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Copper-related ores can be classified into the following categories, depending on the selected useful ingredients:
(1) Single copper mine: its ore is relatively simple, and the only useful component that can be recycled is copper. The gangue minerals are mainly quartz , carbonate and silicate.
(B) a copper sulfide ore: This is called copper pyrite ore, copper ore, in addition to objects, as well as iron sulfide minerals can be recovered. The main mineral of sulfur is pyrite.
(3) Copper pyrite : In addition to the recovery of copper minerals in the ore, pyrite and magnetite are worth recovering. Many of the skarn-type copper mines in China belong to this type.
(4) Copper- molybdenum ore: The useful component of this ore contains molybdenite in addition to copper. In addition to copper and molybdenum minerals, some ore can be recovered from magnetite and pyrite.
(5) Copper- nickel ore: In addition to copper minerals, there are minerals containing nickel, such as nickel sulfide ore and nickel-containing pyrite and pyrrhotite.
(6) Copper- cobalt ore. In addition to copper minerals, there are also cobalt-containing pyrite and other cobalt minerals.
(Vii) containing arsenic copper sulfide. The ore content of the ore is high, and arsenic is mainly present in the form of arsenopyrite. The flotation of this type of ore is mainly to solve the problem of copper and arsenic separation, and to reduce the arsenic content in the copper concentrate as much as possible.
Second, the main copper sulfide minerals and their floatability
There are many types of copper sulfide minerals in nature, but the main copper sulfide minerals with industrial value are: chalcopyrite and chalcopyrite. Bornite, copper blue, beryllium copper, arsenic bismuth copper ore.
(1) Chalcopyrite (CuFeS 2 ). Chalcopyrite (containing Cu34.57%) is the most common copper mineral in China's copper mines. It has both primary and secondary, and has good buoyancy. Chalcopyrite is not susceptible to oxidation, and it can maintain natural floatability for a long time in neutral and weakly alkaline pulps. However, strongly basic (pH> 10) in the pulp, since the receiving surface OH - erosion, forming a hydrophilic film of iron hydroxide, poor floatability. The chalcopyrite located on the surface of the deposit is oxidized for a long time, with low hardness, easy to be pulverized, and the floatability is also deteriorated.
The most commonly used collector for flotation chalcopyrite is xanthate, which is readily available as a xanthate collector in a wide pH range (3 to 12). Black medicine, sulfur nitrogen and thiourethane are more selective in the treatment of copper-bearing pyrite. Chalcopyrite is susceptible to inhibition by cyanide and oxidants in alkaline pulp. Excess lime and sodium sulfide and ammonium sulfide can also inhibit chalcopyrite in alkaline pulp. Chalcopyrite inhibited by cyanide can be activated with copper sulfate.
(2) Copper ore (Cu 2 S): The copper ore is one of the most common secondary copper minerals. It is brittle and easy to be crushed and muddy. It has good floatability in both acidic and alkaline pulps. Sex. The copper minerals of many large porphyry copper mines at home and abroad are chalcopyrite.
Since the crystal lattice energy of copper-sulfur crystals in the chalcopyrite is small, the copper ion radius is small, the sulfur ion radius is large, and the exposure is easily oxidized, the chalcopyrite is more oxidized than the chalcopyrite. After oxidation, more copper ions enter the slurry. In sulphides, or drug consumption, the flotation process is complicated, increasing the separation difficult.
The collectors of the chalcopyrite are mainly xanthate and black medicine. The effective inhibitors are sodium sulphate, sodium sulfite, potassium ferricyanide and potassium ferrocyanide, and a large amount of sodium sulfide also inhibits the chalcopyrite. Cyanide has a weak inhibitory effect on chalcopyrite because the copper ions on the surface of the chalcopyrite are continuously dissolved and react with cyanide to form complex ions, which reduces the inhibition of cyanide.
(3) Copper ore (Cu 5 FeS 4 ): The porphyrite has two kinds of primary and secondary, and its surface properties and floatability are between the copper ore and chalcopyrite.
When xanthate is used as a collector, it can float in both acidic and weakly alkaline media. When the pH is greater than 10, its floatability decreases. In a strongly acidic medium, its floatability is also significantly deteriorated, and it is easily inhibited by cyanide.
Other copper sulfide minerals, such as copper blue (CuS), are similar in floatability to chalcopyrite. The buoyancy of beryllium copper (4Cu 2 S·Sb 2 S 3 ) and arsenic antimony ore (4Cu 2 S·As 2 S 3 ) is similar to that of chalcopyrite.
According to the above analysis of the buoyancy of various copper sulfide ore, the following rules are obtained:
(1) Copper minerals (such as chalcopyrite and copper blue) that do not contain iron in their chemical structures are similar in floatability. Cyanide and lime have weaker inhibition on them, so a large amount of lime can be added to inhibit pyrite in the separation of copper and sulfur without seriously affecting the floatability of copper minerals.
(2) The copper minerals (such as chalcopyrite and porphyry) containing iron in their chemical composition are similar in floatability, and are easily inhibited by cyanide and lime in alkaline pulp. Therefore, separation of copper and sulfur is difficult and strict. Control the amount of cyanide and lime.
(3) Among the chemical composition of minerals, the copper content is high, the floatability is good, and it is easy to obtain high-grade concentrate; the iron content is high and the floatability is poor. The floatability of common copper sulfide minerals is reduced in the following order: chalcopyrite > copper blue > porphyrite > chalcopyrite.
(4) The floatability of copper sulfide minerals is also affected by factors such as crystal grain size, grain size and primary and secondary. Crystallization and inlaying are too fine to be difficult to float. Secondary copper sulfide ore is easily oxidized and is less likely to float than primary copper ore.
Third, the floatability of the main iron sulfide minerals
Almost all copper sulphide ore has iron-containing sulphide, so in a sense, the flotation of copper sulphide ore is essentially to solve the separation of copper sulphide and iron sulphide. The iron sulfide minerals commonly found in copper ore are pyrite and pyrrhotite.
(1) Pyrite (FeS 2 ): Pyrite is the most widely distributed sulfide, which is found in almost all types of deposits. Since pyrite is the main raw material for the production of sulfuric acid, it is customary to refer to the pyrite concentrate as a sulfur concentrate.
The surface state of pyrite is related to the pH value of the slurry. In a strongly acidic (pH=2) medium, the surface will produce a reaction of FeS 2 →FeS+S, while elemental sulfur can improve the surface hydrophobicity. However, in an alkaline (pH=11-12) medium, the surface is covered with FeO(OH), which greatly reduces the floatability.
Pyrite, yellow, black and sulfur nitrogen can be used as collectors in acidic, neutral and weakly alkaline pulps. Among them, diethyl M thiocarbamate (ethyl sulphide) has the strongest ability to capture pyrite in the slurry with pH <10.5. Xanthate is the most widely used collector for pyrite. The adsorbed product is dihuang xanthate. In acidic and weakly alkaline pulp, the use of xanthate as collector is also the most economical and effective method in the industry.
(2) Pyrrhotite (Fe 5 S 6 ~ Fe 16 S 17 ): The pyrite content of pyrrhotite is generally lower than that of pyrite, which is easy to be oxidized and muddy, and the floatability is poor, and it is most easily suppressed. It is the most difficult to float iron sulfide mineral.
The pyrrhotite can be harvested from the long-chain xanthate or fatty acid in the weakly acidic pulp. In the weakly alkaline pulp, it is usually activated by adding copper sulfate or a small amount of sodium sulfide, and then collecting with long-chain yellow medicine.
The inhibitors of pyrrhotite include lime, cyanide, sulfurous acid and salts, among which SO 2 plus aeration, lime plus SO 2 plus aeration are most effective. In order to activate pyrrhotite, it is more effective to use copper sulfate, sodium sulfide, sodium fluorosilicate and sulfuric acid than sulfuric acid alone.
The pyrrhotite is easily oxidized. When oxidizing in the slurry, it will consume oxygen in the slurry, which is unfavorable to the floating of other sulfides. Therefore, when the sulfide ore containing flocite is flotation, it is very important to adjust the aeration of the slurry.
In China's skarn-type copper-iron ore, a large part of the sulfide-containing is pyrrhotite. Because pyrrhotite is not easy to float and has magnetic properties, it is often mixed with magnetically selected iron concentrates, which is the main cause of high sulfur content in iron concentrates.
(3) Pyrite (FeS 2 ): The chemical composition of the pyrite is the same as that of pyrite, but the crystals are different. The floatability of pyrite is similar to that of pyrite, but it is better than pyrite.
The order of floatability of several iron sulfide ore is: pyrite > pyrite > pyrrhotite.
Major copper sulfide minerals and their floatability
I. Types of ore of copper sulfide