Composite collecting agent, composite reagent and application of composite collecting agent and composite reagent in scheelite flotation

Abstract

The invention belongs to the field of mineral flotation, and particularly relates to a composite collecting agent, a composite reagent and application of the composite collecting agent and the composite reagent in scheelite flotation. The composite collecting agent comprises a collecting agent in the formula 1 # imgabs0 # and a collecting agent in the formula 2 # imgabs1 #, the combination of the structure in the formula 1 and the structure in the formula 2 is the key for synergistically improving the separation selectivity of scheelite (CaWO3) and calcium-silicon gangue in ore, and the weight content of the formula 1 is larger than or equal to 45%. By compounding the sodium oleate and the oxidized paraffin soap, the scheelite flotation index is better, and the optimal weight ratio of the sodium oleate to the oxidized paraffin soap needs to be smaller than or equal to 30%. Through the combined action of the composite collecting agent and water glass, silicate gangue and calcium-containing gangue can be selectively inhibited, the tungsten flotation concentrate grade and recovery rate are both remarkably improved, the scheelite loss in tailings is low, and flotation separation between scheelite and gangue minerals is effectively achieved.

Description

Technical field:

[0001] The invention relates to the technical field of ore dressing, in particular to the field of flotation of scheelite. Background technology:

[0002] Tungsten is an important strategic metal, widely used in defense, aerospace, chemical industry and other fields. The main sources of metallic tungsten are wolframite and scheelite (CaWO4). Since wolframite is easy to mine and separate, most mineral processing workers before 2010 focused on the separation of wolframite. At present, the resources of wolframite have been gradually mined out, and the mining and utilization of (difficult to select) scheelite has become increasingly important.

[0003] Wolframite has a high specific gravity, and high grade can usually be obtained by gravity separation or magnetic separation. However, for scheelite, its embedded particle size is fine, it does not have strong (weak) magnetism, and its grade is low, so the method for scheelite ore dressing, purification and enrichment is usually flotation. Flotation is the most widely used mineral purification and enrichment technology in the field of mineral processing, which mainly uses the differences in physical and chemical properties between scheelite and various gangue minerals for separation and purification.

[0004] In skarn-type tungsten deposits, scheelite often coexists with other calcium-containing minerals such as calcite, fluorite, and silicate minerals such as garnet and quartz. Since silicate minerals such as garnet and quartz are present in high concentrations in the deposit, usually exceeding 50%, a large amount of water glass (over 3.0 kg / t) is often added in the roughing stage to suppress them.

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

[0006] Therefore, in order to further inhibit the flotation enrichment of calcium-containing gangue minerals, it is necessary to further add inhibitor water glass to the pulp solution, which results in the amount of water glass used in the roughing stage of scheelite usually exceeding 4.0kg / t. A large amount of water glass will affect the fluidity of the pulp and cause pipeline blockage and other phenomena.

[0007] At present, the most extensive research on the flotation separation of scheelite and calcium-containing minerals calcite and fluorite is the research on highly selective scheelite collectors. However, in these studies, only the efficient separation between collectors and calcium-containing minerals is considered, and the effect of collectors on silicate minerals is not considered. The presence of a large number of silicate minerals requires the addition of inhibitor water glass in the flotation process, so the amount of water glass used in the roughing stage of scheelite is still very large.

[0008] Therefore, the art needs a collector system with strong capture ability and selectivity for scheelite and weak capture ability for silicate minerals and calcium-containing gangue minerals to reduce the amount of water glass inhibitor used in the roughing stage and achieve efficient flotation recovery of scheelite. Summary of the invention:

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

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

[0011] The third purpose of the present invention is to provide a method for reselecting scheelite using the composite collector and flotation reagent.

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

[0013]

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

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

[0016] The n is an integer of 4 to 10;

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

[0018] The innovative research of the present invention shows that the intramolecular synergy of the special group structures of Formula 1 and Formula 2, as well as the intermolecular combined synergy of Formula 1 and Formula 2, can significantly improve the collector's ability to collect scheelite. In addition, it can also avoid the flotation of calcium-silicon gangue and improve the separation selectivity of scheelite and gangue, especially calcium-silicon gangue.

[0019] In the present invention, 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 gangue in the ore, especially calcium-silicon gangue.

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

[0021]

[0022] Preferably, in the collector of formula 2, n is an integer of 7 to 9.

[0023] In the present invention, further controlling the proportion 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 oxidized paraffin sodium salt.

[0027] The present invention has found that, in the synergy of Formula 1 and Formula 2, further using an auxiliary collector, especially a composite auxiliary collector, can reduce the dosage of reagents while obtaining better scheelite collection 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 10-25 wt.%.

[0030] The present invention also provides a flotation reagent, which comprises 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 adjuster 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 in addition, the dosage of the inhibitor can be effectively reduced.

[0035] The present invention also provides a flotation method for scheelite, wherein the ore to be selected including scheelite and a flotation agent are mixed for flotation to obtain scheelite concentrate; the flotation agent comprises 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 include at least one of calcium-containing gangue and silicon-containing gangue. In the present invention, for gangue containing both silicon and calcium, the composite reagent of the present invention can still obtain an ideal separation selectivity.

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

[0039] The usage of the inhibitor is 1000 to 3500 g / t, further can be 1500 to 3000 g / t, further can be 2000 to 2800 g / t.

[0040] Preferably, the pH value in the flotation stage is 9 to 11. Studies have shown that at this pH value, the synergy 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 to 35°C, and may be room temperature, for example, 20 to 30°C.

[0042] In the present invention, except for using the innovative composite collector of the present invention, other flotation processes and operations may be well known.

[0043] The technical solution provided by the present invention has the following beneficial effects:

[0044] 1. The present invention provides a composite collector of Formula 1 and Formula 2, which can synergistically improve the capture 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 using auxiliary collectors, especially composite auxiliary collectors, can further synergistically improve the collection selectivity of scheelite.

[0046] 3. The composite collector provided by the present invention is used for the flotation of scheelite, which has loose requirements on the pH value of flotation and is insensitive to the temperature of the flotation pulp, and can be used in ore dressing plants in cold areas;

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

[0048] 5. The composite collector provided by the present invention has a weak ability to capture silicate minerals, which greatly reduces the amount of water glass used as an inhibitor in the roughing stage of scheelite (about 1 to 3 kg / t). Description of the drawings:

[0049] Figure 1It is a rough selection test flow chart of the present invention; Specific implementation method:

[0050] For example, the steps of flotation separation of scheelite ore of the present invention are:

[0051] S1. Grind the scheelite ore to -200 mesh, accounting for about 60% to 90%;

[0052] S2. Add sodium carbonate to adjust the pH of the slurry to control the pH of the slurry to 9-11;

[0053] S3, add water glass, and stir and slurry for 1 to 2 minutes, the amount of water glass is 1000 to 3000 kg / t;

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

[0055] In the present invention, the collectors described can all be selected from collectors with M=H, which can be partially or completely converted into salt forms (M=Na, K or NH4) through the action of a pH regulator during the flotation stage.

[0056] Embodiment 1:

[0057] A roughing flotation process was used to verify the flotation effect of the composite collector. Figure 1 This is a roughing test flow chart for scheelite flotation. The specific implementation method is:

[0058] 1. The original scheelite ore from Hunan was selected for testing at room temperature. The main useful mineral in the ore is scheelite, and its WO3 content is about 0.31%. The main gangue minerals are calcite, garnet and quartz, among which the calcite content is about 8.79%, and the garnet and quartz content exceeds 60%. The ore is first crushed to -2mm using a crusher and a roller mill, and then shrunk and bagged, with each bag containing 500g of ore;

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

[0060] 3. In a roughing process, first add 1200g / t of sodium carbonate as pH adjuster (to adjust the pH of the pulp to 9.50), and the pulping time is 2 minutes; then add 2.5kg / t of water glass as inhibitor, and the pulping time is 2 minutes; then add 500g / t of collectors in different composite forms, and the pulping time is 3 minutes; finally, flotation scraping is carried out, the flotation time is 6 minutes, and the flotation temperature is 25-30℃;

[0061] In Formula 1-A and Formula 1-B of this case, 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 initial Formula 1 and Formula 2 can also be H, which can be partially or completely converted into a salt form according to the pH in the pulp during the flotation stage.

[0062] 4. Weigh the flotation products, i.e., concentrate and tailings, and then reduce and sample the flotation products for testing. Measure the grade of WO3 in the concentrate and tailings, and calculate the recovery rate, yield and grade of the flotation concentrate. The flotation results of the relevant groups are shown in Table 1 below.

[0063] Table 1

[0064]

[0065]

[0066] Note: Comparison formula a: Comparative formula b: the compound of formula 2 wherein n=2.

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

[0068] By comparing 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 high grade and recovery rate can be obtained;

[0069] Combining the comparison groups 1 and 2, it can be seen that the collectors 1 and 2 have poor effects when acting alone, and the flotation concentrate grade and recovery rate are both lower, and the calcite and silicate contents in the concentrate are higher;

[0070] Combining the comparison 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 achieving the intermolecular synergy between the two.

[0071] The main difference between the comparison group 5 and the three groups A, B and C is that the relative weight contents of Formula 1 and Formula 2 are different. The weight content of Formula 1 must be ≥45%, preferably 50-65%.

[0072] Example 2 - Addition of auxiliary collector:

[0073] Compared with Example 1, the only difference is that the composite collector is changed (proportion see Table 2), which are:

[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 (changing the ratio of the preferred composite collector);

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

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

[0080] Table 2

[0081]

[0082]

[0083] By comparing Example 1 and Example 2, it can be seen that when the composition of the composite collector is changed, that is, sodium oleate and oxidized paraffin soap are added, the grade and recovery rate of the flotation concentrate are significantly improved, and the grade and recovery rate of the concentrate are increased by 0.5% and 3% or more respectively;

[0084] By comparing groups A, B and C of 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 optimal, and the flotation recovery rate and grade are increased by more than 7% and 0.8% respectively;

[0085] By comparing groups C to F of Example 2, it can be seen that when the content of the auxiliary collector is between 10 and 25%, the synergistic effect is optimal and the flotation index is the best.

[0086] Example 3

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

[0088] Table 3

[0089]

[0090]

[0091] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. It should be noted that the above preferred embodiments should not be regarded as limiting the present invention, and the protection scope of the present invention should be based on the scope defined by the claims. For those skilled in the art, several improvements and modifications can be made without departing from the spirit and scope of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A composite collector, characterized in that: Including the collector of formula 1 and the collector of 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; The 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, characterized in that The collector of formula 1 is at least one compound having the structural formula of formula 1-A or formula 1-B; 3. The composite collector according to claim 1, characterized in that 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, characterized in that: In the composite collector, the weight content of the formula 1 is 50-65%.

5. The composite collector according to any one of claims 1 to 4, characterized in that: The invention also comprises an auxiliary collector, wherein the auxiliary collector comprises at least one of oleic acid and its salt, oxidized paraffin and its salt; Preferably, the auxiliary collector comprises oleic acid and its salts and oxidized paraffin and its salts; 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.

6. The composite collector according to claim 5, characterized in that The content of the auxiliary collector is less than or equal to 30 wt.%, preferably 10 to 25 wt.%.

7. A flotation reagent, characterized in that: The invention comprises the composite collector and the inhibitor as described in any one of claims 1 to 6.

8. The flotation reagent according to claim 7, characterized in that: The inhibitor is water glass; Preferably, a pH adjuster is also allowed to be added to the flotation reagent.

9. A method for flotation of scheelite, comprising mixing a mineral to be selected including scheelite and a flotation agent for flotation to obtain scheelite concentrate; characterized in that: The flotation reagent comprises the composite collector according to any one of claims 1 to 6; Preferably, the flotation agent is the flotation agent according to any one of claims 7 to 8; Preferably, the mineral to be selected further comprises gangue minerals, and the gangue minerals include at least one of calcium-containing gangue and silicon-containing gangue.

10. The flotation method according to claim 9, characterized in that: In the flotation stage, the dosage of the composite collector is 150 g / t or more, and can be further 150-1000 g / t, and further 300-900 g / t; Preferably, the dosage of the inhibitor is 1000 to 3500 g / t; Preferably, the pH of the flotation stage is 9-11.

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