CN110038727B - Separation method of scheelite and stannic oxide bulk concentrates - Google Patents
Separation method of scheelite and stannic oxide bulk concentrates Download PDFInfo
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- CN110038727B CN110038727B CN201910319745.7A CN201910319745A CN110038727B CN 110038727 B CN110038727 B CN 110038727B CN 201910319745 A CN201910319745 A CN 201910319745A CN 110038727 B CN110038727 B CN 110038727B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/002—Inorganic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
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- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/025—Precious metal ores
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Abstract
The invention relates to a separation method of scheelite and stannum bulk concentrate, which comprises the following steps: preparing scheelite tin bulk concentrate into ore pulp, adding a regulator into the ore pulp, then adding collecting agents of salicylhydroxamic acid, naphthaloxic acid and pine oil for roughing operation, and obtaining tin rough concentrate and tailings after roughing; and adding inhibitor sodium fluosilicate and sodium hexametaphosphate into the obtained tin rough concentrate to carry out concentration operation, and obtaining a tin concentrate product after the concentration is finished. The flotation process and the reagent are improved, the defects that tailings are difficult to settle, energy consumption is high and the like caused by the adoption of processes of adding a large amount of water glass for heating flotation separation and the like in the separation of the white tungsten and the tin in the prior art are overcome, the environment-friendly and efficient development and utilization of the white tungsten and the tin bulk concentrates are realized, the grades of the white tungsten concentrates and the tin concentrates are improved, and the WO in the white tungsten concentrates3The content is more than or equal to 50 percent, the recovery rate is higher than 98 percent, the Sn content of the tin concentrate is more than or equal to 30 percent, the recovery rate is higher than 85 percent, and the method has good economic benefit and application prospect.
Description
Technical Field
The invention relates to the technical field of mineral processing, in particular to a separation method of scheelite and stannum mixed concentrate, and especially relates to a method containing WO3The separation method of the scheelite and cassiterite-containing bulk concentrate with the Sn content of 5-15% and the scheelite content of not less than 40%.
Background
Tungsten and tin are both important strategic resources of the country. Tungsten is mainly used for products such as hard alloy, special steel and the like, is widely used in national defense industry, aerospace industry, information industry and the like, and is called as 'industrial teeth'. Tin is an indispensable key rare metal in modern industry, is widely applied to industries such as electronics, information, electrical appliances, chemical industry, metallurgy, building materials, machinery, food packaging and the like, and is called industrial monosodium glutamate. More than 20 tungsten minerals and tungsten-containing minerals are found in the crust at present, but the wolframite and scheelite are the most industrially valuable; the tin content in the earth crust was 0.004%, almost all of which existed in the form of cassiterite (tin oxide), and in addition, there was a very small amount of sulfide minerals of tin. Tin is often associated with many tungsten deposits, as is more or less associated with many tin deposits. The coarse fraction tungsten-tin ore is usually recovered by gravity separation, and because tungsten and tin belong to heavy minerals and have similar densities, the tungsten and tin are concentrated in the concentrate together to produce tungsten-tin bulk concentrate; the fine-fraction tungsten-tin ore is generally recovered by adopting a tungsten-tin mixed flotation process to produce tungsten-tin mixed concentrate. Under the common conditions, tungsten and tin in the tungsten-tin bulk concentrate are seriously contained, one component becomes an impurity of the other component, the grade is influenced, the product market price is influenced, the economic benefit of an enterprise is influenced, and the resource waste is also caused. Therefore, the research on the separation method of the tungsten-tin bulk concentrate is of great significance.
At present, the separation method of tungsten-tin bulk concentrate generally comprises a high-gradient strong magnetic separation method and a flotation method. The high-gradient strong magnetic separation method is suitable for separating the mixed concentrate of the black tungsten and the tin, the black tungsten is weak in magnetism, the cassiterite is almost non-magnetic, the black tungsten concentrate is obtained through the high-gradient strong magnetic separation process, and the magnetic separation tailings are the tin concentrate. The flotation method is suitable for separating the mixed concentrate of the scheelite and the tin, the scheelite concentrate is obtained by a dense slurry high-temperature method (namely a Peterov method) or a normal-temperature flotation method, and the cassiterite is recovered from the scheelite flotation tailings by gravity separation. For example, CN109092564A discloses a beneficiation method for mixed black and white tungsten-tin concentrate, which is to concentrate mixed black and white tungsten-tin concentrate to a mass concentration of 25-45%, and perform white tungsten flotation at normal temperature to obtain white tungsten flotation concentrate and white tungsten flotation tailings; the scheelite flotation concentrate is leached by hydrochloric acid with the mass concentration of 5-20% to obtain scheelite concentrate; and (3) leaching the scheelite flotation tailings by hydrochloric acid with the mass concentration of 5-20% to obtain the wolframine bulk concentrate.
The Pederov method has a good separation effect on the scheelite, but a large amount of water glass needs to be added, the ore pulp is heated to 90-100 ℃ for re-flotation, the tailings are difficult to settle due to the large using amount of the water glass, the heating process is complex, the cost is high, and the potential safety hazard is large; and the cassiterite is recovered by gravity separation of the scheelite flotation tailings, and the fine-grade tin is lost in the tailings, so that the recovery rate of tin is low. Therefore, how to separate the scheelite and stannum mixed concentrate efficiently to produce qualified scheelite concentrate and stannum concentrate and improve the comprehensive recovery rate of scheelite and stannum resources is a difficult problem to be solved urgently.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a separation method of scheelite and stannum bulk concentrates, which adopts the technical scheme of floating stannum to inhibit scheelite, overcomes the defects in the scheme of floating scheelite and stannum to inhibit scheelite in the prior art, realizes the environment-friendly and efficient separation of scheelite and stannum bulk concentrate resources under the normal temperature condition, improves the resource utilization rate of scheelite concentrates and stannum concentrates, and has good economic and environmental benefits and application prospects.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a separation method of scheelite and stannum bulk concentrate, which is characterized by comprising the following steps:
(1) preparing scheelite tin bulk concentrate into ore pulp, adding a regulator into the ore pulp, then adding collecting agents of salicylhydroxamic acid, naphthaloxic acid and pine oil for roughing operation, and obtaining tin rough concentrate and tailings after roughing;
(2) and (2) adding inhibitor sodium fluosilicate and sodium hexametaphosphate into the tin rough concentrate obtained in the step (1) to carry out concentration operation, and obtaining a tin concentrate product after the concentration is finished.
The invention improves the flotation mode, selects the technical scheme for floating tin to inhibit scheelite, solves the problems of difficult tailing sedimentation, high energy consumption, large potential safety hazard, low tin recovery rate of gravity separation of flotation tailings and the like caused by the fact that a large amount of water glass is used for heating separation in the scheelite tin inhibition scheme in the prior art, and realizes the environment-friendly and efficient separation of scheelite tin bulk concentrate resources under the normal temperature condition.
The formula of the collector is improved, and the modified collector is obtained by using the combination of salicylhydroxamic acid, naphthaloxic acid and terpineol oil. The salicylhydroxamic acid and cassiterite can form various forms of external complex salts and different forms of internal complex salts when chelated, and the selectivity to tin is strong; the naphthaloxic acid is mainly chemically adsorbed on the surface of the cassiterite, has strong collecting capability and extremely weak collecting capability on scheelite, quartz and the like; pine oil can increase foam viscosity. Salicylhydroxamic acid, naphthaloxic acid and terpineol oil produce the mating reaction between the three, and physical adsorption, chemical adsorption and surface chemical reaction take place on the cassiterite surface for three kinds of combined collecting agent, can be more stable absorption on the cassiterite surface. The combined collecting agent has the characteristics of good selectivity, strong collecting capability and the like, and can achieve a good flotation effect by using a small amount in the rough separation process.
In the invention, the inhibitor formed by combining sodium fluosilicate and sodium hexametaphosphate is added in the tin refining process, and the inhibitor and the sodium hexametaphosphate are matched, so that the optimal inhibition effect can be obtained. Wherein, a proper amount of sodium fluosilicate has an activating effect on cassiterite and an inhibiting effect on silicate gangue minerals, sodium hexametaphosphate has a good inhibiting effect on silicate gangue minerals such as quartz and the like, and the sodium hexametaphosphate and the quartz produce a matching effect, and can activate the cassiterite and strengthen the inhibiting effect on the gangue minerals. The flotation separation effect of cassiterite, quartz and other gangue is improved, and tin concentrate and scheelite concentrate with high grade and recovery rate can be obtained.
The method provided by the invention is applicable to all tungsten-tin white bulk concentrates in the field, and is particularly applicable to mixed concentrates containing WO3More than or equal to 40 percent of mixed concentrate containing scheelite and cassiterite and 5 to 15 percent of Sn.
According to the invention, the mass concentration of the solid phase in the slurry in the step (1) is 20-50%, for example, 20%, 25%, 30%, 35%, 40%, 45% or 50%, which is not exhaustive for reasons of space and simplicity.
The mass concentration of the solid phase in the ore pulp is preferably 30-45%, and the flotation effect is better in the concentration range.
According to the invention, the regulating agents in the step (1) are sodium carbonate and lead nitrate.
According to the invention, the addition amount of the sodium carbonate is 500-2000g/t, such as 500g/t, 800g/t, 1000g/t, 1300g/t, 1500g/t, 1800g/t or 2000g/t, based on the mass of the white tungsten tin bulk concentrate, and the invention is not exhaustive for reasons of space and simplicity.
According to the invention, the addition amount of the lead nitrate is 200-800g/t, such as 200g/t, 300g/t, 400g/t, 500g/t, 600g/t, 700g/t or 800g/t, based on the mass of the scheelite-tin bulk concentrate, which is limited by space and for the sake of brevity, and is not exhaustive.
According to the invention, the adding amount of the collecting agent in the step (1) is 1000g/t based on the mass of the white tungsten tin bulk concentrate, for example, 100g/t, 200g/t, 300g/t, 400g/t, 500g/t, 600g/t, 700g/t, 800g/t, 900g/t or 1000g/t, etc., which is limited in space and for simplicity and brevity, the invention is not exhaustive.
The adding amount of the collecting agent in the step (1) is preferably 200-800 g/t.
According to the invention, the ratio of the salicylic hydroxamic acid to the naphthoic acid to the pine oil in the collecting agent in the step (1) is (12-16): (6-9):1, for example, 12:6:1, 13:6:1, 12:6:1, 14:7:1, 15:8:1, 16:9:1, 15:6.5:1 or 16:7:1, etc., which is not exhaustive for the purpose of space and simplicity.
The mass ratio of the salicylic acid, the naphthalene hydroximic acid and the terpineol oil in the collecting agent in the step (1) is preferably 14:7: 1.
According to the invention, at least one roughing operation is performed in the step (1), for example, 1 time, 2 times or 3 times, and the specific selection is performed according to the actual situation, and the tin rough concentrate obtained after roughing is a foam product.
According to the invention, at least one scavenging operation is carried out on the tailings obtained after the rough concentration in the step (1), for example, the scavenging operation can be carried out for 1 time, 2 times, 3 times, 4 times or 5 times, and the specific selection is carried out according to the actual situation, and the scheelite concentrate product is obtained after the scavenging operation is finished.
According to the invention, the total adding amount of the collecting agent in the scavenging process is 15-90g/t based on the mass of the white tungsten tin bulk concentrate, for example, 15g/t, 20g/t, 30g/t, 40g/t, 50g/t, 60g/t, 70g/t, 80g/t or 90g/t, and the like, and the invention is not exhaustive for reasons of space and simplicity.
Illustratively, when two scavenging operations are performed on the tailings obtained after the rough concentration in the step (1), the addition amount of the collecting agent in the scavenging process I can be 10-60g/t, and the addition amount of the collecting agent in the scavenging process II is 5-30 g/t.
According to the invention, middlings obtained by scavenging are returned to the previous operation in sequence.
According to the invention, the inhibitor is added in the step (2) in an amount of 5-80g/t, for example, 5g/t, 10g/t, 20g/t, 30g/t, 40g/t, 50g/t, 60g/t, 70g/t or 80g/t, based on the mass of the scheelite tin bulk concentrate, and the invention is not exhaustive for reasons of space and simplicity.
The addition amount of the inhibitor in the step (2) is preferably 8-65 g/t.
According to the invention, the inhibitor is added in a total amount of the medicament during the concentration process, for example, four times of concentration are carried out, and the total amount of the inhibitor added during the four times of concentration is 5-80 g/t.
According to the invention, the mass ratio of the sodium fluorosilicate to the sodium hexametaphosphate in the inhibitor in the step (2) is (1-4):1, preferably 3:1, and may be, for example, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1 or 4:1, and the like, and the invention is not exhaustive for reasons of space and simplicity.
According to the invention, at least one concentration operation is carried out in the step (2), for example, 1 time, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times or 8 times and the like, and the specific selection is carried out according to the actual situation, and the tin concentrate product is obtained after the concentration is finished.
According to the invention, middlings obtained by each fine selection are returned to the previous operation in sequence.
The invention separates the scheelite and stannum mixed concentrate under the preferable conditions, and the flotation effect is better.
As a preferable technical scheme, the separation method of the mixed white tungsten-tin concentrate comprises the following steps of:
(1) adding water into the scheelite tin bulk concentrate to prepare ore pulp with the mass concentration of 20-50%, adding sodium carbonate and lead nitrate serving as adjusting agents into the ore pulp, then adding salicylhydroxamic acid, naphthohydroxamic acid and pine oil serving as collecting agents to perform at least one roughing operation, and obtaining tin rough concentrate and tailings after roughing; wherein the adding amount of sodium carbonate is 500-2000g/t, the adding amount of lead nitrate is 200-800g/t, the adding amount of the collecting agent is 100-1000g/t, and the mass ratio of the salicylic acid, the naphthoic hydroxamic acid and the pine alcohol oil in the collecting agent is (12-16): 6-9): 1;
(2) performing scavenging operation on the tailings obtained in the step (1) at least once to obtain a scheelite concentrate product after scavenging is completed; wherein the total adding amount of the collecting agent in the scavenging process is 15-90g/t according to the mass of the white tungsten tin bulk concentrate, and middlings obtained by scavenging are sequentially returned to the previous operation;
(3) adding inhibitor sodium fluosilicate and sodium hexametaphosphate into the tin rough concentrate obtained in the step (1) to carry out concentration operation for at least one time, and obtaining a tin concentrate product after the concentration is finished; wherein, the adding amount of the inhibitor is 5-80g/t, the mass ratio of the sodium fluosilicate to the sodium hexametaphosphate is (1-4) to 1, and the middlings obtained by concentration are returned to the previous operation in sequence.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) according to the invention, the technical scheme of floating tin to inhibit white tungsten under the normal temperature condition is adopted to separate white tungsten from tin, so that the defects of the traditional technical scheme of floating tin to inhibit white tungsten are avoided, the environment-friendly and efficient separation of white tungsten-tin bulk concentrate resources is realized under the normal temperature condition, the resource utilization rate of white tungsten concentrate and tin concentrate is improved, and the method has good economic and environment-friendly benefits and application prospects.
(2) The method adopts the combination of salicylhydroxamic acid, naphthaloxic acid and pinitol oil as the collecting agent, and the salicylhydroxamic acid, the naphthaloxic acid and the pinitol oil produce a cooperation effect, so that the defects of poor water solubility, poor dispersibility, easiness in layering, instable performance, poor selectivity and the like of the fatty acid of the scheelite collecting agent in the prior art are overcome, the scheelite and gangue mineral inclusion entering tin concentrate can be reduced, meanwhile, the using amount of the collecting agent is reduced, and the method has good economic benefit.
(3) In the invention, the inhibitor formed by combining sodium fluosilicate and sodium hexametaphosphate is added in the tin concentration process and is matched with the tin ore, so that the inhibiting effect on gangue minerals is strengthened while the cassiterite is activated, the flotation separation effect of the cassiterite and gangue such as quartz is improved, and tin concentrate and scheelite concentrate with higher grade and recovery rate can be obtained. Wherein WO in the obtained scheelite concentrate3Not less than 50%, up to more than 55%, recovery rate higher than 98%, and tin metal sales requirement; sn in the tin concentrate is more than or equal to 30 percent and can reach more than 40 percent, the recovery rate is higher than 85 percent, and the marketing requirement of tungsten metal is met.
(4) The technical scheme provided by the invention is energy-saving and environment-friendly, is easy to operate, realizes the separation and recovery of scheelite and tin in the scheelite and tin bulk concentrate to the maximum extent, and is particularly suitable for WO-containing ores3The scheelite-stannum bulk concentrate with the Sn content of not less than 40 percent and Sn content of 5-15 percent has good economic benefit and application prospect.
Drawings
Fig. 1 is a process flow diagram of a separation method of scheelite-tin bulk concentrate provided in embodiment 1 of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
Certain scheelite-stannum bulk concentrates contain WO340.71 percent and Sn 14.13 percent. The flotation process provided by the embodiment adopts a one-roughing, two-scavenging and four-fine flow, wherein middlings obtained by first concentration and first scavenging are returned to roughing, middlings obtained by second, third and fourth concentration are sequentially returned to the previous concentration operation, and middlings obtained by second scavenging are returned to first scavenging operation.
As shown in fig. 1, flotation was performed according to the following steps:
(1) adjusting the scheelite and tin bulk concentrate to 42% ore pulp by using water, and performing cassiterite flotation under the normal temperature condition: sequentially adding 1000g/t of sodium carbonate, 700g/t of lead nitrate and 800g/t of collecting agent, and performing primary roughing to obtain foam product tin rough concentrate and tailings, wherein the collecting agent is the combination of salicylhydroxamic acid, naphthaloxic acid and pine oil according to the mass ratio of 14:7: 1;
(2) performing scavenging twice on the tailings obtained after the roughing in the step (1), wherein the adding amount of the collecting agent in the scavenging process is 60g/t and 30g/t respectively, and returning middlings obtained after scavenging to the previous operation in sequence for sorting; and the tailings of the second scavenging are the scheelite concentrate product.
(3) Adding an inhibitor into the tin rough concentrate obtained in the step (1), wherein the inhibitor is a combination of sodium fluosilicate and sodium hexametaphosphate according to a mass ratio of 3:1, carrying out concentration operation for 4 times, wherein 40g/t of the inhibitor is added in the first concentration, 15g/t of the inhibitor is added in the second concentration, 8g/t of the inhibitor is added in the third concentration, 3g/t of the gangue inhibitor is added in the fourth concentration, and obtaining a tin concentrate product after the concentration is finished.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO356.93 percent and the recovery rate is 98.59 percent; the tin concentrate contained 43.51% of Sn and the recovery rate was 90.87%.
Example 2
Certain scheelite-stannum bulk concentrates contain WO341.97 percent of Sn, 8.34 percent of Sn, and a flotation process adopts a one-roughing, two-scavenging and four-fine flow, wherein middlings obtained by the first concentration and the first scavenging return to roughing, middlings obtained by the second, third and fourth concentrations return to the previous concentration operation in sequence, and middlings obtained by the second scavenging return to the first scavenging operation.
The flotation is carried out according to the following steps:
(1) adjusting the scheelite and tin bulk concentrate to 35% ore pulp by using water, and performing cassiterite flotation under the normal temperature condition: sequentially adding 1500g/t of sodium carbonate, 500g/t of lead nitrate and 500g/t of collecting agent, and performing primary roughing to obtain foam product tin rough concentrate and tailings, wherein the collecting agent is the combination of salicylhydroxamic acid, naphthaloxic acid and pine oil according to the mass ratio of 16:9: 1;
(2) performing scavenging twice on the tailings obtained after the roughing in the step (1), wherein the adding amount of the collecting agent in the scavenging process is 50g/t and 20g/t respectively, and returning middlings obtained after scavenging to the previous operation in sequence for sorting; and the tailings of the second scavenging are the scheelite concentrate product.
(3) Adding an inhibitor into the tin rough concentrate obtained in the step (1), wherein the inhibitor is a combination of sodium fluosilicate and sodium hexametaphosphate according to a mass ratio of 2:1, carrying out concentration operation for 4 times, wherein the first concentration is 35g/t of the inhibitor, the second concentration is 15g/t of the inhibitor, the third concentration is 8g/t of the inhibitor, the fourth concentration is 2g/t of the gangue inhibitor, and obtaining a tin concentrate product after the concentration is finished.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO351.03 percent and the recovery rate is 99.10 percent; the tin concentrate contained Sn 38.64%, and the recovery rate was 85.73%.
Example 3
Certain scheelite cassiterite concentrates containing WO344.03 percent and 11.70 percent of Sn, and the flotation process adopts a one-coarse-two-scavenging six-fine flow, wherein middlings in the first concentration and scavenging are returnedAnd (4) performing rough concentration, returning middlings obtained by second, third, fourth, fifth and sixth times of fine concentration to the previous fine concentration operation, and returning middlings subjected to second scavenging to first scavenging operation.
The flotation is carried out according to the following steps:
(1) adjusting the scheelite and tin bulk concentrate to 40% ore pulp by using water, and performing cassiterite flotation under the normal temperature condition: sequentially adding 1500g/t of sodium carbonate, 600g/t of lead nitrate and 600g/t of collecting agent, and performing primary roughing to obtain foam product tin rough concentrate and tailings, wherein the collecting agent is the combination of salicylhydroxamic acid, naphthaloxic acid and pine oil according to the mass ratio of 14:8: 1;
(2) performing scavenging twice on the tailings obtained after the roughing in the step (1), wherein the adding amount of the collecting agent in the scavenging process is 60g/t and 20g/t respectively, and returning middlings obtained after scavenging to the previous operation in sequence for sorting; and the tailings of the second scavenging are the scheelite concentrate product.
(3) Adding an inhibitor into the tin rough concentrate obtained in the step (1), wherein the inhibitor is a combination of sodium fluosilicate and sodium hexametaphosphate according to a mass ratio of 4:1, carrying out concentration operation for 6 times, wherein 25g/t of the inhibitor is added in the first concentration, 15g/t of the inhibitor is added in the second concentration, 10g/t of the inhibitor is added in the third concentration, 8g/t of the gangue inhibitor is added in the fourth concentration, 5g/t of the gangue inhibitor is added in the fifth concentration, 3g/t of the gangue inhibitor is added in the sixth concentration, and obtaining a tin concentrate product after the concentration is finished.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO357.68 percent and the recovery rate is 98.91 percent; the tin concentrate contained 42.42% Sn and the recovery rate was 88.84%.
Example 4
Certain scheelite-stannum bulk concentrates contain WO346.53 percent of Sn and 5.85 percent of Sn, wherein the flotation process adopts a one-roughing, two-scavenging and two-refining flow, middlings obtained in the first concentration and the first scavenging are returned to roughing, middlings obtained in the second concentration are sequentially returned to the previous concentration operation, and middlings obtained in the second scavenging are returned to the first scavenging operation.
The flotation is carried out according to the following steps:
(1) adjusting the scheelite and tin bulk concentrate to ore pulp with the mass concentration of 30% by using water, and performing cassiterite flotation under the normal temperature condition: sequentially adding 500g/t of sodium carbonate, 400g/t of lead nitrate and 400g/t of collecting agent, and performing primary roughing to obtain foam product tin rough concentrate and tailings, wherein the collecting agent is the combination of salicylhydroxamic acid, naphthaloxic acid and pine oil according to the mass ratio of 12:6: 1;
(2) performing scavenging twice on the tailings obtained after the roughing in the step (1), wherein the adding amount of the collecting agent in the scavenging process is 40g/t and 20g/t respectively, and returning middlings obtained after scavenging to the previous operation in sequence for sorting; and the tailings of the second scavenging are the scheelite concentrate product.
(3) Adding an inhibitor into the tin rough concentrate obtained in the step (1), wherein the inhibitor is a combination of sodium fluosilicate and sodium hexametaphosphate according to a mass ratio of 1:1, carrying out concentration operation for 2 times, wherein 30g/t of the inhibitor is added in the first concentration step, 10g/t of the inhibitor is added in the second concentration step, and obtaining a tin concentrate product after the concentration is finished.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO354.71 percent and the recovery rate is 99.35 percent; the tin concentrate contains 32.11% of Sn, and the recovery rate is 85.12%.
Comparative example 1
In comparison to example 1, the procedure and conditions were exactly the same as in example 1 except that the collector was replaced with salicylhydroxamic acid. Namely, only salicylhydroxamic acid is used as a collector, and the total addition amount of the collector is unchanged.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO350.20 percent and the recovery rate is 99.21 percent; the tin concentrate contained 53.35% Sn and the recovery rate was 73.62%.
Comparative example 2
In comparison to example 1, the procedure and conditions were exactly the same as in example 1 except that the collector was replaced with a naphthalene hydroximic acid. Namely, only the naphthaloxic acid is used as the collecting agent, and the total addition amount of the collecting agent is unchanged.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO349.58 percent and the recovery rate is 99.25 percent; the tin concentrate contains Sn 52.43%, and the recovery rate is 68.67%.
Comparative example 3
The procedure and conditions were exactly the same as in example 1, except that the collector was replaced with pine oil, compared to example 1. Namely, only the pine oil is used as the collector, and the total addition amount of the collector is unchanged.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO346.51 percent and recovery rate 98.82 percent; the tin concentrate contained 32.22% Sn and the recovery rate was 30.74%.
Comparative example 4
Compared to example 1, the procedure and conditions were exactly the same as in example 1 except that the collector was replaced with salicylhydroxamic acid and napthalhydroxamic acid (2: 1 mass ratio). Namely, only salicylhydroxamic acid and naphthaloxic acid are selected as collecting agents, and the total addition amount of the collecting agents is unchanged.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO355.47 percent and the recovery rate is 98.74 percent; the Sn content in the tin concentrate is 40.81 percent, and the recovery rate is 79.38 percent.
Comparative example 5
Compared to example 1, the procedure and conditions were exactly the same as example 1 except that the collector was replaced with salicylhydroxamic acid and terpineol oil (14: 1 by mass). Namely, only salicylhydroxamic acid and terpineol oil are selected as collecting agents, and the total addition amount of the collecting agents is unchanged.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO353.07 percent and the recovery rate is 98.87 percent; the tin concentrate contained 42.37% of Sn and the recovery rate was 71.90%.
Comparative example 6
In comparison to example 1, the procedure and conditions were exactly the same as in example 1 except that the collector was replaced with naphthalene hydroximic acid and terpineol oil (7: 1 by mass). Namely, only the naphthalene hydroximic acid and the terpineol oil are selected as the collecting agents, and the total adding amount of the collecting agents is unchanged.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO356.51 percent and the recovery rate is 98.49 percent; the tin concentrate contained Sn 40.07%, and the recovery rate was 82.26%.
Comparative example 7
Compared with example 1, the procedure and conditions were exactly the same as in example 1 except that the inhibitor was replaced with sodium fluorosilicate. Namely, only sodium fluosilicate is selected as an inhibitor, and the total addition amount of the inhibitor in the selection process is not changed.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO357.32 percent and the recovery rate is 97.14 percent; the tin concentrate contained 38.25% Sn and the recovery rate was 83.89%.
Comparative example 8
In comparison with example 1, the procedure and conditions were exactly the same as in example 1 except that the inhibitor was replaced with sodium hexametaphosphate. Namely, only sodium hexametaphosphate is selected as the inhibitor, and the total addition amount of the inhibitor in the selection process is not changed.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO356.84 percent and the recovery rate is 97.04 percent; the tin concentrate contained 36.23% Sn and the recovery rate was 78.21%.
Comparative example 9
Compared with example 1, the steps and conditions were exactly the same as example 1 except that the inhibitor was replaced with conventional water glass. Namely, only the conventional water glass is selected as the concentration inhibitor, and the total addition amount of the inhibitor in the concentration process is unchanged.
Through detection, the finally obtained closed circuit test indexes are as follows: scheelite concentrate containing WO348.93 percent and the recovery rate is 99.16 percent; the tin concentrate contained 48.51% Sn and the recovery rate was 60.11%.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (17)
1. A separation method of scheelite and stannum bulk concentrate is characterized by comprising the following steps:
(1) preparing scheelite tin bulk concentrate into ore pulp, adding a regulator into the ore pulp, then adding collecting agents of salicylhydroxamic acid, naphthaloxic acid and pine oil for roughing operation, and obtaining tin rough concentrate and tailings after roughing; the mass ratio of the salicylic hydroxamic acid to the naphthalene hydroximic acid to the pinitol oil in the collecting agent is (12-16): (6-9): 1;
(2) adding inhibitor sodium fluosilicate and sodium hexametaphosphate into the tin rough concentrate obtained in the step (1) to carry out concentration operation, and obtaining a tin concentrate product after the concentration is finished; the mass ratio of the sodium fluosilicate to the sodium hexametaphosphate in the inhibitor is (1-4) to 1;
the adding amount of the collecting agent in the step (1) is 1000g/t and the adding amount of the inhibitor in the step (2) is 5-80g/t based on the mass of the white tungsten-tin bulk concentrate.
2. The method according to claim 1, characterized in that the mass concentration of the solid phase in the pulp in step (1) is 20-50%.
3. The method of claim 2, wherein the mass concentration of the solid phase in the pulp in step (1) is 30-45%.
4. The method of claim 1, wherein the modifying agents of step (1) are sodium carbonate and lead nitrate.
5. The method as claimed in claim 4, characterized in that the amount of sodium carbonate added is 500-2000g/t, based on the mass of the scheelite tin bulk concentrate.
6. The method as claimed in claim 4, wherein the lead nitrate is added in an amount of 200-800g/t based on the mass of the scheelite-tin bulk concentrate.
7. The method as claimed in claim 1, wherein the adding amount of the collecting agent in the step (1) is 200-800g/t based on the mass of the scheelite tin bulk concentrate.
8. The method as claimed in claim 1, wherein the collecting agent in the step (1) has a mass ratio of salicylic hydroxamic acid, naphthalene hydroximic acid and terpineol oil of 14:7: 1.
9. The method of claim 1, wherein the roughing operation is performed at least once in step (1).
10. The method according to claim 1, characterized in that the tailings obtained after the roughing in step (1) are subjected to at least one scavenging operation, and a scheelite concentrate product is obtained after scavenging.
11. The method of claim 10, wherein the total loading of collector during the scavenging process is 15-90g/t based on the mass of the scheelite tin bulk concentrate.
12. The method of claim 10, wherein the scavenged middlings are returned sequentially to the previous job.
13. The method of claim 1, wherein the inhibitor is added in the step (2) in an amount of 8-65g/t based on the mass of the scheelite tin bulk concentrate.
14. The method of claim 1, wherein the mass ratio of sodium fluorosilicate to sodium hexametaphosphate in the inhibitor of step (2) is 3: 1.
15. The method of claim 1, wherein at least one beneficiation process is performed in step (2).
16. The method of claim 15, wherein the middlings obtained from beneficiation are sequentially returned to a previous operation.
17. The method of claim 1, wherein the method comprises the steps of:
(1) adding water into the scheelite tin bulk concentrate to prepare ore pulp with the mass concentration of 20-50%, adding sodium carbonate and lead nitrate serving as adjusting agents into the ore pulp, then adding salicylhydroxamic acid, naphthohydroxamic acid and pine oil serving as collecting agents to perform at least one roughing operation, and obtaining tin rough concentrate and tailings after roughing; wherein the adding amount of sodium carbonate is 500-2000g/t, the adding amount of lead nitrate is 200-800g/t, the adding amount of the collecting agent is 100-1000g/t, and the mass ratio of the salicylic acid, the naphthoic hydroxamic acid and the pine alcohol oil in the collecting agent is (12-16): 6-9): 1;
(2) performing scavenging operation on the tailings obtained in the step (1) at least once to obtain a scheelite concentrate product after scavenging is completed; wherein the total adding amount of the collecting agent in the scavenging process is 15-90g/t according to the mass of the white tungsten tin bulk concentrate, and middlings obtained by scavenging are sequentially returned to the previous operation;
(3) adding inhibitor sodium fluosilicate and sodium hexametaphosphate into the tin rough concentrate obtained in the step (1) to carry out concentration operation for at least one time, and obtaining a tin concentrate product after the concentration is finished; wherein, the adding amount of the inhibitor is 5-80g/t, the mass ratio of the sodium fluosilicate to the sodium hexametaphosphate is (1-4) to 1, and the middlings obtained by concentration are returned to the previous operation in sequence.
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| CN110756337A (en) * | 2019-08-19 | 2020-02-07 | 湖南柿竹园有色金属有限责任公司 | Method for improving grade of tungsten concentrate |
| CN110614166A (en) * | 2019-08-23 | 2019-12-27 | 湖南柿竹园有色金属有限责任公司 | Flotation method for improving tungsten recovery rate |
| CN111495579B (en) * | 2020-04-28 | 2022-04-12 | 赣州有色冶金研究所有限公司 | Method for recovering tungsten and tin from fine mud and coarse sand |
| CN112264195B (en) * | 2020-11-18 | 2021-10-12 | 东北大学 | Cassiterite mineral flotation inhibitor and application thereof |
| CN112871456A (en) * | 2020-12-04 | 2021-06-01 | 崇义章源钨业股份有限公司 | Method for treating scheelite bulk concentrate |
| CN113106251B (en) * | 2021-03-10 | 2023-03-10 | 湖南柿竹园有色金属有限责任公司 | Chemical beneficiation method for producing tin middling from high-tin wolframite or wolframite and wolframite mixed ore |
| CN112958286B (en) * | 2021-04-08 | 2023-03-10 | 广东省科学院资源综合利用研究所 | Method for enriching tin in tungsten-tin flotation concentrate |
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