Collecting agent, flotation reagent and method for flotation of bastnaesite and / or scheelite

Abstract

The invention belongs to the field of mineral flotation, and particularly relates to a collecting agent and method for flotation of bastnaesite and / or scheelite, and the collecting agent comprises a compound with a structure # imgabs0 # as shown in a formula 1; at least one substituent in R1-R4 is a substituent in the formula 2 # imgabs 1 #; the rest substituent groups are H, hydroxyl, alkyl of C1-C6, alkoxy of C1-C6 or vinyl. Aiming at the problem of difficult flotation caused by the physicochemical characteristics of bastnaesite and / or scheelite minerals, deep dissemination and the like, diphenylmethane is innovatively adopted as a parent nucleus, and bis-2 groups are innovatively modified on the parent nucleus, so that the flotation efficiency of the bastnaesite and / or scheelite is improved on the basis of the joint synergy between the parent nucleus and the groups. And a binding structural domain matched with the bastnaesite and / or scheelite minerals is constructed, so that the collecting effect and selectivity of the bastnaesite and / or scheelite minerals are synergistically improved.

Description

Technical Field

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

[0002] Bastnaesite and scheelite are the primary minerals responsible for light rare earth elements (lanthanum, cerium, praseodymium, and rubidium) and tungsten, respectively. In natural deposits, these two valuable minerals are typically present at low concentrations and are often closely associated with calcium-bearing gangue minerals (including dolomite, calcite, and apatite). Therefore, physical separation, particularly flotation, has become a crucial step in the development and utilization of these two valuable minerals.

[0003] Flotation is a physical separation method based on differences in surface hydrophobicity between minerals. It operates in a three-phase system: slurry, air bubbles (foam), and mineral particles. During the flotation of bastnaesite and scheelite, particles with more hydrophobic surfaces adhere to the bubbles and rise with them to the froth layer on the slurry surface, where they are eventually collected by scrapers and transported into the concentrate tank. Calcium-containing gangue minerals with less hydrophobicity, on the other hand, remain in the flotation tank and are ultimately transported via pipeline to the tailings dam.

[0004] During flotation, collectors are used to enhance the hydrophobicity of the valuable mineral surfaces. Collector selectivity is crucial to the flotation separation of valuable and gangue minerals. Ideally, highly selective collector molecules will adsorb specifically to the surfaces of valuable minerals, while exhibiting weaker adsorption to gangue mineral surfaces.

[0005] Hydroxamic acid collectors, including 3-hydroxy-2-naphthohydroxamic acid and benzohydroxamic acid, are commonly used in the flotation of bastnaesite and scheelite. For example, Chinese patent publication CN111167596A discloses a method for the comprehensive recovery of rare earth minerals and fluorite during bastnaesite processing. The flotation reagents include a conditioning agent, an inhibitor, and a collector, with the collector comprising oleic acid and hydroxamic acid.

[0006] Chinese patent document CN119259268A discloses a composite collector for rare earth ores and its application in flotation. The composite collector is composed of hydroxamic acid organic matter, ether organic matter and phosphate organic matter in a mass ratio of (15-20): (3-8): (1-3).

[0007] While conventional hydroxamic acid flotation methods exist, the selectivity of existing hydroxamic acid collectors has become insufficient to meet the requirements for efficient flotation separation as the content of the two valuable minerals in ores decreases, their embedded particle size becomes finer, and their integration with gangue minerals becomes more complex. Therefore, the development of new, highly selective collectors is urgently needed. Summary of the Invention

[0008] In view of the problems existing in the existing solutions, the present invention aims to provide a collector suitable for the flotation of fluorocarbon cerium ore and / or scheelite, and aims to improve the flotation effect of fluorocarbon cerium ore and / or scheelite based on the new structure.

[0009] The second object of the present invention is to provide a flotation reagent comprising the collector.

[0010] The third object of the present invention is to provide a method for flotating bastnaesite and scheelite using the collector and flotation reagent.

[0011] A collector for flotation of bastnaesite and / or scheelite, comprising a compound having the structure of Formula 1;

[0012]

[0013] At least one substituent among R1 to R4 is a substituent of formula 2; the remaining substituents are H, hydroxyl, C1 to C6 alkyl, C1 to C6 alkoxy or vinyl;

[0014]

[0015] In the formula 2, M is H, Na, K or NH4.

[0016] In order to solve the problem of difficult flotation caused by the physicochemical characteristics and deep embedding of fluorocarbon cerium and / or scheelite minerals, the present invention innovatively adopts diphenylmethane as the parent core and innovatively modifies it with a di-2 group. In this way, based on the combined synergy between the parent core and the group, a binding domain adapted to fluorocarbon cerium and / or scheelite minerals can be constructed, thereby synergistically improving the capture effect and selectivity of fluorocarbon cerium and / or scheelite minerals.

[0017] In the collector of the present invention, the substituent of Formula 2 comprises a hydroxyl group or an alkoxy group at the ortho position. Research in the present invention also shows that, based on the parent core of Formula 2, further modifying the ortho position of Formula 2 with a hydroxyl group or an alkoxy group helps to further construct a binding domain compatible with bastnaesite and / or scheelite minerals, thereby further enhancing its capture ability and selectivity.

[0018] Further preferably, in the collector, the para-position of the substituent of Formula 2 contains a C1-C6 alkyl group, a C1-C6 alkoxy group, or a vinyl group. Research has also shown that this preferred structure, based on the combination of the parent core, hydroxyl group, and the para-position substituent, is expected to further synergistically enhance the capture efficiency of bastnaesite and / or scheelite minerals, particularly improving the capture efficiency of bastnaesite and / or scheelite minerals that are difficult to finely embed.

[0019] In the present invention, the R4 is a substituent of formula 2.

[0020] More preferably, the formula 1 is a compound having the structure of formula 1A:

[0021]

[0022] In Formula 1A, R3 is preferably a hydroxyl group or an alkoxy group; more preferably, R1 is preferably a C1-C6 alkyl group, a C1-C6 alkoxy group or a vinyl group.

[0023] The present invention also provides a flotation agent for flotating bastnaesite and / or scheelite, comprising a collector and other flotation aids, wherein the other flotation aids include at least one of an inhibitor, a frother, and a pH regulator; the collector comprises the collector described in the present invention.

[0024] The flotation reagent of the present invention, in addition to the collector of the present invention, may contain other flotation aids that are well known in the industry, or may be reasonably adjusted based on industry knowledge.

[0025] For example, in the present invention, the flotation aid includes a depressant, wherein the depressant includes at least one of water glass and carboxymethyl cellulose.

[0026] For another example, the flotation aid includes a foaming agent, wherein the foaming agent includes at least one of 2# oil and methyl isobutyl carbinol (MIBC).

[0027] For another example, the flotation aid includes a pH regulator.

[0028] The present invention also provides a method for flotation of bastnaesite and / or scheelite, comprising mixing the minerals to be flotated, including at least one target ore among bastnaesite and / or scheelite, with a flotation agent for flotation to obtain a concentrate of the target ore; wherein the flotation agent comprises the collector described in the present invention.

[0029] The flotation method of the present invention, which benefits from the innovative use of the special collector, can effectively improve the collection effect and selectivity of bastnaesite and / or scheelite minerals based on the adaptive structural domain characteristics of fluorobastnaesite and / or scheelite synergistically constructed within the collector molecules.

[0030] In the flotation method of the present invention, in addition to the use of the collector of the present invention, other operations, methods, and parameters can be controlled based on conventional principles. For example, the flotation process includes a roughing process. In addition, depending on the type of mineral, the roughing concentrate can be subjected to a beneficiation treatment, and the roughing tailings can also be selectively subjected to a scavenging treatment.

[0031] In the present invention, the flotation stage includes a roughing process, wherein the amount of collector used in the roughing stage is 300-700 g / t, preferably 400-500 g / t. The preferred amount has both good cost advantages and excellent collection selectivity.

[0032] Preferably, the flotation stage also includes a concentration and / or scavenging process, wherein the amount of collector used in the concentration stage (referring to a single-stage concentration stage) is 30 to 100 wt.% of the amount used in the roughing stage; the amount of collector used in the scavenging stage (referring to a single-stage scavenging stage) is 30 to 100 wt.% of the amount used in the roughing stage.

[0033] The flotation reagents in the roughing stage include a frother, wherein the amount of the frother is 40-50 g / t;

[0034] The flotation reagents in the roughing and cleaning stages contain inhibitors, wherein the amount of inhibitor is 900-1400 g / t, preferably 1000-1300 g / t; the amount of inhibitor in the cleaning stage (referring to the single-stage cleaning stage) is 40-100 wt.% of the amount of inhibitor in the roughing stage.

[0035] In the present invention, the flotation process and mechanism can be reasonably adjusted based on conventional knowledge.

[0036] Beneficial effects

[0037] The present invention provides a novel collector of formula 1, which uses diphenylmethane as a parent core and innovatively modifies a group of formula 2 thereon. In this way, based on the combined synergy between the parent core and the group, a binding domain adapted to fluorocarbon cerium and / or scheelite minerals can be constructed, thereby achieving synergy and improving the capture effect and selectivity of fluorocarbon cerium and / or scheelite minerals.

[0038] The present invention also shows that reasonable control of the substituent groups and substitution positions of Formula 1 is helpful to further construct a binding domain adapted to bastnaesite and / or scheelite minerals, and is helpful to further improve the flotation effect of bastnaesite and / or scheelite minerals. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is the flotation flow chart of Example 1-1. DETAILED DESCRIPTION

[0040] The following examples are intended to further illustrate the present invention, but the protection scope of the present invention is not limited to these embodiments.

[0041] The collectors that may be cited in the present invention may include compounds of the following structural formulas: at least one of Formulas 1-A, 1-B, 1-C, 1-D, 1-E, or 1-F;

[0042]

[0043] The present invention also provides an application of the collector, which is used as a collector in the flotation of bastnaesite and scheelite.

[0044] As an alternative, it can be used as a collector in the flotation of bastnaesite and scheelite:

[0045] In the present invention, the flotation process includes roughing, beneficiation of the roughing concentrate, and scavenging of the roughing tailings.

[0046] As an optional solution, in the roughing stage of flotation, the amount of the collector is 400-500 g / t;

[0047] As an alternative, the pH of the flotation stage is 8-9;

[0048] As an option, depressants are added during the flotation stage;

[0049] As an optional solution, the inhibitor is water glass;

[0050] As an optional solution, the amount of depressant used in the roughing stage of flotation is 900-1400 g / t; preferably 1000-1300 g / t;

[0051] As an option, a frother is added during the flotation stage;

[0052] As an optional solution, the foaming agent is 2# oil;

[0053] As an optional solution, the flotation process includes three rounds of cleaning and two rounds of scavenging. The cleaned tailings are sequentially returned to the previous flotation operation, and the scavenged concentrates are sequentially returned to the previous flotation operation.

[0054] For example, the process of the present invention comprising one roughing selection, three fine selections, and two scavenging selections is as follows:

[0055] Rough selection:

[0056] The mineral to be selected is placed in a flotation reagent a containing a collector, an inhibitor and a frother for roughing treatment to obtain a roughing concentrate and a roughing tailing.

[0057] Featured:

[0058] The rougher concentrate is subjected to a three-stage concentration process, the steps of which are: the rougher concentrate is subjected to the first stage of concentration to obtain a first stage of concentrated concentrate and a first stage of concentrated tailings, and the first stage of concentrated tailings is returned to the rougher process;

[0059] The first stage concentrated ore is subjected to the second stage of concentrating treatment to obtain the second stage concentrated ore and the second stage concentrated tailings, and the second stage concentrated tailings are returned to the first stage of concentrating process;

[0060] The second-stage concentrated ore is subjected to the third-stage concentrated treatment to obtain the third-stage concentrated ore (final flotation concentrate) and the third-stage concentrated tailings; the third-stage concentrated tailings are subjected to the second concentrating treatment process.

[0061] The flotation reagent used in each stage of the selection process is the flotation reagent B containing an inhibitor and a collector, wherein the amount of the inhibitor used in each stage of the selection process is 30-60% of the amount of the roughing inhibitor used; the amount of the collector used in each stage of the selection process is 30-60% of the amount of the roughing collector used.

[0062] Scan and select:

[0063] The rougher concentrate is subjected to a two-stage scavenging process, the steps of which include: subjecting the rougher concentrate to a first-stage scavenging process to obtain a first-stage scavenged concentrate and a first-stage scavenged tailings; returning the first-stage scavenged concentrate to the rougher process;

[0064] The first stage scavenging tailings are subjected to the second stage scavenging treatment to obtain the second stage scavenging concentrate and the second stage scavenging tailings (the final flotation tailings), and the second stage scavenging concentrate is returned to the first stage scavenging process.

[0065] The flotation reagent in each scavenging process is the flotation reagent C containing the collector, wherein the amount of the collector in each scavenging process is 30-50% of the amount of the roughing collector.

[0066] Example 1-1

[0067] This example describes the application of the collector of Formula 1-A in the flotation of bastnaesite. The experimental ore sample was from a location in Sichuan. The original bastnaesite was closely associated with fluorite, calcite and other oxidized minerals. The test temperature was 25°C. The flotation flow chart is as follows: Figure 1 As shown, the specific steps are as follows:

[0068] (1) Ore sample preparation: The grade of the raw bastnaesite is 10.20%. The ore sample is crushed to less than 2 mm using a jaw crusher. The ore sample is mixed and reduced using the pile transfer method.

[0069] (2) Preparation of roughing slurry: The ore sample obtained in step (1) was ground to a concentration of 90% by -0.074 mm mineral particles using a conical ball mill for roughing test. The flotation slurry was adjusted at a speed of 1922 r / min with a mass concentration of 35% to obtain a roughing slurry of fluorocarbon cerium ore.

[0070] (3) Roughing process: Sodium carbonate is used as a pH adjuster to adjust the pH of the fluorocarbon cerium ore roughing slurry to 9, and then an inhibitor, collector, and foaming agent are added in sequence. In the roughing stage, the amount of inhibitor (water glass in this case) is 1300g / t, the amount of collector (Formula 1-A in this case) is 500g / t, and the amount of foaming agent (2# oil) is 50g / t. After the inhibitor is added, the slurry is stirred for 3 minutes, after the collector is added, the slurry is stirred for 25 minutes, and after the foaming agent is added, the slurry is stirred for 3 minutes. After all the reagents are added, aeration is performed for 1 minute, and then the foam product is collected with a scraper for 5 minutes at a scraper speed of 20r / min. The scraped foam product is the fluorocarbon cerium ore roughing concentrate.

[0071] (4) Preparation of Concentrated Slurry: The bastcerium ore rougher concentrate was ground to a particle size of -0.038 mm with a conical ball mill to a concentration ratio of 90% for concentrating. The flotation slurry was adjusted at a speed of 1922 r / min to obtain the bastcerium ore flotation concentrate slurry.

[0072] (5) Concentration process: The feed in the concentration stage I is the regrinding product of the fluorocarbon cerium ore roughing concentrate. The feed in the concentration (II-III) stage is the fluorocarbon cerium ore flotation concentrate product of the previous concentration stage. Depressants and collectors are added in sequence. In the concentration stage I, the amount of water glass is 650g / t, and the amount of formula 1-A is 250g / t. In the concentration (II-III) stage, the amount of water glass is 350g / t, and the amount of formula 1-A is 250g / t. After adding the inhibitor, the slurry is stirred for 3 minutes, and after adding the collector, the slurry is stirred for 25 minutes. After all the reagents are added, the slurry is aerated for 1 minute, and then the foam product is collected with a scraper for 5 minutes at a scraper speed of 20r / min. The foam product is scraped off as the flotation concentrate.

[0073] (6) Scavenging process: The feed for scavenging stage I is fluorocarbon cerium ore roughing tailings, and the feed for scavenging stage II is fluorocarbon cerium ore scavenging stage I tailings. In all scavenging stages, sodium carbonate is used as a pH adjuster. After adjusting the pH of the fluorocarbon cerium scavenging slurry to 9, the collector is added. In scavenging stage I, the dosage of formula 1-A is 200g / t. In scavenging stage II, the dosage of formula 1-A is 200g / t. After adding the collector, the slurry is stirred for 25 minutes. After all the reagents are added, aeration is carried out for 1 minute, and then the foam product is collected with a scraper for 5 minutes at a scraper speed of 20r / min. The product at the bottom of the tank is the flotation tailings.

[0074] (7) Analysis and Testing: The flotation concentrate and tailings were dried and weighed, the grade of bastnaesite in the flotation concentrate and tailings was tested, the yield of the flotation concentrate and tailings products was calculated, and the recovery rate of bastnaesite was calculated. The flotation results are shown in Table 1.

[0075] Example 1-2

[0076] Compared with Example 1-1, the difference is that Formula 1-B is used to replace the collector 1-A in Example 1-1, the collector dosage and other parameters are the same as Example 1-1, and the flotation results are shown in Table 1.

[0077] Examples 1-3

[0078] Compared with Example 1-1, the difference is that Formula 1-C is used to replace the collector 1-A in Example 1-1, the collector dosage and other parameters are the same as Example 1-1, and the flotation results are shown in Table 1.

[0079] Examples 1-4

[0080] Compared with Example 1-1, the difference is that Formula 1-D is used to replace the collector 1-A in Example 1-1, the collector dosage and other parameters are the same as Example 1-1, and the flotation results are shown in Table 1.

[0081] Examples 1-5

[0082] Compared with Example 1-1, the difference is that Formula 1-E is used to replace the collector 1-A in Example 1-1, the collector dosage and other parameters are the same as Example 1-1, and the flotation results are shown in Table 1.

[0083] Examples 1-6

[0084] Compared with Example 1-1, the difference is that Formula 1-F is used to replace the 1-A collector in Example 1-1, the collector dosage and other parameters are the same as Example 1-1, and the flotation results are shown in Table 1.

[0085] Examples 1-7

[0086] Compared with Example 1-3, the only difference is that low-temperature flotation is used, the flotation temperature is 10°C, the amount of collector used and other parameters are the same as Example 1-1. The flotation results are shown in Table 1.

[0087] Comparative Example 1-1

[0088] The only difference compared to Example 1-1 is that the collector of formula 1-A in Example 1-1 is replaced by 2-A, and the amount of collector and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 1.

[0089] Comparative Example 1-2

[0090] The only difference compared to Example 1-1 is that 2-B is used to replace the collector of formula 1-A in Example 1-1, and the amount of collector and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 1.

[0091] Comparative Examples 1-3

[0092] The only difference compared to Example 1-1 is that 2-C is used to replace the collector of Formula 1-A in Example 1-1, and the amount of collector and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 1.

[0093] Comparative Examples 1-4

[0094] The only difference compared to Example 1-1 is that 2-D is used to replace the collector of Formula 1-A in Example 1-1, and the amount of collector and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 1.

[0095] Comparative Examples 1-5

[0096] The only difference compared to Example 1-1 is that 2-E is used to replace the collector of Formula 1-A in Example 1-1, and the amount of collector and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 1.

[0097] Comparative Examples 1-6

[0098] The only difference compared to Example 1-1 is that 2-F is used to replace the collector of Formula 1-A in Example 1-1, and the amount of collector and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 1.

[0099] Comparative Examples 1-7

[0100] The only difference compared to Example 1-7 is that 2-C is used to replace the collector of formula 1-C in Example 1-7, and the amount of collector and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 1.

[0101]

[0102] Table 1. Separation results of different cases in bastnaesite flotation.

[0103]

[0104]

[0105] The flotation results in Table 1 show that, based on the parent core, Formula 2, further modifying the hydroxyl group at the ortho position of Formula 2 helps to further enhance its capture ability and selectivity. On this basis, the para position of the substituent in Formula 2 further contains a C1-C6 alkyl group, a C1-C6 alkoxy group or a vinyl group. It is expected to further synergistically enhance the capture effect of fluorocarbon cerium ore and / or scheelite minerals, especially to improve the capture effect of fluorocarbon cerium ore and / or scheelite minerals that are difficult to finely embed. Among them, R1 and R2 in the molecular structure of Formula 1-C are both polar solid-loving groups, which have the best flotation effect, and a REO concentrate with a grade of 65.51% and a recovery rate of 73.25% is obtained. Formula 1-C, as a new collector, has the advantage of low temperature resistance (Example 7).

[0106] Example 2-1

[0107] This embodiment describes the application of the collector of Formula 1-A in the flotation of scheelite. The experimental ore sample comes from a place in Sichuan. The scheelite in the sample is closely associated with gangue minerals such as quartz and apatite, with fine embedded particle size and low grade. The test temperature is 25℃. The flotation flow chart is as follows: Figure 1 As shown, the specific steps are as follows:

[0108] (1) Ore sample preparation: The grade of the original scheelite ore is about 0.50%. The ore sample is crushed to less than 2 mm by a jaw crusher. The ore sample is mixed and reduced by the pile transfer method.

[0109] (2) Preparation of roughing slurry: The ore sample obtained in step (1) was ground to a concentration of 90% by -0.074 mm mineral particles using a conical ball mill for roughing test. The flotation slurry was adjusted at a speed of 1922 r / min with a mass concentration of 35% to obtain a roughing slurry of scheelite.

[0110] (3) Roughing process: Sodium carbonate is used as a pH adjuster to adjust the pH of the scheelite roughing slurry to 8, and then inhibitors, collectors, and foaming agents are added in sequence. In the roughing stage, the amount of inhibitor water glass is 1000g / t, the amount of collector 1-A is 400g / t, and the amount of 2# oil is 50g / t. After adding the inhibitor, the slurry is stirred for 3 minutes, after adding the collector, the slurry is stirred for 25 minutes, and after adding the foaming agent, the slurry is stirred for 3 minutes. After all the reagents are added, the slurry is aerated for 1 minute, and then the foam product is collected with a scraper for 5 minutes at a scraper speed of 20r / min. The scraped foam product is the scheelite roughing concentrate.

[0111] (4) Preparation of Concentrated Slurry: The scheelite roughing concentrate was ground to a particle size of -0.038 mm (90%) using a conical ball mill for concentrating. The flotation slurry was adjusted at a speed of 1922 r / min to obtain scheelite flotation concentrated slurry.

[0112] (5) Concentration process: The feed in the concentration stage I is the regrinding product of the rougher concentrate of scheelite. The feed in the concentration (II-III) stage is the flotation concentrate product of scheelite in the previous concentration stage. Depressants and collectors are added in sequence. In the concentration stage I, the amount of water glass is 500g / t, and the amount of formula 1-A is 200g / t. In the concentration (II-III) stage, the amount of water glass is 250g / t, and the amount of formula 1-A is 200g / t. After adding the inhibitor, the slurry is stirred for 3 minutes, and after adding the collector, the slurry is stirred for 25 minutes. After all the reagents are added, the slurry is aerated for 1 minute, and then the foam product is collected with a scraper for 5 minutes at a scraper speed of 20r / min. The foam product is scraped off as the flotation concentrate.

[0113] (6) Scavenging process: The feed for scavenging stage I is scheelite rougher tailings, and the feed for scavenging stage II is scheelite scavenging stage I tailings. In all scavenging stages, sodium carbonate is used as a pH adjuster. After adjusting the pH of the scheelite scavenging slurry to 8, the collector is added. In the scavenging stages (I-II), the dosage of formula 1-A is 150g / t. After adding the collector, the slurry is stirred for 25 minutes. After all the reagents are added, aeration is carried out for 1 minute, and then the foam product is collected with a scraper for 5 minutes at a scraper speed of 20r / min. The bottom product is the flotation tailings.

[0114] (7) Analysis and Testing: Dry and weigh the flotation concentrate and tailings, test the grade of scheelite in the flotation concentrate and tailings, calculate the product yield of the flotation concentrate and tailings, and calculate the recovery rate of scheelite. The flotation results are shown in Table 2.

[0115] Example 2-2

[0116] Compared with Example 2-1, the difference is that Formula 1-B is used to replace the collector 1-A in Example 1, and the collector dosage and other parameters are the same as Example 1-1. The flotation results are shown in Table 2.

[0117] Example 2-3

[0118] Compared with Example 2-1, the difference is that Formula 1-C is used to replace the 1-A collector in Example 1, and the collector dosage and other parameters are the same as Example 1-1. The flotation results are shown in Table 2.

[0119] Examples 2-4

[0120] Compared with Example 2-1, the difference is that Formula 1-D is used to replace the 1-A collector in Example 1, and the collector dosage and other parameters are the same as Example 1-1. The flotation results are shown in Table 2.

[0121] Examples 2-5

[0122] Compared with Example 2-1, the difference is that Formula 1-E is used to replace the collector 1-A in Example 1, the collector dosage and other parameters are the same as Example 1-1, and the flotation results are shown in Table 2.

[0123] Examples 2-6

[0124] Compared with Example 2-1, the difference is that Formula 1-F is used to replace the 1-A collector in Example 1, and the collector dosage and other parameters are the same as Example 1-1. The flotation results are shown in Table 2.

[0125] Examples 2-7

[0126] Compared with Example 1-3, the only difference is that low-temperature flotation is used, the flotation temperature is 10°C, the amount of collector used and other parameters are the same as Example 1-1. The flotation results are shown in Table 2.

[0127] Comparative Example 2-1

[0128] The only difference compared to Example 2-1 is that the collector of formula 1-A in Example 1 is replaced by 2-A, and the collector dosage and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 2.

[0129] Comparative Example 2-2

[0130] The only difference compared to Example 2-1 is that the collector of formula 1-A in Example 1 is replaced by 2-B, and the collector dosage and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 2.

[0131] Comparative Examples 2-3

[0132] The only difference compared to Example 2-1 is that the collector of formula 1-A in Example 1 is replaced by 2-C, and the collector dosage and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 2.

[0133] Comparative Examples 2-4

[0134] The only difference compared to Example 2-1 is that 2-D is used to replace the collector of Formula 1-A in Example 1, and the amount of collector and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 2.

[0135] Comparative Examples 2-5

[0136] The only difference compared to Example 2-1 is that 2-E is used to replace the collector of Formula 1-A in Example 1, and the amount of collector and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 2.

[0137] Comparative Examples 2-6

[0138] The only difference compared to Example 2-1 is that 2-F is used to replace the collector of Formula 1-A in Example 1, and the amount of collector and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 2.

[0139] Comparative Examples 2-7

[0140] The only difference compared to Example 2-7 is that the collector of formula 1-C in Example 7 is replaced by 2-C, and the collector dosage and other parameters are the same as those in Example 1-1. The flotation results are shown in Table 2.

[0141] Table 2. Separation results of different cases in scheelite flotation

[0142]

[0143] The flotation results in Table 2 show that Formula 1-C, as a new type of collector, has the advantage of being resistant to low temperatures (Examples 2-7).

[0144] Example 3

[0145] Compared with Example 1-3, the only difference is that the amount of the collector in the roughing stage of step 3 is changed, wherein:

[0146] The collector dosage of group A was 400 g / t;

[0147] The collector dosage of group B was 600 g / t;

[0148] The collector dosage of group C was 700 g / t;

[0149] Other operations and parameters are the same as those in Example 1-C. The results are shown in Table 3:

[0150] Table 3

[0151]

[0152] Example 4

[0153] Compared with Example 2-3, the only difference is that the amount of the collector in the roughing stage of step 3 is changed, wherein:

[0154] The collector dosage of group A was 400 g / t;

[0155] The collector dosage of group B was 600 g / t;

[0156] The collector dosage of group C was 700 g / t;

[0157] Other operations and parameters are the same as those in Example 2-C. The results are shown in Table 4:

[0158] Table 4

[0159]

[0160] In the above examples, considering the yield, grade, and recovery of REO and WO3 concentrates, the 1C collector dosages for bastnaesite and scheelite were 500 g / t and 400 g / t, respectively. In the above examples, the 1C dosage for cleaning was half that for roughing, and the scavenging dosage was 35-40% of that for roughing.

Claims

1. A collector for flotation of bastnaesite and / or scheelite, characterized in that: comprising a compound having a structure of Formula 1; At least one substituent among R1 to R4 is a substituent of formula 2; the remaining substituents are H, hydroxyl, C1 to C6 alkyl, C1 to C6 alkoxy or vinyl; In the formula 2, M is H, Na, K or NH4.

2. The collector for flotation of bastnaesite and / or scheelite according to claim 1, characterized in that: In the collector, the ortho position of the substituent of formula 2 contains a hydroxyl group or an alkoxy group.

3. The collector for flotation of bastnaesite and / or scheelite according to claim 2, characterized in that: In the collector, the para position of the substituent of formula 2 contains a C1-C6 alkyl group, a C1-C6 alkoxy group or a vinyl group.

4. The collector for flotation of bastnaesite and / or scheelite according to any one of claims 1 to 3, characterized in that: The R4 is a substituent of formula 2.

5. A flotation agent for flotation of bastnaesite and / or scheelite, comprising a collector and other flotation aids, wherein the other flotation aids include at least one of a suppressant, a frother, and a pH regulator; characterized in that: The collector comprises the collector according to any one of claims 1 to 4.

6. The flotation agent for flotation of bastnaesite and / or scheelite according to claim 5, characterized in that: The flotation aid comprises an inhibitor, wherein the inhibitor comprises at least one of water glass and carboxymethyl cellulose; Preferably, the flotation aid comprises a foaming agent, wherein the foaming agent comprises at least one of 2# oil and methyl isobutyl carbinol; Preferably, the flotation aid contains a pH regulator.

7. A method for flotation of bastnaesite and / or scheelite, characterized in that: Mixing the minerals to be selected, including at least one target ore selected from bastnaesite and / or scheelite, and a flotation agent for flotation to obtain a target ore concentrate; Wherein, the flotation reagent comprises the collector according to any one of claims 1 to 4.

8. The method for flotation of bastnaesite and / or scheelite according to claim 7, characterized in that: The flotation stage includes a roughing process, wherein the amount of collector used in the roughing stage is 300-700 g / t, preferably 400-500 g / t; Preferably, the flotation stage also includes a concentration and / or scavenging process, wherein the amount of collector used in the concentration stage is 30-100 wt.% of that used in the roughing stage; the amount of collector used in the scavenging stage is 30-100 wt.% of that used in the roughing stage.

9. The method for flotation of bastnaesite and / or scheelite according to claim 8, characterized in that: The flotation reagents in the roughing stage include a frother, wherein the amount of the frother is 40-50 g / t; The flotation reagents in the roughing and cleaning stages contain inhibitors, wherein the amount of the inhibitor is 900-1400 g / t, preferably 1000-1300 g / t; the amount of the inhibitor in the cleaning stage is 40-100 wt.% of the amount of the inhibitor in the roughing stage.

10. The method for flotation of bastnaesite and / or scheelite according to claim 8, characterized in that: The pH value in the flotation stage is 8-9.

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