The rough selection of antimony ore beneficiation is generally carried out by re-election method. The selection is by re-election, flotation, electromagnetic selection or combined metallurgy. It is used to treat ore with a large content of fine ore or raw mud. efficient grinding and classification equipment to reduce tantalum niobium clay minerals.
Commonly used collectors for flotation are fatty acids, tannins, phosphonic acids, hydroxamic acids, cationic collectors, etc. The environmental pollution of pesticides and the cost of pharmaceuticals are of paramount importance. With the development of the chemical industry, the raw materials are widely available, the synthesis process is simple, the biodegradable, selective, non-toxic and harmless, and reasonably priced chemicals will continue to appear, meeting the needs of the mining plant.
1. Process characteristics of antimony ore minerals
Niobium iron ore - Chemical Formula tantalite as AB2O6, both referred niobium tantalite. A is iron and manganese , and B is strontium and barium. Different forms from pure bismuth to strontium have a series of isomorphous structures characterized by an indeterminate ratio of iron to manganese. Among them, Nb2O5 1.97~78.88%, Ta2O5 5.56~83.57%, MnO 1.26~16.25%, FeO 1.89~16.25%. There are also similar materials such as Ti, Zr, W, TR, and U. In the group, the majority of the sputum is called coltan, and if it is the majority, it is called coltan. The crystal lattice of the mineral is a rhombic structure, and the space group is marked as Pcan. The structure consists of layers of A and B octahedrons. The same octahedron is connected as a chain in the layer by edges, and then connected to a common vertex. An A octahedral layer is connected to the adjacent B-octahedral layer by two vertices to form a BAB structure.
The lattice parameters of many minerals of coltan-niobite are related to the composition of the sample. The fluctuation range is as follows: a=0.5133~0.5054nm; b=1.445~1.405nm; c=0.5762~0.5683nm. The atomic spacing in the manganese ore is Mn-O = 2.12 to 2.14 angstroms, and Ta-O = 1.86 to 2.12 angstroms. Mineral colors are black, brownish black and reddish brown. The Mohs hardness is: bismuth iron ore 4.3~6.5; coltanite 6.5~7.2. The microhardness value of coltan is 2400~8000MPa, and the coltan is 8000~10700Mpa.
The magnetic susceptibility of the coltan-niobite is (22.1~37.2)×10-6. The dielectric constant of coltan is 10~12, and that of coltan is 7~8. The density of minerals is 5.15~8.20 (increased as the content of strontium increases).
2. Yankuang Mineral Processing Technology
Yankuang ore dressing generally adopts re-election to discard most of the gangue minerals and obtain low-grade mixed coarse concentrates. The coarse concentrate minerals entering the selected operations are complex in composition and generally contain a variety of useful minerals. A variety of beneficiation methods such as re-election, flotation, electromagnetic selection or combined metallurgy are selected to achieve separation of a variety of useful minerals.
2.1 Foreign ore dressing
It is essential to wash ore in the processing of ore with a large content of fine ore or raw mud. Australia's Grinbus mine weathered pegmatite alluvial clay rough selection plant, set up two washing system, the original mine with a diameter of 1.5m, a pore size of 10mm cylindrical sieve twice after washing, selected under the sieve, sieve large and The clay ball is ground into a self-grinding mill for about 4 mm, and then sieved with a cylindrical sieve having a hole diameter of 10 mm. The material under the sieve is selected, and the material on the sieve is discarded or returned for regrind. The washing water consumption is 5m3/t, and the cylindrical sieve processing capacity is 350 tons/hour.
Foreign smelting and mining plants attach importance to the use of high-efficiency grinding and grading equipment to reduce the muddy of strontium minerals. Good results were obtained from the surrounding pebble rod mill and vibrating screen closed circuit in the original pegmatite roughing plant of the Greenbus mine. The Borneo Lake antimony mine in Canada has been continuously improved and the current grinding process is very distinctive. The mine is closed with a 2.4m×3.6m Marcy-type lattice ball mill AC horizontal vibrating screen (straight screen), the sieve size is 2.5mm, and the sieve is graded by 0.2mm with Derrick sieve, -2.5+0.2mm The grade is sorted by a spiral concentrator, and the tailings are dehydrated by a curved sieve and returned to re-grind. The ball mill has two kinds of products to form a cycle, that is, a two-stage closed-circuit grinding is realized by one mill. After the adjustment of the grinding circuit, the cyclic load rate is usually about 180%, and the cyclic load is small and easy to form excessive pulverization.
The rough selection of coltan ore in foreign countries is still mainly based on re-election, and more efficient re-election equipment is used , and the process is simple. For example, the Grimbs mine directly uses a jig for rough selection of -10mm ore. The re-election-flotation-re-election process formed in the 1980s in Bonn Lake, Canada, is becoming more and more perfect. The process is still dominated by re-election, and flotation is only used to treat fine mud. The re-election equipment used GEC spiral concentrator, 3-layer suspended Dyest shaker, Holman slime shaker, and cross-flow belt concentrator. The former Soviet Union used flotation to separate the coltan, fine-grain and topaz in the re-selected concentrate. The collector was hydroxamic acid, the regulator was oxalic acid, and it was floated in hydrochloric acid medium (pH 2). When Ta2O5 is contained at 2.52%, the concentrate grade is 27% and the recovery rate is 90%.
The flotation method of the pyrochlore ore is mainly carried out by flotation method. In order to improve the quality of the concentrate and reduce the consumption of the medicament, in recent years, the pyrochlore beneficiation process has strengthened the operations of deliming, removing iron, desulfurization, phosphorus , lead and antimony. Nio Baker pyrochlore mine - 0.2mm was selected into the original mine cyclone to remove -10μm slime, and selected by mud sand. First, float the apatite and carbonate minerals with a fatty acid collector, then perform magnetic separation and de-ironing, then float the pyrochlore with an amine collector, and finally perform pyrite flotation on the pyrochlore concentrate. Leaching with hydrochloric acid to reduce the sulfur, phosphorus and carbonate mineral content. When the ore contains Nb2O5 0.6%~0.7%, the final concentrate grade is 58%~62%, and the recovery rate is 60%~65%.
2.2 Domestic bismuth ore dressing
Rough ore
The ore grade of domestic antimony ore is generally low, and its minerality is brittle and dense. In order to ensure the grinding size and avoid over-grinding, the stage grinding stage selection process is generally adopted. Jiangxi Yichunyu Concentrator uses a horizontal curved screen instead of a linear vibrating screen for screening. The on-site exploration test results show that the fineness on the sieve can be reduced by 14.70%, the coarseness under the sieve can be reduced by 4.3%, and the screening efficiency can be increased by 17.72. %. The successful test of this equipment provides a new way for the field of grinding and screening. Nanping, Fujian Province is a large-scale granitic pegmatite deposit. In 1998, we conducted ore dressing test on the ore, providing design basis for the construction of the plant. Based on the characteristics of the grain size of the bismuth and cassiterite minerals, we proposed the use of stage grinding and stage selection. Do not craft. A section uses a rod mill and forms a closed circuit with the screen to reduce over-grinding. The second-stage grinding uses a ball mill and forms a closed circuit with the high-frequency vibrating fine screen. In addition to strictly controlling the particle size, it can also increase the processing capacity and improve the grinding efficiency. The mine is rough selected using a single re-election process. The re-election equipment has a GL spiral concentrator, a spiral chute and a shaker. The ore is selected from the original ore containing (TaNb)2O5 0.0499%, Sn 0.0598%. The crude concentrate obtained after rough selection has a yield of 0.248%, containing (TaNb)2O514.94% (including Ta2O5 10.79%), and the recovery rate of raw ore is 74.30% (Ta2O5 recovery rate is 74.96%); containing Sn 15.71%, the recovery rate of raw ore is 65.11%.
2. Yankuang selection
The coarse concentrate obtained by the rough selection process is generally a mixed coarse concentrate, which needs to be further selected to separate a variety of useful minerals. The composition of the crude concentrate minerals is different, and the separation methods used are also different. Generally, a plurality of methods are used in combination. For example, Fujian Nanping 钽铌 selects magnetic-heavy-floating combination, first cleans the mineral surface with 6% hydrochloric acid solution, then removes the strong magnetic minerals and iron filings with weak magnetic separation, dries and sifts into +0.2, +0.1 And -0.1mm three levels, respectively, using a dry strong magnetic separator to obtain a bismuth concentrate by one rough selection and one sweep, and the non-magnetic part of the dry strong magnetic separation is re-selected to recover the cassiterite and throw the tail. The selected concentrate is subjected to flotation to remove the sulfide ore to obtain a tin concentrate. Selected results: the yield of strontium concentrate is 0.0764%, containing (TaNb)2O5 45.64% (Ta2O5 32.57%), the recovery rate of raw ore is 69.92% (Ta2O5 recovery rate is 69.071%), the recovery rate of selected operations is 94.11%; tin concentrate The rate is 0.0581%, containing Sn60.25%, the recovery rate of raw ore is 58.49%, and the recovery rate of selected operations is 89.84%.
3. Fine-grained ore flotation
Dajishan Jiangxi tungsten ore in the ore body No. 69 is a large granite containing tantalum, niobium, tungsten ore, the mine is mainly useful minerals wolframite, scheelite, tantalum, niobium, iron ore and microlite, useful minerals disseminated The particle size is very fine, most of the particle size is 40~74μm. Therefore, the conventional re-election method has a lower recovery rate of beneficiation, and the recovery rate of plutonium is only 25%~33%. Guangzhou Institute of nonferrous metal using heavy - floating joint process associated recovering tantalum and niobium and tungsten minerals, ore flotation WO3 0.088%, when Ta2O50.0145%, 0.7% fine mineral flotation concentrate containing WO3 10.84 %, Ta2O51.8%, the recovery rates of tungsten and rhenium were 85% and 87%, respectively, and the enrichment ratio of concentrate was more than 100 times. Then re-select the enrichment and separate the antimony and tungsten from the water. The recovery rate of smelting and smelting is 44%.
The ore properties of Baotou Bayan Obo Mine are very complicated. Especially the niobium minerals are famous for their poor, fine and miscellaneous minerals. Although the current mineral processing technology has made great progress compared with the past, the recovery rate of rare earth ore is still low. Mineral recovery is still in the research stage. The non-ferrous metal research institute of Guangzhou used flotation method to enrich the rare earth flotation tailings with strontium minerals, using Pb(NO3)2 as the activator, D-1 as the inhibitor of calcium minerals, and the combination of hydroxydecanoic acid. The granules are floated in a medium of pH 6 and desulfurized by flotation-enriched slag concentrate, and then selected by a weak magnetic-shaker process to obtain bismuth-rich concentrate and iron concentrate. Fushun Iron Concentrate 1 contains 1.66% of Nb2O5, Concentrate 2 contains 0.59% of Nb2O5, and the total recovery of rhodium is 35.58%. After Chen Quanyuan et al. studied the rare earth flotation tailings in the Bayan Obo mine, it was proposed that after the concentrated desilting of the rare earth flotation tailings, the oxidized wax soap, water glass anti-floated fluorite and residual rare earth minerals were added, and the products in the tank were concentrated. After adding ammonium fluorosilicate, oxide wax, flotation iron mineral to obtain iron concentrate, iron tailings plus sulfuric acid, carboxymethyl cellulose, salicyl hydroxamic acid, C5-9 hydroxamic acid and oxalic acid, once After rough selection and three times selection, a flotation concentrate containing Nb2O5 1.67% and a recovery rate of 40.14% is obtained. The concentrate is further separated by iron and bismuth by strong magnetic, and the bismuth concentrate and magnetic products of non-magnetic products are obtained. Concentrate. In addition, the magnetic-floating process can also obtain rare earth foam products and iron concentrates.
3 Research status and progress of flotation reagents in antimony ore
The mineral resources of the 钽铌 minerals are known for their poor, fine and difficult selection. Although the current mineral processing technology has made great progress compared with the past, the recovery rate of mineral processing is still low. In recent years, many scholars at home and abroad have carried out a lot of research work on the flotation of cockroaches, among which the more effective collectors are fatty acids, tannins, phosphonic acids, hydroxamic acids, cationic collectors. .
钽铌 mineral collector
(1) Fatty acid collectors. The former Soviet Union Polikin С И and Gladgich Ю Рused oxidized ore collectors in 1959: oleic acid, sodium oleate, sodium decanoate, sodium sulphate and sodium isooctyl phosphate. The floatability of coltan, coltan, tourmaline and garnet. Tests have shown that when using fatty acids as collectors, the trapping ability of saturated hydrocarbon groups is worse than that of unsaturated ones. When the pH value is 6~8, the flotation of coltan-column with sodium oleate is very effective, and it is inhibited in both strong acidic medium and strong alkaline medium.
Modification of fatty acids can improve their selective capture. For example, a new effective reactive group sulfonic acid group, polycarboxyl group, sulfuric acid group, halogen, amine (amino) group, aminoacyl group, amide group and the like are introduced into the molecule.
(2) Tannic acid collectors. Tannin can form a strong surface compound with rare metal minerals such as strontium and barium, and the hydrocarbon group is outward to make the mineral hydrophobic. However, this chemical adsorption does not exist with gangue minerals, so the collection ability is strong and the selectivity is good. The disadvantage is that there are pollution problems in the production and use of bismuth-containing substances. Benzyl phthalic acid and toluic acid are effective collectors for strontium minerals and wolframite and cassiterite. The combination of citric acid and xanthate can greatly improve the recovery rate of wolframite and cassiterite, and also improve niobium minerals. Recovery rate.
(3) Phosphonic acid-based traps. The solubility of phosphonic acid in aqueous solution changes with the change of pH value, and generally has good solubility in an alkaline medium, and actually dissolves by forming an alkali metal salt. Phosphonic acid forms a poorly soluble salt with metal ions such as Ca2+, Fe2+, Fe3+, and Sn2+, and thus can capture antimony minerals. The study on the recovery of ruthenium rutile by bisphosphonic acid showed that the bisphosphonic acid is a good collector of ruthenium rutile when the pH value of the slurry is 2~4, and the recovery rate is 90.87%~91.70%. The acid is adsorbed on the surface of the ruthenium rutile, and the adsorption form is mainly chemical adsorption.
(4) Hydroxamic acid collectors. Hydroxamic acid and its salts were used early in the flotation of malachite and hematite, and were subsequently used as collectors for various rare metal ores. Naphthyl hydroxamic acid has a good choice for the collection of hematite, while the ability to capture quartz and fluorite is extremely weak. Flotation of the glauconite with C7~9 hydroxamic acid, the concentrate containing Nb2O5 6~20%, the recovery rate is 65~66%. In China, the industrial hydroxamic acid used in a fine mud mine is matched with transformer oil for rough selection. When the ore contains Nb2O5 0.094%, the crude concentrate grade Nb2O5 is 0.9~1.0%, and the recovery rate is about 90%.
(5) Cationic collector. In neutral medium, the cation collector is an effective collector for strontium minerals; in the strong acid medium, the surface of strontium minerals is mostly positively charged, which is not conducive to the flotation of cation collectors;
From the viewpoint of solution chemistry, the cation collector undergoes a hydrolysis reaction in an aqueous solution. In a strong alkali medium, the OH-concentration is not conducive to the hydrolysis reaction, and the concentration of the collector cation is lowered, which is unfavorable for flotation. The Araxa plant in Brazil uses amines as collectors, and flotation of pyrochlore has achieved good results. Other studies have shown that laurylamine acetate can effectively float coltan-type minerals in neutral media.
(6) Other collectors. The study on the capture performance of strontium minerals by the new agent N2 shows that the high carbon chain N2 is an effective collector for strontium minerals, and the adsorption on the surface of strontium minerals is chemical adsorption. Good results were obtained by flotation of the Bayan Obo ore with N-nitrosophenylamine. The exploratory experiments of the former Soviet Union Bergel Γ С showed that the hydrocarbyl sulfate was also suitable for the flotation of the coltan-tantalite in the pegmatite deposit.
Many flotation agents, especially collectors, are not ideal when used alone. However, when some agents are used in combination in a certain proportion, the effect is not a simple additive effect, but a synergistic effect, that is, 1 +1>2 synergy effect. Such as xanthate and hydroxamic acid combined flotation copper oxide; sodium oleate and hydroxamic acid combined flotation of andalusite ; tannic acid and xanthate mixed, copper iron spirit mixed with benzoic acid, benzoic acid and The mixture of Tal soap and flotation of black tungsten fine mud; F203 and salicyloxyphthalic acid mixed with flotation of cassiterite fine mud have achieved good results.
Antimony ore flotation regulator
The main gangue minerals of antimony ore are silicate minerals, fluorite and carbonate minerals. Typical inhibitors of these minerals are water glass, sodium hexametaphosphate, starch, pyrophosphoric acid, sodium hydrogen phosphate, sodium lignosulfonate, tannin, lactic acid, citric acid, tartaric acid, and the like. The pH value has a great influence on the flotation process, and the modifiers commonly used for adjusting the pH value include sulfuric acid, hydrochloric acid, sodium hydroxide, and soda.
2. Analysis of problems existing in antimony ore flotation
(1) Collection of collectors. The molecule contains functional groups -COOH, -SO4H, -SO3H, which have strong collection ability and poor selectivity, and are only suitable for the fine mud with a simple flotation mineral composition and quartz as the main gangue. Hydroxamic acid has a weaker ability to capture fine mud than fatty acids, but it is better. Phosphonic acid has a strong ability to capture antimony ore, but is sensitive to Fe2+ and Ca2+ ions. It has a greater impact on the flotation process.
(2) Environmental pollution of pesticides and cost of pharmaceuticals. Tannic acid can form strong surface compounds with metal ores such as strontium and barium. The hydrocarbon group is outward and makes the mineral hydrophobic. However, this kind of chemical adsorption exists in the novels of gangue minerals, so the collection ability is strong and the selectivity is good. It is not sensitive to Ca2+ and Mg2+ ions, and has strong adaptability to ore with high calcite . However, citrate is highly toxic and may cause environmental pollution. The sodium fluorosilicate or sodium fluoride, which is used in combination with phosphonic acid and sulfosuccinic acid, is also toxic. In the fine mud flotation, the dosage is large and the price is high. At the same time, some of the chemicals are more toxic and need to increase environmental protection costs, thereby increasing the cost of mineral processing. When using hydroxamic acid flotation, the effect is better, but the amount of the agent is larger.
In recent years, many scholars at home and abroad have done a lot of work in the selection and development of cockroach flotation agents, and found many selective collectors. Although some progress has been made in the research of flotation reagents, due to the high price of pharmaceuticals, only a few foreign mines have adopted flotation methods, such as the Canadian Oka Concentrator and the Brazilian Araksa Mine. With the development of more and more difficult resources, it is expected that the demand for selective and reasonably priced minerals will continue to increase.
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