Application of 2-phospho-1, 2, 4-tricarboxylic acid butane as calcium-containing gangue mineral inhibitor

Abstract

The invention discloses application of 2-phosphate group-1, 2, 4-tricarboxylic acid butane as a calcium-containing gangue mineral inhibitor, and belongs to the technical field of mineral separation. The 2-phosphate group-1, 2, 4-tricarboxylic acid butane has a selective adsorption effect on the surface of calcium carbonate type gangue minerals such as calcite, can realize efficient flotation separation of fluorite and calcite-similar calcium carbonate type gangue minerals, and is particularly suitable for flotation separation of fluorite and calcite and other calcium carbonate type gangue minerals in high-calcium fluorite; chemical-grade and metallurgical-grade double-product fluorite concentrates can be produced, and efficient comprehensive utilization of associated fluorite resources is achieved.

Description

Technical Field

[0001] The present invention relates to a new use of 2-phosphono-1,2,4-tricarboxybutane, and particularly to the application of 2-phosphono-1,2,4-tricarboxybutane as a new calcium-containing gangue mineral inhibitor for calcium carbonate, especially for enhancing the flotation separation of high-calcium fluorite, belonging to the technical field of mineral processing. Background Art

[0002] Fluorite ore is an important strategic mineral resource and also the main raw material for the fluorine chemical industry, which is widely used in fields such as building materials and aerospace. Carbonate-type fluorite is the existing main fluorite resource. The fluorite mineral is rich in various calcium-containing gangue minerals such as calcite, which is generally closely symbiotic with fluorite, and both the surfaces of calcite and fluorite ore contain Ca 2+ active sites, with similar floatability. In the presence of fatty acid collectors, they both have good hydrophobicity, and there is an interconversion of ions on the mineral surface, making the flotation separation difficult. Industrially, sodium silicate is generally used as an inhibitor for calcite, etc., but the dosage of sodium silicate is difficult to control. When the dosage of sodium silicate is small, the inhibition effect is not good, and when the dosage is too much, the target mineral will be inhibited, and the sedimentation of the mineral processing wastewater is difficult. At the same time, the large amount of use of inorganic inhibitors such as sodium silicate will also have a certain impact on the environment, and the mineral processing wastewater is difficult to recycle.

[0003] 2-phosphono-1,2,4-tricarboxybutane belongs to organic phosphates and is an excellent scale inhibitor. For example, 2-phosphono-1,2,4-tricarboxybutane is used in the scale inhibitor formulations involved in Chinese patents CN103232118B, CN115215471B, CN114656046B, etc. However, so far, there has been no relevant report on the application of 2-phosphono-1,2,4-tricarboxybutane as a flotation inhibitor for calcium-containing gangue minerals such as calcite. Summary of the Invention

[0004] Aiming at the deficiencies in the use of conventional inhibitors in the flotation separation process of high-calcium fluorite in the prior art, the purpose of the present invention is to provide a new use of 2-phosphono-1,2,4-tricarboxybutane as a calcium-containing gangue mineral inhibitor. 2-phosphono-1,2,4-tricarboxybutane has a selective adsorption property on the surface of calcium carbonate-type gangue minerals such as calcite, so as to realize the modulation of the surface properties of calcium carbonate-type gangue minerals, so as to achieve the purpose of inhibiting their flotation, which is conducive to the effective flotation separation of useful minerals. Especially for high-calcium fluorite minerals, the effect of 2-phosphono-1,2,4-tricarboxybutane on the surface of carbonate-type calcium-containing gangue ore is much greater than that on fluorine salt-type calcium minerals, thus widening the floatability difference between calcium carbonate-type gangue minerals and calcium fluoride-type calcium minerals, and greatly improving the grade and recovery rate of fluorite concentrate.

[0005] To achieve the above technical objectives, the present invention provides the application of 2-phosphono-1,2,4-tricarboxybutane as an inhibitor for calcium carbonate gangue minerals.

[0006] A large number of experimental studies in the present invention show that: the functional group spacing of 2-phosphono-1,2,4-tricarboxybutane matches the calcium particle spacing on the surface of calcium carbonate gangue minerals, and it can targetedly adsorb on its surface, thereby modulating the surface properties of calcium carbonate gangue minerals and inhibiting their floating. Therefore, 2-phosphono-1,2,4-tricarboxybutane can be widely used as an inhibitor for calcium carbonate gangue minerals.

[0007] As a preferred embodiment, the 2-phosphono-1,2,4-tricarboxybutane is applied as an inhibitor for calcium carbonate gangue minerals in the flotation separation of fluorite and calcium-containing gangue minerals in high-calcium fluorite minerals.

[0008] The present invention also found through a large number of experiments that: fluorite also belongs to calcium-containing minerals, but the ability of 2-phosphono-1,2,4-tricarboxybutane to act on the surface of calcium carbonate gangue minerals is much stronger than its ability to act on the surface of fluorite. Therefore, selective inhibition of calcium carbonate gangue minerals can be achieved in a system where fluorite and calcium carbonate gangue minerals coexist, thereby realizing the efficient flotation separation of fluorite and calcium carbonate gangue minerals.

[0009] As a preferred embodiment, the calcium carbonate gangue mineral is specifically calcite, for example.

[0010] As a preferred embodiment, the process of the flotation separation is as follows: after the high-calcium fluorite raw ore is ground and pulp-adjusted, flotation reagents including a siliceous gangue mineral inhibitor and a fluorite collector are added for rough selection to obtain a rough concentrate and a rough tailing; after the rough fluorite concentrate is pulp-adjusted, a calcium-containing gangue mineral inhibitor including 2-phosphono-1,2,4-tricarboxybutane is added for at least one cleaning to obtain a fluorite concentrate and a calcium-containing tailing. Based on the use of the 2-phosphono-1,2,4-tricarboxybutane calcium-containing gangue mineral inhibitor, the present invention develops a stepped enhanced flotation separation technology for high-calcium fluorite, that is, a new two-stage step-by-step flotation process of "alkaline system enhanced inhibition - acidic system enhanced calcium inhibition". Through the "double middlings - low grade" flotation, the efficient open-circuit cleaning of calcium carbonate is realized, and chemical-grade and metallurgical-grade double-product fluorite concentrates are produced, realizing the efficient comprehensive utilization of associated fluorite resources.

[0011] As a preferred embodiment, the grinding is carried out to achieve a mass ratio of -0.074mm particle size of more than 85%.

[0012] As a preferred embodiment, the pulp-adjusting Adjust the pH to alkaline. Under alkaline conditions, it is mainly beneficial to inhibit the flotation of siliceous gangue minerals, such as quartz.

[0013] As a preferred solution, in the roughing process, the inhibitor of siliceous gangue minerals is acidified water glass, and its relative dosage to minerals is 200 - 600 g / t. The collector for fluorite is sodium oleate, and its relative dosage to minerals is 300 - 500 g / t.

[0014] As a preferred solution, for the pulp conditioning Adjust the pH ≤ 6. 2 - Phosphono - 1,2,4 - butanetricarboxylic acid of the present invention is more beneficial to exert its high - selectivity inhibitory effect on calcium carbonate gangue minerals under acidic conditions.

[0015] As a preferred solution, in the cleaning process, the relative dosage of 2 - phosphono - 1,2,4 - butanetricarboxylic acid to minerals is 100 - 200 g / t, and during multiple cleaning processes, 2 - phosphono - 1,2,4 - butanetricarboxylic acid follows the principle of halving the dosage of the reagent.

[0016] 2 - Phosphono - 1,2,4 - butanetricarboxylic acid (PBTCA) of the present invention is a commercial product.

[0017] The present invention realizes the flotation recovery of high - calcium fluorite minerals by using a stepped enhanced flotation separation technology, specifically a new two - stage step - by - step flotation process of enhancing the inhibition of silicon in an alkaline system and enhancing the inhibition of calcium in an acidic system.

[0018] The acid - base regulators used by the present invention to adjust the pulp pH are at least one of HCl, H2SO4, NaOH, and NaCO3.

[0019] The time of the roughing process of the present invention is about 4 min.

[0020] In the cleaning process of the present invention, the time of each cleaning is about 3 min.

[0021] The flotation separation process of fluorite and gangue minerals such as calcite in high - calcium fluorite of the present invention is as follows: After grinding the high - calcium fluorite raw ore, add regulators to adjust the pH of the pulp to alkaline, add inhibitors of siliceous gangue minerals and collectors for fluorite (such as sodium oleate), obtain rough - selected fluorite concentrate and rough - selected tailings. Add regulators to adjust the pH of the pulp of the rough - selected fluorite concentrate to acidic, and perform two - stage cleaning using the inhibitor PBTCA to obtain the final flotation concentrate K and middlings m1, m2 and tailings X.

[0022] Compared with the prior art, the beneficial technical effects brought by the technical solution of the present invention:

[0023] (1) The PBTCA of the present invention has a strong inhibitory ability for calcium carbonate gangue minerals and has selective adsorption. The spacing of its functional groups matches the spacing of calcium particles in calcium carbonate gangue minerals such as calcite, and it targets and adsorbs on their surfaces, realizing the efficient flotation separation of fluorite and calcium carbonate-like gangue minerals similar to calcite, achieving the effective flotation separation of minerals.

[0024] (2) The flotation separation process of the high-calcium fluorite of the present invention is divided into two steps. First, silicon minerals such as quartz are inhibited under alkaline conditions, and then calcium-containing gangue minerals such as calcite are strongly inhibited under acidic conditions, which is beneficial to improving the concentrate grade of fluorite flotation.

[0025] (3) The high-calcium fluorite flotation process flow of the present invention realizes the efficient open-circuit separation of calcium carbonate through "double middlings - low grade" flotation, produces double-product fluorite concentrates of chemical grade and metallurgical grade, and realizes the efficient comprehensive utilization of associated fluorite resources. After re-grinding and flotation, the grade of the chemical-grade fluorite concentrate powder can reach more than 97%. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a flotation flow chart for the separation of high-calcium fluorite ore. DETAILED DESCRIPTION OF THE INVENTION

[0027] The present invention will be further described below in conjunction with the drawings of the specification and specific preferred embodiments, but the protection scope of the present invention is not limited thereby. The materials and instruments used in the following embodiments are all commercially available.

[0028] The high-calcium carbonate-type fluorite ore used in the following embodiments is a mineral resource in a certain place in Xinjiang. The main minerals in the ore sample are CaCO3 and CaF2, and secondly, SiO2 is also contained. Calcium in the ore is mainly present in fluorite and calcite, and a small amount is present in other minerals. The calcium content in fluorite is about 17.89%, and the calcium content in calcite is about 23.4%.

[0029] Example 1

[0030] The following is a beneficiation method for high-calcium fluorite ore, which specifically includes the following steps:

[0031] (1) Grind the high-calcium fluorite raw ore. Specifically: use a roller mill to grind the high-calcium fluorite ore, with a ball-to-material ratio of 10:1, a grinding time of 15 minutes, and the proportion of -0.074mm particle size being 92wt%. Then make it into a pulp with a concentration of about 35%.

[0032] (2) Conduct rough flotation using a flotation machine. Specifically: Add the above-mentioned pulp into the flotation machine, stir for three minutes to fully disperse it, add 1000 g / t of soda ash, stir for 3 min, add 450 g / t of collector sodium oleate, stir for 3 min, and add 400 g / t of acidified water glass, stir for 3 min. Obtain the rough flotation concentrate and tailings of fluorite.

[0033] (3) Conduct the first stage of fine flotation on the rough flotation concentrate. Specifically: Feed the rough flotation concentrate into the flotation machine, add 1000 g / t of sulfuric acid to adjust the pulp pH, and use 150 g / t of organic inhibitor PBTCA. Obtain the fine flotation concentrate of fluorite and middlings m1.

[0034] (4) Conduct the second stage of fine flotation on the fine flotation concentrate. Specifically: Feed the fine flotation concentrate into the flotation machine, and use 80 g / t of organic inhibitor PBTCA. Obtain fluorite concentrate K and middlings m2. The experimental results are shown in Table 1 below.

[0035]

[0036] According to the above process method and the data results in Table 1, conduct flotation recovery on high-calcium fluorite ore multiple times. The grade of the fluorite concentrate obtained from the first stage of fine flotation can reach 75.23%, and the grade of the fluorite concentrate K obtained from the second stage of fine flotation can reach 93.4%. The recovery rate of calcite is 10.2%. Subsequently, grind the fluorite concentrate K again, add inhibitor PBTCA and collector sodium oleate and then conduct flotation again, and the grade can reach 97.6%. Obviously, the beneficiation process of the present invention can separate fluorite and gangue minerals such as calcite from high-calcium fluorite ore, and can produce metallurgical-grade and chemical-grade fluorite concentrates, which can achieve effective resource recovery and has broad practical significance for improving the comprehensive utilization rate of fluorite resources.

[0037] Example 2

[0038] The present invention provides an organic inhibitor for the flotation of high-calcium fluorite minerals, and the following is a beneficiation method for high-calcium fluorite ore, which specifically includes the following steps:

[0039] (1) Grind the high-calcium fluorite raw ore. Specifically: Use a roller mill to grind the high-calcium fluorite ore, with a ball-to-material ratio of 10:1, a grinding time of 20 min, and the proportion of -0.074 mm particle size being 89 wt%. Then make it into a pulp with a concentration of about 35%.

[0040] (2) Conduct rough flotation using a flotation machine. Specifically: Add the above-mentioned pulp into the flotation machine, stir for three minutes to fully disperse it, add 900 g / t of soda ash, stir for 3 min, add 500 g / t of collector sodium oleate, stir for 3 min, and add 450 g / t of acidified water glass, stir for 3 min. Obtain the rough flotation concentrate and tailings of fluorite.

[0041] (3) Conduct the first stage of flotation concentration on the rough concentrate of flotation. Specifically: Feed the rough concentrate of flotation into a flotation machine, add 1100 g / t of sulfuric acid to adjust the pH value of the pulp, and use 200 g / t of the organic inhibitor PBTCA to obtain the concentrated concentrate of fluorite and middlings m1.

[0042] (4) Conduct the second stage of flotation concentration on the concentrated concentrate of flotation. Specifically: Feed the concentrated concentrate of flotation into a flotation machine, and use 100 g / t of the organic inhibitor PBTCA to obtain fluorite concentrate K and middlings m2.

[0043]

[0044] From the data in Table 2, it can be seen that after multiple flotation recoveries of high-calcium fluorite ore, the grade of the fluorite concentrate obtained in the first stage of concentration can reach 75%, and the grade of the fluorite concentrate K obtained in the second stage of concentration can reach 92.6%. Subsequently, after the fluorite concentrate K is reground, and the inhibitor PBTCA and collector sodium oleate are added and then floated again, the grade can reach 97.2%. Obviously, the beneficiation process of the present invention can separate fluorite and gangue minerals such as calcite from high-calcium fluorite ore, and can produce metallurgical-grade and chemical-grade fluorite concentrates, which can effectively recover resources and has broad practical significance for improving the comprehensive utilization rate of fluorite resources.

[0045] Example 3

[0046] The present invention provides an organic inhibitor for the flotation of high-calcium fluorite minerals, and the following is a beneficiation method for high-calcium fluorite ore, which specifically includes the following steps:

[0047] (1) Grind the original high-calcium fluorite ore. Specifically: Use a roller mill to grind the high-calcium fluorite ore, with a ball-to-material ratio of 10:1, a grinding time of 20 min, and the proportion of the -0.074 mm particle size being 96 wt%. Then make it into a pulp with a concentration of about 35%.

[0048] (2) Conduct rough flotation through a flotation machine. Specifically: Add the above pulp into a flotation machine, stir for three minutes to fully disperse, add 800 g / t of soda ash, stir for 3 min, add 400 g / t of the collector sodium oleate, stir for 3 min, and add 400 g / t of acidified water glass, stir for 3 min. Obtain the rough concentrate of fluorite and tailings.

[0049] (3) Conduct the first stage of flotation concentration on the rough concentrate of flotation. Specifically: Feed the rough concentrate of flotation into a flotation machine, add 1000 g / t of sulfuric acid to adjust the pH of the pulp, and use 150 g / t of the organic inhibitor PBTCA to obtain the concentrated concentrate of fluorite and middlings m1.

[0050] (4)Perform flotation concentration II on the flotation concentrated concentrate, specifically: Feed the flotation concentrated concentrate into a flotation machine, with the dosage of the organic inhibitor PBTCA being 100 g / t, to obtain fluorite concentrate K and middlings m2. The test results are shown in Table 3.

[0051]

[0052] According to the above process method and the results in Table 3, the high-calcium fluorite ore is subjected to flotation recovery multiple times. The grade of the fluorite concentrate obtained from the first concentration can reach 76.2%, and the grade of the fluorite concentrate K obtained from the second concentration can reach 95.1%. Subsequently, the fluorite concentrate K is reground, and after adding the inhibitor PBTCA and the collector sodium oleate, it is floated again, and the grade can reach 98.4%.

[0053] Comparative Example 1

[0054] Use the ore material and method of Example 1 to recover fluorite from high-calcium fluorite ore, with the difference being: no organic inhibitor PBTCA is added. The specific ore dressing test results are shown in Table 4.

[0055]

[0056] It can be seen from the results in Table 4 that without adding the organic inhibitor PBTCA, the grade and recovery rate of the obtained fluorite concentrate are significantly lower than the test indexes of Example 1.

[0057] Comparative Example 2

[0058] Use the ore material and method of Example 2 to recover fluorite from high-calcium fluorite ore, with the difference being: no organic inhibitor PBTCA is added. The specific ore dressing test indexes are shown in Table 5.

[0059]

[0060] It can be seen from the results in Table 5 that without adding the organic inhibitor PBTCA, the grade and recovery rate of the obtained fluorite concentrate are significantly lower than the test indexes of Example 2.

[0061] Comparative Example 3

[0062] Use the ore material and method of Example 3 to recover fluorite from high-calcium fluorite ore, with the difference being: no organic inhibitor PBTCA is added. The specific ore dressing test indexes are shown in Table 6.

[0063]

[0064] It can be seen from the results in Table 6 that without adding the organic inhibitor PBTCA, the grade and recovery rate of the obtained fluorite concentrate are significantly lower than the test indexes of Example 3.

[0065] Comparative Example 4

[0066] The fluorite in the high-calcium fluorite ore was recovered using the ore materials and method of Example 3, with the difference that: instead of adding the organic inhibitor PBTCA, the conventional calcite inhibitor acidified water glass was selected to replace the organic inhibitor PBTCA. The specific ore dressing test indexes are shown in Table 7.

[0067]

[0068] As can be seen from the results in Table 7, without adding the organic inhibitor PBTCA and selecting the conventional calcite inhibitor acidified water glass, the grade and recovery rate of the obtained fluorite concentrate are significantly lower than the test indexes of Example 3.

[0069] As mentioned above, it is only the preferred embodiment of the present invention, and it does not impose any form of limitation on the present invention. Although the present invention has been disclosed above with the preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can, without departing from the spirit and technical solution of the present invention, make many possible changes and modifications to the technical solution of the present invention by using the methods and technical contents disclosed above, or modify it into an equivalent embodiment with equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the technical solution of the present invention still fall within the scope of protection of the technical solution of the present invention.

Claims

1. Application of 1,2,4 - butanetricarboxylic acid - 2 - phosphate, characterized in that: It is used as an inhibitor for calcium carbonate-type gangue minerals.

2. Use of butane 2-phosphono-1,2,4-tricarboxylate according to claim 1, characterized in that: It is used as an inhibitor for calcium-containing gangue minerals in the flotation separation of fluorite and calcium carbonate-type gangue minerals in high-calcium fluorite minerals.

3. Use of butane-1,2,4-tricarboxylic acid 2-phosphate according to claim 2, characterized in that: The process of the flotation separation is as follows: the high-calcium fluorite raw ore is subjected to grinding and pulp conditioning After that, flotation reagents including a siliceous gangue mineral depressant and a fluorite collector are added for roughing to obtain a rougher concentrate and a rougher tailing; the rougher fluorite concentrate is subjected to pulp conditioning After that, a calcium-containing gangue mineral depressant including 2-phosphono-1,2,4-tricarboxybutane is added for at least one cleaning to obtain a fluorite concentrate and a calcium-containing tailing.

4. Use of butane-1,2,4-tricarboxylic acid 2-phosphate according to claim 3, characterized in that: The grinding is carried out to achieve a mass ratio of -0.074 mm particle size of more than 85%.

5. Use of butane-1,2,4-tricarboxylic acid 2-phosphate according to claim 3, characterized in that: The sizing is adjusted to an alkaline pH.

6. Use of butane-1,2,4-tricarboxylic acid 2-phosphate according to claim 3, characterized in that: In the process of rough selection, the siliceous gangue mineral inhibitor is acidified water glass, and its relative dosage to minerals is 200 - 600 g / t. The fluorite collector is sodium oleate, and its relative dosage to minerals is 300 - 500 g / t.

7. Use of butane-1,2,4-tricarboxylic acid 2-phosphate according to claim 3, characterized in that: The sizing slurry is adjusted to pH ≤ 6.

8. Use of butane-1,2,4-tricarboxylic acid 2-phosphate according to claim 3, characterized in that: In the process of cleaning, the relative dosage of 2-phosphono-1,2,4-tricarboxylic acid butane to minerals is 100 - 200 g / t. And in the process of multiple cleanings, 2-phosphono-1,2,4-tricarboxylic acid butane follows the principle of halving the dosage of the reagent.

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