In 2015, a copper mine customer came to our company and hoped that we could help him flotation of the copper mine in Tanzania. Before doing the formal beneficiation, the customer brought his ore to our factory and did the ore taste analysis and flotation experiment. The experimental results are as follows:
Combining the above experimental results and the customer's strength of our factory, the customer decided to choose us to do the copper ore dressing test for him. The experiment process is as follows: feeding-crushing-grinding-flotation.
The main equipment included are:Feeder-Jaw Crusher-Hammer Crusher-Ball Mill-Spiral Classifier-Mixing Barrel-Flotation MachineAt the same time, flotation reagents are also used.The project began infrastructure construction in April 2016 and successfully ran in May. The highest taste of copper and gold powder can reach 52%.
Tetrazinan-thione collector was used in flotation of copper oxide minerals.HTT held better flotation selectivity to malachite versus calcite than OHA.HTT covered on malachite to improve its surface hydrophobicity.Malachite chemisorbed HTT via forming CuN and CuS bonds.
Novel tetrazinan-thione compounds including 6-hexyl-1,2,4,5-tetrazinan-3-thione (HTT), 6-propyl-1,2,4,5-tetrazinan-3-thione (PrTT) and 6-phenyl-1,2,4,5-tetrazinan-3-thione (PhTT) were synthesized and originally introduced as collectors for beneficiation of copper oxide mineral. The micro-flotation investigations exhibited that HTT achieved higher malachite recovery with better flotation selectivity against calcite than octyl hydroxamic acid (OHA). The three tetrazinan-thione surfactants significantly improved the hydrophobicity of malachite surfaces as followed: HTT>PhTT>PrTT, matching well with their hydrophobic-hydrophilic index LogP value, as well as their flotation response to malachite. In-situ AFM images clearly presented that HTT firmly covered on malachite surfaces. Zeta potential suggested the chemisorption of malachite towards HTT. FTIR and XPS offered additional evidences that malachite chemisorbed HTT on to its surfaces where the CuS and CuN bonds were generated. The heptyl group possesses stronger hydrophobic than the hexyl group, while, HTT exhibited better hydrophobization towards malachite than OHA, which might be attributed to their different bonding mode on malachite surfaces.
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All available copper-bearing natural mineral aggregates are called copper mines. The high-grade copper concentrate can be obtained by the coarse grinding, roughing, scavenging of copper ore, then grinding and concentrating of coarse concentrate.
Due to the different types of ore, the nature of the ore is also different, so the beneficiation process needs to be customized. The specific process for selecting copper ore depends mainly on the material composition, structure and copper occurrence state of the original copper ore.
Before the beneficiation of copper ores, crushing and grinding are required. The bulk ores are crushed to about 12cm by a jaw crusher or a cone crusher. Then the crushed materials are sent to the grinding equipment, and the final particle size of the copper ore is reduced to 0.15-0.2mm.
Copper sulfide can be divided into single copper ore, copper sulfur ore, copper-molybdenum deposit, copper nickel, carrollite and so on. Basically, only flotation can be considered in its separation.
Almost all copper sulphide ores contain iron-bearing sulfides, so in a sense, the flotation of copper sulfide is essentially the separation of copper sulfide from iron sulfide. The common iron sulfide minerals in copper ore are pyrite and pyrrhotite.
1 Disseminated grain size and symbiotic relationship of copper and iron sulfide. Generally, pyrite has a coarse grain size, while copper ore, especially secondary copper sulfide, is closely associated with pyrite. Only when the copper ore is finely ground can it be dissociated from pyrite. This characteristic can be used to select copper-sulphur mixed concentrates, discard the tailings, and then grind and separate the mixed concentrate.
2 The influence of secondary copper sulfide minerals. When the secondary copper sulfide mineral content is high, the copper ions in the slurry will increase, which will activate the pyrite and increase the difficulty of Cu-S separation.
3 The influence of pyrrhotite. The high content of pyrrhotite will affect the flotation of copper sulfide. Pyrrhotite oxidation will consume the consumption of oxygen in the pulp. In severe cases, the copper minerals do not float at the beginning of flotation. This can be improved by increasing inflation.
Generally, copper is floated firstly and then sulfur. The content of pyrite in dense massive copper-bearing pyrite is quite high and high alkalinity (free CaO content> 600800g/m3) and high dosage of xanthine are often used to suppress the pyrite. There is mainly pyrite in its tailings with few gangues, so the tailings are sulfur concentrates.
For the disseminated copper-sulfur ore, the preferential flotation process is adopted, and the sulphur in the tailings must be re-floated. To reduce the consumption of sulfuric acid during the floatation and ensure safe operation, the process condition of low alkalinity should be adopted as far as possible.
It is more advantageous for copper sulfur ore containing less sulfur with copper easy to be floated. Carry out the bulk flotation firstly in the weakly alkaline pulp and then add lime to the mixed concentrate to separate the copper and sulfur in the highly alkaline pulp.
In semi-preferential bulk-separation flotation, Z-200, OSN-43 or ester-105 with good selectivity are used as collectors to float copper minerals firstly. The copper concentrate is then subjected to copper-sulfur bulk flotation and the obtained copper-sulfur mixed concentrate is subjected to separation flotation of floating copper and suppressing sulfur.
It avoids the inhibition of the easily floating copper under high lime consumption and does not require a large amount of sulfuric acid-activated pyrite. It has the characteristics of reasonable structure, stable operation, a good index and early recovery of target minerals.
3 The xanthate collector mainly plays the role of chemisorption together with the cation Cu (2 +), so minerals whose surface contains more Cu (2 +) minerals have a strong effect with the xanthate. The order of the effect is: chalcocite > covellite > porphyrite> chalcopyrite.
4 The floatability of copper sulfide minerals is also affected by factors such as crystal size, mosaic size, being original or secondary. The minerals with fine crystal and mosaic size are difficult to float. Secondary copper sulfide ore is easy to oxidize and more difficult to float than original copper ore.
As for the grinding and floating process, it is more advantageous to adopt the stage grinding and floating process for refractory copper ore, such as the re-grinding and re-separation of coarse concentrate, re-grinding and re-separation of bulk concentrate, and separate treatment of medium ore.
Copper oxide (CuO) is insoluble in water, ethanol, soluble acid, ammonium chloride and potassium cyanide solutions. It can react with alkali when slowly dissolving in ammonia solution. The beneficiation methods of oxidized copper ore mainly include gravity separatio, magnetic separation (see details on copper ore processing plant), flotation and chemical beneficiation.
Flotation is one of the commonly used mineral processing techniques for copper oxide ores. According to the different properties of copper oxide ores, there are sulphidizing flotation, fatty acid flotation, amine flotation, emulsion flotation and chelating agent-neutral oil flotation method.
Process flow: The dosage of sodium sulfide can reach 1~2kg/t during vulcanization. Because the film produced by vulcanization is not stable and is easy to fall off after vigorous stirring, and sodium sulfide itself is easily oxidized, sodium sulfide should be added in batches.
Besides, the vulcanization speed of malachite and azurite is relatively fast, so the vulcanizing agent can be directly added to the first flotation cell with no need to stir in advance during vulcanization and adjust the amount of vulcanizing agent according to the foam state.
Fatty acids and their soaps are mainly used as collectors of fatty acid floatation, also known as direct flotation. During flotation, water glass (gangue inhibitor), phosphate, and sodium carbonate (slurry regulator) are also usually added.
There is a practice of mixing vulcanization and fatty acid methods. Firstly float the copper sulfide and part of the copper oxide with sodium sulfide and xanthate, and then float the residual copper oxide with fatty acid.
For example, the ore in the Nchanga processing plant in Zambia contains 4.7% copper. The copper content achieved to 50% ~ 55% through flotation by adding 500g/t of lime (pH 9 ~ 9.5), 10g/t of cresol (foaming agent), 60g/t of ethylxanthate, 35g/t of amyl xanthate, 1kg/t of sodium sulfide, 40g/t of palmitic acid and 75g/t of fuel oil.
It is mainly to sulfurize the copper oxide mineral firstly and then add the copper accessory ingredient to create a stable oil-wet surface. Then, the neutral oil emulsion is used to cover the mineral surface, resulting in a strong hydrophobic floating state. In this way, the mineral can be attached to the foams firmly to complete the separation.
Many problems should be paid attention to in the flotation of copper ore, such as the length of the vulcanization time, whether to add sodium sulphide in batches and the proportion of chemicals. Here is a brief introduction.
1 The vulcanization time. Different ores require different vulcanization times. Generally speaking, it should be short rather than longer. The suitable vulcanization time is 1 to 3 minutes. After 6 minutes, the recovery rate and concentrate grade will decrease.
2 Add sodium sulfide in batches. The roughing time for processing the ore in the concentrator is about ten minutes, while the ore contains a large amount of carbonaceous gangue and the divalent sulfur ions disappear quickly in the slurry. So the effect of adding sodium sulfide in batches is better than that of adding it once.
3 Add sodium sulfide proportionally. Generally, copper oxide floats in the liquid at a slower speed, and reduce the number of cycles of the mineral in the flotation process can obtain a higher recovery rate. It is of great significance to study the distribution ratio of sodium sulfide among different operations to catch the mineral at the right time.
The chemical beneficiation method is often used for refractory copper oxide and mixed copper. For some copper oxide minerals with high copper content, fine mosaic size and rich sludge, the chemical beneficiation method will be used to obtain good indicators because the flotation method is difficult to realize the separation.
The solution of ammonia and ammonium carbonate in a concentration of 12.5% was used as the solvent to leach for 2.5h at a temperature of 150, a pressure of 1925175~2026500Pa. The mother liquor can be distilled by steam at 90 to separate ammonia and carbon dioxide. Copper, on the other hand, is precipitated from the solution as black copper oxide powder.
Because some copper oxide minerals are not tightly combined with iron, manganese, etc., it is difficult to separate them by using the magnetic separation method alone, and flotation has a good separation effect.
Therefore, the flotation method is used to obtain high-grade concentrates, the magnetic separation is for tailings and wet smelting is carried out finally. This process combines flotation, magnetic and wet smelting very well, which greatly increases the recovery rate and reduces the beneficiation cost.
The above are several common beneficiation methods for copper oxide minerals. For the selection of copper oxide minerals, it is best to conduct a professional beneficiation test and customize the process according to the report.
Flotation is the most widely used method in copper mine production. The copper ore pulp is stirred and aerated, and the ore particles adhere to the foams under the action of various flotation agents. The foams rise to form a mineralized foam layer, which is scraped or overflowed by the scraper. This series of flotation processes are all completed in the flotation machine. (Contact Manufacturer)
The internal magnetic system of the barrel adopts a short circuit design to ensure that the barrel skin has no magnetic resistance at high speeds, and the stainless-steel barrel skin does not generate high temperatures, extending the life of the magnetic block.
Since it adopts a dynamic magnetic system design, the roller does not stick to the material, which is conducive to material sorting. The selected grade can be increased by 3-6 times to more than 65%.
Copper mines are generally purified by flotation, but for the beneficiation of copper minerals with coarser grain size and higher density, the pre-selection by the gravity separation method will greatly reduce the cost and achieve flotation indicators.
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Sherwood Coppers Minto Mine processes a high grade coppergold deposit in Yukon, Canada. The ore mined is from a primary copper sulphide deposit with separate additional deposits of copper oxides. In conjunction with Ausmelt Chemicals, Minto is currently investigating options to recover copper oxide and sulphide minerals using flotation by blending their primary sulphide ore with oxide ores. The blend used in this laboratory scale investigation was 70% sulphide ore and 30% oxide ore on a weight basis. The copper sulphides present in the blend were bornite and chalcopyrite, while the oxides were malachite and minor azurite.
From previous flotation investigations of mixed copper oxide and sulphide minerals using xanthate and hydroxamate collectors it was hard to distinguish the impact of the alkyl hydroxamate collector on sulphide recovery as the sulphide and oxide minerals occurred naturally together. In the case of the Minto operation the copper oxide and sulphide minerals occur in separate ore deposits and can be treated separately or blended together. This investigation has shown that using n-octyl hydroxamates (AM28 made by Ausmelt Limited) in conjunction with traditional sulphide collectors can successfully simultaneously recover copper sulphides and oxides by flotation from blended ore minerals. The copper sulphide recovery did not decrease when processing the blended ore compared to treating the sulphide ore independently. At a blend of 70% sulphide ore and 30% oxide ore, the rougher scavenger copper recovery was as high as 95.5%. The copper recovery from the blended ore using a mixture of collectors was shown to be superior to the recovery obtained using only xanthate after controlled potential sulphidisation.
Copper oxideore is used to refine copper oxide. Copper oxide ore is produced in the Philippines, Pakistan and other regions. The monthly supply is about 1,000 tons to 2,000 tons. Copper oxide (CuO) is a black oxide of copper. The most common on the market today is 98% copper oxide and 99.95% copper oxide. The flotation method is still the main method for the treatment of copper oxide ore. According to the nature of the copper oxide ore and the nature of the collector used, the copper oxide ore flotation method is divided into direct flotation and stage vulcanization-flotation.
Copper exists mainly in the form of sulfide ore and oxidized ore in nature, the most important of which is sulfide ore, which is formed by the slow oxidative deterioration of sulfide ore. With the development of the defense industry, the electronics and electrical industries, and new technologies, the demand for copper is increasing, and although copper production is growing, it still cannot meet the needs. Copper resources are in short supply, and sulfide ore and copper-rich ore are decreasing. The mining grade of many copper mines abroad has dropped to 0.4%. Therefore, lean ore and a large number of difficult-to-select copper oxide deposits are in urgent need of development and utilization.The direct flotation method is the first method to use flocculant instead of sodium sulfide activation, including fatty acid flotation, amine flotation, neutral oil emulsion flotation and chelation collector. Flotation method, etc. It is suitable for copper oxide ore with simple mineral composition and uncomplicated properties. The direct flotation of complex copper oxide ore still has no breakthrough. Efficient selective collectors are especially important for direct flotation. In the early application of copper oxide ore flotation research, fatty acid salt was used as a collector for direct flotation, but this method is only applicable to ores with mainly malachite, simple gangue and high ore grade. The direct flotation method is applied earlier, but it lacks selectivity. So far, only the fatty acid flotation method has been applied to large-scale industrial applications. For decades, people have tried to develop a highly selective collector to float copper oxide minerals. Although some studies have achieved good results, they have not been widely used due to separation difficulties.
In thecopper oxideflotation, direct flotation method usually can not achieve better results. Sulfuration flotation method is the main flotation method for treating copper oxide ore and mixed ore at home and abroad. For malachite, azurite, and red copper. Mine-based copper oxide ore can get better indicators. The method used to treat the mixed ore is the vulcanization-flotation method, and the individual plant uses the separation-flotation method. Under normal circumstances, copper oxide ore mostly has high oxidation rate, large mud content, high combined copper content, uneven grain intercalation, mixed oxygen and sulfur, coarse and fine mixing, coexistence of various minerals, etc. Copper ore contains low copper, which determines the difficulty of copper oxide ore beneficiation.
Copper oxide minerals are generally highly hydrophilic due to their molecular structure. They attract the dipoles of water in the slurry and cause the water dipoles to form aligned hydrated films on the mineral surface. Therefore, the collector is difficult to adsorb to the surface of the mineral, and after the vulcanization treatment, the surface of the oxidized mineral changes radically. The essence of the vulcanization flotation is to vulcanize the ground copper oxide slurry with a vulcanizing agent, and then add the xanthate collector to float. The vulcanizing agents are: sodium sulfide, sodium hydrosulfide, hydrosulfide ammonia, hydrogen sulfide, potassium sulfide, etc., and the most commonly used is sodium sulfide. A copper sulfide film is formed on the surface of the sulfided copper oxide ore to make the surface of the copper oxide mineral have the surface property of the copper sulfide mineral, and then floated by the action of the collector. The collectors used after vulcanization are: ethyl xanthate and high-grade (butyl, isobutyl, pentyl, etc.) xanthate, black medicine and fatty acid, etc., which are more commonly used as advanced xanthate. Therefore, the quality of the vulcanization process plays a key role in this method.
The degree of vulcanization increases with the increase of sodium sulfide concentration and the contact time with minerals; the vulcanization rate of malachite and chrysocolla increases with the decrease of pH value in solution, especially for cyanite. When the temperature is increased from 10 C to 60 C, the adsorption amount of sodium malachate to sodium sulfide is increased by 4.5 times, and the amount of chrysocolla is increased by 3 times; since the CuS film formed on the surface of malachite is not stable enough, when the slurry is too strong, If the time is too long, the copper sulfide film will easily fall off into colloidal copper sulfide, and the formation of colloidal copper sulfide is very harmful to flotation. Therefore, the selection of copper oxide ore is suitable for early harvesting and multi-receiving. The production process often carries out stage grinding and stage selection, which can achieve the fineness of grinding required for the selection of fine-grained copper oxide ore. Moreover, the easily floatable copper sulfide and partial copper oxide can be preferentially floated.