Black tungsten ore flotation due to the fine grain size and other argillaceous minerals, the black tungsten ore collector needs strong selectivity, and its research has gone from fatty acids, amphoteric collectors, tannins, phosphonic acids to The development of hydroxamic acid chelation collectors. Fatty acid collectors have a certain effect on flotation of tungsten fine mud, but their selectivity is poor. Tannins and phosphonic acid collectors have better selectivity than fatty acid collectors, but their toxicity is more likely to cause environmental pollution. Chelating collectors have good selectivity and low toxicity in the wolframite flotation. However, due to the high price of the chelate collector, its application and promotion are limited. Therefore, it is cheap and inexpensive. The combination of conventional pharmaceuticals, the development of new cheap chelating collectors and other types of combined collectors have become the focus and hotspot of black tungsten flotation research.
Hydroxamic acid, also known as hydroxamic acid, has two tautomers, hydroxamic acid and hydroxamic acid, of which hydroxamic acid is the predominant form. Hydroxamic acid is a good selectivity of organic chelating collector can with Cu2 +, Zn2 +, Ni2 + , Fe3 +, Co2 + and other ions to form stable metal chelate compound, a hydroxamic group can cooperate with a metal ion mineral surface Produces a more stable chelate and adsorbs on the mineral surface. Hydroxamic acid optimal flotation pH=9, close to the pKa value of hydroxamic acid. In this pH range, the adsorption amount of the agent on these mineral surfaces also reached the maximum; mineral surface potential, infrared spectrum and other studies showed that oxindole The adsorption of acid on the surface of tungsten minerals is mainly chemical adsorption, and there is uneven physical adsorption. Multi-layer adsorption is formed on the surface of tungsten minerals, and the hydrophobicity of mineral surface is significantly enhanced. Hydroxyphthalic acid collectors have good collection performance, but they have good collection performance. The price is relatively high, and it is often used in combination with other collectors in practical applications to exert complementary performance and synergistic effects between the medicaments, enhance the effect of the collector, and reduce the cost of the medicament.
Zhang Yusheng and Zhu Jianguang studied the effects of benzyl hydroxamic acid, and the research showed that when pH
Luo Liying studied the flotation performance of five kinds of collectors of mediline, octyl hydroxamic acid, benzoxamic acid, salicyl hydroxamic acid and 8-hydroxyquinoline on wolframite, quartz , fluorite and calcite . The conclusions are as follows: when Pb(NO3)2 is activated, the flotation performance of octyl hydroxydecanoic acid and dexamethasone on wolframite is better, and the optimal flotation pH is about 7; benzoic acid, salicyl hydroxamic acid The three collectors of 8-hydroxyquinoline have poor flotation performance on the wolframite. The order of flotation performance of five collectors for wolframite is: octyl hydroxy decanoic acid > mediline > 8-hydroxyquinoline > benzyl hydroxamic acid > salicyl hydroxamic acid. The results of infrared spectroscopy test prove that the action of the five collectors on the surface of the wolframite is chemisorption. The results of contact angle measurement showed that the contact angle of the surface of the wolframite was larger with the use of Medan and octyl hydroxamic acid as the collector, and the contact angle reached the maximum at the optimal flotation pH of 7, and the benzoic acid was obtained. After tannic acid, salicyl hydroxamic acid and 8-hydroxyquinoline act on the wolframite, the contact angle of the wolframite is not much different and generally small. The ξ-potential measurement results show that the ξ-potential of the surface of the scheelite after the treatment with the methadone and octyl hydroxamic acid is lower than that of the non-collector, indicating that the added collector is in the black tungsten. Adsorption occurs on the surface of the mine. However, the ξ-potential negative shift of methotrexate at pH 7 is higher, and it can be inferred that the two adsorb more on the surface of the wolframite under this condition, again confirming the single Mineral flotation test results.
MengQingyou studied the interaction mechanism between fine-grained wolframite and hydroxamic acid (OHA). The results of the flotation test showed that the wolframite exhibited better floatability due to the adsorption of hydroxamic acid in the pH range of 7.0-10.0. By measuring the zeta potential, it can be found that the adsorption of hydroxamic acid on the surface of the wolframite is characteristic adsorption. The dissolution of the wolframite indicates that the OHA- in the solution and the anion exchange of WO2-4 in the crystal lattice. With the advent of WO2-4, OHA- may form hydroxamic acid precipitation with Mn2+/Fe2+ ions on the ore surface. XPS energy spectrum analysis confirmed the existence of this OHA adsorption mechanism. OHA can be combined with iron / manganese on the surface of the ore, while OHA molecules can be physically adsorbed in the chemisorbed layer of hydroxamic acid precipitation. This reaction process ensures sufficient floatability of the OHA to the surface of the ferromanganese ore and also makes the wolframite have good hydrophobicity.
Fu Guangqin studied the effect of GYB and TAB-3 alone or in combination on the flotation of wolframite by a single mineral test. Under the same dosage of collector, there is a synergistic effect between GYB and TAB-3. The recovery of tungsten ore is best. When GYB is combined with TAB-3, the surface potential of the wolframite is reduced more than that of the single use. It is speculated that GYB and TAB-3 combine to adsorb more on the surface of the wolframite. Infrared spectroscopy analysis of the black tungsten ore after the action of the agent proves that the GYB agent or the TAB-3 agent can be adsorbed on the surface of the wolframite for chemical adsorption.
3. Black mixed scheelite ore collector
Most of the black and white tungsten mixed mines in China are complex, and the useful mineral inlays are fine in size and difficult in mineral processing . The flotation black and white tungsten ore may be a fatty acid collector, a chelate collector, or a mixture of the two, and the black and white tungsten mineral may be recovered by the synergistic action of the agent.
Huang Jianping studied scheelite and wolframite as the research object, and investigated the cyclohexylmethyl hydroxamic acid, p-tert-butyl benzoic acid, benzyl hydroxamic acid, salicyl hydroxamic acid, and octyl hydroxamic acid to white tungsten. The influence of the floatability of ore and wolframite results in the following conclusions: Hydroxamic acid collectors can be used for flotation of scheelite and wolframite, and the ability to collect scheelite is slightly stronger than black. Tungsten ore, the best flotation pH is about 9.0; the structure of hydroxamic acid significantly affects its ability to capture scheelite and wolframite; the order of five hydroxydecanoic acid to scheelite and wolframite is : cyclohexylmethyl hydroxamic acid > p-tert-butyl benzyl hydroxamic acid > octyl hydroxamic acid > salicyl hydroxamic acid > benzyl hydroxamic acid. Sodium oleate has the same ability to capture scheelite and wolframite, and is superior to the storage capacity of hydroxamic acid. The total amount of collector is the same. The combination of hydroxamic acid and sodium oleate is scheelite and black tungsten. The mine's ability to capture is stronger than sodium oleate, producing a positive synergy. The optimum adsorption pH of hydroxamic acid on the surface of scheelite and wolframite is close to the pKa of hydroxamic acid. Hydroxamic acid ion molecules are adsorbed on the surface of scheelite and wolframite. The collector is on the surface of scheelite. The adsorption capacity is larger than that of black tungsten ore, and the adsorption amount of cyclohexylmethyl hydroxamic acid is higher than that of benzyl hydroxamic acid, which is consistent with the flotation of single mineral; the effect of temperature on the adsorption amount of sodium oleate on the surface of the wolframite is greater than The scheelite or hydroxamic acid promotes the adsorption of sodium oleate on the surface of scheelite and wolframite, and this effect is particularly remarkable at low temperatures (15 °C). Zeta-potential and infrared spectroscopy analysis showed that hydroxamic acid and sodium oleate co-adsorbed on the surface of scheelite and wolframite, and it was a process of chemisorption.
Sun Wei studied the capture performance of F-305 new agent on tungsten minerals. The single-mineral test and actual ore test were used to study the capture performance of the new chelation agent F-305 on the wolframite and scheelite. The test results show that compared with the conventional tungsten ore flotation agent 733 oxide oxide wax, F-305 has a strong ability to capture scheelite, and can obtain good flotation index at room temperature. The infrared spectra before and after the action of scheelite indicate that F-305 is mainly adsorbed on the surface of scheelite; the infrared spectrum before and after the action of scheelite indicates that F-305 has strong chemical bonding and chemistry on the surface of scheelite. Adsorption. Fe2+ ​​and Mn2+ ions are the localized ions on the surface of the wolframite and can form a chelate with F-305. This is the reason why F-305 has a particularly strong ability to capture hematite.
Yang Yinglin studied the collection performance of GYB and different fatty acid agents (GYR, TAB-3, 731) in different proportions of black and white tungsten ore through a single mineral experiment, revealing that different combinations of chemicals can capture black and white tungsten ore in different proportions. The difference in ability. The results show that when the content of black tungsten ore in black and white tungsten mixed ore is relatively high, the combination of GYB and GYR can obtain good mixed flotation recovery and concentrate grade; when the content of scheelite is relatively high in black and white tungsten mixed ore The combination of GYB and TAB-3 can achieve good mixed flotation recovery and concentrate grade. The results of simulating tungsten-manganese ore, tungsten iron ore, scheelite crystals and surface by MS-castep showed that the nucleophilic reagents such as fatty acid collector GYR, TAB-3 and chelating collector GYB were in the tungsten-manganese [001] surface. The adsorption is closely related to the hybrid orbital composed of the 5d orbital of W and the 3d orbital of Mn; the adsorption on the surface of tungsten iron ore [001] is composed of the 2p orbital of O, the 3p orbital of Fe, and the 5d orbital of tungsten. It is related to hybrid orbital; the adsorption on the [001] surface of scheelite is affected by the hybrid orbital composed of 3d, oxygen 2p and tungsten 5d. Infrared spectroscopy indicated that GYB and fatty acid collectors GYR and TAB-3 were chemisorbed on the surface of the wolframite and scheelite in the black and white tungsten symbiotic ore mixed flotation system.
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