A flotation inhibitor, a flotation process for calcium carbonate minerals and its application

Abstract

The present invention relates to a flotation depressant, a flotation process and application of calcium-containing carbonate minerals, and belongs to the field of mineral processing. In parts by mass, the flotation depressant includes 5 to 20 parts of sodium gluconate, 5 to 15 parts of CH-R concrete water reducer, and 1 to 10 parts of polyacrylate concrete water reducer. The flotation depressant of the present invention is efficient, green and environmentally friendly, and can effectively solve the problems of similar floatability, great difficulty in flotation separation, and low separation efficiency among calcium-containing minerals, and can achieve effective separation of calcium carbonate-type gangue minerals and useful minerals; the flotation depressor of the present invention is used to solve the problems of separation of scheelite and calcite, separation of scheelite and dolomite, separation of fluorite and calcite, separation of fluorite and dolomite, separation of apatite and calcite, and separation of apatite and dolomite, and excellent results can be achieved.

Description

Technical Field

[0001] The invention relates to a flotation inhibitor, a flotation process of a calcium-containing carbonate mineral and application thereof, and belongs to the technical field of mineral processing engineering. Background Art

[0002] Calcium-containing minerals are polar salt minerals that contain calcium ions on the mineral lattice, mainly including scheelite, calcite, dolomite, fluorite, apatite, wollastonite, etc. Calcium-containing minerals play a large role in my country's national economy. For example, phosphate rock is the main raw material for the production of fertilizers, the food of grain, and an important guarantee for my country's food security; scheelite is the main raw material for the production of tungsten and an important strategic metal; fluorite is an important source of raw materials for fluorine chemical industry, and calcite can be used as a raw material for building materials. At present, the main separation method of scheelite, fluorite, and apatite is flotation, but due to the same surface active sites, the floatability of calcium-containing minerals is similar, making flotation separation difficult.

[0003] The main mineral components of skarn-type scheelite are scheelite, fluorite, calcite, dolomite and silicate gangue. Among them, the separation of scheelite from fluorite, calcite and dolomite is the most difficult and is also the focus of current research. In the flotation of scheelite, the inorganic inhibitors of calcium-containing gangue minerals mainly include water glass, modified water glass, sodium hexametaphosphate and sodium fluorosilicate, among which water glass and modified water glass are the most widely used. Organic inhibitors of calcium-containing minerals include polyhydroxycarboxylic acids, polyhydroxyphenols, phenoxyacetic acids and phosphonic acids. At present, the most successful application in industrial production is to use water glass as a calcium-containing mineral inhibitor, but the process uses a high amount of water glass and it is difficult to reuse the mineral processing wastewater.

[0004] According to the type of gangue, fluorite can be divided into silicate gangue type, calcite gangue type, dolomite gangue type and barite gangue type. At present, there are a large number of calcite and dolomite fluorite resources in my country, which are difficult to be efficiently and reasonably developed and utilized due to the problems of mineral processing technology. In fluorite flotation, the commonly used calcium-containing mineral inhibitors are a combination of acidified water glass, salted water glass and tannin extract. Although this process can obtain high-grade fluorite concentrate, the fluorite recovery rate is low when flotating fluorite in weakly acidic or neutral media. In addition, the inhibitor combination is not ideal for the separation of dolomite fluorite ores.

[0005] Gangue minerals in phosphate rock mainly include silicate gangue minerals such as calcite, dolomite, quartz and feldspar. According to the types of gangue minerals, it can be divided into: siliceous phosphate rock, calcium phosphate rock, and siliceous calcium phosphate rock. The beneficiation technology for phosphate rock with a single gangue type is relatively mature. For example, in alkaline medium, siliceous phosphate rock uses water glass as an inhibitor and sodium oleate as a collector to directly float apatite, and qualified phosphate concentrate can be obtained. In acidic medium, calcium phosphate rock uses sulfuric acid, phosphoric acid, fluorosilicic acid and other inorganic acids as apatite inhibitors to reverse float dolomite and calcite. For siliceous calcium phosphate rock, its gangue minerals contain both silicate gangue and carbonate gangue. It is difficult to obtain qualified phosphate concentrate with a single flotation process. Therefore, combined processes are often used, such as direct and reverse flotation process, reverse flotation process, and double reverse flotation process. The direct and reverse flotation processes and reverse flotation processes are long, and the pH of the flotation pulp often needs to be adjusted between acid and alkaline, which requires a large amount of pH adjuster, and it is difficult to reuse the mineral processing wastewater. The double reverse flotation process is more sensitive to fine mud and is prone to form overstable foam accumulation, making foam control more difficult.

[0006] Chinese invention patent application CN201911261050.4 introduces a method of using naphthalene-based water reducer as a flotation inhibitor for collophanite, which mainly inhibits silicate minerals, dolomite and calcite. Its flotation process is a forward and reverse flotation process, that is, phosphate is enriched by a forward flotation process in a weakly alkaline environment to remove gangue minerals, and then sulfuric acid is added to the forward flotation concentrate to adjust the slurry to acidity, and a reverse flotation collector is added to flotate and remove dolomite and calcite. The naphthalene-based water reducer is added in the forward flotation operation. From the analysis of its process flow structure, adding a naphthalene-based water reducer in the forward flotation operation cannot effectively inhibit dolomite and calcite, so the reverse flotation operation is added to flotate and remove calcite and dolomite. At the same time, the MgO content in its flotation concentrate is only <1.2%, indicating that the demagnesization effect of adding a naphthalene-based water reducer and a reverse flotation demagnesization process in combination cannot reach the target of <0.5%. Therefore, developing an efficient calcium carbonate inhibitor that can inhibit calcite and dolomite in alkaline media and realize the one-stage flotation of silico-calcic phosphate ore is the current research focus and also a technical difficulty that needs to be solved urgently for the efficient development and utilization of silico-calcic phosphate ore. Summary of the invention

[0007] In view of the shortcomings of the prior art, one of the objects of the present invention is to provide a flotation depressant having excellent inhibitory effect on calcium carbonate type gangue minerals, which can improve the grade and recovery rate of flotation concentrate; the second object of the present invention is to provide a flotation process for calcium carbonate minerals; the third object of the present invention is to provide an application of a flotation depressant in the flotation separation of calcium carbonate minerals.

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

[0009] A flotation inhibitor comprises, by weight, 5 to 20 parts of sodium gluconate, 5 to 15 parts of CH-R concrete water reducing agent (CH-R type concrete water reducing agent) and 1 to 10 parts of polyacrylate concrete water reducing agent.

[0010] The applicant has found through research that the flotation depressant of the present invention can be used as an inhibitor of calcium carbonate-type gangue minerals such as calcite and dolomite, and has a significant selective inhibitory effect, while the inhibitory effect on useful minerals such as scheelite, fluorite and apatite is relatively weak. Therefore, it can be used for the separation and flotation of scheelite, fluorite, apatite and calcium-containing carbonate minerals, and has the advantages of good inhibitory effect, low dosage, low cost, stable performance indicators, etc., and can effectively improve the separation indicators of scheelite, fluorite and apatite.

[0011] Furthermore, the flotation depressant comprises, by weight, 7 to 16 parts of sodium gluconate, 8 to 11 parts of CH-R concrete water reducer, and 5 to 8 parts of polyacrylate concrete water reducer.

[0012] Furthermore, the polymerization degree of the CH-R concrete water reducing agent is 8 to 15, preferably 12 to 15. The applicant has found that a good inhibition effect cannot be obtained when the polymerization degree is too low or too high. When the CH-R concrete water reducing agent in the above range is used, a good inhibition effect can be obtained.

[0013] Furthermore, the molecular weight of the polyacrylate concrete water reducing agent is 20000 to 80000. The applicant has found that if the molecular weight is too low or too high, the inhibition ability is poor, and controlling it within the above range is helpful to obtain a good separation effect.

[0014] Furthermore, it also comprises water, wherein the content of the water is 10 to 100 times, further 20 to 80 times, and further 40 to 60 times the total mass of the sodium gluconate, the CH-R concrete water reducing agent and the polyacrylate concrete water reducing agent.

[0015] Optionally, sodium gluconate, CH-R concrete water reducer, polyacrylate concrete water reducer and water are weighed according to the proportion, and mixed evenly to form a flotation inhibitor aqueous solution, which can help to better exert the effect of the flotation inhibitor.

[0016] Based on the same inventive concept, the present invention also provides a flotation process for calcium carbonate minerals, wherein flotation is performed through one roughing, three cleaning, and three scavenging closed-circuit tests; wherein the amount of flotation depressant is 100-800 g / t of the original ore. Further, during roughing, the flotation depressant as described above is added at an amount of 200-300 g / t; during cleaning, the flotation depressant as described above is added at an amount of 100-200 g / t; the calcium carbonate mineral contains calcium carbonate type gangue minerals.

[0017] Optionally, in the roughing, the dosage of the adjusting agent (which can be sodium carbonate) is 400-600g / t of original ore (mainly used to adjust the pH value of the slurry), the dosage of the flotation depressant is 200-300g / t of original ore, and the dosage of the collector (which can be saponified oleic acid) is 100-200g / t of original ore; the dosage of the flotation depressant in the first, second and third selections is 40-60g / t of original ore, 40-60g / t of original ore, and 40-60g / t of original ore, respectively; the dosage of the collector (which can be saponified oleic acid) in the first and second selections is 40-60g / t of original ore, 40-60g / t of original ore, and 40-60g / t of original ore, respectively.

[0018] Furthermore, the calcium carbonate mineral includes one or more of scheelite ore, fluorite ore, and phosphate ore.

[0019] Optionally, during roughing and cleaning, the pH value of the slurry is controlled to be 1-13 and the temperature to be 0-100°C.

[0020] Furthermore, during roughing, the pH value of the pulp is controlled to be 8-10, preferably 9-10. The applicant has found that under this pH condition, the selective suppression performance is better. In particular, in the flotation process of apatite and scheelite, the grade and recovery rate of the concentrate are further improved under this pH condition.

[0021] Furthermore, when the gangue mineral in the calcium-containing carbonate mineral is calcite, the flotation depressant includes 10 to 20 parts of sodium gluconate, 5 to 12 parts of CH-R concrete water reducer, and 1 to 8 parts of polyacrylate concrete water reducer; when the gangue mineral in the calcium-containing carbonate mineral is dolomite, the flotation depressant includes 5 to 15 parts of sodium gluconate, 8 to 15 parts of CH-R concrete water reducer, and 3 to 10 parts of polyacrylate concrete water reducer.

[0022] Furthermore, the flotation process is carried out at room temperature.

[0023] Based on the same inventive concept, the present invention also provides the use of the flotation depressant as described above in the flotation separation of useful minerals and calcium carbonate type gangue minerals, wherein the useful minerals include one or more of scheelite, fluorite, and apatite; and the calcium carbonate type gangue minerals include one or more of calcite and dolomite.

[0024] The flotation depressant of the present invention is efficient, green and environmentally friendly, can effectively solve the problems of similar floatability between calcium-containing minerals, great difficulty in flotation separation and low separation efficiency, and can achieve effective separation of calcium carbonate-type gangue minerals and useful minerals; specifically, the flotation depressant of the present invention is used to solve the difficult problems of separation of scheelite and calcite, separation of scheelite and dolomite, separation of fluorite and calcite, separation of fluorite and dolomite, separation of apatite and calcite, and separation of apatite and dolomite, and excellent effects can be achieved.

[0025] Polyacrylate concrete water reducer and other materials are common concrete water reducers and are easy to obtain. For example, they are recorded in the "Concrete Admixture Formula Handbook" (edited by Xia Shourong and published by Chemical Industry Press).

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) The flotation depressant of the present invention has strong selective inhibition performance. While inhibiting calcite and dolomite, it has little effect on the floatability of useful minerals such as scheelite, apatite and fluorite, and can achieve effective separation of calcium carbonate-type gangue minerals such as calcite and dolomite and useful minerals, thereby obtaining a high concentrate recovery rate and a high grade.

[0028] (2) The raw material of the flotation depressant of the present invention is low in price, widely available, simple to prepare, and has a low dosage, which is conducive to industrial application.

[0029] (3) The flotation depressant of the present invention can exert excellent effects even at room temperature, thus helping to reduce the cost of flotation separation.

[0030] (4) The flotation depressant of the present invention has a better selective inhibition effect than the traditional depressant water glass, and its dosage is lower than that of water glass, which can greatly improve the comprehensive benefits of the flotation process. DETAILED DESCRIPTION

[0031] The present invention is further described below in conjunction with examples, which obviously do not limit the scope of protection of the claims of the present invention.

[0032] In the present invention, the scheelite ore used in the relevant embodiments includes WO 3 The mass percentage of CaCO is 0.22%, 3 The mass percentage of CaF is 18.05%, and the mass percentage of MgO is 2.95%. 2 The mass percentage of CaCO is 22.50%, 3 The mass percentage of P is 32.05%, and the mass percentage of MgO is 5.85%; in the phosphate ore used in the relevant embodiments of the present invention, P 2 O5 The mass percentage of CaCO is 24.80%, 3 The mass percentage of MgO is 3.62%, and the mass percentage of MgO is 4.86%. Unless otherwise specified, the ore raw materials or chemical reagents used in the embodiments of the present invention are obtained through conventional commercial channels.

[0033] Example 1

[0034] Sodium gluconate, CH-R concrete water reducer (polymerization degree 12-15), and polyacrylate concrete water reducer (molecular weight 20000-80000) are weighed in parts by weight, and mixed to obtain a combined inhibitor (flotation inhibitor); water 48 times the total weight of the combined inhibitor is weighed, and then the combined inhibitor is slowly and evenly added into the water while constantly stirring to fully dissolve it, to prepare an inhibitor solution with a mass concentration of 2%.

[0035] The prepared inhibitor is applied to the flotation of the above-mentioned scheelite ore, which is a typical scheelite-fluorite-calcite-dolomite ore, that is, the carbonate-type gangue minerals are mainly calcite and dolomite, and the remaining gangue minerals include silicate minerals such as quartz and feldspar. Table 1 is the raw material components and proportions of the inhibitor used in Example 1, and Table 2 is the test results of using the inhibitor formula in Table 1 as calcite and dolomite inhibitors. The flotation test was carried out at room temperature, and the flotation process was a closed-circuit test of one roughing, three cleaning, and three scavenging. Combined depressant group flotation reagent system: in roughing, the dosage of adjusting agent (sodium carbonate) is 500g / t of raw ore (slurry pH 8-9), the dosage of combined depressant is 250g / t of raw ore, and the dosage of collector (saponified oleic acid) is 150g / t of raw ore; the dosage of combined depressant in selection 1, selection 2, and selection 3 is 50g / t of raw ore, 50g / t of raw ore, and 50g / t of raw ore respectively; the dosage of collector (saponified oleic acid) in scavenging selection 1 and scavenging selection 2 is 50g / t of raw ore, 50g / t of raw ore, and 50g / t of raw ore respectively. Water glass group reagent system: the dosage of water glass in roughing is 1200g / t of raw ore, and the dosage of water glass in selection 1, selection 2, and selection 3 is 200g / t of raw ore, 200g / t of raw ore, and 200g / t of raw ore respectively, and other conditions are the same.

[0036] Table 1 Inhibitor raw material components and ratios in Example 1

[0037]

[0038] Table 2 Flotation test results of each formulation in Example 1

[0039]

[0040] As shown in Table 2, Formula 7, Formula 8, and Formula 9 are polyacrylate concrete water reducer, CH-R concrete water reducer, and sodium gluconate used alone. From the test data, it can be seen that when used alone, the inhibitor has poor inhibition ability on calcite and dolomite, the grade and recovery rate of scheelite are low, the selective inhibition ability is poor, and the flotation effect is even worse than the water glass group. Formula 4, Formula 5, and Formula 6 are polyacrylate concrete water reducer, CH-R concrete water reducer, and sodium gluconate used in combination. From the test data, it can be seen that the effect of the combination of two is better than that of using them alone, but worse than that of the three combined. Formula 1, Formula 2, and Formula 3 are polyacrylate concrete water reducer, CH-R concrete water reducer, and sodium gluconate used in combination. The effect is significantly higher than that of using them alone and in combination. Among them, Formula 2 is within the optimal ratio range, and its effect is significantly better than Formula 1 and Formula 3. It can be seen that the combination of polyacrylate concrete water reducer, CH-R concrete water reducer, and sodium gluconate has a synergistic effect. The flotation depressant provided by the embodiment of the present invention has a better selective inhibition effect than the traditional depressant water glass, and its dosage is lower than that of water glass. By adopting the flotation depressant of the present invention, the calcite and dolomite in the ore are significantly inhibited, the calcite and dolomite content in the concentrate is greatly reduced compared with the original ore, and the flotation enrichment effect on scheelite and fluorite is relatively low, and the grade and recovery rate of scheelite concentrate are significantly higher than those of the traditional depressant water glass. At the same time, because the flotation depressant can selectively inhibit calcite and dolomite, the inhibitory effect on fluorite is not significant, and the mixed flotation of scheelite and fluorite ore can be achieved. The fluorite grade in the concentrate is relatively high. After the subsequent heating flotation separation of scheelite and fluorite, the fluorite can be directly sold as a product.

[0041] Example 2

[0042] By weight, 8 parts of sodium gluconate, 10 parts of CH-R concrete water reducer (divided into 4 groups based on the polymerization degree of CH-R concrete water reducer, see Table 3), and 6 parts of polyacrylate concrete water reducer (molecular weight of 20000-80000) were weighed and mixed to form a combined inhibitor; water 48 times the total weight of the combined inhibitor was weighed, and then the combined inhibitor was slowly and evenly added into the water while constantly stirring to fully dissolve it, to prepare an inhibitor solution with a mass concentration of 2%.

[0043] The prepared inhibitor solution was applied to the above-mentioned scheelite flotation. Table 3 shows the polymerization degree test conditions of CH-R concrete water reducer. Table 4 shows the test results of using the inhibitor formula in Table 3 as calcite and dolomite inhibitors. The flotation test was carried out at room temperature. The flotation process was a closed-circuit test of one roughing, three cleaning, and three scavenging. Combined inhibitor group flotation reagent system: In the roughing, the dosage of the adjuster (sodium carbonate) was 500g / t of ore (slurry pH value 8-9), the dosage of the combined inhibitor was 250g / t of ore, and the dosage of the collector (saponified oleic acid) was 150g / t of ore; the dosage of the combined inhibitor in the first, second, and third cleaning was 50g / t of ore, 50g / t of ore, and 50g / t of ore respectively; the dosage of the collector (saponified oleic acid) in the first and second cleaning was 50g / t of ore, 50g / t of ore, and 50g / t of ore respectively.

[0044] Table 3 Test conditions for polymerization degree of CH-R concrete water reducer

[0045]

[0046] Table 4 Flotation test results under different polymerization degrees of CH-R concrete water reducer

[0047]

[0048] As shown in Table 4, when the ratio of sodium gluconate, CH-R concrete water reducer, and polyacrylate concrete water reducer in the combined inhibitor is constant, the yield of tungsten concentrate gradually decreases with the increase of the polymerization degree of CH-R concrete water reducer, indicating that the inhibition ability of the combined inhibitor gradually increases. When the polymerization degree is between 8 and 15, the indicators of tungsten concentrate are equivalent. This may be because the selectivity of the combined inhibitor decreases as the polymerization degree of CH-R concrete water reducer continues to increase. While the combined inhibitor inhibits calcite and dolomite, it also inhibits part of scheelite, resulting in a decrease in the quality of the concentrate product. Therefore, the polymerization degree of CH-R concrete water reducer in the combined inhibitor is preferably between 8 and 15.

[0049] Example 3

[0050] By weight, 8 parts of sodium gluconate, 10 parts of CH-R concrete water reducer (polymerization degree of 12-15), and 6 parts of polyacrylate concrete water reducer (divided into 3 groups according to different molecular weight ranges, see Table 5) were weighed and mixed to obtain a combined inhibitor; water 48 times the total weight of the combined inhibitor was weighed, and then the combined inhibitor was slowly and evenly added into the water while constantly stirring to fully dissolve it, to prepare an inhibitor solution with a mass concentration of 2%.

[0051] The configured inhibitor was applied to the above-mentioned scheelite flotation. Table 5 shows the test conditions for the molecular weight of polyacrylate concrete water reducer. Table 6 shows the test results of using the inhibitor formula in Table 5 as a calcite and dolomite inhibitor. The flotation test was carried out at room temperature. The flotation process was a closed-circuit test of one roughing, three cleanings, and three scavengings. The flotation reagent system of the combined inhibitor group: the dosage of the roughing adjustment agent (sodium carbonate) is 500g / t of raw ore (slurry pH value 8-9), the combined inhibitor is 250g / t of raw ore, and the collector (saponified oleic acid) is 150g / t of raw ore; the dosage of the combined inhibitor for cleaning one, cleaning two, and cleaning three is 50g / t of raw ore, 50g / t of raw ore, and 50g / t of raw ore respectively; the dosage of the collector (saponified oleic acid) for scavenging one and cleaning two is 50g / t of raw ore, 50g / t of raw ore, and 50g / t of raw ore respectively.

[0052] Table 5 Test conditions for molecular weight of polyacrylate concrete water reducer

[0053] Polyacrylate concrete water reducing agent molecular weight 10000～20000 20000～80000 80000～100000

[0054] Table 6 Flotation test results of polyacrylate concrete water reducer with different molecular weights

[0055]

[0056] It can be seen from Table 6 that when the ratio of sodium gluconate, CH-R concrete water reducer and polyacrylate concrete water reducer in the combined inhibitor is constant, the yield of tungsten concentrate gradually decreases with the increase of the molecular weight of polyacrylate concrete water reducer, indicating that the inhibition ability of the combined inhibitor gradually increases. When the molecular weight of polyacrylate concrete water reducer is 20000-80000, it can effectively inhibit dolomite and calcite in the ore, while the inhibition effect on scheelite is not significant, and the mineral processing index is good. This may be because the selectivity of the combined inhibitor decreases as the molecular weight of polyacrylate concrete water reducer is further increased. While the combined inhibitor inhibits calcite and dolomite, it also inhibits part of scheelite, resulting in the concentrate product WO 3 Therefore, the molecular weight of polyacrylate concrete water reducer in the combined inhibitor is preferably 20,000 to 80,000.

[0057] Example 4

[0058] Weigh 8 parts of sodium gluconate, 10 parts of CH-R concrete water reducer (polymerization degree 12-15), and 6 parts of polyacrylate concrete water reducer (molecular weight 20000-80000) by weight, mix them well, and obtain a combined inhibitor; weigh 48 times the total weight of water of the combined inhibitor, and then slowly and evenly add the combined inhibitor into the water while constantly stirring to fully dissolve it, to prepare an inhibitor solution with a mass concentration of 2%.

[0059] The configured inhibitor was applied to the above-mentioned scheelite flotation. Table 7 shows the test results of the pulp pH condition. The flotation test was carried out at room temperature. The flotation process was a closed-circuit test of one roughing, three cleaning, and three scavenging. Combined inhibitor group flotation reagent system: the roughing adjustment agent was sodium carbonate, and the comparative test was adjusted to different pH conditions. The combined inhibitor was 250g / t of raw ore, and the collector (saponified oleic acid) was 150g / t of raw ore; the combined inhibitor dosages of cleaning one, cleaning two, and cleaning three were 50g / t of raw ore, 50g / t of raw ore, and 50g / t of raw ore respectively; the collector (saponified oleic acid) dosages of scavenging one and cleaning two were 50g / t of raw ore, 50g / t of raw ore, and 50g / t of raw ore respectively.

[0060] Table 7 Slurry pH condition test results

[0061]

[0062] It can be seen from Table 7 that when the pH value of the slurry is low, the combined inhibitor has a stronger inhibition ability, and the concentrate WO 3 The grade is the highest among the three groups, but its recovery rate is low. When the pH value is between 10 and 11, the concentrate WO 3 The grade and recovery rate are both lower among the three groups. When the pH value is between 8 and 10, the concentrate grade is WO 3 The grade is slightly lower, but its recovery rate is significantly higher than the other two groups, indicating that the slurry pH value is more suitable at 8-10.

[0063] Comparative Example 1

[0064] Weigh 8 parts of sodium gluconate, 10 parts of CH-R concrete water reducer (polymerization degree 12-15), and 6 parts of polyacrylate concrete water reducer (molecular weight 20000-80000) by weight, mix them well, and obtain a combined inhibitor; weigh 48 times the total weight of water of the combined inhibitor, and then slowly and evenly add the combined inhibitor into the water while constantly stirring to fully dissolve it, to prepare an inhibitor solution with a mass concentration of 2%.

[0065] The configured inhibitor was applied to the above-mentioned scheelite flotation. The flotation test was carried out at room temperature. The flotation process was one roughing, three cleaning, and three scavenging closed-circuit tests. Combined inhibitor group flotation reagent system: In the roughing, the dosage of the adjusting agent (sodium carbonate) was 500g / t of raw ore (slurry pH value 8-9), the combined inhibitor was 250g / t of raw ore, and the collector (saponified oleic acid) was 150g / t of raw ore; the dosage of the combined inhibitor in the first, second, and third cleaning was 50g / t of raw ore, 50g / t of raw ore, and 50g / t of raw ore respectively; the dosage of the collector (saponified oleic acid) in the first and second cleaning was 50g / t of raw ore, 50g / t of raw ore, and 50g / t of raw ore respectively. Naphthalene water-reducing agent group dosage system: the dosage of naphthalene water-reducing agent in rough selection is 800g / t original ore, the dosage of naphthalene water-reducing agent in selection one, selection two and selection three are 100g / t original ore, 100g / t original ore and 100g / t original ore respectively, and the other conditions are the same.

[0066] Table 8 Inhibitor comparison test results

[0067]

[0068] As shown in Table 8, when naphthalene-based water reducer is used as an inhibitor, the calcite and dolomite contents in the concentrate are relatively high, and the naphthalene-based water reducer has no inhibitory effect on calcite. It has a certain inhibitory ability on the dolomite inhibitor, but it cannot meet the application requirements. Comparing the two sets of data, it can be seen that the selective inhibitory effect of the combined inhibitor on dolomite and calcite is significantly higher than that of the naphthalene-based water reducer. It can also be seen that not all water reducers can achieve an ideal inhibitory effect.

[0069] Example 5

[0070] Sodium gluconate, CH-R concrete water reducer (polymerization degree 12-15), and polyacrylate concrete water reducer (molecular weight 20000-80000) were weighed in parts by weight (see Table 9), and mixed to obtain a combined inhibitor; water 48 times the total weight of the combined inhibitor was weighed, and then the combined inhibitor was slowly and evenly added into the water while constantly stirring to fully dissolve it, to prepare an inhibitor solution with a mass concentration of 2%.

[0071] The prepared inhibitor solution is applied to the flotation of the above-mentioned fluorite ore, which is a typical fluorite-calcite-dolomite type ore, that is, the carbonate gangue minerals are mainly calcite and dolomite, and the remaining gangue minerals include silicate minerals such as quartz. Table 9 is the raw material components and proportions of the inhibitor used in Example 5, and Table 10 is the test results of using the inhibitor formula in Table 9 as calcite and dolomite inhibitors. The flotation test was carried out at room temperature, and the flotation process was a closed-circuit process of one roughing, five cleaning, and two scavenging. Flotation reagent system of combined depressant group: in roughing, the dosage of combined depressant is 250g / t of raw ore, and the dosage of collector (oleic acid) is 400g / t of raw ore; the dosage of combined depressant in selection 1, selection 2, selection 3, selection 4, and selection 5 is 100g / t of raw ore, 50g / t of raw ore, 25g / t of raw ore, 25g / t of raw ore, and 25g / t of raw ore respectively; the dosage of collector (oleic acid) in scavenging selection 1 and scavenging selection 2 is 50g / t of raw ore and 50g / t of raw ore respectively. Reagent system of acidified water glass group: in roughing, the dosage of acidified water glass is 800g / t of raw ore, and the dosage of acidified water glass in selection 1, selection 2, selection 3, selection 4, and selection 5 is 100g / t of raw ore, 50g / t of raw ore, 50g / t of raw ore, 50g / t of raw ore, and 50g / t of raw ore respectively, and other conditions are the same.

[0072] Table 9 Inhibitor raw material components and ratios in Example 5

[0073]

[0074]

[0075] Table 10 Experimental results of Example 5

[0076]

[0077] As shown in Table 10, formulas 5, 6, and 7 are polyacrylate concrete water reducer, CH-R concrete water reducer, and sodium gluconate used alone, while fluorite concentrate CaF 2 The grade is low, and the content of calcite and dolomite is high, indicating that the above water reducers have poor selective inhibition ability against calcite and dolomite when used alone. Formulas 2, 3, and 4 are polyacrylate concrete water reducers, CH-R concrete water reducers, and sodium gluconate. Compared with using them alone, the concentrate CaF 2 The grade is significantly improved, the calcite and dolomite content in the concentrate is reduced, and the inhibition effect is significantly improved. Formula 1 is a combination of polyacrylate concrete water reducer, CH-R concrete water reducer, and sodium gluconate. Fluorite concentrate CaF 2The grade is the highest among all the formulas, and the calcite and dolomite content in the concentrate is the lowest. The combination of the three has a significant synergistic effect. The combined inhibitor of the three is significantly better than the traditional acidic water glass in separation, not only the concentrate CaF 2 With high grade and recovery rate and low dosage, it can realize acid-free flotation of high calcite and dolomite fluorite.

[0078] Comparative Example 2

[0079] Weigh 15 parts of sodium gluconate, 10 parts of CH-R concrete water reducer (polymerization degree 12-15), and 8 parts of polyacrylate concrete water reducer (molecular weight 20000-80000) by weight, mix them well, and obtain a combined inhibitor; weigh 48 times the total weight of water of the combined inhibitor, and then slowly and evenly add the combined inhibitor into the water while constantly stirring to fully dissolve it, to prepare an inhibitor solution with a mass concentration of 2%.

[0080] The configured inhibitors were applied to the above fluorite flotation. Table 11 shows the test results of the combined inhibitor and naphthalene water reducer as calcite and dolomite inhibitors respectively. The flotation test was carried out at room temperature. The flotation process was a closed-circuit process of one roughing, five cleaning and two scavenging. Flotation reagent system of the combined inhibitor group: in the roughing, the dosage of the combined inhibitor was 250g / t of raw ore, and the dosage of the collector (oleic acid) was 400g / t of raw ore; the dosage of the combined inhibitor in the first, second, third, fourth and fifth cleaning was 100g / t of raw ore, 50g / t of raw ore, 25g / t of raw ore, 25g / t of raw ore, and 25g / t of raw ore respectively; the dosage of the collector (oleic acid) in the first and second cleaning was 50g / t of raw ore and 50g / t of raw ore respectively. Naphthalene water-reducing agent group dosage system: the dosage of naphthalene water-reducing agent in rough selection is 600g / t original ore, and the dosage of acidified water glass in selection one, selection two, selection three, selection four and selection five are 100g / t original ore, 80g / t original ore, 50g / t original ore, 50g / t original ore and 50g / t original ore respectively, and other conditions are the same.

[0081] Table 11 Comparative Example 2 Test Results

[0082]

[0083] As shown in Table 11, in the fluorite flotation system, the effect of using naphthalene-based water reducer as a depressant for calcite and dolomite is not significant. When using naphthalene-based water reducer, the calcium carbonate content in the concentrate is higher than that in the original ore, indicating that calcium carbonate is enriched during flotation, and the naphthalene-based water reducer has poor depressant ability for calcite; the dolomite content in the concentrate is lower than that in the original ore, but the MgO content is still high. When using a combined depressant, the calcium carbonate and MgO contents in the concentrate are 1.08% and 0.30% respectively, and the selective depressant ability is significantly better than that of the naphthalene-based water reducer. At the same time, the combined depressant dosage is low and the economic benefit is better.

[0084] Example 6

[0085] Sodium gluconate, CH-R concrete water reducer (polymerization degree of 12 to 15), and polyacrylate concrete water reducer (molecular weight of 20,000 to 80,000) were weighed in parts by weight (see Table 9), and mixed to obtain a combined inhibitor; water was weighed in an amount of 48 times the total weight of the combined inhibitor, and then the combined inhibitor was slowly and evenly added into the water while constantly stirring to fully dissolve it, to prepare an inhibitor solution with a mass concentration of 2%.

[0086] The prepared inhibitor is applied to the above-mentioned phosphate ore flotation, which is a high calcium and magnesium type ore, that is, the carbonate gangue minerals are mainly calcite and dolomite, and the remaining gangue minerals include silicate minerals such as quartz. Table 12 is the raw material components and proportions of the inhibitor used in Example 6, and Table 13 is the test results of using the inhibitor formula in Table 12 as calcite and dolomite inhibitors. The flotation test was carried out at room temperature, and the flotation process was a closed-circuit process of one roughing, three cleaning, and two scavenging. Flotation reagent system of combined depressant group: in roughing, the dosage of sodium carbonate is 4500g / t of raw ore, the dosage of combined depressant is 350g / t of raw ore, and the dosage of collector (saponified oleic acid) is 600g / t of raw ore; the dosage of combined depressant in selection 1, selection 2, and selection 3 is 50g / t of raw ore, 50g / t of raw ore, and 50g / t of raw ore respectively; the dosage of saponified oleic acid in scavenging selection 1 and scavenging selection 2 is 100g / t of raw ore and 100g / t of raw ore respectively. Reagent system of water glass group: the dosage of water glass in roughing is 1000g / t of raw ore, and the dosage of water glass in selection 1, selection 2, and selection 3 is 200g / t of raw ore, 200g / t of raw ore, and 100g / t of raw ore respectively, and other conditions are the same.

[0087] Table 12 Inhibitor raw material components and proportions in Example 6

[0088]

[0089] Table 13 Experimental results of Example 6

[0090]

[0091]

[0092] As shown in Table 12, formulas 5, 6, and 7 are polyacrylate concrete water reducer, CH-R concrete water reducer, and sodium gluconate used alone, while phosphate concentrate P 2 O 5 The grade is low, and the content of calcite and dolomite is high, indicating that when the above water reducers are used alone, the selective inhibition ability of calcite and dolomite is poor. Formulas 2, 3, and 4 are polyacrylate concrete water reducers, CH-R concrete water reducers, and sodium gluconate. Compared with using them alone, the phosphate concentrate P 2 O 5 The grade is significantly improved, the calcite and dolomite content in the concentrate is reduced, and the inhibition effect is significantly improved. Formula 1 is a combination of polyacrylate concrete water reducer, CH-R concrete water reducer, and sodium gluconate. 2 O 5 The grade is the highest among the listed formulas, and the calcite and dolomite content in the concentrate is the lowest. The combination of the three has a significant synergistic effect. The combined depressant using the three together has a significantly better sorting effect than the traditional depressant water glass.

[0093] Comparative Example 3

[0094] Weigh 15 parts of sodium gluconate, 10 parts of CH-R concrete water reducer (polymerization degree 8-15), and 8 parts of polyacrylate concrete water reducer (molecular weight 20000-80000) by weight, mix them well, and obtain a combined inhibitor; weigh 48 times the total weight of water of the combined inhibitor, and then slowly and evenly add the combined inhibitor into the water while constantly stirring to fully dissolve it, to prepare an inhibitor solution with a mass concentration of 2%.

[0095] The prepared inhibitor solution was applied to the above-mentioned phosphate ore flotation. Table 14 shows the test results of the combined inhibitor and naphthalene-based water reducer as calcite and dolomite inhibitors respectively. The flotation test was carried out at room temperature. The flotation process was a closed-circuit process of one roughing, three cleanings and two scavengings. Flotation reagent system of the combined inhibitor group: in the roughing, the dosage of sodium carbonate was 4500g / t of raw ore, the dosage of the combined inhibitor was 350g / t of raw ore, and the dosage of the collector (saponified oleic acid) was 600g / t of raw ore; the dosage of the combined inhibitor in the first, second and third cleanings was 50g / t of raw ore, 50g / t of raw ore and 50g / t of raw ore respectively; the dosage of saponified oleic acid in the first and second cleanings was 100g / t of raw ore and 100g / t of raw ore respectively. Naphthalene water-reducing agent group dosage system: the dosage of naphthalene water-reducing agent is 1200g / t original ore, the dosage of selected one, selected two, and selected three naphthalene water-reducing agent is 200g / t original ore, 200g / t original ore, and 100g / t original ore respectively, and other conditions are the same.

[0096] Table 14 Comparative Example 3 Test Results

[0097]

[0098] As shown in Table 14, in the phosphate ore flotation system, the effect of using naphthalene-based water reducer as a depressant for calcite and dolomite is not significant. When using naphthalene-based water reducer, the calcium carbonate content in the concentrate is higher than that in the original ore, indicating that calcium carbonate is enriched during flotation and the naphthalene-based water reducer has poor ability to inhibit calcite; the dolomite content in the concentrate is lower than that in the original ore, but the MgO content is still high. When using combined depressants, the concentrate P 2 O 5 The grade and recovery rate are higher than those of the naphthalene-based water reducer group. The contents of calcium carbonate and MgO in the concentrate are 1.85% and 0.82%, respectively, which are significantly lower than those of the naphthalene-based water reducer group, indicating that the selective inhibition ability of the combined inhibitor is significantly better than that of the naphthalene-based water reducer. At the same time, the dosage of the combined inhibitor is low and the economic benefit is better.

[0099] The contents explained in the above embodiments should be understood as these embodiments are only used to more clearly illustrate the present invention, and are not used to limit the scope of the present invention. After reading the present invention, various equivalent forms of modifications to the present invention by those skilled in the art all fall within the scope defined by the claims attached to this application.

Claims

1. A flotation depressant for calcium carbonate minerals, It is characterized in that Calculated by mass, it includes 5 to 20 parts of sodium gluconate, 5 to 15 parts of CH-R concrete water reducing agent and 1 to 10 parts of polyacrylate concrete water reducing agent.

2. The flotation depressant according to claim 1, It is characterized in that Calculated by weight, the flotation depressant includes 7 to 16 parts of sodium gluconate, 8 to 11 parts of CH-R concrete water reducer, and 5 to 8 parts of polyacrylate concrete water reducer.

3. The flotation depressant according to claim 1, It is characterized in that The polymerization degree of the CH-R concrete water reducer is 8 to 15; the molecular weight of the polyacrylate concrete water reducer is 20,000 to 80,000.

4. The flotation depressant according to claim 1, It is characterized in that The polymerization degree of the CH-R concrete water reducer is 12-15.

5. The flotation depressant according to claim 1, It is characterized in that The method further comprises water, wherein the content of the water is 10 to 100 times the total mass of the sodium gluconate, the CH-R concrete water reducing agent and the polyacrylate concrete water reducing agent.

6. A flotation process for calcium carbonate minerals, It is characterized in that Flotation is carried out through a closed-circuit test of one roughing, three cleaning and three scavenging; wherein, during the roughing, the flotation depressant as described in any one of claims 1 to 5 is added in an amount of 200-300 g / t; during the cleaning, the flotation depressant as described in any one of claims 1 to 5 is added in an amount of 100-200 g / t; the calcium carbonate mineral contains calcium carbonate type gangue minerals.

7. The flotation process according to claim 6, It is characterized in that The calcium carbonate minerals include one or more of scheelite ore, fluorite ore and phosphate ore.

8. The flotation process according to claim 6, It is characterized in that During roughing, the pH value of the slurry is controlled at 8~10.

9. The flotation process according to claim 8, It is characterized in that During roughing, the pH value of the slurry is controlled at 9-10.

10. The flotation process according to claim 6, It is characterized in that When the gangue mineral in the calcium-containing carbonate mineral is calcite, the flotation depressant includes 10 to 20 parts of sodium gluconate, 5 to 12 parts of CH-R concrete water reducer, and 1 to 8 parts of polyacrylate concrete water reducer; when the gangue mineral in the calcium-containing carbonate mineral is dolomite, the flotation depressant includes 5 to 15 parts of sodium gluconate, 8 to 15 parts of CH-R concrete water reducer, and 3 to 10 parts of polyacrylate concrete water reducer.

11. The flotation process according to claim 6, It is characterized in that The flotation process is carried out at room temperature.

12. Use of the flotation depressant according to any one of claims 1 to 5 in the flotation separation of useful minerals and calcium carbonate type gangue minerals, It is characterized in that The useful minerals include one or more of scheelite, fluorite, and apatite; the calcium carbonate type gangue minerals include one or more of calcite and dolomite.

Images