Cassiterite flotation collecting agent and application thereof
By using di(2-ethylhexyl) phosphate as a flotation collector for cassiterite, the hydrophobicity of the cassiterite surface is improved, which solves the problem of poor selectivity of cassiterite collectors in the prior art. This achieves efficient separation and recovery of cassiterite and gangue, and has good environmental friendliness and adaptability.
Patent Information
- Application Number
- CN202511253580.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-03
- Publication Date
- 2025-11-18
AI Technical Summary
Existing cassiterite collectors have poor selectivity, are prone to co-adsorption with gangue minerals, and are sensitive to temperature and ions, resulting in lower concentrate grades and limiting their application in complex ores.
Di(2-ethylhexyl) phosphate was used as a flotation collector for cassiterite. By improving the hydrophobicity of the cassiterite surface, efficient separation of cassiterite and gangue minerals was achieved. The multi-branched structure was used to enhance the collecting ability.
It significantly improves the recovery rate and selectivity of cassiterite, achieving efficient separation of cassiterite from gangue. Moreover, this collector is non-toxic, environmentally friendly, highly adaptable, and suitable for low-alkaline environments.
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Figure CN120961311A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of mineral flotation, in particular to a cassiterite flotation collector and application thereof. BACKGROUND
[0002] Cassiterite is an important strategic mineral resource, and its main component is tin dioxide. The efficient flotation recovery of cassiterite has long relied on the application of high-performance collectors. The early widely used collectors are fatty acid reagents such as oleic acid and oxidized paraffin soap, which are widely available and low in cost. However, such collectors have obvious shortcomings, and their selectivity is generally poor, which can easily co-absorb with gangue minerals such as calcite and fluorite, resulting in a decrease in concentrate grade. At the same time, they are very sensitive to pulp temperature and calcium and magnesium ions, and usually need to be used at a high temperature above 30℃ and in softened water to achieve good results, which not only increases the cost of mineral processing, but also greatly limits their application in complex ores. The current development of cassiterite collectors is towards low-temperature high-efficiency, environmental friendliness and strong adaptability, in order to meet the challenges of lean and complex ore resources. Therefore, the development of new high-efficiency collectors has become an urgent need in this field. SUMMARY
[0003] In order to solve the problem of poor selectivity of collectors in cassiterite flotation and complex flotation conditions, the present application provides a cassiterite flotation collector and application thereof, which can realize efficient separation of cassiterite and gangue minerals by improving the hydrophobicity of the surface of cassiterite.
[0004] The collector according to the present application is di(2-ethylhexyl) phosphate, and the molecular formula of the collector is C 20 H 27 O4P; The structural formula of the collector is: The cassiterite flotation collector according to the present application can be applied to the flotation of cassiterite and gangue.
[0005] The flotation according to the present application includes 1 roughing, 2-3 scavenging and 1-2 cleaning, and the collector is added in the roughing and scavenging processes.
[0006] As a preferred embodiment of the present application, the addition amount of the collector in the 1 roughing process is 400-1000g / t.
[0007] As a preferred embodiment of the present application, in the 2-3 scavenging processes, the addition amount of the collector in scavenging I operation is 200-500g / t, the addition amount of the collector in scavenging II operation is 100-250g / t, and the addition amount of the collector in scavenging III operation is 50-125g / t.
[0008] The application of the collector in the flotation separation of cassiterite and gangue specifically comprises the following steps: (1) Preparing a cassiterite slurry and adjusting the pH value of the slurry to 7-9.
[0009] (2) Adding an activator, an inhibitor, a collector and a frother into the slurry in sequence to perform rough separation and obtain a rough concentrate and a rough tailing.
[0010] (3) Adding the collector and the frother into the rough tailing to perform 2-3 times of scavenging separation and obtain a scavenging concentrate, and no frother is added in the last scavenging operation.
[0011] (4) Adding the inhibitor into the rough concentrate to perform 1-2 times of cleaning separation and obtain a tin concentrate.
[0012] The rough separation, the scavenging separation and the cleaning separation are conventional operations, and as a preferred embodiment of the present application, in the rough separation process, the activator is lead acetate, and the addition amount of the lead acetate is 40-80 g / t; the inhibitor is a mixture of sodium carboxymethyl starch (hereinafter referred to as CMS) and sodium hexametaphosphate, and the addition amount of the inhibitor is 300-500 g / t, wherein the mass ratio of the CMS to the sodium hexametaphosphate is 1:0.5-1.5; and the frother is methyl isobutyl carbinol (hereinafter referred to as MIBC), and the addition amount of the MIBC is 20-40 g / t.
[0013] As a preferred embodiment of the present application, in the scavenging separation process, the frother is methyl isobutyl carbinol; the addition amount of the frother in the first scavenging operation is 10-20 g / t, and the addition amount of the frother in the second scavenging operation is 10-20 g / t.
[0014] As a preferred embodiment of the present application, in the cleaning separation process, the inhibitor is a mixture of sodium carboxymethyl starch and sodium hexametaphosphate, and the mass ratio of the CMS to the sodium hexametaphosphate is 1:0.5-1.5; the addition amount of the inhibitor in the first cleaning operation is 150-250 g / t; and the addition amount of the inhibitor in the second cleaning operation is 75-125 g / t.
[0015] As a preferred embodiment of the present application, the di(2-ethylhexyl) phosphate is added in the form of an aqueous solution with a mass percentage concentration of 0.1-1%; the MIBC is added in the form of a stock solution; the lead acetate is added in the form of an aqueous solution with a mass percentage concentration of 1-5%; the CMS is added in the form of an aqueous solution with a mass percentage concentration of 1-5%; and the sodium hexametaphosphate is added in the form of an aqueous solution with a mass percentage concentration of 1-5%.
[0016] Compared with the prior art, the present application provides a tin ore flotation collector and an application thereof, and has the following beneficial effects: (1) The application adopts an organic phosphoric acid compound di(2-ethylhexyl) phosphate with a multi-branched structure as a cassiterite flotation collector, di(2-ethylhexyl) phosphate enhances the selectivity to cassiterite minerals while significantly improving the hydrophobic properties thereof, the introduction of the multi-branched structure effectively enhances the collecting capacity of the reagent, so that the recovery rate and selectivity of cassiterite are simultaneously improved, and finally the efficient separation of cassiterite flotation is realized.
[0017] (2) The multi-branched phosphoric acid collector di(2-ethylhexyl) phosphate used in the application is non-toxic and environmentally friendly, has good water solubility, which helps the reagent to quickly dissolve and disperse in the ore pulp, the collector can be used in a low alkaline environment, has strong adaptability, and has good industrial application prospect. BRIEF DESCRIPTION OF DRAWINGS
[0018] Figure 1 is a tin stone flotation flow chart of the embodiment 1 of the application.
[0019] Figure 2 is a tin stone flotation flow chart of the comparative example 1 of the application.
[0020] Figure 3 is a tin stone flotation flow chart of the embodiment 2 of the application.
[0021] Figure 4 is a tin stone flotation flow chart of the comparative example 2 of the application.
[0022] Figure 5 is a tin stone flotation flow chart of the embodiment 3 of the application.
[0023] Figure 6 is a tin stone flotation flow chart of the comparative example 3 of the application.
[0024] Figure 7 is a tin stone flotation flow chart of the embodiment 4 of the application. DETAILED DESCRIPTION
[0025] The technical solutions in the embodiments of the application will be described clearly and completely in combination with the drawings in the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.
[0026] Embodiment 1 The application of the tin stone flotation collector described in this embodiment in tin stone pure mineral flotation specifically includes the following steps, and the flow chart is shown in Figure 1 : (1) Preparation of cassiterite slurry: 2 g of mixed ore (cassiterite and quartz / calcite mass ratio of 1:1) with particle size of -74~+38 μm and 35 mL of distilled water were added into a 40 mL hanging tank flotation machine, and the slurry was stirred at a speed of 1600 r / min to obtain the cassiterite slurry, and the pH value of the slurry was adjusted to about 7~9.
[0027] (2) First, the collector di(2-ethylhexyl) phosphate was added, and the collector concentration was controlled to be 25 mg / L, 30 mg / L, 35 mg / L, 40 mg / L, and 45 mg / L, respectively; then MIBC frother (concentration of 15 mg / L) was added; after all the flotation reagents were added, air flotation was carried out, and after the flotation was completed, the obtained foam product and tailings in the flotation tank were obtained.
[0028] (3) The foam product and tailings were dried and weighed to calculate the yield, i.e. the recovery rate. The pure mineral flotation results are shown in Table 1. According to the results, the phosphoric acid collector can effectively separate cassiterite from quartz and calcite, and the indicators are similar. When the concentration of the collector in the slurry is in the range of 30~45 mg / L, the recovery rate of cassiterite is about 92%, and the grade of cassiterite is above 74%. Too low concentration will lead to low recovery rate of cassiterite, and too high concentration will lead to meaningless reagent consumption and increased recovery rate of quartz or calcite.
[0029] Table 1 Comparative Example 1 This comparative example uses JG-12 (dodecyl phosphite) and JG-8 (octyl phosphite) as collectors in the application of pure cassiterite flotation, which specifically includes the following steps, and the flow chart is shown in Figure 2 : (1) Preparation of cassiterite slurry: 2 g of mixed ore (cassiterite and quartz / calcite mass ratio of 1:1) with particle size of -74~+38 μm and 35 mL of distilled water were added into a 40 mL hanging tank flotation machine, and the slurry was stirred at a speed of 1602 r / min to obtain the cassiterite slurry, and the pH value of the slurry was adjusted to about 7~9.
[0030] (2) First, the collector JG-12 (dodecyl phosphite) and JG-8 (octyl phosphite) were added, and the collector concentration was controlled to be 25 mg / L, 30 mg / L, 35 mg / L, 40 mg / L, and 45 mg / L, respectively; then MIBC frother (concentration of 15 mg / L) was added; after all the flotation reagents were added, air flotation was carried out, and after the flotation was completed, the obtained foam product and tailings in the flotation tank were obtained.
[0031] (3) The foam product and tailings were dried and weighed to calculate the yield, i.e. the recovery rate.
[0032] The pure mineral flotation results are shown in Table 2. From the results, it can be seen that JG-12 and JG-8 can both have an effect on the flotation separation of cassiterite from quartz and calcite, and the indexes are similar, but far lower than the flotation indexes of bis(2-ethylhexyl)phosphate.
[0033] Table 2 Example 2 This example uses a certain cassiterite mountain raw ore in Guangxi with a tin grade of 0.28%, and bis(2-ethylhexyl)phosphate is used as a collector for flotation. The specific steps include the following, and the flow chart is shown in Figure 3 : (1) In the preparation of the ore sample, the ore is first ground in a grinding machine until the mineral monomers are dissociated, and a slurry of -200 mesh accounting for 90% is obtained. The pH value of the slurry is adjusted to the range of 7-9.
[0034] (2) 40 g / t of lead acetate, 150 g / t of CMS, 150 g / t of sodium hexametaphosphate and 400 g / t of bis(2-ethylhexyl)phosphate are sequentially added to the slurry, followed by the addition of 20 g / t of MIBC, and then aeration is performed for roughing to obtain a rough concentrate and a rough tailing.
[0035] (3) 200 g / t of bis(2-ethylhexyl)phosphate is added to the obtained rough tailing, followed by the addition of 10 g / t of MIBC, and then the first scavenging is performed; 100 g / t of bis(2-ethylhexyl)phosphate is added to the obtained first scavenging tailing, and then the second scavenging is performed, to obtain a flotation tailing (scavenging middlings are returned to the previous flotation operation to form a closed circuit).
[0036] (4) 75 g / t of CMS and 75 g / t of sodium hexametaphosphate are added to the obtained rough concentrate, and then the first cleaning is performed to obtain a flotation concentrate (cleaning middlings are returned to the previous flotation operation to form a closed circuit).
[0037] (5) The obtained froth product concentrate and tailing are dried and weighed to calculate the recovery rate.
[0038] Under the condition of a given ore tin grade of 0.28%, after one roughing, one cleaning and two scavengings, a tin concentrate with a tin grade of 33.23% and a recovery rate of 84.36% can be obtained.
[0039] Comparative Example 2 This comparative example uses a certain cassiterite mountain raw ore in Guangxi with a tin grade of 0.28%, and JG-12 is used as a collector for flotation. The specific steps include the following, and the flow chart is shown in Figure 4 : (1) In the preparation of the ore sample, the ore is first ground in a grinding machine until the mineral monomers are dissociated to obtain an ore slurry with 90% of -200 mesh, and then the pH value of the ore slurry is adjusted to the range of 7-9.
[0040] (2) 40 g / t of lead acetate, 150 g / t of CMS, 150 g / t of sodium hexametaphosphate and 400 g / t of JG-12 are sequentially added to the ore slurry, 20 g / t of MIBC is then added, and then roughing is carried out under aeration to obtain a rough concentrate and a rough tailing.
[0041] (3) 200 g / t of JG-12 is added to the obtained rough tailing, 10 g / t of MIBC is then added, and then the first scavenging is carried out; 100 g / t of JG-12 is added to the obtained first scavenging tailing, and then the second scavenging is carried out to obtain a flotation tailing (scavenging middlings are returned to the previous flotation operation to form a closed circuit).
[0042] (4) 75 g / t of CMS and 75 g / t of sodium hexametaphosphate are added to the obtained rough concentrate, and then the first cleaning is carried out to obtain a flotation concentrate (cleaning middlings are returned to the previous flotation operation to form a closed circuit).
[0043] (5) The obtained froth product concentrate and tailing are dried and weighed to calculate the recovery rate.
[0044] Under the condition that the tin grade of the given ore is 0.28%, after one roughing, one cleaning and two scavengings, a tin concentrate with a tin grade of 10.48% and a recovery rate of 50.40% is obtained, which is far lower than the flotation index of di(2-ethylhexyl) phosphate collector.
[0045] Example 3 This example uses a certain tin stone in Yunnan Province with a tin grade of 0.32%, and di(2-ethylhexyl) phosphate is used as a collector for flotation, which specifically includes the following steps, and the flow chart is shown in Figure 5 : (1) In the preparation of the ore sample, the ore is first ground in a grinding machine until the mineral monomers are dissociated to obtain an ore slurry with 90% of -200 mesh, and then the pH value of the ore slurry is adjusted to the range of 7-9.
[0046] (2) 60 g / t of lead acetate, 240 g / t of CMS, 120 g / t of sodium hexametaphosphate and 750 g / t of di(2-ethylhexyl) phosphate are sequentially added to the ore slurry, 30 g / t of MIBC is then added, and then roughing is carried out under aeration to obtain a rough concentrate and a rough tailing.
[0047] (3) To the obtained rough tailings, 375 g / t of di(2-ethylhexyl) phosphate was added, stirred for 3 min, 15 g / t of MIBC was added, and then the first scavenging was carried out; to the obtained first scavenging tailings, 180 g / t of di(2-ethylhexyl) phosphate was added, and then the second scavenging was carried out, to obtain the flotation tailings (scavenging middlings returned to the previous flotation operation to form a closed circuit).
[0048] (4) To the obtained rough concentrate, 120 g / t of CMS and 60 g / t of sodium hexametaphosphate were added, and then the first cleaning was carried out, to obtain the flotation concentrate (cleaning middlings returned to the previous flotation operation to form a closed circuit).
[0049] (5) The obtained froth product concentrate and tailings were dried and weighed to calculate the recovery rate.
[0050] Under the condition that the tin grade of the given ore is 0.32%, after one roughing, one cleaning and two scavengings, a tin concentrate with a tin grade of 34.18% and a recovery rate of 85.49% can be obtained.
[0051] Comparative Example 3 This comparative example uses a certain tin stone mountain raw ore in Yunnan Province with a tin grade of 0.32%, and JG-8 is used as the collector for flotation, which specifically includes the following steps, and the flow chart is shown in Figure 6 : (1) In the preparation of the ore sample, the ore was first ground in a grinding machine to obtain a mineral slurry with 90% of -200 mesh after the mineral monomer was dissociated, and then the pH value of the mineral slurry was adjusted to be in the range of 7-9.
[0052] (2) To the mineral slurry, 60 g / t of lead acetate, 240 g / t of CMS, 120 g / t of sodium hexametaphosphate and 750 g / t of JG-8 were added in turn, 30 g / t of MIBC was added, and then roughing was carried out by aeration to obtain rough concentrate and rough tailings.
[0053] (3) To the obtained rough tailings, 375 g / t of JG-8 was added, stirred for 3 min, 15 g / t of MIBC was added, and then the first scavenging was carried out; to the obtained first scavenging tailings, 180 g / t of JG-8 was added, and then the second scavenging was carried out, to obtain the flotation tailings (scavenging middlings returned to the previous flotation operation to form a closed circuit).
[0054] (4) To the obtained rough concentrate, 120 g / t of CMS and 60 g / t of sodium hexametaphosphate were added, and then the first cleaning was carried out, to obtain the flotation concentrate (cleaning middlings returned to the previous flotation operation to form a closed circuit).
[0055] (5) The obtained froth product concentrate and tailings were dried and weighed to calculate the recovery rate.
[0056] Under the condition of the tin grade of the given ore being 0.32%, after one roughing, one cleaning and two scavenging, a tin concentrate with a tin grade of 11.38% and a recovery rate of 49.68% is obtained, which is far lower than the flotation index of di(2-ethylhexyl) phosphate collector.
[0057] Example 4 This example uses a certain tin stone mountain raw ore in Yunnan Province with a tin grade of 0.45%, and di(2-ethylhexyl) phosphate is used as a collector for flotation, which specifically includes the following steps, and the flow chart is shown in Figure 7 : (1) In the preparation of the ore sample, the ore is first ground in a grinding machine to obtain a slurry with 90% of -200 mesh mineral monomers, and then the pH value of the slurry is adjusted to be in the range of 7-9.
[0058] (2) 80 g / t of lead acetate, 200 g / t of CMS, 300 g / t of sodium hexametaphosphate and 1000 g / t of di(2-ethylhexyl) phosphate are sequentially added to the slurry, then 40 g / t of MIBC is added, and then roughing is performed under aeration to obtain a rough concentrate and a rough tailing.
[0059] (3) 500 g / t of di(2-ethylhexyl) phosphate is added to the obtained rough tailing, then 20 g / t of MIBC is added, and then the first scavenging is performed; 250 g / t of di(2-ethylhexyl) phosphate is added to the obtained first scavenging tailing, then 10 g / t of MIBC is added, and then the second scavenging is performed; 125 g / t of di(2-ethylhexyl) phosphate is added to the obtained second scavenging tailing, and then the third scavenging is performed to obtain a flotation tailing (the middling of scavenging is returned to the previous flotation operation to form a closed circuit).
[0060] (4) 100 g / t of CMS and 150 g / t of sodium hexametaphosphate are added to the obtained rough concentrate, and then the first cleaning is performed; 50 g / t of CMS and 75 g / t of sodium hexametaphosphate are added to the obtained first cleaning concentrate, and then the second cleaning is performed to obtain a flotation concentrate (the middling of cleaning is returned to the previous flotation operation to form a closed circuit).
[0061] (5) The obtained froth product concentrate and tailing are dried and weighed to calculate the recovery rate.
[0062] Under the condition of the tin grade of the given ore being 0.45%, after one roughing, two cleanings and three scavengings, a tin concentrate with a tin grade of 45.23% and a recovery rate of 81.49% is obtained.
[0063] The di(2-ethylhexyl) phosphate organic phosphoric acid compound with multiple branched chains is used as a flotation collector for cassiterite, and the collecting capacity and selectivity of the cassiterite are significantly improved, so that efficient separation of the cassiterite in mixed ore flotation can be realized.
[0064] While embodiments of the application have been shown and described, it is to be understood that the application is not limited to the details of the embodiments described, since numerous changes, modifications, substitutions and variations can be made thereto without departing from the spirit and scope of the application as defined by the appended claims and their equivalents.
Claims
1. A cassiterite flotation collector, characterized in that, The collector is di(2-ethylhexyl) phosphate, and the molecular formula of the collector is C2. 20 H 27 O4P; The structural formula of the collector is: 。 2. The application of the cassiterite flotation collector according to claim 1 in cassiterite flotation.
3. The application of the cassiterite flotation collector according to claim 2 in cassiterite flotation, characterized in that, The flotation process includes one roughing stage, two to three scavenging stages, and one to two cleaning stages, with the collector added during the roughing and scavenging stages.
4. The application of the cassiterite flotation collector according to claim 2 in cassiterite flotation, characterized in that, The amount of collector added during the first roughing process is 400-1000 g / t.
5. The application of the cassiterite flotation collector according to claim 2 in cassiterite flotation, characterized in that, During the 2nd to 3rd scavenging processes, the amount of collector added in scavenging operation I is 200-500 g / t, the amount of collector added in scavenging operation II is 100-250 g / t, and the amount of collector added in scavenging operation III is 50-125 g / t.