Progress in molybdenum ore beneficiation process technology

Progress in molybdenum ore beneficiation process technology

1 crushing and grading and grinding classification

The SABC grinding process refers to the semi-autogenous grinding + ball milling + crushing process. Usually, the ore directly enters the semi- autogenous mill for self-grinding. The semi-autogenous mill product is fed into the vibrating screen. The qualified fractions under the sieve are fed into the subsequent ball mill grading system, and finally the qualified grinding products are obtained. The "hard stone" is broken by the crusher and returned to the semi-self-grinding operation. The utility model is characterized in that a fine crusher is introduced to crush the hard-to-grind gravel, the accumulation of the hard-to-grind gravel in the self-grinding machine is eliminated, the granularity property of the natural grinding medium in the self-grinding machine can be changed, and the material with suitable granularity is provided for the subsequent operation.

Wu Nuge spit Hill copper-molybdenum mine (referred to Osan copper-molybdenum mine) Barr Right Banner in Inner Mongolia new, low-grade copper reserves belong to a large copper-molybdenum-ferrous metal mines, is a large porphyry copper-molybdenum mine, huge reserves, as 3 million tons, molybdenum metal reserves up to 600,000 tons. The grade of the ore is lower, the copper grade is only 0.3%, and the molybdenum grade is only 0.03%. Osan copper-molybdenum ore beneficiation plant design capacity of 75 000 t / d, constructed in two phases: one 35,000 t / d, two of 40,000 t / d. The crushing system of the ore dressing adopts the SABC grinding process. The grinding equipment adopts domestic large-scale mineral processing equipment such as Φ8.8m×4.8m semi-autogenous grinding machine and Φ6.2m×9.5m overflow ball mill .

The SABC grinding process of Wushan Copper-Molybdenum Mine has the advantages of short process, advanced and reliable, greatly reduced floor space, reduced dust pollution and reduced maintenance strength. Its stable operation provides reference for the construction of other domestic crushing process. Such as Heilongjiang Yichun Luming Molybdenum Mine, Tibet Jiama Mine Phase II, etc. In order to prevent the system from breaking the hard- core cone crusher and causing equipment damage, the Wushan copper-molybdenum ore dressing plant adopts the MA-2211 type iron removal device. The iron removal device is installed at a critical position in the system, and the broken steel ball in the system can be removed at the first time to ensure the normal operation of the system.

2 sorting process technology flow

With the deepening of molybdenum resource development, the easy-selection deposits are gradually reduced, the ore is gradually depleted, and the molybdenum grade is getting lower and lower. Therefore, the current beneficiation requires not only the development of new high-efficiency pharmaceuticals, but also the overall optimization of the beneficiation process and process. In order to achieve full utilization of molybdenum resources.

2.1 Copper and molybdenum sorting

When the copper-molybdenum ore ore has a high molybdenum grade, a partial mixing flotation process is generally employed. The process first uses molybdenum ore collector to float part of the easy-to-float molybdenum to obtain a part of molybdenum concentrate, followed by copper-molybdenum mixed flotation with a sulfide ore collector to obtain a copper-molybdenum mixed concentrate, and finally a copper-molybdenum concentrate. Perform copper and molybdenum separation. The process scheme can effectively reduce the difficulty of separating copper and molybdenum.

For low-grade porphyry copper-molybdenum ore, flocculent copper-molybdenum is generally floated with a sulfide ore collector, followed by copper-molybdenum separation, and the preferential flotation process and the medium-mineral regrind process are rarely used. When mixing flotation, copper is floated as completely as possible, and molybdenum is also floated into copper concentrate. When the content of molybdenum in copper-molybdenum ore is too low, it is impossible to separate the copper-molybdenum ore by flotation, or it can be separated but the cost is too high. The plant generally only produces copper-molybdenum mixed concentrate. The advantages of the mixed flotation re-separation process are: low grinding cost, low circulation in the middle mine, easy operation and control of the process, and easy implementation on site. Therefore, the process can effectively reduce the cost of the copper-molybdenum ore flotation process. However, since the mixed concentrate contains excess agent during the mixed flotation, the separation of the concentrate is difficult. Therefore, the process is usually carried out in the copper-molybdenum separation to improve the separation effect.

Zimin Aleksej Vladimirovich and others have introduced a new flotation method for copper-molybdenum ore. The method comprises: first selecting copper-molybdenum mixed coarse concentrate, de-doping, rinsing, concentrating and classifying the copper-molybdenum prior to separation, and then re-grinding the coarse concentrate, and the de-drug surfactant and inhibitor have good effect. .

M. Poorkan et al. studied the copper-molybdenum separation of the Iranian Sarcheshmeth copper-molybdenum concentrator (production scale 41000t/d). Separation of copper-molybdenum sulfide minerals NaCl inhibits chalcopyrite, chalcopyrite and pyrite, and floats molybdenite. Studies have shown that the inhibition of copper sulfide minerals such as chalcopyrite by NaHS first desorbs the xanthate adsorbed on the surface of the chalcopyrite to deactivate the chalcopyrite. In traditional aerated flotation, NaHS inhibitors are easily oxidized and lose their effect. To separate the chalcopyrite from molybdenite, it consumes up to 17.7 kg/t of NaHS. With such a large amount of NaHS, the cost of the drug accounts for about 58% of the total cost of the entire plant. For this reason, the researchers replaced the traditional air with nitrogen. Since nitrogen effectively prevented the oxidation of NaHS, the consumption of NaHS was reduced to 14.2 kg. /t, up to 10kg / t, while also slightly increasing the recovery of molybdenum, the level of molybdenum concentrate maintained in air.

The molybdenum flotation plant of the Ellatzite-MedAB copper mine in Bulgaria, which was relaunched in 2008, uses a sealed Wemco-type inert gas flotation machine with a flotation gas of O28% and N292%. Inhibition of chalcopyrite with NaHS, with kerosene molybdenite flotation, to give a 80% recovery of molybdenum concentrate containing Mo44% -48% of, NaHS decreased consumption, reduced amount of 7kg / t.

Shao Fuguo et al. used a molybdenum-copper asynchronous mixed flotation re-separation-sulfur flotation process for a schist-type copper-molybdenum ore in a mining area in Henan. In the floatable stage such as molybdenum and copper, the collector with strong selectivity to molybdenum minerals can be used to improve the grade and recovery of molybdenum in coarse concentrates as much as possible. In the separation of copper and molybdenum, high-efficiency inhibitors are used to reduce vulcanization. The amount of sodium; in the sulfur flotation operation, according to the nature of the ore to enhance the flotation of sulfur, improve the sulfur recovery rate. The good index of molybdenum concentrate grade is 47.02%, molybdenum recovery rate is 87.91%, copper concentrate grade is 14.33%, and copper recovery rate is 82.61%. It provides a technical basis for the development and utilization of low-grade copper-molybdenum resources of this type.

At the University of Utah, scholars used sodium thioglycolate as a chalcopyrite inhibitor for the separation of copper and molybdenum. The diesel floatation molybdenum ore was used. It was found that sodium thioglycolate with a mass ratio of 1:1 was combined with activated carbon in an amount of 20 At -80g/t, not only the chalcopyrite is well suppressed, but also the molybdenum ore flotation recovery rate is also significantly increased. Some scholars believe that the combination of activated carbon and diesel or kerosene can form activated carbon-oil-molybdenum agglomeration, thereby increasing the recovery rate of molybdenum. When activated carbon is used, most of the activated carbon is enriched in the molybdenum concentrate, which reduces the grade of the molybdenum concentrate by 1-2 percentage points.

2.2 lead and molybdenum sorting

The Northwest Institute of Nonferrous Metals has studied a new process for the comprehensive recovery of lead from lead-containing molybdenum ore. The new process includes: molybdenum-lead mixed flotation- phosphorox and activated carbon separation molybdenum-lead-molybdenum ore flotation separation and recovery of lead. The new process can achieve a recovery rate of molybdenum and lead of 82% and 65%, respectively, and a lead concentrate grade of 62%.

Many mineral processing scholars have studied a large number of molybdenum-lead ore deposits in the areas of Hubei and Chongqing. An ore contains Mo1.58%, Pb4.25%, Ba25.61%, Fe2O323.65%, Re0.0062%. Mo and Pb in the ore are molybdenum-lead ore, Ba is barite , and Fe2O3 is brown. Iron ore exists. The gangue is mainly quartz . The most important feature of the ore is that the molybdenum-lead ore is in the form of fine-grained honeycomb, which is closely symbiotic with barite and limonite. Molybdenum, lead, antimony and iron account for about 1/3 of the -0.038mm grain size, and the particle size of the impregnation is extremely fine. Zhang.YS et al. studied the selection of this refractory molybdenum-lead ore by single re-election, strong magnetic separation and flotation process. The results show that the ore is ground to -0.074mm, accounting for 92%, using 1 coarse, 2 fine and 1 sweeping flotation process with sodium sulfide as activator (2.1kg/t), sodium carbonate (1.7kg/t), sodium silicate (1.5kg/t) and aluminum sulfate (800g/t) The agent and xanthate (360g/t) are collectors and terpineol (80g/t) is a foaming agent. After flotation, the molybdenum concentrate containing Mo7.06% is obtained, and the molybdenum recovery rate is 62.63%. The yield was 15.14%.

Chen Jianhua et al. studied a high-iron molybdenum-lead ore beneficiation containing Mo0.92%, Pb3.9%, and Fe2O329%. Sodium sulfide (10kg/t) as vulcanizing agent, copper sulfate (67g/t) as activator, sodium hydroxide (pH=9-10), sodium hexametaphosphate (100g/t) as regulator, isoamyl Sodium sulfonate (330g / t) and kerosene (100g / t) are collectors, terpineol (60g / t) is a foaming agent, grinding fineness -0.074mm accounted for 78%, after 1 coarse 1 sweep After the selection, the flotation concentrate grade Mo was 5.8%, and the molybdenum recovery rate was 76%. Tests have shown that several of the added agents are indispensable, in the potassium ethyl xanthate, potassium butyl xanthate, potassium isoamyl xanthate, xanthate, dithiophosphate (black drug) Among the six collectors such as ethyl sulphide and nitrogen, the best performance was obtained by using isoamyl xanthate. If the slurry temperature is increased from 30 ° C to 50 ° C, the grade of molybdenum concentrate can be increased to 8.87%, and the recovery rate is 79%.

Wang Anli et al. developed a new ore dressing method containing Mo0.13%, Pb 0.02%-0.03% and Au0.4g/t molybdenum ore: grinding the ore to -0.074mm, accounting for 55% to 60%, with a small amount of yellow The crude sulphur gold-lead concentrate containing Mo4%~6% and Au2.0g/t is coarsely selected from medicine and kerosene, and re-grinded by vertical ball mill (closed operation with hydrocyclone) to -0.04mm accounted for 60%-70 After the %, the gold is recovered by the carbon slurry method. The cyanide tailings are selected 8 to 10 times for molybdenum selection. P-Nokes is used to suppress galena in selected operations, and molybdenum concentrate containing Mo45% to 47% is obtained. The molybdenum recovery rate is about 85%, and the gold recovery rate is 75%. Since the molybdenite is selected after cyanidation, the copper sulfide ore, zinc sulfide ore and pyrite are “completely” suppressed. The molybdenum concentrate contains copper and iron, which is low, and does not inhibit copper minerals with sodium thioglycolate. . Lead is selected from the molybdenum selected tailings by the yellow medicine, and the lead intermediate product containing about 30% of Pb is sent to the smelting plant for lead smelting. If the molybdenum content is high, the molybdenum intermediate product can also be sold.

Wu Xian et al used Knox and activated carbon in the separation of molybdenum and lead. Compared with Knox-suppressed galena alone, the kerosene flotation molybdenum ore has improved its grade and recovery rate.

2.3 nickel- molybdenum sorting

Wang Mingyu from Central South University studied a new technology for extracting molybdenum from low-grade nickel-molybdenum ore. The main process flow is roasting nickel-molybdenum ore, and then the calcined product is subjected to alkali leaching with sodium carbonate and sodium hydroxide, and then molybdenum is enriched by ion exchange to obtain a molybdenum-containing solution. Purification operations such as removal of vanadium are carried out, and crystallization is performed to obtain ammonium molybdate in accordance with quality standards. The process has a molybdenum recovery rate of 89.06%.

Marcantomio.PJ introduced a molybdenum-nickel sulfide treatment method, which oxidizes the material at a concentration of 10% to 15% at 200 ° C and 2.5 MPa, ammonia leaching, conversion of molybdenum sulfide to (NH 4 ) 2 MoO 4 , nickel sulphide Converted to Ni(NH3)6SO4. Nickel was extracted with LIX-84-1, nickel was supported in the organic phase, and nickel sulfate was obtained by reverse stripping with H2SO4, and the aqueous phase molybdenum was recovered as a low concentration of ammonium molybdate. The molybdenum molybdate product is obtained by extracting molybdenum with N235 and extracting ammonia with high concentration of ammonium molybdate, purifying, acid-sinking and crystallizing. This is another technical route to recover molybdenum from molybdenum-nickel ore. The process also has no roasting operation and does not cause harm to the environment.

2.4 tungsten and molybdenum sorting

Tubes and the like on the Southern China Gao containing WO30.23%, Mo0.018% veinlets black - white tungsten-molybdenum ore was studied, using the recovered coarse fraction reselection wolframite and scheelite, reselection tailed The ore flotation molybdenum ore with the combination of ore and fine fraction. Using kerosene as a collector and pine oil as a foaming agent, the crude concentrate contains Mo2.31% and the molybdenum recovery rate is 50.54%. The molybdenum flotation tailings activates scheelite with lead nitrate, floats scheelite with GYB and GYR mixed collector, is roughly selected as room temperature, and is selected for heating. The integrated scheelite concentrate contains WO357.53% and tungsten. The recovery rate is 80.59%.

2.5 é“‹ molybdenum sorting

For low-grade tungsten-molybdenum-niobium ore, the process of mixing and re-separation of molybdenum-niobium is used, and the mixed coarse and fine concentrate is obtained by molybdenum-niobium mixed coarse selection, followed by molybdenum-sulfur separation and molybdenum-ruthenium separation. The molybdenum in the persimmon garden polymetallic ore mainly exists in the form of molybdenum ore, which is close to the floatability of the stibnite. Therefore, it is preferred to float the molybdenum crucible with good floatability by using a floatable process to prevent heavy pressure re-drawing. First, add a small amount of non-polar oil and foaming agent to float molybdenum and so on. Then use SN-9 collector or Dinghuang to carry out sulphur-sulfur mixing, and use selective modifier sodium sulfide and activated carbon to float. The molybdenum-niobium mixed concentrate is obtained by flotation separation of bismuth-sulfur mixed concentrate by lime and aerated oxidation method to obtain molybdenum concentrate and antimony concentrate, respectively. The grades of molybdenum and antimony ore were 0.069% and 0.163%, and the grades of molybdenum concentrate and antimony concentrate were 48.26% and 38.93%, respectively, and the recovery rates were 86.02% and 72.96%, respectively. Compared with the original production method (molybdenum-bismuth mixed flotation), the recovery rates of molybdenum and antimony concentrates increased by 2.85% and 12.64%, respectively.

2.6 other

Chen Jiadong et al. aimed at the high content of pyrite and talc in the molybdenum concentrate of the new plant of Luoyang Copper Co., Ltd., Huili County, Sichuan Province, and the fine grain size of molybdenite. The grinding fineness -45mm accounted for 95%, Z200 As a collector, lime inhibits pyrite, and sodium hexametaphosphate inhibits the flotation test of gangue minerals. After a rough sweep and four fine operations, the molybdenum concentrate has a molybdenum grade of 45% and a recovery rate of 80% or more. Better technical indicators.

Martin.C.Kuh et al. developed a new process for flotation of talc-type copper-molybdenum ore. Ore grinding to -0.15mm accounted for 80%, using low-grade copper-molybdenum mixed coarse concentrate with potassium pentyl xanthate, diesel, foaming agent Aerofloat-238 and AF-65, coarse concentrate containing Cu25.99% Mo0.49%, acid insoluble matter (mainly talc) 7.24%. After regrind, the copper was selected three times, and the molybdenite or flotation copper sulfide ore was suppressed by CMC (carboxymethyl cellulose) to obtain a copper concentrate, and the molybdenum remains in the tailings. The tailings were warmed and activated, treated at 85 ° C for 30 min, then molybdenum was selected with diesel, and the tailings were talc. The obtained molybdenum concentrate is calcined in a rotary kiln at a low temperature of 230-260 ° C for 30-60 min. At this time, the surface of the molybdenum ore is oxidized, and the floatability is significantly reduced. Under this condition flotation talc (reverse flotation), the grade of molybdenum concentrate increased significantly. The final molybdenum concentrate contains Mo42%~45% (the original ore contains Mo0.013%), and the recovery rate is 55%.

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