A method for flotation separation and recovery of tungsten and fluorite from high-calcium tungsten-fluorite associated ores and its application

Abstract

The present invention relates to a method and application for flotation separation and recovery of tungsten and fluorite from high-calcium tungsten-fluorite associated ores, belonging to the field of mineral processing. The method of the present invention is to crush and wet-grind the high-calcium tungsten-fluorite associated ores until monomer dissociation is achieved, use melamine resin superplasticizer as an efficient depressant for calcite, saponified oleic acid as a collector, and flotation-separate scheelite, fluorite and calcite to obtain a mixed concentrate of scheelite and fluorite. For the mixed concentrate, water glass and naphthalene sulfonate-polyformaldehyde condensate are used as fluorite depressants, and saponified oleic acid is used as a collector to flotation-separate scheelite and fluorite, respectively obtaining qualified tungsten concentrate and fluorite concentrate. The process of the present invention is simple, has a short flow, does not require heating, is easy to operate, has strong stability, is green and clean, and greatly improves the resource utilization rate and comprehensive recovery rate.

Description

Technical Field

[0001] The present invention relates to a method for flotation separation and recovery of tungsten and fluorite from a high-calcium tungsten-fluorite associated ore, belonging to the technical field of ore dressing. Background Art

[0002] Scheelite is an important part of China's tungsten ore resources. The grade of scheelite in China is low and the components are complex. Especially, it is associated with calcium-containing minerals such as fluorite, calcite, and garnet, making the ore dressing difficult. There are relatively large reserves of high-calcium tungsten-fluorite ores in China, and their main calcium-containing minerals are scheelite, fluorite, and calcite. Since the three minerals have similar active sites on the surface, their floatabilities are similar, resulting in great difficulty in flotation separation. In addition, both scheelite and fluorite ores belong to important strategic mineral resources in China. How to efficiently recover tungsten and fluorite comprehensively is the focus of current research by relevant scientific researchers.

[0003] At present, a large amount of research has been done by domestic and foreign scientific researchers on the comprehensive recovery of tungsten and fluorite. There are mainly three process routes: (1) Prior flotation of tungsten and then flotation of fluorite, that is, in a weakly alkaline medium, by adding a large amount of water glass to inhibit fluorite and calcite, and preferentially obtaining tungsten concentrate. After the tailings of tungsten flotation are subjected to de-drug treatment, fluorite and calcite are flotated and separated to obtain fluorite concentrate. However, due to the addition of a large amount of water glass during the prior flotation of tungsten, the floatability of fluorite is poor, and the comprehensive recovery rate of fluorite is relatively low, and the ore dressing index is not ideal. (2) Prior flotation of fluorite and then flotation of tungsten, that is, by adding a macromolecular organic inhibitor and inorganic acid to inhibit scheelite and calcite, preferentially flotation of fluorite, and then adjusting the pulp pH value to weakly alkaline and then flotation of tungsten. The fluorite recovery effect of this process is good, but a large amount of tungsten is enriched in the fluorite concentrate, resulting in a relatively low flotation recovery rate of tungsten, and the ore dressing index is not ideal. (3) Tungsten-fluorite bulk flotation process, that is, in a weakly alkaline medium, by adding an inhibitor to inhibit the floating of calcite, realizing the bulk flotation of tungsten and fluorite to obtain a tungsten-fluorite bulk concentrate, and then adding a fluorite inhibitor or a scheelite inhibitor to separate scheelite and fluorite. While this process can obtain qualified tungsten and fluorite concentrates, the ore dressing process flow is relatively concise, and the ore dressing recovery rate is relatively ideal. However, the main difficulty and technical core of this process are the development and application of efficient calcite inhibitors and fluorite inhibitors.

[0004] Chinese Patent Application CN202010530240.8 discloses a beneficiation method for high-calcium type low-grade scheelite ore. Its beneficiation process is heavy medium pre-tailing - rough flotation of tungsten and fluorite mixture - cleaning of tungsten and fluorite mixture - heating separation of tungsten and fluorite - heating separation of tungsten and calcium carbonate, so as to obtain tungsten concentrate and fluorite concentrate. This process flow is complex. When using water glass as gangue inhibitor in the mixed flotation, the inhibitory effect on calcite is poor. A large amount of calcite enters the subsequent heating cleaning section, and a large amount of water glass needs to be added to achieve the separation of tungsten - fluorite and tungsten - calcite, and heating is required, resulting in high energy consumption. At the same time, due to the addition of water glass in the roughing and mixed flotation, part of the fluorite is inhibited and enters the tailings, resulting in a low fluorite recovery rate.

[0005] Chinese Patent Application CN201610008530.X discloses a method for comprehensive recovery of associated tungsten and fluorite resources. Its beneficiation process is desulfurization tailings tungsten and fluorite mixed flotation + acid leaching of mixed concentrate to remove calcium + tungsten and fluorite flotation separation. Although this process can achieve the separation after the mixed flotation of tungsten - fluorite and obtain qualified fluorite concentrate, the tungsten concentrate still needs to be further enriched to be used as a qualified concentrate product. And when adding tannin extract and tannin in the mixed flotation of tungsten - fluorite, scheelite will be inhibited, resulting in a decrease in tungsten recovery rate. In addition, when using hydrochloric acid leaching to remove calcium from the mixed concentrate, a large amount of acidic high-calcium wastewater will be generated, which pollutes the environment. At the same time, the floatability of the ore after acid leaching is poor, and a large amount of alkali and collector are required to achieve the separation of tungsten and fluorite.

[0006] From the current technology, the comprehensive recovery indexes of tungsten and fluorite in high-calcium type tungsten-fluorite associated ore are not ideal. Therefore, it is urgent to develop a beneficiation method for efficient comprehensive recovery of tungsten and fluorite from high-calcium type tungsten-fluorite associated ore. Summary of the Invention

[0007] Aiming at the deficiencies of the prior art, one of the purposes of the present invention is to provide a method for flotation separation and recovery of tungsten and fluorite from high-calcium type tungsten-fluorite associated ore to achieve efficient separation of tungsten concentrate, fluorite and calcium carbonate minerals; the second purpose of the present invention is to provide the application of melamine resin superplasticizer as an inhibitor of calcium carbonate minerals.

[0008] To solve the above technical problems, the technical solution of the present invention is as follows:

[0009] A method for flotation separation and recovery of tungsten and fluorite from high-calcium type tungsten-fluorite associated ore, comprising the following steps:

[0010] S1. Grind the to-be-treated high-calcium type tungsten-fluorite associated ore to obtain pulp;

[0011] S2. Add a pH adjuster, a first inhibitor, and a collector to the pulp obtained in S1, and conduct rough flotation 1 to obtain rough concentrate 1 and rough tailings 1;

[0012] Among them, the first inhibitor is a melamine resin superplasticizer;

[0013] S3. Conduct at least 2 times of cleaning on the rough concentrate 1 obtained in S2 to obtain cleaned concentrate;

[0014] Among them, before each cleaning, first add the first inhibitor and stir evenly; return the middlings obtained from each cleaning to the previous stage of flotation;

[0015] S4. Add a second inhibitor and a collector to the cleaned concentrate obtained in S3, and conduct rough flotation 2 to obtain rough concentrate 2 and rough tailings 2;

[0016] Among them, the second inhibitor includes a naphthalene sulfonate-polyformaldehyde condensate;

[0017] S5. Conduct at least 2 times of cleaning on the rough concentrate 2 obtained in S4 to obtain tungsten concentrate;

[0018] Conduct at least 2 times of scavenging on the rough tailings 2 obtained in S4 to obtain fluorite concentrate;

[0019] Among them, before each cleaning, first add the third inhibitor and stir evenly; return the middlings obtained from each cleaning to the previous stage of flotation; the third inhibitor is a naphthalene sulfonate-polyformaldehyde condensate;

[0020] Before each scavenging, first add a collector and stir evenly; return the scavenged tailings obtained from each scavenging to the previous stage of flotation.

[0021] In this way, after the original ore is ground in the present invention, first, tungsten and fluorite are mixed and floated through rough flotation 1 and cleaning to remove calcium carbonate minerals such as calcite and other silicate gangues in the ore, and a tungsten-fluorite mixed flotation concentrate is obtained; then, tungsten-fluorite normal-temperature flotation separation is carried out through rough flotation 2, cleaning, and scavenging to obtain tungsten concentrate and fluorite concentrate, and efficient separation of tungsten concentrate, fluorite, and calcite can be achieved.

[0022] Furthermore, the structural formula of the melamine resin superplasticizer is as follows:

[0023]

[0024] Among them, M is Na + or K + .

[0025] Preferably, the molecular weight of the melamine resin superplasticizer is 30000 - 50000. In this way, it is helpful to obtain a better separation effect.

[0026] Further, the naphthalene sulfonate polyoxymethylene condensate is a sodium naphthalene sulfonate polyoxymethylene condensate, and its structural formula is as follows:

[0027]

[0028] Preferably, the degree of polymerization of the naphthalene sulfonate polyoxymethylene condensate is 9 - 13.

[0029] Further, in S2, the addition amount of the first inhibitor is 200 - 800 g / t - raw ore (that is, 200 - 800 g of the first inhibitor is added to the pulp corresponding to every 1 t of the high - calcium tungsten fluorite associated ore), preferably 250 - 600 g / t - raw ore; optionally, after adding the first inhibitor, stir for 1 - 5 min to mix evenly;

[0030] In S3, before each roughing, the addition amount of the first inhibitor is 10 - 80 g / t - raw ore. Optionally, after adding the first inhibitor, stir for 1 - 5 min.

[0031] Furthermore, in S3, three roughings are carried out. Optionally, during roughing, aeration flotation is carried out for 1 - 4 min.

[0032] Further, in S4, the addition amount of the second inhibitor is 1100 - 3300 g / t - raw ore; further, the second inhibitor is composed of a naphthalene sulfonate polyoxymethylene condensate and water glass in a mass ratio of 1 - 3:10 - 30. Optionally, after adding the second inhibitor, stir for 15 - 60 min.

[0033] Further, in S4, the addition amount of the collector is 5 - 20 g / t - raw ore. Optionally, after adding the collector, mix evenly by stirring, and the stirring time is 1 - 5 min.

[0034] Preferably, in S4, the time of aeration flotation is 2 - 5 min.

[0035] Further, in S5, the addition amount of the third inhibitor is 0 - 50 g / t - raw ore, preferably 5 - 35 g / t - raw ore. Preferably, after adding the third inhibitor, mix evenly by stirring, and the stirring time is 1 - 5 min; preferably, the time of aeration flotation is 2 - 5 min.

[0036] Further, in S5, roughing is carried out 2 - 6 times; scavenging is carried out 2 - 4 times.

[0037] Further, in each scavenging operation in S5, the addition amount of the collector is 1 - 10 g / t - raw ore; preferably, after adding the collector, mix evenly by stirring, and the stirring time is 1 - 5 min; preferably, the time of aeration flotation is 1 - 5 min.

[0038] Further, in S1, the mass concentration of the pulp is 25 - 38%.

[0039] Further, in S2, the rougher tailings 1 are scavenged multiple times, and the obtained scavenging concentrates are returned to the previous stage of flotation.

[0040] Among them, when scavenging each time, 40 - 100 g / t - of the original ore of collector is added. Optionally, the scavenging tailings obtained by scavenging are sent to the next - stage scavenging or directly discarded as tailings.

[0041] Even further, in S2, scavenging is carried out 3 times.

[0042] Further, in S2, a pH adjuster is added first to adjust the pH value of the pulp to 8 - 9. Generally, after adding the pH adjuster, it can be mixed evenly by stirring, and the stirring time is 1 - 3 min.

[0043] Further, the pH adjuster is sodium hydroxide or / and sodium carbonate, and the collector is one or several of oleic acid, saponified oleic acid, oxidized paraffin soap, naphthenic acid soap, and hydroxamic acid soap. Generally, the collector components used in different steps can be the same or different, and preferably the collectors with the same components are used.

[0044] Optionally, both roughing 1 and roughing 2 are air - inflated flotation. Further, the air - inflated flotation time in roughing 1 is 2 - 8 min.

[0045] Further, in S1, in the high - calcium type tungsten - fluorite associated ore, the mass percentage content of WO3 is 0.05% - 1.0%, preferably 0.2 - 0.6%; the mass percentage content of CaF2 is 4.0% - 30.0%, preferably 10 - 25%; the mass percentage content of CaCO3 is 5.0% - 50.0%, preferably 10% - 35%.

[0046] Further, in S1, when grinding, the mass of the added water is 0.5 - 0.8 times the mass of the original ore, and wet - ground to the mass of the ore passing through a 0.074 mm sieve / the total mass of the original ore = 50% - 75%. At the grinding fineness ratio, it is more conducive to the monomer dissociation between the useful minerals and gangue minerals. Optionally, after grinding, water is further added for pulp adjustment to adjust the concentration of the pulp to the target concentration.

[0047] Further, S2 - S5 are all carried out under normal temperature conditions.

[0048] Based on the same inventive concept, the present invention also provides the application of melamine resin superplasticizer as an inhibitor for calcium carbonate minerals or silicate minerals.

[0049] The applicant's research found that the melamine resin superplasticizer has a good inhibitory effect on calcium carbonate minerals and silicate minerals, and can be used as an inhibitor for calcium carbonate minerals or silicate minerals to achieve efficient flotation separation of calcium carbonate minerals or silicate minerals from other valuable minerals.

[0050] Optionally, the calcium carbonate mineral is calcite.

[0051] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0052] (1) By adopting the process of combined flotation of tungsten and fluorite + separation flotation of tungsten and fluorite, the melamine resin superplasticizer inhibitor added in the combined flotation operation of tungsten and fluorite can efficiently inhibit calcite and silicate minerals, while having no significant inhibitory effect on scheelite and fluorite. This avoids the loss of tungsten and fluorite to the tailings, and can effectively improve the comprehensive recovery rates of tungsten and fluorite while obtaining qualified tungsten concentrate and fluorite concentrate.

[0053] (2) In the beneficiation process of the present invention, no acid or acidic substances are added, and no acidic wastewater or high-salt wastewater is generated; the dosage of water glass in the whole process is small, which is beneficial to the treatment and reuse of beneficiation wastewater, and has good environmental benefits.

[0054] (3) Since most of the calcite gangue minerals are removed in the combined flotation operation of tungsten and fluorite, and the combined inhibitor of water glass and naphthalene sulfonate formaldehyde condensate can efficiently inhibit the flotation of fluorite in the separation flotation operation of tungsten and fluorite, the normal-temperature flotation separation of tungsten and fluorite can be achieved.

[0055] (4) The process of the present invention is simple, the process flow is short, no heating is required, the operation is simple, the stability is strong, it is green and clean, and the resource utilization rate is greatly improved.

[0056] (5) The melamine resin superplasticizer has a good inhibitory effect on calcium carbonate minerals and silicate minerals, and can be used as an inhibitor for calcium carbonate minerals or silicate minerals. Description of the Drawings

[0057] Figure 1 is a flow chart of flotation separation and recovery of tungsten and fluorite from a high-calcium type tungsten-fluorite associated ore of the present invention. Detailed Embodiments

[0058] The following further illustrates the present invention in combination with embodiments, and it is obvious that it is not required to limit the protection scope of the claims of the present invention. Unless otherwise specified, the relevant percentages refer to mass percentages.

[0059] Example 1

[0060] Taking a high-calcium tungsten fluorite ore in Guangxi as an example, in the original ore, the mass percentage of WO3 content is 0.28%, the mass percentage of CaF2 content is 23.00%, and the mass percentage of CaCO3 content is 18.05%. The method for flotation separation and recovery of tungsten and fluorite from the above-mentioned high-calcium tungsten fluorite associated ore in this embodiment includes the following steps:

[0061] Mixed flotation of tungsten and fluorite: The original ore is crushed and wet-ground to a particle size of less than 0.074 mm, and the mass of the undersize ore is 56.0% of the total original ore mass. Then, water is added to adjust the pulp concentration to 32%. Next, sodium carbonate, a pH adjuster, is added to the pulp to control the pulp pH value at 8.5. A first inhibitor (melamine resin superplasticizer) is added at a dosage of 450 g / t - original ore, and the mixture is stirred for 2 min. Then, saponified oleic acid, a collector, is added at a dosage of 300 g / t - original ore, and the mixture is stirred for 2 min. After that, it is aerated and floated for 5 min to obtain the rough concentrate 1 of the mixed flotation of tungsten and fluorite and the rough tailings 1. The rough tailings 1 are scavenged three times. The dosages of the collector (both saponified oleic acid) for the first scavenging, the second scavenging, and the third scavenging are 80 g / t - original ore, 50 g / t - original ore, and 50 g / t - original ore respectively, the stirring time is 2 min for each, and the aerated flotation time is 3 min for each. The scavenged concentrates are sequentially returned to the previous flotation operation, and the tailings of the third scavenging are the final tailings. The rough concentrate 1 is cleaned three times. The dosages of the inhibitor (melamine resin superplasticizer) for the first cleaning, the second cleaning, and the third cleaning are 40 g / t - original ore, 20 g / t - original ore, and 20 g / t - original ore respectively, the stirring time is 2 min for each, and the aerated flotation times are 2 min, 1.5 min, and 1 min respectively. The middlings from the cleaning are sequentially returned to the previous flotation operation, and the concentrate of the third cleaning is the mixed flotation concentrate of tungsten and fluorite.

[0062] Tungsten-fluorite flotation separation: Add a second inhibitor (sodium silicate 1500 g / t of raw ore + naphthalene sulfonate formaldehyde condensate 200 g / t of raw ore) to the tungsten-fluorite bulk flotation concentrate pulp, stir for 30 min, then add a collector (saponified oleic acid) 10 g / t of raw ore, stir for 2 min, and conduct aerated flotation for 4 min to obtain the roughing concentrate 2 and roughing tailings 2 of tungsten-fluorite separation flotation. Conduct scavenging on the roughing tailings 2, and the number of scavenging times is three. The dosages of the collector (saponified oleic acid) for the first scavenging, the second scavenging, and the third scavenging are 5 g / t of raw ore, 2 g / t of raw ore, and 2 g / t of raw ore respectively, the stirring time is 2 min for all, and the aerated flotation time is 3 min for all. The scavenging concentrates are sequentially returned to the previous flotation operation, and the tailings of the third scavenging are the fluorite concentrate. Conduct cleaning on the roughing concentrate 2, and the number of cleaning times is five. The dosages of the inhibitor (naphthalene sulfonate formaldehyde condensate) for the first cleaning, the second cleaning, the third cleaning, the fourth cleaning, and the fifth cleaning are 20 g / t of raw ore, 10 g / t of raw ore, 10 g / t of raw ore, 10 g / t of raw ore, and 10 g / t of raw ore respectively, the stirring time is 2 min for all, and the aerated flotation times are 2 min, 2 min, 1.5 min, 1.5 min, and 1 min respectively. The cleaning middlings are sequentially returned to the previous flotation operation, and the concentrate of the fifth cleaning is the tungsten concentrate.

[0063] Among them, the structural formula of the melamine resin superplasticizer is as follows:

[0064]

[0065] Among them, M is Na + ; the molecular weight of the melamine resin superplasticizer is 30000 - 50000.

[0066] The structural formula of the naphthalene sulfonate formaldehyde condensate is as follows:

[0067]

[0068] The degree of polymerization of the naphthalene sulfonate formaldehyde condensate is 9 - 13.

[0069] After detection, the analysis results of the products in this example are shown in Table 1:

[0070] Table 1 Analysis results of each product in Example 1 (unit: wt%)

[0071]

[0072] As can be seen from Table 1, for a high-calcium tungsten-fluorite ore with a WO3 content of 0.28%, a CaF2 content of 23.00%, and a CaCO3 content of 18.05%, the method of the present invention can obtain tungsten concentrate with a WO3 content of 52.80% and a recovery rate of 87.25%, and fluorite concentrate with a CaF2 content of 92.88% and a recovery rate of 84.52%. It can also be seen that the melamine resin superplasticizer has a good inhibitory effect on calcium carbonate minerals, causing most of the calcium carbonate minerals to remain in the tailings.

[0073] Comparative Example 1:

[0074] Taking a certain high-calcium tungsten-fluorite ore in Guangxi as an example, in the original ore, the mass percentage of WO3 content is 0.28%, the mass percentage of CaF2 content is 23.00%, and the mass percentage of CaCO3 content is 18.05%. The method for flotation separation and recovery of tungsten and fluorite from the above high-calcium tungsten-fluorite associated ore in this example includes the following steps:

[0075] Mixed flotation of tungsten and fluorite: The original ore is crushed and wet-ground to a particle size of less than 0.074 mm, and the mass of the undersize ore is 56.0% of the total mass of the original ore. Then, water is added to adjust the pulp concentration to 32%. Next, sodium carbonate, a pH adjuster, is added to the pulp to control the pulp pH value at 8.5. Sodium silicate is added at a dosage of 2000 g / t of the original ore and stirred for 2 min. Then, saponified oleic acid, a collector, is added at a dosage of 300 g / t of the original ore and stirred for 2 min. After that, it is aerated and floated for 5 min to obtain the rough concentrate 1 of the mixed flotation of tungsten and fluorite and the rough tailings 1. The rough tailings 1 are scavenged three times. The dosages of the collector (saponified oleic acid) for the first scavenging, the second scavenging, and the third scavenging are 80 g / t of the original ore, 50 g / t of the original ore, and 50 g / t of the original ore, respectively. The stirring time is 2 min for each, and the aerated flotation time is 3 min for each. The scavenged concentrates are sequentially returned to the previous flotation operation, and the tailings of the third scavenging are the final tailings. The rough concentrate 1 is cleaned three times. The dosages of the inhibitor (sodium silicate) for the first cleaning, the second cleaning, and the third cleaning are 600 g / t of the original ore, 400 g / t of the original ore, and 400 g / t of the original ore, respectively. The stirring time is 2 min for each, and the aerated flotation times are 2 min, 1.5 min, and 1 min, respectively. The middlings from the cleaning are sequentially returned to the previous flotation operation, and the concentrate of the third cleaning is the mixed flotation concentrate.

[0076] Tungsten-fluorite flotation separation: Add a second inhibitor (1500 g / t of sodium silicate - raw ore + 200 g / t of naphthalene sulfonate-polyoxymethylene condensate - raw ore) to the tungsten-fluorite bulk flotation concentrate pulp, stir for 30 min, then add a collector (saponified oleic acid) at 10 g / t of raw ore, stir for 2 min, and perform air flotation for 4 min to obtain the roughing concentrate 2 and roughing tailings 2 of tungsten-fluorite separation flotation. The roughing tailings 2 are scavenged, and the scavenging is carried out three times. The dosages of the collector (saponified oleic acid) for the first scavenging, the second scavenging, and the third scavenging are 5 g / t of raw ore, 2 g / t of raw ore, and 2 g / t of raw ore respectively, the stirring time is 2 min for all, and the air flotation time is 3 min for all. The scavenging concentrates are sequentially returned to the previous flotation operation, and the tailings of the third scavenging are the fluorite concentrate. The roughing concentrate 2 is cleaned, and the cleaning is carried out five times. The dosages of the inhibitor (naphthalene sulfonate-polyoxymethylene condensate) for the first cleaning, the second cleaning, the third cleaning, the fourth cleaning, and the fifth cleaning are 20 g / t of raw ore, 10 g / t of raw ore, 10 g / t of raw ore, 10 g / t of raw ore, and 10 g / t of raw ore respectively, the stirring time is 2 min for all, and the air flotation times are 2 min, 2 min, 1.5 min, 1.5 min, and 1 min respectively. The middlings from the cleaning are sequentially returned to the previous flotation operation, and the concentrate from the fifth cleaning is the tungsten concentrate.

[0077] Table 2 Analysis results of each product in Comparative Example 1 (unit: wt%)

[0078]

[0079] As can be seen from Table 2, for a high-calcium type tungsten-fluorite ore with a WO3 content of 0.28%, a CaF2 content of 23.00%, and a CaCO3 content of 18.05%, a tungsten concentrate with a WO3 content of 45.50% and a recovery rate of 85.74% and a fluorite concentrate with a CaF2 content of 65.42% and a recovery rate of 73.27% can be obtained by using the beneficiation process and reagent system of Comparative Example 1. By comparing Comparative Example 1 with Example 1, it can be seen that when the melamine resin superplasticizer is not added, even if a larger amount of conventional inhibitor is added, the inhibitory effect of calcium carbonate during bulk flotation is poor, the CaF2 grade of the fluorite concentrate is greatly reduced, and the produced fluorite concentrate cannot meet the product quality requirements of the fluorite concentrate.

[0080] Example 2

[0081] Taking a high-calcium type tungsten-fluorite ore in Hunan as an example, the mass percentage of the WO3 content in the raw ore is 0.39%, the mass percentage of the CaF2 content is 12.80%, and the mass percentage of the CaCO3 content is 13.15%. This example includes the following steps:

[0082] Mixed flotation of tungsten and fluorite: The original ore is crushed and wet-ground to a particle size where the mass of the ore passing through a 0.074 mm sieve is 72.20% of the total original ore mass. Then, water is added to adjust the pulp density to 32%. Sodium carbonate, a pH adjuster, is added, and the pulp pH is controlled at 8.5. An inhibitor, melamine resin superplasticizer, is added at a dosage of 300 g / t - original ore and stirred for 2 min. Then, a collector, saponified oleic acid, is added at a dosage of 350 g / t - original ore and stirred for 2 min. After that, it is aerated and floated for 5 min to obtain the rough concentrate 1 of the mixed flotation of tungsten and fluorite and the rough tailing 1. The rough tailing 1 is scavenged three times. The dosages of the collector (saponified oleic acid) in the first scavenging, the second scavenging, and the third scavenging are 80 g / t - original ore, 80 g / t - original ore, and 80 g / t - original ore respectively, the stirring time is 2 min for each, and the aerated flotation time is 3 min for each. The scavenged concentrates are sequentially returned to the previous flotation operation, and the tailing of the third scavenging is the final tailing. The rough concentrate 1 is cleaned three times. The dosages of the inhibitor (melamine resin superplasticizer) in the first cleaning, the second cleaning, and the third cleaning are 30 g / t - original ore, 15 g / t - original ore, and 15 g / t - original ore respectively, the stirring time is 2 min for each, and the aerated flotation times are 2 min, 1.5 min, and 1 min respectively. The middlings from the cleaning are sequentially returned to the previous flotation operation, and the concentrate of the third cleaning is the concentrate of the mixed flotation of tungsten and fluorite.

[0083] Flotation separation of tungsten and fluorite: An inhibitor (sodium silicate 1200 g / t - original ore + naphthalene sulfonate formaldehyde condensate 150 g / t - original ore) is added to the pulp of the concentrate of the mixed flotation of tungsten and fluorite and stirred for 30 min. Then, a collector (saponified oleic acid) is added at a dosage of 15 g / t - original ore and stirred for 2 min. After that, it is aerated and floated for 4 min to obtain the rough concentrate 2 of the flotation separation of tungsten and fluorite and the rough tailing 2. The rough tailing 2 is scavenged three times. The dosages of the collector (saponified oleic acid) in the first scavenging, the second scavenging, and the third scavenging are 6 g / t - original ore, 3 g / t - original ore, and 3 g / t - original ore respectively, the stirring time is 2 min for each, and the aerated flotation time is 3 min for each. The scavenged concentrates are sequentially returned to the previous flotation operation, and the tailing of the third scavenging is the fluorite concentrate. The rough concentrate 2 is cleaned five times. The dosages of the inhibitor (naphthalene sulfonate formaldehyde condensate) in the first cleaning, the second cleaning, the third cleaning, the fourth cleaning, and the fifth cleaning are 20 g / t - original ore, 10 g / t - original ore, 10 g / t - original ore, 10 g / t - original ore, and 10 g / t - original ore respectively, the stirring time is 2 min for each, and the aerated flotation times are 2 min, 2 min, 1.5 min, 1.5 min, and 1 min respectively. The middlings from the cleaning are sequentially returned to the previous flotation operation, and the concentrate of the fifth cleaning is the tungsten concentrate.

[0084] Among them, the structural formula of the melamine resin superplasticizer is as follows:

[0085]

[0086] Among them, M is Na + ; The molecular weight of the melamine resin superplasticizer is 30,000 - 50,000.

[0087] The structural formula of the naphthalene sulfonate polyformaldehyde condensate is as follows:

[0088]

[0089] The degree of polymerization of the naphthalene sulfonate polyformaldehyde condensate is 9 - 13.

[0090] After detection, the analysis results of the product in this example are shown in Table 3:

[0091] Table 3 Analysis results of each product in Example 2 (unit: wt%)

[0092]

[0093] As can be seen from Table 3, for the high-calcium tungsten fluorite ore with WO3 content of 0.39%, CaF2 content of 12.80%, and CaCO3 content of 13.15%, the tungsten concentrate with WO3 content of 58.22% and recovery rate of 88.40% and the fluorite concentrate with CaF2 content of 90.50% and recovery rate of 80.85% can be obtained by using the method of the present invention.

[0094] Example 3

[0095] Taking a high-calcium tungsten fluorite ore in Hunan as an example, the mass percentage of WO3 content in the raw ore is 0.53%, the mass percentage of CaF2 content is 16.05%, and the mass percentage of CaCO3 content is 27.80%. This example includes the following steps:

[0096] Mixed flotation of tungsten and fluorite: The raw ore is crushed and wet-ground to a particle size where the mass of the ore passing through a 0.074 mm sieve accounts for 65.70% of the total raw ore mass. Then, water is added to adjust the pulp density to 32%. Sodium carbonate, a pH adjuster, is added, and the pulp pH is controlled at 8.5. An inhibitor, melamine resin superplasticizer, is added at a dosage of 500 g / t-raw ore and stirred for 2 min. Then, a collector, saponified oleic acid, is added at a dosage of 320 g / t-raw ore and stirred for 2 min. After that, it is aerated and floated for 5 min to obtain the rough concentrate 1 and rough tailings 1 of the mixed flotation of tungsten and fluorite. The rough tailings 1 are scavenged three times. The dosages of the collector (saponified oleic acid) in the first, second, and third scavenging are 50 g / t-raw ore, 50 g / t-raw ore, and 50 g / t-raw ore respectively, with a stirring time of 2 min each and an aerated flotation time of 3 min each. The scavenged concentrates are successively returned to the previous flotation operation, and the tailings of the third scavenging are the final tailings. The rough concentrate 1 is cleaned three times. The dosages of the inhibitor (melamine resin superplasticizer) in the first, second, and third cleaning are 50 g / t-raw ore, 30 g / t-raw ore, and 30 g / t-raw ore respectively, with a stirring time of 2 min each. The aerated flotation times are 2 min, 1.5 min, and 1 min respectively. The middlings from the cleaning are successively returned to the previous flotation operation, and the concentrate of the third cleaning is the concentrate of the mixed flotation of tungsten and fluorite.

[0097] Flotation separation of tungsten and fluorite: In the concentrate pulp of the mixed flotation of tungsten and fluorite, 1800 g / t-raw ore of the inhibitor sodium silicate and 180 g / t-raw ore of the inhibitor naphthalene sulfonate formaldehyde condensate are added and stirred for 30 min. Then, 12 g / t-raw ore of the collector (saponified oleic acid) is added and stirred for 2 min. After that, it is aerated and floated for 4 min to obtain the rough concentrate 2 and rough tailings 2 of the flotation separation of tungsten and fluorite. The rough tailings 2 are scavenged three times. The dosages of the collector (saponified oleic acid) in the first, second, and third scavenging are 5 g / t-raw ore, 3 g / t-raw ore, and 3 g / t-raw ore respectively, with a stirring time of 2 min each and an aerated flotation time of 3 min each. The scavenged concentrates are successively returned to the previous flotation operation, and the tailings of the third scavenging are the fluorite concentrate. The rough concentrate 2 is cleaned five times. The dosages of the inhibitor (naphthalene sulfonate formaldehyde condensate) in the first, second, third, fourth, and fifth cleaning are 30 g / t-raw ore, 20 g / t-raw ore, 15 g / t-raw ore, 10 g / t-raw ore, and 10 g / t-raw ore respectively, with a stirring time of 2 min each. The aerated flotation times are 2 min, 2 min, 1.5 min, 1.5 min, and 1 min respectively. The middlings from the cleaning are successively returned to the previous flotation operation, and the concentrate of the fifth cleaning is the tungsten concentrate.

[0098] Among them, the structural formula of the melamine resin superplasticizer is as follows:

[0099]

[0100] Among them, M is Na + ; The molecular weight of the melamine resin superplasticizer is 30,000 - 50,000.

[0101] The structural formula of the naphthalene sulfonate polyformaldehyde condensate is as follows:

[0102]

[0103] The degree of polymerization of the naphthalene sulfonate polyformaldehyde condensate is 9 - 13.

[0104] After testing, the analysis results of the products in this example are shown in Table 4:

[0105] Table 4 Analysis results of each product in Example 3 (unit: wt%)

[0106]

[0107] As can be seen from Table 4, for the high - calcium type tungsten fluorite ore with WO3 content of 0.53%, CaF2 content of 16.05%, and CaCO3 content of 27.80%, by using the method of the present invention, tungsten concentrate with WO3 content of 54.76% and recovery rate of 85.60% and fluorite concentrate with CaF2 content of 90.88% and recovery rate of 82.43% can be obtained.

[0108] The content clarified in the above - mentioned embodiments should be understood that these embodiments are only used to illustrate the present invention more clearly, rather than to limit the scope of the present invention. After reading the present invention, various equivalent forms of modification by those skilled in the art fall within the scope defined by the appended claims of this application.

Claims

1. A method for flotation separation and recovery of tungsten and fluorite from a high-calcium tungsten-fluorite associated ore, characterized in that, It includes the following steps: S1. Grind the high-calcium tungsten-fluorite associated ore to be processed to obtain pulp; S2. Add a pH adjuster, a first inhibitor, and a collector to the pulp obtained in S1, and perform the first rough selection to obtain the first rough concentrate and the first rough tailings; Among them, the first inhibitor is a melamine resin superplasticizer; S3. Perform at least two times of cleaning on the first rough concentrate obtained in S2 to obtain a cleaned concentrate; Among them, before each cleaning, first add the first inhibitor and stir evenly; return the cleaned middlings obtained each time to the previous stage of flotation; S4. Add a second inhibitor and a collector to the cleaned concentrate obtained in S3, and perform the second rough selection to obtain the second rough concentrate and the second rough tailings; Among them, the second inhibitor includes a naphthalene sulfonate-polyformaldehyde condensate; S5. Perform at least two times of cleaning on the second rough concentrate obtained in S4 to obtain tungsten concentrate; Perform at least two times of scavenging on the second rough tailings obtained in S4 to obtain fluorite concentrate; Among them, before each cleaning, first add a third inhibitor and stir evenly; return the cleaned middlings obtained each time to the previous stage of flotation; the third inhibitor is a naphthalene sulfonate-polyformaldehyde condensate; Before each scavenging, first add a collector and stir evenly; return the scavenged tailings obtained each time to the previous stage of flotation.

2. The method according to claim 1, wherein The structural formula of the melamine resin superplasticizer is as follows: ； where M is Na + or K + .

3. The method according to claim 2, wherein The molecular weight of the melamine resin superplasticizer is 30,000 - 50,000.

4. The method according to claim 1, characterized in that The naphthalene sulfonate-polyformaldehyde condensate is a sodium naphthalene sulfonate-polyformaldehyde condensate, and its structural formula is as follows: 。 5. The method according to claim 4, characterized in that, The degree of polymerization of the naphthalene sulfonate-polyformaldehyde condensate is 9 - 13.

6. The method according to any one of claims 1-5, characterized in that, In S2, the addition amount of the first inhibitor is 200 - 800 g / t - raw ore; In S3, before each cleaning, the addition amount of the first inhibitor is 10 - 80 g / t - raw ore.

7. The method according to claim 6, wherein In S2, the addition amount of the first inhibitor is 250 - 600 g / t - raw ore.

8. The method according to any one of claims 1-5, characterized in that, In S4, the addition amount of the second inhibitor is 1100 - 3300 g / t - raw ore.

9. The method according to any one of claims 1-5, characterized in that, In S4, the second inhibitor is composed of a naphthalene sulfonate-polyformaldehyde condensate and water glass in a mass ratio of 1 - 3:10 - 30.

10. The method according to any one of claims 1-5, characterized in that, In S5, the addition amount of the third inhibitor is 0 - 50 g / t - raw ore.

11. The method according to claim 10, wherein In S5, the addition amount of the third inhibitor is 5 - 35 g / t - raw ore.

12. The method according to any one of claims 1-5, characterized in that, In S1, the mass concentration of the pulp is 25 - 38%.

13. The method according to any one of claims 1-5, characterized in that, In S2, perform multiple scavengings on the first rough tailings, and return the obtained scavenged concentrate to the previous stage of flotation; Among them, when performing each scavenging, add 40 - 100 g / t - raw ore of the collector.

14. The method according to any one of claims 1-5, characterized in that, The pH adjuster is sodium hydroxide or / and sodium carbonate, and the collector is one or several of oleic acid, saponified oleic acid, oxidized paraffin soap, naphthenic acid soap, and hydroxamic acid soap.

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