Composite collector, composite reagent and application thereof in scheelite flotation

Abstract

The present application belongs to the field of mineral flotation, and particularly relates to a composite collector, a composite reagent and application thereof in scheelite flotation. The composite collector comprises a collector of formula 1 and formula 2, wherein the combination of the structure of formula 1 and the structure of formula 2 is the key to synergistically improving the separation selectivity of scheelite (CaWO3) and calcium-silicon gangue in the ore, and the weight content of formula 1 is greater than or equal to 45%. By compounding with sodium oleate and oxidized paraffin soap, the scheelite flotation index is better, and the best weight ratio of sodium oleate and oxidized paraffin soap is less than or equal to 30%. The composite collector can selectively inhibit silicate gangue and calcium-containing gangue by the combined action with water glass, the grade and recovery of tungsten flotation concentrate are significantly improved, the loss of scheelite in tailings is low, and the flotation separation between scheelite and gangue minerals is effectively realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ore dressing, and relates to a flotation field of scheelite. BACKGROUND

[0002] Tungsten is an important strategic metal, which is widely used in the fields of national defense, aerospace, chemical industry and the like. The main source of metal tungsten is wolframite and scheelite (CaWO4). Since wolframite is easy to mine and separate, most of the research focus of ore dressing workers before 2010 is on the separation of wolframite. At present, the wolframite resources have been gradually exhausted, and the exploitation and utilization of (refractory) scheelite become increasingly important.

[0003] The specific gravity of wolframite is large, and a high grade can be obtained by using gravity separation or magnetic separation method. However, for scheelite, the embedded particle size is fine, it does not have strong (weak) magnetism, and the grade is low, so the method for purifying and enriching scheelite is usually flotation. Flotation is the most widely used mineral purification and enrichment technology in the field of ore dressing, which mainly separates and purifies scheelite and various gangue minerals by using the difference in physical and chemical properties.

[0004] In skarn type tungsten deposits, scheelite is often associated with other calcium-containing minerals such as calcite, fluorite and silicate minerals such as garnet, quartz and the like. Since the content of silicate minerals such as garnet and quartz is usually more than 50% in the deposit, a large amount of sodium silicate (more than 3.0 kg / t) needs to be added to inhibit them in the roughing stage.

[0005] For other calcium-containing minerals such as fluorite and calcite, since the mineral composition of scheelite and them is similar, they have similar Ca active sites; and the surface of calcium-containing minerals will dissolve, causing the physical and chemical properties of scheelite, calcite and fluorite surfaces to change, even the flotation behavior to change, that is, the different mineral surfaces have similar physical and chemical properties and floatability, which ultimately affects the selective action of the collector.

[0006] Therefore, in order to further inhibit the flotation and enrichment of calcium-containing gangue minerals, it is necessary to continue adding the depressant sodium silicate to the ore pulp solution, which causes the dosage of sodium silicate in the roughing stage of scheelite to be usually more than 4.0 kg / t. A large amount of sodium silicate will affect the fluidity of the ore pulp, causing pipe blockage and the like.

[0007] At present, the flotation separation of scheelite and calcium-containing minerals such as calcite and fluorite is the most widely studied, especially the research on high-selectivity scheelite collectors. However, in these studies, only the high-efficiency separation between the collector and the calcium-containing minerals is considered, and the effect of the collector on silicate minerals is not considered. The presence of a large amount of silicate minerals makes it necessary to add the depressant sodium silicate in the flotation process, so the dosage of sodium silicate in the roughing stage of scheelite is still large.

[0008] Therefore, there is a need in the art for a collector system with strong collecting ability and selectivity for scheelite, and weak collecting ability for silicate minerals and calcium-containing gangue minerals, so as to reduce the amount of depressant water glass used in the roughing stage and realize efficient flotation recovery of scheelite. SUMMARY

[0009] To overcome the problem of unsatisfactory separation selectivity of scheelite and calcium-silicate gangue, the first object of the present application is to provide a composite collector for scheelite flotation, aiming to improve the separation selectivity of scheelite and calcium-silicate gangue.

[0010] The second object of the present application is to provide a flotation reagent comprising the composite collector.

[0011] The third object of the present application is a method for re-concentration of scheelite using the composite collector and the flotation reagent.

[0012] A composite collector comprising a collector of formula 1 and a collector of formula 2:

[0013]

[0014] In formula 1, one of the substituents R1 and R2 is -SO3M, and the remaining substituents are H;

[0015] M is H, Na, K or NH4;

[0016] n is an integer from 4 to 10;

[0017] In the composite collector, the weight content of formula 1 is greater than or equal to 45%.

[0018] The present application shows that the intramolecular synergy of the special group structure of formula 1 and formula 2, and the intermolecular synergy of formula 1 and formula 2, can significantly improve the collecting ability of the collector for scheelite, and can also avoid the flotation of calcium-silicate gangue and improve the separation selectivity of scheelite and gangue, especially calcium-silicate gangue.

[0019] In the present application, the combination of formula 1 and formula 2 structures is the key to improving the separation selectivity of scheelite (CaWO3) and gangue, especially calcium-silicate gangue, in ores.

[0020] As a preferred embodiment, the collector of formula 1 is at least one compound having the structural formula of formula 1-A or formula 1-B;

[0021]

[0022] As a preferred embodiment, in the collector of formula 2, n is an integer from 7 to 9.

[0023] In the present invention, further controlling the ratio of the components in the composite collector is helpful to further improve the synergistic effect of the components and further improve its selectivity in the separation of scheelite-calcium-silicon gangue.

[0024] Preferably, in the composite collector, the weight content of Formula 1 is 50-65%.

[0025] Preferably, the composite collector further comprises an auxiliary collector, wherein the auxiliary collector comprises at least one of oleic acid and its salts, oxidized paraffin and its salts;

[0026] Preferably, the auxiliary collector includes oleic acid and its salts and oxidized paraffin and its salts. In the present invention, the oleic acid salt is such as sodium oleate. The oxidized paraffin salt is such as sodium oxidized paraffin.

[0027] The present invention has found that, in the synergy of Formula 1 and Formula 2, further use of an auxiliary collector, especially a composite auxiliary collector, can reduce the dosage of the reagent while obtaining a better scheelite capture selectivity, which helps to further improve the separation selectivity of scheelite and calcium-silicon gangue.

[0028] Preferably, in the auxiliary collector, the weight ratio of oleic acid and its salts to oxidized paraffin and its salts is 0.5 to 2:1.

[0029] Preferably, in the composite collector, the content of the auxiliary collector is less than or equal to 30 wt.%, preferably 10 to 25 wt.%.

[0030] The present invention also provides a flotation reagent comprising the composite collector of the present invention.

[0031] The composite pharmaceutical composition of the present invention further comprises an inhibitor;

[0032] Preferably, the inhibitor may be a gangue inhibitor known in the industry, such as water glass.

[0033] Preferably, a pH regulator is also allowed to be added to the flotation reagent.

[0034] In the present invention, based on the combination of the composite collector, the flotation effect of scheelite can be effectively improved, and the dosage of the inhibitor can also be effectively reduced.

[0035] The present invention also provides a flotation method for scheelite, wherein the ore to be selected containing scheelite and a flotation agent are mixed and flotated to obtain scheelite concentrate; the flotation agent contains the composite collector of the present invention;

[0036] Preferably, the flotation agent is the flotation agent described in the present invention.

[0037] Preferably, the mineral to be selected further comprises gangue minerals, and the gangue minerals comprise at least one of calcium-containing gangue and silicon-containing gangue. In the present application, for the gangue containing both silicon and calcium, the desired separation selectivity can still be obtained based on the composite reagent.

[0038] Preferably, the amount of the composite collector used in the flotation stage is 150 g / t or more, and can be further 150-1000 g / t, further 300-900 g / t, and further 400-600 g / t, considering the effect and cost.

[0039] The amount of the depressant used is 1000-3500 g / t, further 1500-3000 g / t, and further 2000-2800 g / t.

[0040] Preferably, the pH in the flotation stage is 9-11. Studies have shown that at this pH, the synergistic effect of the components can be effectively exerted, and the flotation effect and selectivity of scheelite can be enhanced.

[0041] The flotation temperature is, for example, -5-35℃, and can be further room temperature, for example, 20-30℃.

[0042] In the present application, in addition to the use of the innovative composite collector, other flotation processes and operations can be known.

[0043] The technical scheme provided by the present application has the following beneficial effects:

[0044] 1. The present application provides a composite collector of formula 1 and formula 2, which can synergistically improve the collection selectivity of scheelite based on the combination of formula 1 and formula 2.

[0045] 2. On the basis of the synergy of formula 1 and formula 2, further combined with auxiliary collectors, especially composite auxiliary collectors, the collection selectivity of scheelite can be further synergistically improved.

[0046] 3. The composite collector provided by the present application is used for scheelite flotation, which has a relatively loose requirement for the flotation pH and is not sensitive to the temperature of the flotation slurry, and can be used in cold area concentrators.

[0047] 4. The composite collector provided by the present application has the advantages of good flotation effect, strong selectivity, no pollution, etc.

[0048] 5. The composite collector provided by the present application has weak silicate mineral collection ability, which greatly reduces the amount of the depressant water glass (about 1-3 kg / t) used in the roughing stage of scheelite. BRIEF DESCRIPTION OF DRAWINGS

[0049] Figure 1A roughing test flow chart of the present application; DETAILED DESCRIPTION

[0050] For example, a step of scheelite mineral flotation separation of the present application is as follows:

[0051] S1, grinding the scheelite ore to about 60% to 90% of -200 mesh;

[0052] S2, adding sodium carbonate to adjust the pH of the ore pulp, and controlling the pH of the ore pulp to be 9 to 11;

[0053] S3, adding water glass, and stirring and conditioning the pulp for 1 to 2 minutes, and the amount of water glass is 1000 to 3000 kg / t;

[0054] S4, adding a composite collector, and adding the composite collector into the ore pulp for flotation to collect scheelite, and the flotation time is 5 to 10 minutes.

[0055] In the present application, the collectors can all be selected as M=H collectors, which can be partially or completely converted into salt types (M=Na, K or NH4) through the action of pH adjusters in the flotation stage

[0056] Example 1

[0057] The flotation process of one-stage roughing is used to verify the flotation effect of the composite collector, Figure 1 A roughing test flow chart of scheelite flotation. The specific implementation method is as follows:

[0058] 1. A scheelite ore from a certain place in Hunan is selected for testing at room temperature. The main useful mineral in the ore is scheelite, and the WO3 content is about 0.31%. The main gangue minerals are calcite, garnet and quartz, etc., among which the calcite content is about 8.79%, and the garnet and quartz content is more than 60%. The ore is first crushed to -2mm by a crusher and a roller mill, and then divided and bagged, with 500g of ore per bag;

[0059] 2. Through grinding operation, 500g of scheelite ore and 250g of tap water are loaded into a laboratory small mill to grind the ore to -200 mesh (i.e. -74μm) of 75%;

[0060] 3. In the one-stage roughing process, first, 1200g / t of pH adjuster sodium carbonate is added (to control the pH of the ore pulp to be 9.50), and the conditioning time is 2 minutes; then 2.5kg / t of depressant water glass is added, and the conditioning time is 2 minutes; then 500g / t of collector with different composite forms is added, and the conditioning time is 3 minutes; finally, the flotation is scraped, the flotation time is 6 minutes, and the flotation temperature is 25 to 30℃;

[0061] In the case of Formula 1-A and Formula 1-B, M is Na; Formula 2 refers to the compound of Formula 2 with n = 5, and M therein also refers to Na. In addition, M in the starting Formula 1 and Formula 2 can also be H, which can be partially or completely converted into salt form in the flotation stage according to the pH in the ore slurry.

[0062] 4. The flotation products, i.e. the concentrate and the tailings, were weighed, and then the flotation products were sub-sampled for assay. The grade of WO3 in the concentrate and the tailings was measured, and the recovery, yield and grade of the flotation concentrate were calculated. The flotation results of the relevant groups are shown in Table 1.

[0063] Table 1

[0064]

[0065]

[0066] Note: Comparative Formula a: Comparative Formula b: the compound of Formula 2 with n = 2.

[0067] The total amount of collector used in each group of cases and other conditions were the same.

[0068] From the comparison of the data of Groups A, B and C, it can be seen that when Formula 1 and Formula 2 are mixed in a certain proportion, a flotation concentrate with higher grade and recovery can be obtained.

[0069] From the comparison of Comparative Groups 1 and 2, it can be seen that when the collectors Formula 1 and Formula 2 act alone, the effect is poor, and the grade and recovery of the flotation concentrate are both low, and the content of calcite and silicate in the concentrate is higher.

[0070] From the comparison of Comparative Groups 3 and 4, it can be seen that the control of the intramolecular structure of Formula 1 and Formula 2 is the key to realizing the intermolecular synergy of the two.

[0071] The main difference between Comparative Group 5 and Groups A, B and C is that the relative weight content of Formula 1 and Formula 2 is different. The weight content of Formula 1 needs to be ≥ 45%, and preferably 50-65%.

[0072] Example 2 - addition of auxiliary collector:

[0073] Compared with Example 1, the only difference is that the complex collector (the ratio is shown in Table 2) is changed, which is respectively:

[0074] Group A: Formula 1 + Formula 2 + sodium oleate;

[0075] Group B: Formula 1 + Formula 2 + oxidized paraffin soap;

[0076] Group C: Formula 1 + Formula 2 + sodium oleate + oxidized paraffin soap;

[0077] Group D: Formula 1 + Formula 2 + sodium oleate + oxidized paraffin soap (change the proportion of the preferred composite collector);

[0078] Group E: Formula 1 + Formula 2 + sodium oleate + oxidized paraffin soap (change the proportion of the preferred composite collector);

[0079] Group F: Formula 1 + Formula 2 + sodium oleate + oxidized paraffin soap (change the proportion of the preferred composite collector).

[0080] Table 2

[0081]

[0082]

[0083] From the comparison of Comparative Example 1 and Example 2, it can be seen that when the composition of the composite collector is changed, i.e. sodium oleate and oxidized paraffin soap are added, the grade and recovery of the flotation concentrate are both significantly improved, and the grade and recovery of the concentrate are increased by more than 0.5% and 3%, respectively;

[0084] From the comparison of Groups A, B and C of Comparative Example 2, it can be seen that when sodium oleate and oxidized paraffin soap are mixed with Formula 1 and Formula 2 in a certain proportion, the synergistic effect of the collector is best, and the flotation recovery and grade are increased by more than 7% and 0.8%, respectively;

[0085] From the comparison of Groups C to F of Comparative Example 2, it can be seen that when the content of the auxiliary collector is 10-25%, the synergistic effect is best, and the flotation index is best.

[0086] Example 3

[0087] The most important difference between Example 3 and Example 2 is that the conditions of the flotation stage are adjusted, and the weight content of the composite collector is consistent with that of Group E of Example 2, and the relevant test results are shown in Table 3.

[0088] Table 3

[0089]

[0090]

[0091] The above examples are only used to illustrate the technical solutions of the present application and not to limit it, and it should be noted that the above preferred embodiments should not be regarded as a limitation of the present application, and the protection scope of the present application should be limited by the scope defined in the claims. For ordinary skilled persons in the art, several improvements and refinements can be made without departing from the spirit and scope of the present application, and these improvements and refinements should also be regarded as the protection scope of the present application.

Claims

1. A composite collector, characterized in that: Including the collector of formula 1 and the collector of formula 2: Formula 1 Formula 2 In formula 1, one of the substituents in R1 and R2 is -SO3M, and the remaining substituents are H; The M is H, Na, K or NH4; Said n is an integer of 4 to 10; Wherein, in the composite collector, the weight content of Formula 1 is greater than or equal to 45%.

2. The composite collector according to claim 1, wherein The collector of formula 1 is at least one compound having the structural formula of formula 1-A or formula 1-B; Formula 1-A Formula 1-B.

3. The composite collector according to claim 1, wherein In the collector of formula 2, n is an integer of 7 to 9.

4. The composite collector according to any one of claims 1 to 3, wherein In the composite collector, the weight content of Formula 1 is 50-65%.

5. The composite collector according to any one of claims 1 to 4, wherein The invention also comprises an auxiliary collector, which comprises at least one of oleic acid and its salt, oxidized paraffin and its salt.

6. The composite collector according to claim 5, wherein The auxiliary collectors include oleic acid and its salts and oxidized paraffin and its salts.

7. The composite collector according to claim 6, wherein In the auxiliary collector, the weight ratio of oleic acid and its salts to oxidized paraffin and its salts is 0.5-2:

1.

8. The composite collector according to claim 5, wherein The content of the auxiliary collector is less than or equal to 30 wt.%.

9. The composite collector according to claim 8, wherein The content of the auxiliary collector is 10~25wt.%.

10. A flotation reagent, characterized in that: Comprising the composite collector and inhibitor according to any one of claims 1 to 9.

11. The flotation reagent according to claim 10, characterized in that The inhibitor is water glass.

12. The flotation reagent according to claim 10, characterized in that A pH regulator is also added to the flotation reagent.

13. A flotation method for scheelite, comprising mixing a mineral to be selected including scheelite with a flotation agent and performing flotation to obtain scheelite concentrate; characterized in that: The flotation reagent comprises the composite collector according to any one of claims 1 to 9.

14. The flotation method of scheelite according to claim 13, wherein: The flotation agent is the flotation agent according to any one of claims 10 to 12.

15. The flotation method of scheelite according to claim 14, characterized in that: The minerals to be selected also include gangue minerals, and the gangue minerals include at least one of calcium-containing gangue and silicon-containing gangue.

16. The flotation method according to claim 14, wherein: During the flotation stage, the dosage of the composite collector is more than 150g / t.

17. The flotation method according to claim 16, wherein: During the flotation stage, the dosage of composite collector is 150~1000 g / t.

18. The flotation method according to claim 16, wherein: During the flotation stage, the dosage of composite collector is 300~900 g / t.

19. The flotation method according to claim 14, wherein: The dosage of inhibitor is 1000~3500 g / t.

20. The flotation method according to claim 14, wherein: The pH value in the flotation stage is 9~11.

Images