Collector, flotation agent and method for flotation of fluorite

Abstract

The present invention belongs to the field of flotation, and specifically relates to a collector, a flotation agent and a method for flotation of fluorite, wherein the collector comprises a compound of formula 1 (#imgabs0#). The present invention shows that o-COOR, -SO3 ‑ The combination of β-COOR can achieve intramolecular synergy, enhance the targeting ability and selectivity of fluorite, and especially improve the low-temperature capture ability, capture selectivity and low-temperature capture stability of fluorite.

Description

Technical Field

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

[0002] Flotation is the primary method for separating fluorite (CaF2) from other oxidized minerals (such as scheelite, calcite, and quartz). Existing fluorite collectors primarily include fatty acid collectors (such as oleic acid and its derivatives), anionic collectors (such as alkyl sulfonates and alkyl sulfates), and amine collectors (such as dodecylamine).

[0003] For example, Chinese Patent Publication No. CN114130542A reports a collector, a preparation method, and a method for flotation of fluorite using the collector. The collector is prepared by mixing oleic acid and triethanolamine. Another example is Chinese Patent Publication No. CN113441285A, which discloses a fluorite flotation collector, a preparation method, and an application. The collector raw materials include sulfonated oleic acid and emulsified oleic acid.

[0004] Although existing collectors can achieve good fluorite collection capabilities, their low-temperature collection capabilities, selectivity, and process stability need to be improved. For example: (1) Conventional collectors such as oleic acid have poor low-temperature adaptability, poor solubility and dispersibility at low temperatures, and require additional slurry heating (to 20-25°C) to maintain flotation indicators. (2) Conventional collectors such as oleic acid are not stable enough. Low-temperature environments can easily cause crystallization of the reagent, reducing the adsorption efficiency of the effective ingredients and causing the concentrate recovery rate to fluctuate by as much as 20%. (3) Under low-temperature conditions, the interference of other minerals on fluorite flotation is aggravated, and the selectivity of conventional inhibitors such as sodium silicate is significantly reduced, resulting in an increase in the inclusion rate of other minerals (such as calcite) and a decrease in the concentrate grade.

[0005] In summary, how to improve the fluorite collection capacity and selectivity under low-temperature flotation conditions is still one of the technical difficulties in the industry. Summary of the Invention

[0006] In view of the problems existing in the prior art, the first object of the present invention is to provide a collector for flotation of fluorite, aiming to improve the low-temperature collection ability and selectivity of fluorite.

[0007] The second object of the present invention is to provide a flotation agent for flotating fluorite comprising the collector.

[0008] The third object of the present invention is to provide a method for flotation of fluorite.

[0009] Fluorite is often interwoven with other oxide minerals such as calcite, scheelite, and quartz, making flotation separation difficult. Especially under low-temperature flotation conditions, the flotation capacity and selectivity of fluorite are even more difficult to ensure. To address this issue, the present invention provides the following improvements:

[0010] A collector for flotation of fluorite, comprising a compound of formula 1;

[0011] Formula 1

[0012] In formula 1, R1 and R2 are respectively a C1-C8 saturated carbon chain, a C2-C8 carbon chain with an unsaturated double bond, a phenyl group or a substituted phenyl group; M1 is H, NH4, Na or K.

[0013] The present invention shows that the o-COOR, -SO3 - And the combination of β-COOR can achieve intramolecular synergy, enhance the targeting ability and selectivity of fluorite, and especially improve the low-temperature capture ability, capture selectivity and low-temperature capture stability of fluorite.

[0014] In the present invention, the saturated carbon chain is a straight chain alkyl or a branched chain alkyl. The substituted phenyl group is, for example, a phenyl group having at least one substituent selected from the group consisting of an alkyl group, an alkoxy group, a halogen group, and a hydroxyl group.

[0015] In the present invention, the collector for flotation of fluorite further comprises an auxiliary collector having a structure of formula 2;

[0016] Formula 2

[0017] In formula 2, R3 is H, halogen, hydroxyl, carboxyl, C1~C8 alkyl or C1~C8 alkoxy; M2 is H, NH4, Na or K.

[0018] The present invention shows that the combination of Formula 1 and Formula 2 can further enhance the targeting ability and selectivity of fluorite based on the intermolecular interaction of the components, and can further enhance the capture ability and selectivity of fluorite at low temperatures.

[0019] Preferably, the auxiliary collector is a compound having the structure of Formula 2A;

[0020] Formula 2A;

[0021] In Formula 2A, R3 is a C1-C4 alkane or a C1-C4 alkoxy group.

[0022] The present invention also shows that the para-structured formula 2A, combined with formula 1, can further enhance the adaptability and synergy between the components, and help to further enhance the capture capacity and selectivity of fluorite, especially the capture capacity and selectivity of fluorite at low temperatures.

[0023] In the present invention, the molar ratio of the compound of formula 1 to the auxiliary collector is 1-5: 1-5; preferably 1.5-3.5: 1; and more preferably 2.5-3.5: 1. Studies have shown that the preferred ratio is expected to further enhance the low-temperature capture ability, capture selectivity, and capture stability of fluorite.

[0024] The present invention also provides a flotation agent for flotation of fluorite, comprising a collector and a flotation aid, wherein the flotation aid comprises at least one of a pH regulator, a frother and an inhibitor, and the collector is the collector described in the present invention.

[0025] In the present invention, the flotation aid can be composed of any conventional ingredients in the industry. For example, the frother can be any ingredient with foaming ability in the industry, such as No. 2 oil, terpineol, BK201, methyl isobutyl carbinol (MIBC), methyl pentanol, 2-ethyl hexanol, C6-C8 mixed fatty alcohols, mixed hexamethylol (P-MPA), C5-C7 mixed secondary alcohol 1,1,3-triethoxybutane (TEB), methyl alcohol ether, ethyl alcohol ether, butyl alcohol ether, C5-C6 and C5-C9 mixed fatty acid ethyl esters, diethyl phthalate, and at least one of the BK, RB, and 730 series frothers.

[0026] The inhibitor can be, for example, water glass, potassium silicate, aluminum silicate, sodium fluorosilicate, potassium fluorosilicate, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, disodium hydrogen phosphate, sodium fluoride, ammonium fluoride, calcium fluoride, sodium sulfide, sodium thiosulfate, sodium sulfite, sodium carbonate, sodium oxalate, sodium molybdate, sodium tungstate, oxalic acid, citric acid, tartaric acid, malic acid, maleic acid, malonic acid, gluconic acid, lactic acid, salicylic acid, aminotrimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, thioglycolic acid, dithiocarbamate, tannic acid, gallic acid, tannic acid, humic acid, starch, dextrin, carboxymethyl starch, oxidized starch, carboxymethyl cellulose, guar gum, chitosan, sodium lignin sulfonate, calcium lignin sulfonate, sulfonated lignin, polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyethylene glycol, gelatin, peptone, soy protein, and at least one of the combinations or modified products thereof.

[0027] The pH regulator can be any acidic and / or alkaline component capable of adjusting pH, including but not limited to at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium oxide, ammonia water, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or oxalic acid.

[0028] The flotation reagent described in the present invention includes the following preferred embodiment: the collector is a single collector of Formula 1, and the flotation reagent (also referred to as flotation reagent a) comprises a collector of Formula 1, a pH adjuster, and a frother. In another embodiment of the present invention, when the collector is a combined collector comprising Formulas 1 and 2, the flotation reagent (also referred to as flotation reagent b) comprises a combined collector of Formulas 1 and 2, a pH adjuster, and a depressant. Research conducted in the present invention has shown that using a single collector of Formula 1 can achieve excellent low-temperature collection capacity, selectivity, and stability without the need for a depressant. Furthermore, when the collector is a combined collector comprising Formulas 1 and 2, the addition of a depressant is preferred to further enhance the synergistic effect of Formulas 1 and 2, potentially further improving the low-temperature collection capacity, selectivity, and collection stability of fluorite.

[0029] In the present invention, a frother can be added to the flotation reagent a and the flotation reagent b as needed. In addition, an inhibitor can also be added to the flotation reagent a as needed.

[0030] In the present invention, the dosage of the components in the flotation reagent can be reasonably adjusted as needed. For example, the dosage of the pH regulator is used to adjust the pH of the flotation pulp to 7-12; further to 7.5-10.5; further to 8-10. The dosage of the collector is used to control the concentration of the flotation pulp in the range of 1×10 -7 ~ 1×10 -4 mol / L; preferably 0.5×10 -6 ~ 1×10 -4 mol / L; more preferably 1×10 -6 ~ 1×10 -5 The dosage of frother is used to control the concentration of frother in flotation slurry to be between 1×10 -7 ~ 1×10 -4 mol / L; preferably 0.5×10 -6 ~ 1×10 -4 mol / L; more preferably 1×10 -6 ~ 1×10 -5 The molar ratio of the inhibitor to the collector can be 10:5-10.

[0031] The present invention also provides a method for flotation of fluorite, comprising mixing a mineral to be selected containing fluorite with a flotation agent, and performing flotation to obtain a fluorite concentrate, wherein the flotation agent comprises the collector of the present invention.

[0032] In the present invention, the mineral to be selected further comprises gangue, and the gangue comprises at least one of calcite, scheelite and quartz.

[0033] The flotation method of the present invention is applicable to fluorite ores of any grade and characteristics. In particular, for existing low-grade ores, the flotation method employing the collector of the present invention can also achieve selective fluorite flotation under weakly alkaline conditions.

[0034] In the present invention, the grade of fluorite in the ore to be selected can be low-grade ore, for example, the CaF2 content can be lower than 20%.

[0035] In the flotation process of the present invention, the amount of collector used can be reasonably adjusted according to the grade and type of the mineral, the processing volume and processing flow, the flotation cost and economic benefits, etc.

[0036] The flotation reagent of the present invention is a flotation reagent comprising the collector of the present invention.

[0037] In the present invention, the amount of the collector is 1×10 -7 ~ 1×10 -4 mol / L; preferably 0.5×10 -6 ~ 1×10 -4 mol / L; more preferably 1×10 -6 ~ 1×10 -5 mol / L.

[0038] When the flotation reagent is allowed to contain frothers, inhibitors and other ingredients, their contents can be reasonably controlled according to conventional principles. For example, the concentration of frother in the pulp can be 1×10 -7 ~ 1×10 -4 mol / L; further 0.5×10 -6 ~ 1×10 -4 mol / L; further 1×10 -6 ~ 1×10 -5 The molar ratio of the inhibitor to the collector can be 10:5~10.

[0039] The pH during flotation is 7-12; further 7.5-10.5; further 8-10.

[0040] The temperature of the flotation process is 5-25°C; for example, it can be 5°C, 10°C, 15°C, 20°C, etc.

[0041] In the present invention, the flotation can be roughing. In the present invention, the concentrate and tailings from the roughing can be subjected to beneficiation or scavenging treatment as needed.

[0042] Beneficial effects

[0043] 1. The present invention's research shows that the structure of Formula 1 has excellent specific targeting ability for fluorite, and has excellent fluorite targeting ability and selectivity, and can obtain excellent targeting ability, selectivity and process stability even at lower temperatures.

[0044] 2. Combining Formula 1 and Formula 2 can further achieve intermolecular synergy, further enhancing the low-temperature flotation capacity and selectivity of fluorite. On this basis, further adding inhibitors can further enhance the low-temperature capture capacity, selectivity and process stability of fluorite.

[0045] 3. In the present invention, thanks to the innovative use of the collector, better flotation indicators can be obtained at a lower collector dosage and a more environmentally friendly pulp pH condition (weakly alkaline), which can improve the resource utilization rate of fluorite ore and the environmental friendliness of the flotation process, and can significantly reduce the heating energy consumption required for the original low-temperature flotation of fluorite, thereby reducing flotation costs and carbon emissions. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 The flotation flow chart of single mineral and mixed ore for the embodiments and comparative examples is shown.

[0047] Figure 2 This is a diagram of the single mineral flotation results of Example 1 (fluorite low-temperature resistant collector dosage experiment).

[0048] Figure 3 This is a diagram of the single mineral flotation results of Example 2 (slurry pH condition experiment). DETAILED DESCRIPTION

[0049] The effects of the present invention are illustrated using single minerals and artificial mixed minerals of fluorite, calcite, scheelite, and quartz (① fluorite and calcite weight ratio of 1:1; ② fluorite and scheelite weight ratio of 1:1; ③ fluorite and quartz weight ratio of 1:1). Unless otherwise stated, the mineral compositions used in the following cases are as shown in Table 1:

[0050]

[0051] In the following cases, the flotation pH refers to the pH of the pulp during the flotation stage. The acidic regulator in the pH adjuster may be hydrochloric acid, and the alkaline regulator may be sodium hydroxide.

[0052] In addition, each collector can be a hydrogen type (in Formula 1-2, M1 / M2 is H agent) and / or a salt type (in Formula 1-2, M1 / M2 is NH4 + 、Na + or K +). During the flotation process, the hydrogen form and salt form of the reagent are related to the pH of the flotation stage. For example, when the pH of the flotation stage is acidic, the reagent in the flotation system mainly or entirely exists in the hydrogen form. When the pH of the flotation stage is alkaline, part or all of M (M1 / M2) in the reagent exists in the salt form of alkaline cations. When the pH is neutral, the hydrogen form and the salt form tend to exist at the same time. In the present invention, as an illustrative method, in the following cases, the reagent used initially in Formula 1 and Formula 2 can be a Na salt type (refer to the following structure of -O - ).

[0053] In the following cases, the inhibitors described can be conventional inhibitors in the industry for inhibiting gangue such as calcite and quartz. As an optional solution, unless otherwise stated, the following cases all use water glass (Na2O·nSiO2) as an example, whose modulus is, for example, 2 to 2.3.

[0054] Example 1

[0055] In order to verify the flotation effect of the fluorite low temperature resistant collector, single fluorite, calcite, scheelite, and quartz (Table 1) were first used. Figure 1 In the single mineral flotation process shown, the flotation temperature is 15°C, and the fluorite is collected using the low-temperature resistant collector of this case. Except for the collector dosage, the flotation process parameters of each group of cases are the same. In this example, terpineol is added as a frother, and hydrochloric acid and sodium hydroxide are used as pH adjusters.

[0056] Fluorite low temperature resistant collector in this embodiment: Formula 1A.

[0057] use Figure 1 The process shown in the figure is as follows: the single pure mineral ore (particle size of 3 mm to 0.5 mm) in Table 1 is dry ball milled, 2.0 g of the single mineral sample with a particle size of 0.074 to 0.038 mm is weighed from each group and poured into a 40 mL flotation cell, a pH adjuster is added to adjust the slurry to pH = 8, 35 mL of deionized water is added, and the fluorite low-temperature resistant collector of this embodiment (dosage of 0.5×10 -6 ~2×10 -6 mol / L), add appropriate amount of deionized water, stir for 3 min, add terpineol (dosage of 1×10 -6 mol / L), stirred for 3 min, and began to scrape foam for 3 min. The concentrate was scraped into the concentrate basin along with the foam, and the tailings remained in the flotation tank. The concentrate and tailings were filtered and dried, and then weighed separately to calculate the recovery rate. Each group of experiments was carried out in three parallel groups, and the average value was taken. Figure 2 It is the recovery rate of fluorite and other pure oxide minerals in Example 1 under different dosages of fluorite low-temperature resistant collector.

[0058] like Figure 2 As shown in the figure, the composite reagent of this embodiment has a selective capture ability for fluorite when the pulp pH is 8, while the capture ability for other oxide minerals is very weak. At a low reagent dosage (1×10 -6 mol / L), fluorite can be efficiently captured (recovery rate exceeds 90%), while the recovery rates of calcite and scheelite are less than 30% and 20% respectively, and the recovery rate of quartz is less than 3%, which proves that the fluorite low-temperature resistant collector of this embodiment has excellent flotation performance.

[0059] Example 2

[0060] In order to verify the effect of regulating pulp pH on the flotation effect of the fluorite low-temperature resistant collector, high-purity fluorite and other pure oxide minerals (Table 1) were used. Figure 1 The single mineral flotation process shown in the figure uses the fluorite low-temperature resistant collector in this case to collect pure minerals. The flotation temperature is 15℃ and the dosage of the fluorite low-temperature resistant collector is 1×10 -6 mol / L, except for the different pulp pH, the flotation process parameters of each group of cases are the same. In this example, terpineol is added as a frother, and hydrochloric acid and sodium hydroxide are used as pH adjusters.

[0061] The fluorite low-temperature resistant collector of this embodiment is as follows: Formula 1A;

[0062] use Figure 1 The process shown in the figure is as follows: pure mineral ore (particle size 3 mm~0.5 mm) is dry ball milled, 2.0 g of single mineral sample with a particle size of 0.074~0.038 mm is weighed for each group and poured into a 40 mL flotation cell, a pH adjuster is added to adjust the pH of the pulp to 8, 9 or 10, 35 mL of deionized water is added, and the fluorite low-temperature resistant collector of this embodiment (dosage of 1×10 -6 mol / L), add appropriate amount of deionized water, stir for 3 min, add terpineol (dosage of 1×10 -6 mol / L), stirred for 3 min, and began to scrape foam for 3 min. The concentrate was scraped into the concentrate basin along with the foam, and the tailings remained in the flotation tank. The concentrate and tailings were filtered and dried, and then weighed separately to calculate the recovery rate. Each group of experiments was carried out in three parallel groups, and the average value was taken. Figure 3 is the recovery rate of each sulfide mineral in Example 2 under different slurry pH conditions.

[0063] like Figure 3As shown, under low-alkali, environmentally friendly slurry pH conditions (pH = 8-10), the fluorite low-temperature-resistant collector of this example can effectively separate fluorite from other oxidized minerals. After flotation with the fluorite low-temperature-resistant collector, fluorite is enriched in the flotation concentrate, while other oxidized minerals are enriched in the flotation tailings. The difference in recovery rates between the two is large, and the separation effect is excellent. The results of Example 2 also confirm that the fluorite low-temperature-resistant collector of this example is suitable under environmentally friendly pH conditions, has excellent performance under weakly alkaline slurry conditions, and can achieve differential capture of fluorite and other oxidized minerals.

[0064] Example 3

[0065] In order to verify the flotation performance of the fluorite low-temperature resistant collector or low-temperature resistant flotation agent in dealing with mixed ore flotation, high-purity fluorite with a particle size range of 0.074-0.038 mm and other oxide mineral pure mineral samples were compounded in a 1:1 ratio to obtain an artificial mixed ore (Table 1). Figure 1 The mixed ore flotation process shown in the figure has a flotation temperature of 20℃, 15℃ or 10℃. The mixed ore is collected by the fluorite low temperature resistant collector in this case. The dosage of the fluorite low temperature resistant collector is 1×10 -6 mol / L, pulp pH = 8, and other flotation process parameters of each case group are the same. If only fluorite low-temperature resistant collector is used, terpineol needs to be added as a frother (dosage is 1×10 -6 mol / L). If fluorite low-temperature resistant flotation reagent is used, no additional frother is needed. In this embodiment, hydrochloric acid and sodium hydroxide are used as pH adjusters.

[0066] The flotation reagents in the following groups are as follows (Note: the frother and pH adjuster have the same ingredients and dosage):

[0067] Example 3-1: The flotation reagent includes a collector, a pH regulator and a frother, wherein the collector is of Formula 1A.

[0068] Example 3-2: The flotation reagent includes a collector, a pH regulator and a frother, wherein the collector is a compound of formula 1B ( ).

[0069] Example 3-3: The flotation reagent includes a collector, a pH regulator and a frother, wherein the collector is a compound of formula 1C ( ).

[0070] Example 3-4: The flotation reagent includes a collector, a depressant, a pH regulator and a frother, wherein the collector includes Formula 1A and Formula 2A ( ); The molar ratio of the total collector and the inhibitor is 8: 10.

[0071] Example 3-5: Compared with Example 3-4, the only difference is that the collector includes Formula 1A and Formula 2A in a molar ratio of 5:3.

[0072] Example 3-6: Compared with Example 3-4, the only difference is that the collector includes Formula 1A and Formula 2B ( ).

[0073] Example 3-7: Compared with Example 3-4, the only difference is that the collector includes Formula 1A and Formula 2C ( ).

[0074] Example 3-8: Compared with Example 3-4, the only difference is that the collector includes Formula 1A and Formula 2D ( ).

[0075] Example 3-9: Compared with Example 3-4, the only difference is that the collector is only Formula 1A and there is no Formula 2A; the molar ratio of the total collector to the inhibitor is 6:10.

[0076] Example 3-10: Compared with Example 3-4, the only difference is that no foaming agent is added.

[0077] Example 3-11: Compared with Example 3-4, the only difference is that no inhibitor is added.

[0078] Example 3-12: Compared with Example 3-4, the only difference is that the collector includes Formula 1A and Formula 2A in a molar ratio of 2:6.

[0079] Note: In the above cases, the total amount of collector is 1×10 -6 mol / L; the inhibitors are all water glass, and their molar mass is calculated based on the sodium silicate therein.

[0080] use Figure 1 The specific operation is as follows: weigh 2.0 g of the mixed ore sample per group and pour it into a 40 mL flotation tank. Add pH adjuster to adjust the slurry to pH = 8. Add 35 mL of deionized water and then add flotation reagent. Add appropriate amount of deionized water and stir for 3 minutes. If a single type 1 collector is used, terpineol needs to be added as a foaming agent (dosage is 1×10 -6 mol / L). If a combined collector of Formulas 1 and 2 is used, a frother can be optionally added. Stir for 3 minutes, then begin scraping. Scrape for 3 minutes. The concentrate, along with the foam, is scraped into the concentrate basin, and the tailings remain in the flotation tank. The concentrate and tailings are filtered, dried, and weighed separately to calculate the recovery. Each experiment is repeated three times in parallel, and the average value is taken. Table 2 shows the recovery and grade of the mixed ore in Example 3 under different slurry pH conditions.

[0081]

[0082] As shown in Table 2, when dealing with artificial mixed ore, the use of the fluorite low-temperature resistant collector and the low-temperature resistant flotation agent of this embodiment achieved good fluorite separation and enrichment effects.

[0083] In Example 3-1, in the fluorite-calcite mixed ore (1:1), the fluorite recovery rate reached 92.7%, 88.5% and 85.2% at 20°C, 15°C and 10°C, respectively, while the CaF2 grade increased with decreasing temperature (71.4%~75.0%).

[0084] In Example 3-2, in the fluorite-scheelite mixed ore (1: 1), the fluorite recovery rate was maintained at 86.6%~92.3%, and the grade was significantly improved (62.2%~67.9%).

[0085] In Example 3-3, for the fluorite-quartz mixed ore (1: 1), the fluorite recovery rate is as high as 87.3%~94.5%, and the CaF2 grade exceeds 95%, indicating that quartz is almost not captured.

[0086] In addition, Examples 3-4, 3-5, 3-6, 3-9, and 3-11 show that the addition of a certain auxiliary collector, in conjunction with the use of an inhibitor, further enhances the fluorite capture capacity and selectivity. In addition, Examples 3-4, 3-7, and 3-8 show that the use of a para-positioned auxiliary collector can further synergize with Formula 1 to further enhance the fluorite capture capacity and selectivity.

[0087] It can be seen from Examples 3-4 and 3-10 that adding a certain foaming agent can further synergistically optimize the selectivity of fluorite.

[0088] It can be seen from Examples 3-4 and 3-12 that when Formula 1 and Formula 2 are combined, controlling the ratio of the two can further enhance the synergy between the two.

[0089] Comparative Example 1

[0090] Compared with Example 3-4, the only difference is that both are artificial mixed ore ① (fluorite: calcite = 1: 1) and the composition of fluorite flotation reagent is changed. The experimental groups are:

[0091] Comparative Example 1-1: Sodium oleate was used to replace Formula 1A in the flotation reagent of Example 3-4, and the other ingredients and amounts were the same as those of Example 3-4.

[0092] Comparative Example 1-2: Sodium dodecyl sulfate was used to replace Formula 1A in the flotation reagent of Example 3-4, and the other ingredients and amounts were the same as those of Example 3-4.

[0093] Comparative Examples 1-3: Using Comparative Formula A ( ) replaces Formula 1A in the flotation reagent of Example 3-4, and the other ingredients and amounts are the same as those of Example 3-4.

[0094] Comparative Example 1-4: The collector of Example 3-4 lacks Formula 1A and only contains Formula 2A, and the collector flow rate and other components are the same as those of Example 3-4.

[0095] Comparative Examples 1-5: Only sodium oleate was added to the flotation reagent, without adding a frother or an inhibitor, and the amount of the collector and other conditions remained unchanged.

[0096] Comparative Examples 1-6: Only Formula 2A was added to the flotation reagent, without adding a frother or an inhibitor, and the amount of the collector and other conditions remained unchanged.

[0097] Comparative Examples 1-7: Using Comparative Formula B ( ) replaces Formula 1A in the flotation reagent of Example 3-4, and the other ingredients and amounts are the same as those of Example 3-4.

[0098] Comparative Example 1-8: Only sodium dodecyl sulfate was added to the flotation reagent, without adding a frother or an inhibitor. The amount of collector and other conditions were the same as those of Example 3-4.

[0099] Comparative Example 1-9: Compared with Example 3-4, the only difference is that Formula 1A is replaced by Comparative Formula A and Comparative Formula B with a molar ratio of 1:1, and the total molar amount of Comparative Formula A and Comparative Formula B is the same as Formula 1A.

[0100] The flotation results of each group are shown in Table 3.

[0101]

[0102] As shown in Table 3, Examples 3-4 and Comparative Examples 1-1 to 1-9 show that the low-temperature collection stability and selectivity of the collectors without the key Formula 1 of the present invention are unsatisfactory. For example, the fluorite recovery rate of Comparative Example 1-1 is as high as 98.2% at 20°C, but drops sharply to 70.3% at 10°C, a decrease of 27.9%, indicating insufficient low-temperature stability and unsatisfactory low-temperature selectivity.

[0103] In summary, the present invention shows that the o-COOR, -SO3 - And the combination of β-COOR can achieve intramolecular synergy, which can enhance the targeting ability and selectivity of fluorite, especially under low-temperature flotation conditions, it can also obtain excellent fluorite targeting selectivity.

Claims

1. A collector for flotation of fluorite, characterized in that: Contains a compound of formula 1 and further comprises an auxiliary collector having a structure of formula 2; Formula 1 Formula 2 In formula 1, R1 and R2 are respectively a C1-C8 saturated carbon chain, a C2-C8 carbon chain with an unsaturated double bond, a phenyl group or a substituted phenyl group; M1 is H, NH4, Na or K; In formula 2, R3 is H, halogen, hydroxyl, carboxyl, C1~C8 alkane or C1~C8 alkoxy; M2 is H, NH4, Na or K.

2. The collector for flotation fluorite according to claim 1, wherein The auxiliary collector is a compound having the structure of formula 2A; Formula 2A; In Formula 2A, R3 is a C1-C4 alkane or a C1-C4 alkoxy group.

3. The collector for flotation fluorite according to claim 1 or 2, characterized in that: The molar ratio of the compound of formula 1 to the auxiliary collector is 1-5:1-5.

4. A flotation agent for flotation of fluorite, comprising a collector and a flotation aid, wherein the flotation aid comprises at least one of a pH regulator, a frother and an inhibitor, characterized in that: The collector is the collector according to any one of claims 1 to 3.

5. The flotation reagent for flotation of fluorite according to claim 4, characterized in that: The flotation agent is flotation agent a or flotation agent b; Wherein, the flotation reagent a comprises a collector of formula 1, a pH regulator and a frother; The flotation reagent b comprises a collector of formula 1 and formula 2, a pH adjuster and an inhibitor.

6. A method for flotation of fluorite, characterized in that: The mineral to be selected containing fluorite and a flotation agent are mixed and flotation is performed to obtain a fluorite concentrate, wherein the flotation agent contains the collector according to any one of claims 1 to 3.

7. The method for flotation of fluorite according to claim 6, wherein: The flotation agent is the flotation agent according to any one of claims 4 to 5.

8. The method for flotation of fluorite according to claim 6, wherein: The minerals to be selected also include gangue, which includes at least one of calcite, scheelite, and quartz.

9. The method for flotation of fluorite according to any one of claims 6 to 8, characterized in that: The amount of collector is 1×10 -7 ~ 1×10 -4 mol / L; The pH during flotation is 7-12; The temperature of the flotation process is 5~25℃.

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