.0 |
Partial mixing flotation process | Copper concentrate Lead concentrate Copper-lead mixed float ore total Zinc concentrate Floating zinc in the total of mines Tailings Feed mine | 0.69 4.79 2.87 5.76 9.78 76.11 100.0 | 27.48 0.53 0.79 2.17 0.33 0.06 0.44 | 3.85 48.95 7.39 6.69 1.98 0.19 3.31 | 5.02 5.62 13.82 48.61 3.89 0.38 4.17 | 43.09 5.78 5.15 28.41 7.34 10.23 100.0 | 0.80 70.83 6.41 11.64 5.85 4.47 100.0 | 0.83 6.46 9.51 67.14 9.12 6.94 100.0 |
Floating process | Copper concentrate Lead concentrate Zinc concentrate 1 Copper, lead and zinc mixed float ore total Zinc concentrate 2 Floating zinc in the total of mines Tailings Feed mine | 0.75 5.71 2.62 3.34 3.55 10.51 73.52 100.0 | 24.94 0.42 0.58 0.54 2.74 0.46 0.07 0.44 | 3.65 42.86 3.04 7.75 7.24 1.46 0.24 3.40 | 6.78 6.32 47.40 8.76 45.52 2.99 0.47 4.22 | 42.51 5.45 3.45 4.09 22.11 10.99 11.40 100.0 | 0.81 71.98 2.34 7.61 7.56 4.51 5.19 100.0 | 1.20 8.55 29.43 6.93 38.29 7.45 8.15 100.0 |
Partial mixing flotation process: raw ore grinding to 80%-74μm, coarse selection of Na 2 S0 3 2000g / t, ZnS0 4 4000g / t inhibition of zinc minerals, addition of ethyl xanthate 70g / t as collector, 730A 24g / t as a foaming agent, sweeping and adding Na 2 S0 3 750g / t, ZnS0 4 1500g / t inhibition of zinc minerals, adding ethyl xanthate 30g / t as a collector, using a rough selection, a selection, a sweep The selection process (selected as a blank selection) is carried out by copper-lead mixed flotation to obtain a copper-lead mixed concentrate. After the copper-lead mixed concentrate was deactivated with activated carbon, K 2 Cr 2 O 7 300g/t was added to inhibit lead minerals, and then 730A 12g/t was added as a foaming agent to separate copper and lead to obtain copper concentrate and lead concentrate. The copper-lead mixed flotation tailings are obtained by one rough selection, two selections, and one sweeping process to obtain zinc concentrate. The amount of zinc coarse CuS0 4 is 300g/t, and the amount of butyl yellow is 70g/t. The amount of 730A was 12 sand, and the two sections were added with Ca0 700g/t and 600g/t respectively. The amount of CuS0 4 was 100g/t, and the amount of butyl yellow was 20g/t. See Table 8 for the open-circuit test indicators of some mixed flotation processes.
Wait for the float process: after the original ore is ground to 80%-74μm, use a rough selection, one selection, one sweeping process (rough selection of ethyl xanthate 8020g/t, 730A 24g/t, sweeping to add ethyl yellow) 30g/t of medicine, all copper sulfide ore, lead sulfide ore and zinc sulfide ore with the same floatability are floated to obtain copper-lead-zinc mixed concentrate. The tailings are added with CuSO 4 to activate zinc minerals with poor floatability. The base xanthate is used as a collector, and a part of zinc concentrate is obtained by flotation by one rough selection, two selections, and one sweeping process. The copper, lead and zinc mixed concentrate is dehydrated with Na 2 S and activated carbon, and then Na 2 S0 is added. 3 +ZnS0 4 inhibits zinc sulfide minerals, uses ethyl xanthate as collector, and uses a rough selection and a selective process to separate copper lead concentrate and another part of zinc concentrate. Copper lead concentrate is deactivated with activated carbon. After that, K 2 Cr 2 0 7 was added to inhibit lead minerals, and copper and lead were separated to obtain copper concentrate and lead concentrate. The open-circuit test indicators of the floatable process are shown in Table 8.
Exploring the test results from the flotation process, the mixed flotation process can discard the tailings in the case of coarse grinding (70%-74μm), reduce the amount of fine grinding, reduce the grinding cost, and at the same time, after the rough grinding Process sorting can discard the tailings, greatly reducing the amount of slurry entering the subsequent operations, which can greatly reduce the number of flotation machines and reduce the production cost, but all the target minerals in the ore are activated by the activator and collected during the mixed flotation. The agent acts to make the zinc sulfide mineral difficult to inhibit and enter the copper-lead concentrate during the separation flotation, which reduces the zinc recovery rate. Partially mixed flotation process suppresses the poorly floatable zinc sulfide mineral to the next flotation operation according to the difference in the floatability of the target mineral, and floats the copper sulfide and lead sulfide minerals which are better in floatability and similar. The copper-lead mixed concentrate is separated and then separated. The process conforms to the difference in mineral floatability, avoiding the difficulty in inhibiting the activated zinc sulfide mineral from entering the copper-lead concentrate during the separation of the mixed concentrate in the full flotation process. The loss of zinc in copper-lead concentrates makes it difficult to obtain better sorting indicators, and the flotation process is relatively simple. The floatable process is also separated according to the difference in the floatability of the mineral, but the process is long, the flotation operation is difficult, and the production cost is relatively high. According to the test results and the above process analysis, it is determined that part of the mixed flotation process is selected.
(2) Partial mixed flotation process test and results
1, open circuit exploration test
The copper ions produced in the ore by the copper minerals in the ore process cause the activation of sphalerite, which makes the sphalerite floatable and difficult to inhibit. It enters the copper-lead concentrate during the flotation process and reduces the copper-lead concentrate. Grade also increases the loss of zinc in copper-lead concentrates. The main purpose of the exploratory test was to find inhibitors that better inhibit sphalerite and selective collectors to reduce the loss of zinc in copper-lead mixed concentrates.
Usually, flotation of copper, lead, and zinc polymetallic ores requires the addition of cyanide to inhibit zinc minerals. This experiment uses a variety of modifiers and inhibitors to determine the experiment, using lime to inhibit pyrite and pyrrhotite, using sodium sulfide as a regulator to eliminate the activation of sphalerite by copper ions, using flash sulfite + zinc sulfate Inhibitors of zinc ore can better suppress sphalerite and achieve cyanide-free flotation. During the test, it was found that all of the above-mentioned several agents were added to the grinding machine, which could further reduce the zinc grade in the copper-lead concentrate, reduce the loss of zinc in the copper-lead concentrate, and improve the grade of copper-lead concentrate. The collector used for copper-lead mixed selection is compared with ethyl xanthate, isopropyl xanthate, isobutyl xanthate, black no. 25, butylammonium black, ethyl sulphide and YR-2. The copper-lead concentrate obtained by the YR-2 is high in grade, the copper and lead recovery rate is high, and the zinc grade is low, and the zinc loss is small. Determine the use of YR-2 as a collector for copper and lead mixing. The separation of copper and lead has been explored. After the removal of the activated carbon from copper-lead mixed concentrate, even if the lead inhibitor K 2 Cr 2 0 7 is not added, the separation can be well achieved, and a high-grade copper concentrate is obtained. Loss in copper concentrates <1%.
2. Open circuit condition test
The open circuit condition test is to reveal the effect of each flotation condition on the sorting index. Open circuit test procedure: copper and lead mixed selection, rough selection, one sweep, three selections, copper and lead separation flotation, rough selection, one selection, zinc flotation, rough selection, one sweep, two selections . The results of grinding fineness test show that the symbiotic relationship of the target minerals in the ore is close, and the particle size is unevenly embedded in the thickness. After the grinding fineness reaches 90%-74μm, the target mineral can be dissociated well. The grade and recovery rate are higher, the impurity content of the concentrate is lower, and the metal loss in the tailings is small. The CaO added in the rough selection of copper and lead should not be too much, and the pH value can be controlled at about 9. Otherwise, the pH value is too high, so that the zinc mineral floatability becomes better, and the loss of zinc in the copper-lead concentrate is increased; The dosage of Na 2 S is more suitable for 300g/t. If it is too large or too small, the copper grade and recovery rate will be reduced. The dosage of inhibitor Na 2 S0 3 + ZnSO 4 is more suitable for 2000+4000. Too little can not make zinc better. The suppression is too large to cause unnecessary waste; the mixed collector YR-2 can be controlled at 30g/t, and the excessive loss of zinc is excessive. The copper-lead mixed-sweeping operation requires only 1000+2000g/t of Na 2 S0 3 +ZnS0 4 and 20g/t of YR-2. In order to completely remove the collector adsorbed on the lead mineral surface in the next copper-lead mixed concentrate separation flotation operation, the purpose of separating copper and lead is achieved, and the copper-lead coarse concentrate is selected without adding a chemical agent, and the blank is fine. Select to reduce the adsorption of the agent on the mineral surface, when the slurry surface is unstable, add an appropriate amount of foaming agent. The copper-lead separation operation process is a rough selection and a tip selection. The concentrate is a copper concentrate, and the middle or tailings are lead concentrates. It is found in the open-circuit exploration test that as long as the copper-lead mixed concentrate can be well decontaminated Even if the lead mineral inhibitor K 2 Cr 2 0 7 is not added, the lead mineral can be well suppressed. The amount of activated carbon added to the copper-lead mixed concentrate is 550+70g/t (rough selection + selection). Fortunately, the amount of lead is not well suppressed, and the excess will cause an increase in the loss of copper in the lead concentrate. Zinc flotation adopts one rough selection, one sweeping and two selection processes. The coarse selection of CaO is used to control the pulp sound to 9-10, and the zinc activator CuS0 4 is 300+100g/t (rough selection + sweep). Optional) is appropriate, too little zinc mineral activation is not good, concentrate grade and recovery rate are low, too much waste; collector (butyl yellow, medicine) dosage is controlled at 60 + 10g / t (rough selection + sweep Select), too little zinc recovery rate, excessive zinc ore grade reduction; zinc selection only need to add CaO (both operations plus 1000g / t) to inhibit pyrite to obtain qualified zinc concentrate.
(3) Closed circuit test
According to the process and flotation conditions determined according to the open circuit test results, the closed circuit test was carried out according to the flow and conditions shown in Fig. 1. The test results are shown in Table 8.
Third, the problem and discussion
From the results of closed-circuit tests, the copper metal lost in the tailings reached 21.46%. Except for the combined copper oxide which could not be recovered by flotation and accounted for about 10% of the original ore, more than 10% of the copper sulfide was lost in the tailings. In view of the inlaid properties of copper in the ore, some of the copper is in the form of fine veins and veins embedded in pyrite. Under the condition of grinding fineness of 90%-74μm, this part of the steel is difficult to resolve with pyrite. Off, as pyrite is inhibited from entering the tailings, the loss of copper in the tailings is higher. Some of the chalcopyrite in the ore is covered with sphalerite, which leads to higher zinc content in the copper concentrate. However, due to the lower yield of copper concentrate, the loss of zinc in the copper concentrate is not large. The copper-lead mixed coarse concentrate is separated by copper and lead after three selections. The lead concentrate contains only 0.51% copper, but the lead grade is still low, only 51.45%, because the galena is wrapped with yellow. iron ore.
Fourth, the conclusion
The ore is a complex polymetallic ore containing copper, lead, zinc and sulfur. Copper, lead and zinc minerals are mainly sulfide ore. The copper, lead and zinc minerals are inhomogeneous in size and embedded in gangue, embedded in pyrite or filled in pyrite, or symbiotic with each other, or encapsulated in microparticles. The embedding properties of the ore are given. Flotation brings certain difficulties. Through different flotation process experiments, it was determined that the ore was sorted by a part of the mixed flotation process with better sorting index. Adding the modifier and inhibitor (CaO, Na 2 S, Na 2 S0 3 , ZnSO 4 ) to the mill can better inhibit the zinc and greatly reduce the zinc in the copper and lead concentrate. Loss, achieving non-cyanide flotation. At the same time, the use of the selective mixed collector YR-2 can effectively recover copper and lead, and reduce the loss of zinc. Copper and lead separation only need to remove the copper-lead mixed concentrate with activated carbon, which can perform separation flotation well without using K 2 Cr 2 O 7 to inhibit lead minerals. The raw ore was subjected to closed-circuit flotation test according to the process and conditions shown in Figure 1, and good experimental indexes were obtained.
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