Composite collecting agent, flotation reagent and method for selective flotation separation of barite and fluorite

Abstract

The invention belongs to the field of flotation, and particularly relates to a composite collecting agent, a flotation reagent and a method for barite and fluorite selective flotation separation, the composite collecting agent comprises a formula 1 component # imgabs0 # and a formula 2 component # imgabs1 # with the weight ratio of (1-3): 1, the research shows that the formula 1 component and the formula 2 component are creatively combined, and combined control of the proportion of the formula 1 component and the formula 2 component is matched, so that the flotation efficiency is improved, and the flotation efficiency is improved. In this way, synergy can be achieved accidentally, and the selective separation effect of barite and fluorite can be enhanced. The flotation collecting agent has the wide temperature range application advantage, and in addition, the ideal flotation effect can still be obtained under the condition that the flotation process and the reagent dosage are shortened.

Description

Technical Field

[0001] The present invention belongs to the field of flotation, and in particular relates to the field of barite-fluorite flotation separation. Background Art

[0002] Barite is one of the major barium-containing minerals in nature, with a chemical composition of BaSO₄. Barite reserves are vast worldwide, but development suffers from extensive and inefficient utilization, preventing its maximum economic value. Furthermore, barite often coexists with fluorite (CaF₂), which is also an important non-metallic strategic material. Therefore, selective separation of barite and fluorite using flotation methods is crucial for effectively realizing the value of these mineral resources.

[0003] Several methods for separating barite and fluorite using direct flotation or reverse flotation have been reported in the prior art. For example, Chinese patent publication CN110102412A discloses a method for producing high-purity fluorite powder and efficiently utilizing tailings barite. Specifically, the method uses oleic acid as a collector and acidified water glass, YZ-1, and YZ-4 in a two-coarse, two-sweep, seven-fine closed-circuit flotation process to produce a high-purity fluorite concentrate.

[0004] Chinese patent document CN109261369A discloses a barite inhibitor in fluorite flotation, specifically reporting a scheme of using a combination of dextrin, ferrous sulfate, and carboxymethyl cellulose as the barite inhibitor.

[0005] Chinese patent document with publication number CN103521344A discloses a method for separating and purifying low-grade fluorite-barite paragenetic ore. The specific reagents reported include starch, NAS, MDK, TF2-8, etc.

[0006] In summary, although there are some barite-fluorite flotation separation methods in the existing technology, flotation is difficult to adapt to the requirements of low-temperature flotation, and the selectivity of flotation needs to be further improved. Summary of the Invention

[0007] In order to solve the problem that barite and fluorite are difficult to separate in the existing process, the present invention provides a composite collector for selective flotation separation of barite and fluorite, which aims to selectively capture barite and realize selective flotation separation of barite and fluorite.

[0008] The second object of the present invention is to provide a flotation reagent comprising the composite collector.

[0009] The third object of the present invention is to provide a method for flotation separation of barite and fluorite using the composite collector and flotation agent.

[0010] A composite collector for selective flotation separation of barite and fluorite, comprising a component of formula 1 and a component of formula 2 in a weight ratio of 1 to 3:1;

[0011]

[0012] R1 is C6~C 15 alkyl, alkoxy-substituted alkyl, alkoxy, benzene ring, phenoxy or alkyl-substituted benzene ring; M is H, Na, K or NH4.

[0013] Research in this invention demonstrates that the innovative combination of Formula 1 and Formula 2, along with the coordinated control of their ratios, can unexpectedly achieve synergy, enhancing the selective separation of barite and fluorite. The flotation collector of this invention has the advantage of wide temperature range applicability and can achieve ideal flotation results while shortening the flotation process and reagent dosage.

[0014] In the present invention, the R1 can further be C8~C 12 wherein the alkyl group may be a straight chain or a branched chain alkyl group.

[0015] In the present invention, the joint control of Formula 1 and Formula 2 and the ratio thereof is the key to synergistically improving the flotation separation selectivity of barite and fluorite.

[0016] Preferably, in the composite collector, the weight ratio of Formula 1 to Formula 2 is preferably 1 to 2:1; most preferably 1 to 1.5:1.

[0017] The study found that under the optimal ratio, the sorting selectivity of barite and fluorite can be further enhanced, effectively achieving highly selective separation and recovery of barite and fluorite.

[0018] The present invention also provides a flotation agent for selective flotation separation of barite and fluorite, comprising a collector and an inhibitor, wherein the collector is the composite collector described in the present invention.

[0019] The inhibitor of the present invention may be a component known in the industry that can inhibit fluorite, for example, at least one of water glass, tannin extract, starch, and metal salt inhibitors.

[0020] In the present invention, the dosage of the composite collector and the inhibitor in the flotation reagent can be reasonably adjusted according to factors such as the grade of the mineral and the embedding method.

[0021] In the present invention, the flotation reagent may further contain components such as a foaming agent and a pH regulator that are permitted to be added in the flotation field.

[0022] The present invention also provides a method for selective flotation separation of barite and fluorite, wherein the mineral to be selected containing barite and fluorite and the flotation agent containing the composite collector of the present invention are mixed for roughing, thereby obtaining a roughing concentrate enriched in barite and a roughing tailing enriched in fluorite.

[0023] In the present invention, thanks to the innovative use of the composite collector, excellent barite and fluorite flotation selectivity can be obtained under low reagent, wide temperature range and short process.

[0024] In the present invention, the mineral to be separated is a low-grade, fine-grained fluorite-barite ore with a dissemination size of -0.037μm. The method of the present invention can be applied to the flotation separation of any fluorite and barite-containing mineral, especially for ultrafine dissemination of low-grade minerals, and can also achieve excellent separation results, achieving better separation value than existing technologies.

[0025] In the present invention, the flotation agent is the flotation agent described in the present invention.

[0026] In the present invention, the amount of the composite collector used in the roughing process is 50-500 g / t, preferably 150-450 g / t, more preferably 250-400 g / t, and even more preferably 280-320 g / t. Studies have shown that optimal collector amounts can achieve better separation selectivity.

[0027] The dosage of the inhibitor is 150 to 500 g / t, further 50 to 400 g / t, and more preferably 280 to 320 g / t.

[0028] In the present invention, the pH of the roughing process is 6 to 10, preferably 6 to 8. Studies have shown that better separation selectivity can be obtained under the preferred conditions.

[0029] In the present invention, the roughing temperature is 5 to 45° C., and can be further set to room temperature, for example, 15 to 30° C., for convenience of operation.

[0030] The present invention also includes a process of beneficiating the rougher concentrate; and / or a process of scavenging the rougher tailings.

[0031] Beneficial effects

[0032] 1. The present invention innovatively combines the components of Formula 1 and Formula 2, and coordinates the controlled ratio of the two, thereby unexpectedly achieving synergy and enhancing the selective separation of barite and fluorite. The flotation collector of the present invention has the advantages of a wide temperature range and a wide particle size range. In addition, it can also achieve ideal flotation results while shortening the flotation process and reagent dosage.

[0033] 2. The compound agent provided by the present invention has a simple agent system and is easy to operate, and can achieve efficient and selective capture of barite. Moreover, the compound agent provided by the present invention can achieve efficient separation of barite and fluorite while reducing the dosage of the agent through the synergy of the corresponding ingredients. The preparation process of the compound agent is green, environmentally friendly and low in cost, and is particularly suitable for industrial scale-up production. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is the flotation flow chart of Example 1.

[0035] Figure 2 This is a dosage-flotation result diagram of Example 1.

[0036] Figure 3 This is a flotation flow chart of Example 2-4.

[0037] Figure 4 This is the dosage-flotation result diagram of Example 2.

[0038] Figure 5 This is a pH-flotation result diagram of Example 3. DETAILED DESCRIPTION

[0039] The following embodiments of the present invention are described in further detail with reference to the accompanying drawings, examples and comparative examples. The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0040] In the present invention, the flotation operation method and steps may be those known in the industry, for example, including the following steps:

[0041] 1. Add the flotation reagent of the present invention in the order of deionized water, formula 2, and formula 1 into a mechanical stirrer and stir at room temperature (25°C) and normal pressure for 2 hours to obtain a uniformly mixed light yellow composite flotation reagent;

[0042] 2. Flotation is to mix the prepared composite flotation reagent with water at a ratio of 1:800-1500, put it into an ultrasonic device for ultrasonic dispersion for 10 minutes, and then add as needed to obtain a composite flotation reagent solution.

[0043] During the flotation process, the mixed minerals of barite and fluorite are first pulped, stirred for 3 minutes, and then the inhibitor is added. After stirring for 5 minutes, the required amount of the composite flotation agent solution of the present invention is added.

[0044] The present invention can adopt existing flotation equipment and known flotation methods to carry out flotation. For example, the rotation speed of the flotation agent rotor is controlled between 1600 and 1800 rpm.

[0045] The flotation feed particle size is controlled at -0.074 mm, with no lower limit, and the flotation system temperature is controlled at 5-45° C. The flotation system pH is controlled between pH 6 and 10.

[0046] In the following cases, Formula 1 is represented by Formula 1A, which is Formula 1 in which R1 is n-dodecyl and M is Na.

[0047] Example 1

[0048] Flotation reagent ingredients used:

[0049] The composite collector comprises formula 1A and formula 2 in a weight ratio of 1:1.

[0050] The total dosage of the composite collector of the present invention is 300g / t.

[0051] Inhibitor: starch 300g / t.

[0052] Flotation process see Figure 1 :

[0053] 160g of the actual barite-fluorite ore of different particle sizes shown in Table 1 was placed in a 500mL flotation cell. The actual ore had a BaSO4 grade of 35.16% and a CaF2 grade of 40.84%. An appropriate amount of water was added and the mixture was stirred and aerated for 3 minutes to form a pulp. An inhibitor was added and the mixture was stirred and aerated for 5 minutes. A composite collector was added and the mixture was stirred and aerated for 3 minutes. The concentrate that floated up with the foam was scraped 30 times per minute for 5 minutes. The concentrate and tailings were dried and weighed separately. The recovery rate was calculated as shown in Table 1. Figure 2 (The pH of the slurry during the flotation process is 7, the temperature is 25°C; the pH adjusters are NaOH aqueous solution and HCl aqueous solution)

[0054] Table 1

[0055]

[0056] From Table 1 and Figure 2 The results show the effect of the flotation reagent of the present invention on the grade and recovery of the useful components of barite and fluorite under different particle size ranges. When the particle size decreases from 0.074mm-0.037mm to -0.015mm, the barite recovery rate and fluorite grade increase, while the barite grade and fluorite recovery rate decrease, but the reduction is small. This shows that the flotation effect of the present invention on fine particles is significantly better than that of traditional fatty acid reagents, and it can efficiently and selectively capture fine-grained barite ore.

[0057] Example 2

[0058] According to the flotation process Figure 3 The flotation process is shown in the figure, where:

[0059] A composite collector comprises formula 1A and formula 2 in a weight ratio of 1:1.

[0060] The total dosage of the composite collector of the present invention is 300g / t.

[0061] Inhibitor: starch 300g / t.

[0062] Flotation process:

[0063] 160 g of actual fluorite ore associated with barite (same as in Example 1, ground to 0.037-0.015 mm) was placed in a 500 mL flotation tank, and appropriate amounts of deionized water at different temperatures were added to adjust the slurry temperature to the required temperature. The slurry was stirred for 3 minutes to form a slurry. An inhibitor was added and the mixture was stirred and aerated for 5 minutes. The composite collector described in Example 2 was added and stirred and aerated for 3 minutes. The concentrate floating together with the foam was scraped and scraped 30 times per minute for 5 minutes. The concentrate and tailings were dried and weighed respectively. The recovery rate was calculated as shown in Table 2. Figure 4 As shown. (The pH of the ore pulp during the flotation process is 7; the pH adjusters are NaOH aqueous solution and HCl aqueous solution)

[0064] Table 2

[0065]

[0066] From Table 2 and Figure 4 The effects of the flotation reagents of the present invention on the grade and recovery of the useful components of barite and fluorite at different pulp temperatures are shown. At temperatures between 5 and 25°C, the grade of barite and the recovery of fluorite gradually decrease, while the recovery of barite and the grade of fluorite gradually increase, but the magnitude of each increase is relatively small. At temperatures above 25°C, the grade and recovery of these two minerals do not change significantly. This demonstrates that the flotation performance of the present invention is significantly superior to that of traditional fatty acid collectors under low-temperature conditions, and that it has the advantage of a wide temperature range, making it suitable for use in low-temperature regions and improving resource utilization efficiency.

[0067] Example 3

[0068] according to Figure 3 The flotation process is used for flotation, wherein the composite collector of this case includes Formula 1A and Formula 2 in a weight ratio of 1:1.

[0069] The total dosage of the composite collector of the present invention is 300 g / t.

[0070] Inhibitor: starch 300g / t.

[0071] Flotation process:

[0072] 160 g of actual fluorite ore associated with barite (same as in Example 1, ground to 0.037-0.015 mm) was placed in a 500 mL flotation tank, an appropriate amount of water was added, and the mixture was stirred and aerated for 3 minutes to pulp it. Then, pH adjusters (NaOH aqueous solution and HCl aqueous solution) were added to adjust the slurry pH to the desired pH. An inhibitor was added, and the mixture was stirred and aerated for 5 minutes. The composite collector described in Example 3 was added, and after stirring and aerating for 3 minutes, the concentrate floating together with the foam was scraped, 30 times per minute, and continued for 5 minutes. The temperature of the flotation process was 25 ° C. The concentrate and tailings were dried and weighed respectively, and the recovery rate was calculated as shown in Table 3. Figure 5 As shown in the figure, the flotation process is as follows Figure 3 shown.

[0073] Table 3

[0074]

[0075]

[0076] Table 3 and Figure 5 The effect of the flotation reagent of the present invention on the grade and recovery rate of useful components of barite and fluorite at different pH values is shown. When pH = 6 to 10, the gap between the grade and recovery rate of the two minerals is large, but as the pH value decreases or increases, the recovery rate of BaSO4 in the concentrate gradually decreases, and the recovery rate of CaF2 gradually increases. When pH = 6 to 10, the separation effect of barite and fluorite is very good. The preferred pH range of the flotation pulp is 6 to 8. The flotation reagent of the present invention can maintain selective strong capture and strong sorting properties for the target mineral barite under a wide range of pH (pH = 6 to 10), which further shows that the reagent of the present invention can be applied to a variety of flotation environments, thereby simplifying the flotation process and saving manpower and material resources.

[0077] Example 4

[0078] Flotation process such as Figure 3 As shown, the steps are: 160g of fluorite actual ore associated with barite (same as in Example 1, ground to 0.037-0.015mm) is placed in a 500mL flotation tank, appropriate amount of water is added, stirring and aerating for 3 minutes to pulp it, and then pH adjusting agent (NaOH aqueous solution and HCl aqueous solution) is added to adjust pH=8, the pulp temperature is adjusted to 25 ° C, an inhibitor is added, stirring and aerating for 5 minutes, and the flotation agent solution described in Example 4 is added. After stirring and aerating for 3 minutes, the concentrate floating together with the foam is scraped, scraped 30 times per minute for 5 minutes, and the concentrate and tailings are dried and weighed respectively. The recovery rate is calculated, and the different proportion cases, different composite collector dosage cases and different inhibitors and dosage cases within the range are shown in Table 4, and the comparison group is shown in Tables 5 and 6.

[0079] Implementation group: 4.1-4.4: cases within the ratio range of different inhibitory components A and formula 2.

[0080] Implementation group: 4.5-4.8: Cases within different inhibitor types and ratios.

[0081] Comparison group:

[0082] Comparative group A: the case where only composite flotation reagent was added without inhibitor;

[0083] Comparative Group B: a comparative example without Formula 1 (only Formula 2 + inhibitor added);

[0084] Comparative Group C: a comparative example without Formula 2 (only Formula 1 + inhibitor added);

[0085] Comparative group D: a case where dodecyl carboxylic acid was used to replace formula 1A;

[0086] Comparative group E: a case where benzohydroxamic acid was used instead of formula 1A;

[0087] Comparative group F: the case where oleic acid was used instead of formula 2;

[0088] Comparative Group G: A comparative example of a composite collector in which the ratio of Formula 1 is higher than the required ratio range (the ratio of Formula 2 is lower than the required ratio range);

[0089] Comparative Group H: A comparative example of a composite collector in which the ratio of Formula 1 is lower than the required ratio range (the ratio of Formula 2 is higher than the required ratio range);

[0090] Table 4

[0091]

[0092] Table 5

[0093]

[0094] Table 6

[0095]

[0096]

[0097] As can be seen from Tables 4, 5, and 6, Formulas 1 and 2 of the present invention can produce a synergistic effect, significantly improving the separation selectivity of barite and fluorite, and increasing the grade of useful components in the flotation product. Furthermore, in combination with the use of the inhibitor, while ensuring a good flotation concentrate grade, the flotation recovery rate of the target mineral can be further significantly improved. Under the premise of the innovative flotation reagents, further controlling the ratio of each reagent can further synergistically balance the grade and recovery rate, helping to further improve the flotation effect (Comparative Examples 5.1 to 5.4).

[0098] In summary, the present invention applies Formula 2 to the field of mineral flotation for the first time. The flotation agent composition, proportion and preparation method provided can maximize the efficacy of each agent component and the positive synergistic effect between the agents. Compared with existing agents, under the premise of reducing the dosage of the agent, the flotation agent provided by the present invention has strong capture and selectivity for barite, which can significantly improve the recovery rate and grade of complex and difficult-to-select barite-fluorite type minerals, and provides a new idea and method for solving the difficult problem of separating barite and fluorite.

Claims

1. A composite collector for selective flotation separation of barite and fluorite, characterized in that: The invention comprises a component of formula 1 and a component of formula 2 in a weight ratio of 1 to 3:1; R1 is C6~C 15 alkyl, alkoxy-substituted alkyl, alkoxy, benzene ring, phenoxy or alkyl-substituted benzene ring; M is H, Na, K or NH4.

2. A flotation agent for selective flotation separation of barite and fluorite, comprising a collector and an inhibitor, characterized in that: The collector is the composite collector according to claim 1.

3. The flotation agent for selective flotation separation of barite and fluorite according to claim 2, characterized in that: The inhibitor comprises at least one of water glass, tannin extract, sodium lignin sulfonate, starch and metal salt inhibitors.

4. A method for selective flotation separation of barite and fluorite, characterized in that: The mineral to be selected containing barite and fluorite is mixed with a flotation agent containing the composite collector according to claim 1 for roughing, thereby obtaining a roughing concentrate enriched in barite and a roughing tailing enriched in fluorite.

5. The method for selective flotation separation of barite and fluorite according to claim 4, wherein: The mineral to be selected is a low-grade fine-grained fluorite-containing barite ore with an embedded particle size of -0.037 μm.

6. The method for selective flotation separation of barite and fluorite according to claim 4, wherein: The flotation agent is the flotation agent according to any one of claims 2 to 3.

7. The method for selective flotation separation of barite and fluorite according to claim 6, wherein: During the roughing process, the dosage of the composite collector is 50-500 g / t; the dosage of the inhibitor is 150-500 g / t.

8. The method for selective flotation separation of barite and fluorite according to claim 6, wherein: The pH of the roughing process is 6 to 10, preferably 6 to 8.

9. The method for selective flotation separation of barite and fluorite according to claim 6, wherein: The temperature for roughing is 5-45°C.

10. The method for selective flotation separation of barite and fluorite according to any one of claims 4 to 9, characterized in that: It also includes the process of beneficiating the rougher concentrate; and / or the process of scavenging the rougher tailings.

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