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1. Xanthate and its derivatives
So far, the vulcanization-xanthate float is the main method for selecting copper oxide ore. The xanthate is the main collector of copper oxide or a mixture of xanthate collector and other collectors. Medication.
The xanthate collector used in most copper oxide plants in China is n-butyl xanthate. The Yunnan Dongchuan copper oxide PBM several plant are selected from n-butyl xanthate as collector, sodium sulfide, phosphoric acid ethylene diamine, ammonium sulfate as a modifier, pine oil as a frother , got a good sorting effect.
In order to meet the needs of various ores for other types of xanthate, the relevant departments have also done research work in this area, such as isobutyl xanthate, isoamyl xanthate and miscellaneous xanthate. In many cases, these agents can replace n-butyl xanthate, while also having certain advantages.
The performance of isobutyl xanthate is similar to that of n-butyl xanthate, but it is more stable and more selective than n-butyl xanthate. Many domestic and foreign plants have used isobutyl xanthate as a trap to do some experiments. For example, the red permeable mountain copper mine uses isobutyl xanthate, which is 20g/t less than n-butyl xanthate, and the second oil is reduced. 5.5g / t, and the copper concentrate grade increased by 1.2% in the case of similar recovery; after the change of the use of isobutyl xanthate in the Baifang copper mine, the copper concentrate grade increased by 2.25%, and the recovery rate increased by 0.3%.
Zhongxinji xanthate has also been reported in this regard as a copper oxide mineral collector. The collector has a strong ability to capture copper oxide minerals and has a certain foaming property, which can reduce the amount of foaming agent.
2. Hydrocarbyl oxyacids and their salts
Such collectors usually contain atoms such as oxygen and nitrogen in their polar groups, and the non-polar groups have a relatively high molecular weight and belong to an anionic collector.
(1) Application of carboxylic acids. In the early stage of copper oxide mineral flotation, fatty acids (such as sodium oleate, palmitic acid) are generally used as collectors for direct flotation. However, due to the limited source of fatty acids, and the large amount, the copper oxide mineral flotation is gradually replaced by other collectors.
In the late 1970s, there were C5～C9 or C7～C9 synthetic fatty acids, which were used in the production of copper malachite and copper oxide ore flotation.
In recent years, many methods have been studied at home and abroad to improve their performance, and a series of related collectors have been obtained, some of which have the ability to improve the flotation results of fatty acid collectors, so-called fatty acid synergists. . However, fatty acid collectors are currently used less in the flotation of copper oxide ore.
(2) Sulfonic acid (salt) and sulfate. Such collectors have foaming properties and are sometimes used as foaming agents. As a collector, its selectivity is strong.
Hunan Institute of non-ferrous metal Weihua Zu sodium dodecyl sulfate, sodium dodecyl sulfate of Malachite pure mineral flotation were studied and compared with sodium COLLECTING oil. The results show that sodium lauryl sulfate and sodium dodecyl sulfate have a strong collection effect on malachite and a wide range of flotation pH, and have the same collection performance as sodium oleate. Since sodium dodecyl sulfate and sodium dodecyl sulfate have a weaker ability to capture calcium-containing minerals than sodium oleate, the selectivity is better and can be used in hard water, which is superior to sodium oleate.
(3) Phosphonic acids. The main varieties of phosphonic acid collectors used in the flotation of copper oxide ore are alkylphosphonates and dihydrocarbylphosphonic acids (R 2 PO 2 H, R is octyl, sec-octyl, ethyl, ring, respectively). Ethyl and phenyl).
Dihydrocarbylphosphinic acid is a new class of copper oxide ore flotation collectors. Lin Qiang and Wang Dianzuo of Central South University of Technology have done research in this area. The results show that the dihydrocarbylphosphinic acid is an effective collector for fine-grained malachite. The collection performance is sequentially decreased in the order of diethylphosphinic acid > di-n-octylphosphinic acid > di-sec-octylphosphinic acid > cycloethylphosphinic acid > diphenylphosphoric acid. For muddy malachite, a suitable agent is diethylphosphinic acid (total carbon number 11 to 12).
(4) Hydroxamic acids. Hydroxamic acid (or hydroxamic acid) is an N-acyl derivative of hydrazine, and the enol tautomer thereof is hydroxamic acid: 
Their Cu 2 + reaction produces a chelate that is poorly soluble in water.
Currently widely used is sodium alkyl oxonium hydride, sodium citrate preparation has different methods. C 5 ～ 9 and C 7 ～ 9 alkyl oxonium sulphate synthesized by Kunming Metallurgical Research Institute, hydrolyzed with low-grade sand base to prepare hydroxysulphate, and then reacted with equivalent male hydroxy acid ester, without acidification and saponification A liquid sodium oxysilicate product having an active ingredient of about 30% was prepared.
Factors affecting the flotation process of the hydroxamic acid collector are the pH of the pulp, the use of a mixture of collectors, the necessity of pre-vulcanization, and the role of the gangue preparation.
The Guangzhou Institute of Nonferrous Metals research on the Tonglushan copper oxide ore shows that the best flotation effect can be obtained at pH=9. The reason is that the pK α value of hydroxamic acid is 9.5, so at pH=9, the ionic state of hydroxamic acid and the co-adsorption of molecules on the mineral surface, and the hydrophobicity of the magnetic minerals, the best recovery rate, May play a major role.
Although the storage capacity of hydroxamic acid (sodium) is strong, the use of hydroxamic acid (sodium) alone does not give a good flotation effect. Numerous studies have shown that the combination of hydroxamic acid (sodium) and xanthate is much better than the use of xanthate or hydroxamic acid (sodium) alone. Kunming Institute of Metallurgy use of excessive mud flat DONGCHUAN selected from C 5 ~ 9 and Plant C 7 ~ 9 mixed medication results alkyloxy oxime sodium butyl xanthate, mineral recovery plant net increase more than 5%, with the original The consumption of various flotation reagents has been reduced to varying degrees. The amount of lime and No. 2 oil is reduced by half, and the amount of sodium sulfide and butyl xanthate is also reduced by nearly one-fifth. The flotation rate and foam fluidity are greatly improved and the operating conditions are improved. In addition, add an appropriate amount of neutral oil (such as diesel). It can improve the foam characteristics of hydroxamic acid (sodium) flotation, and reduce the yield of concentrate and improve the quality of concentrate.
Since sodium oxyhydroxide is capable of flotation of calcium and magnesium carbonate minerals, it is also an important factor for the flotation of calcium and magnesium oxidized copper ore to effectively inhibit the use of sodium hexametaphosphate. Simultaneous addition of ammonium sulfate and water glass can improve the selectivity of the flotation process and does not affect copper ore flotation.
The flotation test results of several copper oxide ore beneficiation plants using hydroxamic acid (sodium) are shown in Table 1. The test results show that hydroxamic acid (sodium) is an effective collector for copper oxide ore.
Table 1 Flotation test results using sodium oxonium
Most of the amine collectors used in flotation are the first amines. It has been reported in the literature that quaternary ammonium salts are used as collectors for flotation of copper oxide ore, and good results have been obtained.
Mercaptan and polysulfide collectors are mostly used for flotation of carbonates in copper oxide ore flotation. For example, octanethiol is used as a collector to float malachite. It can form a relatively stable copper octane thiolate on the surface of malachite and adsorb it on the surface of malachite. It is one of the effective collectors for malachite.
The application of chelating collectors in the flotation of copper oxide ore has been extensively researched at home and abroad in recent years and has made great progress. The hydroxamic acid collector as described above is actually a chelate collector. N-phenyl-2-mercaptobenzimidazole (abbreviated as imidazole) which has been produced in China is a new type of chelate collector. The test results of the flotation expansion of the Tangdan Copper Oxide Mine of Dongshan Mining Bureau can increase the recovery rate of copper by about 3%.
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Research and Application of Copper Oxide Flotation Collector
According to different copper oxide mineral flotation collectors flotation process classified into the following categories: (1) xanthate and its derivatives; (2) an oxygen-containing hydrocarbyl acid (salt) -based; (3) Other comprehensive class.
Plant name
Collector name
Raw ore grade /%
Concentrate grade /%
Tailings grade /%
Recovery rate/%
Tang Dan (oxidation rate 80%)
Butyl xanthate
Butyl xanthate + sodium oxonate
0.66
0.67
8.6
8.4
0.273
0.231
60.40
67.24
Indiscriminate mud (oxidation rate 80%)
Butyl xanthate
Butyl xanthate + C5-9 sodium citrate
0.85
0.87
10.30
10.24
0.251
0.215
72.13
77.01
Stone mouth (oxidation rate 80%)
Butyl xanthate
Butyl xanthate + sodium oxonate
2.03
2.03
11.76
14.12
0.67
0.38
74.84
77.60
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