A depressant and flotation method for high-calcium fluorite ore

Abstract

The invention discloses a high-calcium fluorite inhibitor and a flotation method, wherein the high-calcium fluorite inhibitor comprises a modified water glass and a calcium carbonate strengthening inhibitor, wherein the modified water glass is a complex of an organic acid and water glass, wherein the organic acid is one or more of 3-carboxyl-3-hydroxyglutaric acid, 2-hydroxysuccinic acid, and 2,3-dihydroxysuccinic acid; the calcium carbonate strengthening inhibitor is one or two of sulfonated asphalt powder or sulfonated phenolic resin, wherein the structural formula of the sulfonated phenolic resin is shown in formula (III); wherein n is an integer. The invention combines a new flotation reagent system and a new process flow, and can achieve low-cost, efficient, and accurate separation of fluorite and calcite, and obtain high-quality fluorite concentrate.

Description

Technical Field

[0001] The invention belongs to the technical field of fluorite flotation, and in particular relates to a depressant and a flotation method for high-calcium fluorite ore. Background Art

[0002] Fluorite is the most important fluorine-containing industrial raw material and an important raw material in the fields of metallurgy, aluminum smelting, glass, ceramics, cement, chemistry and other industries. Its products are widely used in aerospace, medicine and pesticides, mechanical electronics, air conditioning and refrigeration, anti-corrosion and fire extinguishing, atomic energy and other fields. With the rapid development of economy and society, fluorite, as an important mineral raw material in modern industry, has been reserved as an important strategic material by many developed countries. my country is rich in fluorite resources, but the reserves of single-type fluorite deposits are small, and the reserves of associated (or symbiotic) fluorite deposits are rich, and most of them are low-grade and difficult-to-select fluorite ores.

[0003] Fluorite often coexists with various minerals such as quartz and calcite, forming polymetallic associated fluorite, quartz-fluorite, barite-fluorite, calcite-fluorite and sulfide-fluorite. Among them, the reserves of calcite-fluorite are huge, and the development and utilization are also difficult. Fluorite and calcite have similar physical and chemical properties. In the flotation system with fatty acids as collectors, the floatability of the two is similar. Generally, it is necessary to acidify or salinize the water glass with sulfuric acid, metal salts, etc., and then suppress calcite.

[0004] Chinese patent CN102658242B provides a complex and difficult-to-select fluorite ore beneficiation process, which uses sodium hydroxide to treat oleic acid to obtain modified oleic acid; uses concentrated sulfuric acid to treat water glass to obtain acidified water glass; grinds the fluorite ore according to the existing process, performs rough selection at a temperature of 25-30°C, and then selects the rough selection foam seven times, and adds acidified water glass in the first four selections to obtain fluorite concentrate. This process can increase the separation efficiency of calcium fluoride, silicon dioxide and calcite, improve the quality and recovery rate of fluorite concentrate, obtain high-quality acid-grade fluorite concentrate, and solve the problem of difficult flotation of complex fluorite ore; the application effect in the beneficiation of complex and difficult-to-select fluorite ore is significant and repeatable; at the same time, it reduces the requirements for slurry temperature of fluorite mineral flotation and reduces energy consumption; reduces the amount of collector oleic acid, reduces the environmental pollution caused by the discharge of a large amount of oleic acid-containing wastewater, and has good economic and social benefits, but this technology uses concentrated sulfuric acid to prepare water glass. The process is complicated and the safety is not guaranteed. At the same time, the dosage of sodium hexametaphosphate as an inhibitor is difficult to control. When the dosage is too high, it will inhibit fluorite, and when the dosage is low, it cannot effectively inhibit calcite. For example, the fluorite concentrate obtained by the new process in the embodiment still contains 0.95% CaCO3, and the quality of fluorite still has room for improvement.

[0005] Patent document WO2021179814A1 uses acidified water glass, fulvic acid and sodium naphthalenesulfonate to selectively inhibit barite, calcite and a small amount of silicate minerals through synergistic action, and obtains high-quality acid-grade fluorite concentrate with a CaF2 content of ≥98%, achieving the effect of improving flotation efficiency; but it can only be used for fluorite with a low calcium carbonate content, and the separation effect is not ideal for fluorite with a high calcium carbonate content. Moreover, this process is more suitable for the separation of fluorite and barite, and the separation effect of fluorite and calcite is not ideal.

[0006] Chinese patent CN 107377198 B discloses a method for beneficiating high calcium carbonate fluorite, comprising the following steps: S1, raw material grinding; S2, coarse concentrate preparation; S3, five beneficiation processes; S4, the sixth beneficiation process. The unevenness of the mineral surface and the interaction between various reagents are utilized to improve the selective inhibition of calcium carbonate by the reagents, thereby achieving the effect of effectively inhibiting calcium carbonate to ensure the recovery rate of fluorite; while using acidified water glass, pyrogallic acid, sodium hexametaphosphate, starch, etc., a synergistic effect can be produced to improve the flotation effect and obtain high-quality fluorite concentrate. However, the reagent preparation process is complicated, there are many types of reagents, the price of reagents such as pyrogallic acid is high, and the processing cost of the ore is high.

[0007] Chinese patent CN 111215247 A provides a depressant for high calcium fluorite positive flotation, wherein the depressant is an aqueous solution of ethylenediaminetetramethylenephosphonic acid. This invention also provides a high calcium fluorite positive flotation method, firstly crushing the fluorite ore into powder and preparing a pulp, then adding a pH adjuster to the pulp to control the pH value of the pulp at 6-8, adding water glass and sodium oleate to the pulp, roughing and scavenging the fluorite ore to obtain a fluorite rough concentrate, finally adding a depressant containing ethylenediaminetetramethylenephosphonic acid to the pulp containing the fluorite rough concentrate, and concentrating the fluorite rough concentrate to obtain a fluorite concentrate, wherein the total amount of ethylenediaminetetramethylenephosphonic acid used per ton of fluorite ore is 70-450g. The depressant in this invention has the advantages of low cost, significant selectivity, mild use environment and no secondary pollution, but the process selection process is relatively long, and the final fluorite grade can only be maintained at more than 95%, and there is still room for further improvement.

[0008] Chinese patent CN 113522517 A discloses a fluorite ore beneficiation method, which belongs to the technical field of fluorite ore separation process, and includes roughing: crushing the fluorite ore and grinding it to the required fineness for beneficiation, adding sodium carbonate, water glass and collector to the pulp successively, and flotation with alkaline medium to obtain roughing concentrate and roughing tailings; concentrating: concentrating the roughing concentrate obtained by roughing for multiple times, adding acidic water glass to the pulp during each concentrating process, and flotation with acidic medium; adding collector to the pulp to scavenge the first concentrating tailings, and flotation with acidic medium, and the scavenge concentrate is returned to the first concentrating; the concentrating tailings of multiple remaining concentrating operations are returned to the concentrating operation. The process flow and reagent system of this application can effectively remove carbonate and quartz gangue ore in fluorite ore, significantly improve the system stability and beneficiation quality of fluorite ore flotation, and can be widely used in industrial beneficiation operations of fluorite-carbonate-quartz type ore. However, this process returns all the concentrated tailings in the concentration process, which may lead to a large amount of calcium carbonate circulation in the concentration I operation, and requires that the CaF2 content of the processed fluorite ore be greater than 20%, resulting in a low grade and recovery rate of the obtained fluorite concentrate.

[0009] Chinese patent CN 113731639 A discloses a flotation method for low-grade fluorite ore containing tungsten and molybdenum, comprising the following steps: (1) crushing, grinding, magnetic separation and flotation of the raw ore to obtain tungsten and molybdenum flotation tailings; (2) roughing the tungsten and molybdenum flotation tailings with sodium carbonate and sodium hydroxide as pH adjusters, water glass and polycarboxylic acid as inhibitors, and mixed fatty acids as collectors to obtain fluorite roughing concentrate and roughing tailings; (3) adding mixed fatty acids to the fluorite roughing tailings for a rough scavenging to obtain a rough scavenging concentrate and a rough scavenging tailings; (4) the fluorite roughing concentrate is sequentially scavenged, acidified water glass is used as an inhibitor in the first and second scavenging, and the middlings are combined and fine scavenged to obtain a fine scavenging concentrate and a fine scavenging tailings; (5) the fluorite scavenging third scavenging uses acidified water glass as an inhibitor, and the scavenging fourth, fifth and sixth scavenging uses an organic phosphonic acid as an inhibitor to obtain a fluorite concentrate. However, this process only targets associated fluorite resources and does not require high quality of the fluorite concentrate obtained. The final fluorite grade only reaches more than 85%. Summary of the invention

[0010] The present invention provides a depressant and a flotation method for high-calcium fluorite ore, so as to achieve low flotation cost and stable concentrate quality, and to recover high-calcium fluorite resources with high efficiency at a lower cost as much as possible.

[0011] To achieve the above object, the present invention provides the following technical solutions:

[0012] A high-calcium fluorite inhibitor, comprising a modified water glass and a calcium carbonate strengthening inhibitor, wherein the modified water glass is a complex of an organic acid and water glass, wherein the organic acid is one or more of 3-carboxy-3-hydroxyglutaric acid, 2-hydroxysuccinic acid, and 2,3-dihydroxysuccinic acid; the calcium carbonate strengthening inhibitor is one or two of sulfonated asphalt powder or sulfonated phenolic resin, wherein the structural formula of the sulfonated phenolic resin is shown in formula (III);

[0013]

[0014] Wherein, n is an integer.

[0015] Preferably, the organic acid is 3-carboxy-3-hydroxyglutaric acid.

[0016] The 3-carboxyl-3-hydroxyglutaric acid has a better inhibitory effect, and its inhibitory ability is stronger because it contains three carboxyl groups in its molecular structure.

[0017] Preferably, the ratio of organic acid to water glass is in the range of 5-20:80-95.

[0018] If the ratio of organic acid to water glass is too large, the inhibition ability is strong, resulting in fluorite loss; if the ratio is too small, the fluorite recovery rate is low.

[0019] Preferably, the water-soluble components in the sulfonated asphalt powder are not less than 70%.

[0020] The sulfonated asphalt powder is a product obtained by sulfonating asphalt with oleum or sulfur trioxide and then hydrolyzing it. The sulfonated asphalt powder is a mixture, and some of the components are insoluble in water. Only when the water-soluble components in the sulfonated asphalt powder are not less than 70% and the hydrophilicity is very good, can the floating of calcite be effectively inhibited.

[0021] The sulfonated asphalt powder includes an asphaltene portion and a resin heterocyclic portion, wherein the asphaltene portion includes a compound as shown in structural formula (I), and the resin heterocyclic portion includes a compound as shown in structural formula (II);

[0022]

[0023] A flotation method for high-calcium fluorite ore comprises the following steps:

[0024] (1) grinding high calcium fluorite ore to obtain slurry; flotation of the slurry, adding sodium carbonate, the above inhibitor and collector in sequence, stirring for 1-3 minutes, flotation for 2.5-5 minutes, to obtain fluorite coarse concentrate and fluorite coarse tailings;

[0025] (2) The fluorite rough concentrate is beneficiated, and the above inhibitor is added in the first beneficiation, the third beneficiation, and the fifth beneficiation process, respectively, and no reagent is added in the second beneficiation, the fourth beneficiation, and the sixth beneficiation process. After six beneficiations, the fluorite concentrate is obtained, and the beneficiation time for each time is 1.5-4 minutes;

[0026] The obtained fluorite rough tailings are scavenged by adding a collector, and each scavenging time is 2-4 minutes; the obtained medium ore is returned to the previous operation;

[0027] The tailings from the first and second concentrations are supplemented with inhibitors and collectors for fine scavenging. The fine scavenging foam obtained is returned to the previous operation as the middlings. The fine scavenging tailings are combined with the rough scavenging tailings as the final tailings.

[0028] The tailings from the third, fourth, fifth and sixth concentrations are returned to the previous level of operation as middlings in sequence;

[0029] The CaF2 content in the high-calcium fluorite ore is 12-45%, and the CaCO3 content is 2-50%.

[0030] Wherein, the percentage contents described in the present invention are all percentage contents by mass.

[0031] Preferably, 50-85% of the particles in the slurry have a particle size of 0.074 mm.

[0032] Preferably, the amount of sodium carbonate used is between 0 and 1000 g / t depending on the properties of the original ore.

[0033] Sodium carbonate is used to adjust the pH value of the slurry on the one hand, and to remove inevitable ions such as calcium and magnesium in the slurry on the other hand.

[0034] Preferably, the inhibitor is added in an amount of 1200-3300 g / t.

[0035] More preferably, the total amount of modified water glass is 800-2500 g / t, and the total amount of calcium carbonate strengthening inhibitor is 400-800 g / t.

[0036] The total amount of the inhibitor added in the present invention is much smaller than that in the prior art.

[0037] Preferably, the collector is a complex of fatty acids, soaps thereof and diesel, and the total amount of the collector is 400-1000 g / t.

[0038] When the amount of collector is too much, the separation effect of fluorite and calcium-containing gangue minerals such as calcium carbonate is affected, resulting in poor grade of fluorite concentrate; when the amount of collector is too little, the fluorite recovery rate is low.

[0039] Preferably, the fatty acid and soap thereof include one or more of oleic acid, sodium oleate, oxidized paraffin soap, and tall oil.

[0040] Further preferably, the fatty acid and soap thereof are oleic acid or sodium oleate.

[0041] Preferably, the ratio of fatty acids and soaps thereof to diesel in the collector is 5:95.

[0042] If the ratio of soap to diesel is too large, it will have a defoaming effect and will be detrimental to fluorite recovery.

[0043] The present invention is further explained below:

[0044] The present invention combines a new flotation reagent system and a new process flow to achieve low-cost, high-efficiency and accurate separation of fluorite and calcite, and obtain high-quality fluorite concentrate. The main principles are:

[0045] (1) The flotation agent is mainly adsorbed on the surface of fluorite and calcite through the chemical interaction between the bonded atoms and the calcium ions. When the inhibitor occupies the calcium ion sites on the mineral surface and is adsorbed, the adsorption sites left for the fatty acid collector will be reduced, and the mineral surface will show hydrophilicity, making it difficult to float. Due to the difference in crystal structure properties, the bonded atoms of the flotation agent are less subject to steric hindrance when coordinating with the calcium ions on the surface of calcite. Therefore, the pre-added inhibitor is more easily adsorbed on the surface of calcite, hindering the adsorption of the collector on the surface of calcite and inhibiting its floating; and the inhibitor added in the present invention is small in number and low in unit price, which has obvious cost advantages.

[0046] (2) Compared with conventional water glass, the water glass modified by organic acid in this method will hydrolyze to produce more silicon-containing single colloids, thereby improving the selective inhibition of water glass on calcite. However, sulfuric acid itself has no inhibitory effect on gangue minerals, while the organic acid used in this method contains a large number of carboxyl and hydroxyl groups, has good hydrophilicity, has a stronger inhibitory effect on calcite and siliceous gangue, and has a good dispersing effect on ore pulp. In addition, compared with conventional strong acids such as sulfuric acid, organic acids are safer and easier to degrade.

[0047] (3) Sulfonated asphalt powder contains sulfonic acid groups and has a strong hydration effect. When adsorbed on the shale interface, it can prevent the hydration and dispersion of shale particles and play a role in preventing collapse. At the same time, the water-insoluble part can fill pores and cracks to play a plugging role, and can cover the shale interface to improve the quality of mud cake; sulfonated asphalt also plays a role in lubrication and reducing high-temperature and high-pressure filtration loss in drilling fluid. Therefore, in the prior art, sulfonated asphalt powder is a multifunctional organic drilling fluid treatment agent with plugging, anti-collapse, lubrication, drag reduction, and inhibition.

[0048] However, the inventors have found through many experiments that the molecules of sulfonated asphalt powder and sulfonated phenolic resin contain abundant sulfonic acid groups, hydroxyl groups, etc., and have good selective inhibition effect on calcite. Therefore, sulfonated asphalt powder and sulfonated phenolic resin can cooperate with acidified water glass to improve the separation effect. In particular, the inventors have also found that although the inhibition effect of sulfonated phenolic resin and sulfonated asphalt is not as strong as that of traditional inhibitors such as tannin, tannin, starch, etc., it is precisely because of their suitable relatively weak inhibition effect, combined with the relatively strong inhibition effect of organic acid-modified water glass, that a relatively good and moderate inhibition effect is produced, which can inhibit calcium carbonate and ensure a higher fluorite recovery rate.

[0049] (4) Diesel is a non-polar collector and is often used as an auxiliary agent. Adding diesel to fatty acids and their soaps can enhance the hydrophobicity of the collector, promote the hydrophobic aggregation of mineral particles, change the foam structure, and thus improve the grade and recovery rate of fluorite concentrate.

[0050] The advantages of the present invention are:

[0051] 1. In actual production, it is found that the calcium carbonate content in the tailings of primary and secondary concentration is high, and the fluorite content is low. Directly discharging the tailings of primary and secondary concentration after reselection can reduce the circulation of calcite in the system, improve the stability of system operation, ensure the quality and recovery rate of the final fluorite concentrate, reduce the amount of inhibitors used, and have stronger applicability;

[0052] 2. Compared with common strong acids such as sulfuric acid, the organic acid used in the present invention is safer, more operable, environmentally friendly, and easily degradable, and has practical promotion value and market potential.

[0053] 3. The calcite enhancement inhibitors used in the present invention, sulfonated asphalt powder and sulfonated phenolic resin, are common industrial products, which are cheaper than traditional calcite inhibitors and have a wide source, and can reduce the overall cost of high-calcium fluorite recovery. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 The present invention is a process flow chart of the flotation of high calcium carbonate fluorite ore.

[0055] Figure 2 This is the traditional process flow chart for the flotation of high calcium carbonate fluorite ore. DETAILED DESCRIPTION

[0056] The following examples are intended to further illustrate the present invention, but are not intended to limit the present invention. Various process schemes that are not substantially different from the present invention are within the scope of protection of the present invention. The g / t in the present invention refers to the mass of the reagent added per ton of raw ore, and the percentages are all mass percentages.

[0057] Embodiment 1:

[0058] The flotation separation method of this embodiment was used to conduct a flotation test on a high calcium carbonate type fluorite ore (the CaF2 content in the original ore was 26.9%, the CaCO3 content was 5.11%, and the SiO2 content was 25.25).

[0059] The test steps are as follows:

[0060] (1) Grinding: Grind the high calcium carbonate fluorite ore in an XMQ ball mill at a grinding concentration of 67%. After grinding to a particle size of 50% or less than 0.074 mm, flush the ore pulp with clean water to obtain the selected ore pulp for flotation;

[0061] (2) Roughing of fluorite: The pulp is placed in a flotation machine, and then a pH adjuster, a calcium carbonate combination inhibitor and a collector are added in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is performed for 4 minutes to obtain fluorite rough concentrate and fluorite rough tailings;

[0062] (3) When selecting fluorite coarse concentrate, inhibitors are added in the first, third and fifth selections, and no reagents are added in the second, fourth and sixth selections. The tailings of the first and second selections are combined and then swept twice. Inhibitors and collectors are added in the first fine sweep, and only collectors are added in the second fine sweep. The remaining selected middlings are returned to the previous level of operation in sequence. The stirring time for each addition of reagents is 1 minute, and the flotation is 2.5 minutes to obtain fluorite concentrate.

[0063] (4) Sweeping and screening of fluorite coarse tailings. Collectors are added in the first, second and third sweeping processes respectively. The stirring time for each addition is 1 min and the sweeping time for each time is 2.5 min. The scavenged concentrate is returned to the previous operation in sequence.

[0064] See the process flow adopted Figure 1 The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by 3-carboxy 3-carboxy-3-hydroxyglutaric acid: water glass according to a mass ratio of 20:80, the calcium carbonate strengthening inhibitor is sulfonated asphalt powder (water-soluble component = 78%) of Renqiu Shengtong Chemical Co., Ltd., and the capture agent is a mixed capture agent mixed by oleic acid: diesel according to a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 1. The test results obtained are shown in Table 9.

[0065] Table 1 Reagents added in Example 1

[0066]

[0067] Comparative Example 1:

[0068] The traditional flotation separation method was used to carry out flotation test on a high calcium carbonate type fluorite ore (the original ore has CaF2 content of 26.9%, CaCO3 content of 5.11%, and SiO2 content of 25.25%).

[0069] The test steps are as follows:

[0070] (1) Grinding: Grind the high calcium carbonate fluorite ore in an XMQ ball mill at a grinding concentration of 67%. After grinding to a particle size of 50% or less than 0.074 mm, flush the ore pulp with clean water to obtain the selected ore pulp for flotation;

[0071] (2) Fluorite roughing The pulp is placed in a flotation machine, and then a pH adjuster, a calcium carbonate combination inhibitor and oleic acid are added in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is performed for 4 minutes to obtain fluorite rough concentrate and fluorite rough tailings;

[0072] (3) When selecting fluorite coarse concentrate, inhibitors are added in the first, third and fifth selections, and no reagents are added in the second, fourth and sixth selections. The selected middlings are returned to the previous operation in sequence. The stirring time for each addition of reagents is 1 minute, and the flotation is 2.5 minutes to obtain fluorite concentrate.

[0073] (4) Sweeping and selection of fluorite coarse tailings. Collectors are added in the first, second and third sweeping processes respectively. The stirring time for each addition is 1 min and the sweeping time for each time is 2.5 min. The scavenged concentrate is returned to the previous operation in sequence.

[0074] See the process flow adopted Figure 2 The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by sulfuric acid: water glass according to a mass ratio of 50:50, the calcium carbonate strengthening inhibitor is sodium lignin sulfonate, and the capture agent is a mixed capture agent mixed by oleic acid: diesel according to a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 2. The test results obtained are shown in Table 9.

[0075] Table 2 Reagents added in Comparative Example 1

[0076]

[0077] Comparative Example 2:

[0078] A flotation test was conducted on a high calcium carbonate type fluorite ore (the original ore has a CaF2 content of 26.9%, a CaCO3 content of 5.11%, and a SiO2 content of 25.25) by using a conventional flotation separation process and the reagent system of the present invention.

[0079] The flotation process is the same as that of Comparative Example 1, and the process flow adopted is shown in Figure 2 The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by 3-carboxy 3-carboxy-3-hydroxyglutaric acid: water glass according to a mass ratio of 20:80, the calcium carbonate strengthening inhibitor is sulfonated asphalt powder (water-soluble component = 78%) of Renqiu Shengtong Chemical Co., Ltd., and the capture agent is a mixed capture agent mixed by oleic acid: diesel according to a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 3. The test results obtained are shown in Table 9.

[0080] Table 3 Reagents added in Comparative Example 2

[0081]

[0082] Comparative Example 3:

[0083] The flotation separation method of this embodiment was used to conduct a flotation test on a high calcium carbonate type fluorite ore (the CaF2 content in the original ore was 26.9%, the CaCO3 content was 5.11%, and the SiO2 content was 25.25).

[0084] The flotation process is the same as in Example 1, and the process flow adopted is shown in Figure 1 The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by sulfuric acid: water glass at a mass ratio of 50:50, the calcium carbonate strengthening inhibitor is sodium lignin sulfonate, and the capture agent is a mixed capture agent mixed by oleic acid: diesel at a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 4. The test results obtained are shown in Table 9.

[0085] Table 4 Reagents added in Comparative Example 3

[0086]

[0087]

[0088] Comparative Example 4:

[0089] The traditional flotation separation method was used to carry out flotation test on a high calcium carbonate type fluorite ore (the original ore has CaF2 content of 26.9%, CaCO3 content of 5.11%, and SiO2 content of 25.25%).

[0090] The flotation process is the same as that of Comparative Example 1, and the process flow adopted is shown in Figure 2The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by sulfuric acid: water glass at a mass ratio of 50:50, the calcium carbonate strengthening inhibitor is sulfonated asphalt powder (water-soluble component = 78%) of Renqiu Shengtong Chemical Co., Ltd., and the capture agent is a mixed capture agent mixed by oleic acid: diesel at a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 5. The test results obtained are shown in Table 9.

[0091] Table 5 Reagents added in Comparative Example 4

[0092]

[0093] Comparative Example 5:

[0094] The traditional flotation separation method was used to carry out flotation test on a high calcium carbonate type fluorite ore (the original ore has CaF2 content of 26.9%, CaCO3 content of 5.11%, and SiO2 content of 25.25%).

[0095] The flotation process is the same as that of Comparative Example 1, and the process flow adopted is shown in Figure 2 The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by 3-carboxy 3-carboxyl-3-hydroxyglutaric acid: water glass = 20:80, the calcium carbonate strengthening inhibitor is sodium lignin sulfonate, and the capture agent is a mixed capture agent mixed with oleic acid and diesel in a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 9. The test results obtained are shown in Table 9.

[0096] Table 6 Reagents added in Comparative Example 5

[0097]

[0098]

[0099] Comparative Example 6:

[0100] The flotation separation method of this embodiment was used to conduct a flotation test on a high calcium carbonate type fluorite ore (the CaF2 content in the original ore was 26.9%, the CaCO3 content was 5.11%, and the SiO2 content was 25.25).

[0101] The flotation process is the same as in Example 1, and the process flow adopted is shown in Figure 1The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by 3-carboxy 3-carboxy-3-hydroxyglutaric acid: water glass according to a mass ratio of 20:80, the calcium carbonate strengthening inhibitor is sodium lignin sulfonate, and the capture agent is a mixed capture agent mixed by oleic acid: diesel according to a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 7. The test results obtained are shown in Table 9.

[0102] Table 7 Reagents added in Comparative Example 6

[0103]

[0104] Comparative Example 7:

[0105] The flotation separation method of this embodiment was used to conduct a flotation test on a high calcium carbonate type fluorite ore (the CaF2 content in the original ore was 26.9%, the CaCO3 content was 5.11%, and the SiO2 content was 25.25).

[0106] The flotation process is the same as in Example 1, and the process flow adopted is shown in Figure 1 The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by sulfuric acid: water glass = 50:50, the calcium carbonate strengthening inhibitor is sulfonated asphalt powder (water-soluble component = 78%) of Renqiu Shengtong Chemical Co., Ltd., and the capture agent is a mixed capture agent mixed with oleic acid and diesel in a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 8. The test results obtained are shown in Table 9.

[0107] Table 8 Reagents added in Comparative Example 7

[0108]

[0109] Table 9 Ore dressing results of each embodiment

[0110]

[0111] The data of the medicines in each example are shown in Table 10.

[0112] Table 10 Total dosage of each example

[0113]

[0114] From the comparison results, it can be seen that the CaF2 grade of the fluorite concentrate obtained by the eight beneficiation methods is more than 96%, the CaCO3 grade is less than 1%, and the SiO2 grade is less than 1.0%. However, the method provided by the present invention can better take into account the recovery rate and grade of CaF2, and the CaF2 grade is more than 98%, and the recovery rate is more than 82%. Using other methods, the recovery rate of CaF2 and the quality of the concentrate in the fluorite concentrate are lower than the new method, and the dosage of the reagent is larger. Comparative Example 1 uses traditional processes and traditional reagents to obtain a low-quality fluorite concentrate, and the fluorite concentrate contains higher CaCO3 and SiO2 contents, and the fluorite recovery rate is lower, because the CaCO3 circulating in the system cannot be discharged in time, the quality of the fluorite concentrate is reduced, and the inhibitor dosage is also larger. Comparative Example 2 uses a new reagent system in combination with traditional processes, and the organic acid-modified water glass is combined with the calcium carbonate inhibitor to show moderate selective inhibition ability. The content of CaCO3 in the fluorite concentrate is low, but the CaCO3 in the system cannot be discharged in time, and the recovery rate of the fluorite concentrate is not as good as that of Example 1. Comparative Example 3 uses the process of the present invention in combination with traditional reagents. Although some CaCO3 can be discharged in time, the dosage of traditional reagents is too large and will affect the fluorite recovery rate to a certain extent. Comparative Example 4 uses the traditional process in combination with sulfuric acid-modified water glass + calcium carbonate inhibitor provided by the present invention. The inhibition ability of both reagents is relatively weak, resulting in a weak overall inhibition ability, resulting in a low quality of fluorite concentrate; Comparative Example 5 uses the traditional process in combination with organic acid-modified water glass + conventional calcium carbonate inhibitor. Since both have strong inhibition ability, the inhibition ability of the overall reagent is too strong, resulting in a large loss in the recovery rate of fluorite concentrate; similarly, when the new process flow is adopted, Comparative Example 6 and Comparative Example 7 show the same rule. Whether it is the new process combined with the traditional reagent system, or the traditional process combined with the new reagent system, the effect is not as good as Example 1. It shows that the matching between the process and the reagent provided by the present invention is good, and the process and the reagent show a good synergistic effect.

[0115] Secondly, sulfuric acid-acidified water glass combined with the calcium carbonate inhibitor of the present invention, and organic acid-acidified water glass combined with traditional calcium carbonate inhibitor, also showed poor recovery rates, indicating that the inhibitory ability of the agent should not be too strong or too weak. Only the organic acid-acidified water glass with strong inhibitory ability provided by the present invention combined with sulfonated asphalt powder and sulfonated resin with weak inhibitory ability can show a more moderate inhibitory effect and improve the CaF2 recovery rate and concentrate quality in fluorite concentrate.

[0116] Embodiment 2:

[0117] The flotation separation method of this embodiment was used to conduct a flotation test on a high calcium carbonate type fluorite ore (the CaF2 content in the original ore was 37.44%, the CaCO3 content was 19.37%, and the SiO2 content was 13.98%).

[0118] The specific process is as follows:

[0119] (1) Grinding: Grind the high calcium carbonate fluorite ore in an XMQ ball mill at a grinding concentration of 67%. After grinding to a particle size of 60% or less of 0.074 mm, flush the ore pulp with clean water to obtain the selected ore pulp for flotation;

[0120] (2) Fluorite roughing: The pulp is placed in a flotation machine, and then a pH adjuster, a calcium carbonate combination inhibitor, and oleic acid are added in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is performed for 5 minutes to obtain fluorite rough concentrate and fluorite rough tailings;

[0121] (3) When selecting fluorite coarse concentrate, inhibitors are added in the first, third and fifth selections, and no reagents are added in the second, fourth and sixth selections. The tailings of the first and second selections are combined and then two fine sweeping operations are performed. Inhibitors and collectors are added in the first fine sweeping, and only collectors are added in the second fine sweeping. The remaining selected middlings are returned to the previous operation in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is 3 minutes to obtain fluorite concentrate.

[0122] (4) Sweeping and screening of fluorite coarse tailings. Collectors are added in the first, second and third sweeping processes respectively. The stirring time for each addition is 1 min and the sweeping time for each time is 2 min. The scavenged concentrate is returned to the previous operation in sequence.

[0123] See the process flow adopted Figure 1 The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by 3-carboxyl-3-hydroxyglutaric acid: water glass according to a mass ratio of 5:95, the calcium carbonate strengthening inhibitor is a sulfonated phenolic resin from Hebei Yanxing Chemical Co., Ltd., and the capture agent is a mixed capture agent mixed by oxidized paraffin soap: diesel according to a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 11. The test results obtained are shown in Table 13.

[0124] Table 11 Example 2 dosage

[0125]

[0126]

[0127] Comparative Example 8:

[0128] The flotation separation method of the present invention was used to conduct a flotation test on a high calcium carbonate type fluorite ore (the original ore has a CaF2 content of 37.44%, a CaCO3 content of 19.37%, and a SiO2 content of 13.98%).

[0129] (1) Grinding: Grind the high calcium carbonate fluorite ore in an XMQ ball mill at a grinding concentration of 67%. After grinding to a particle size of 60% or less of 0.074 mm, flush the ore pulp with clean water to obtain the selected ore pulp for flotation;

[0130] (2) Fluorite roughing: The pulp is placed in a flotation machine, and then a pH adjuster, a calcium carbonate combination inhibitor, and oleic acid are added in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is performed for 5 minutes to obtain fluorite rough concentrate and fluorite rough tailings;

[0131] (3) When selecting fluorite coarse concentrate, inhibitors are added in the first, third and fifth selections, and no reagents are added in the second, fourth and sixth selections. The tailings of the first and second selections are combined and then two fine sweeping operations are performed. Inhibitors and collectors are added in the first fine sweeping, and only collectors are added in the second fine sweeping. The remaining selected middlings are returned to the previous operation in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is 3 minutes to obtain fluorite concentrate.

[0132] (4) Sweeping and screening of fluorite coarse tailings. Collectors are added in the first, second and third sweeping processes respectively. The stirring time for each addition is 1 min and the sweeping time for each time is 2 min. The scavenged concentrate is returned to the previous operation in sequence.

[0133] See the process flow adopted Figure 1 The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by sulfuric acid: water glass according to a mass ratio of 50:50, the calcium carbonate strengthening inhibitor is tannin, and the capture agent is a mixed capture agent mixed by oxidized paraffin soap: diesel according to a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 12. The test results obtained are shown in Table 13.

[0134] Table 12 Comparative Example 8 Medicament Dosage

[0135]

[0136]

[0137] Table 13 Ore dressing results of each embodiment

[0138]

[0139] Table 14 Total dosage of each example

[0140]

[0141] From the comparison results, it can be seen that the new process proposed in the present invention combined with the new reagent proposed in the present invention has better flotation indicators and lower dosage. Although the new process combined with the traditional reagent system can obtain high-quality fluorite concentrate, the dosage of inhibitor is large and the processing cost is higher.

[0142] Example 3

[0143] The flotation separation method of the present invention was used to conduct a flotation test on a high calcium carbonate type fluorite ore (the original ore has a CaF2 content of 26.05%, a CaCO3 content of 2.06%, and a SiO2 content of 34.98%).

[0144] The specific process is as follows:

[0145] (1) Grinding: Grind the high calcium carbonate fluorite ore in an XMQ ball mill at a grinding concentration of 67%. After grinding to a particle size of 85% or less of 0.074 mm, flush the ore pulp with clean water to obtain the selected ore pulp for flotation;

[0146] (2) Fluorite roughing: The pulp is placed in a flotation machine, and then a pH adjuster, a calcium carbonate combination inhibitor, and oleic acid are added in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is performed for 5 minutes to obtain fluorite rough concentrate and fluorite rough tailings;

[0147] (3) When selecting fluorite coarse concentrate, inhibitors are added in the first, third and fifth selections, and no reagents are added in the second, fourth and sixth selections. The tailings of the first and second selections are combined and then two fine sweeping operations are performed. Inhibitors and collectors are added in the first fine sweeping, and only collectors are added in the second fine sweeping. The remaining selected middlings are returned to the previous operation in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is 3 minutes to obtain fluorite concentrate.

[0148] (4) Sweeping and screening of fluorite coarse tailings. Collectors are added in the first, second and third sweeping processes respectively. The stirring time for each addition is 1 min and the sweeping time for each time is 2 min. The scavenged concentrate is returned to the previous operation in sequence.

[0149] See the process flow adopted Figure 1 The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by 2-hydroxysuccinic acid: water glass according to a mass ratio of 20:80, the calcium carbonate strengthening inhibitor is sulfonated asphalt powder of Hebei Xinzhi Trading Co., Ltd., and the capture agent is a mixed capture agent mixed by tall oil: diesel according to a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 15. The test results obtained are shown in Table 17.

[0150] Table 15 Example 3 dosage

[0151]

[0152] Comparative Example 9

[0153] The following flotation separation method was used to conduct a flotation test on a high calcium carbonate fluorite ore (the CaF2 content in the original ore was 26.05%, the CaCO3 content was 2.06%, and the SiO2 content was 34.98%).

[0154] (1) Grinding: Grind the high calcium carbonate fluorite ore in an XMQ ball mill at a grinding concentration of 67%. After grinding to a particle size of 85% or less of 0.074 mm, flush the ore pulp with clean water to obtain the selected ore pulp for flotation;

[0155] (2) Fluorite roughing: The pulp is placed in a flotation machine, and then a pH adjuster, a calcium carbonate combination inhibitor, and oleic acid are added in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is performed for 5 minutes to obtain fluorite rough concentrate and fluorite rough tailings;

[0156] (3) When selecting fluorite coarse concentrate, inhibitors are added in the first, third and fifth selections, and no reagents are added in the second, fourth and sixth selections. The remaining selected middlings are returned to the previous operation in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is 3 minutes to obtain fluorite concentrate.

[0157] (4) Sweeping and screening of fluorite coarse tailings. Collectors are added in the first, second and third sweeping processes respectively. The stirring time for each addition is 1 min and the sweeping time for each time is 2 min. The scavenged concentrate is returned to the previous operation in sequence.

[0158] See the process flow adopted Figure 2 The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by 2-hydroxysuccinic acid: water glass according to a mass ratio of 20:80, the calcium carbonate strengthening inhibitor is sulfonated asphalt powder of Hebei Xinzhi Trading Co., Ltd., and the capture agent is a mixed capture agent mixed by tall oil: diesel according to a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 16. The test results obtained are shown in Table 17.

[0159] Table 16 Comparative Example 9 Medicament Dosage

[0160]

[0161] Table 17 Ore dressing results of each embodiment Ore dressing process

[0162]

[0163]

[0164] Table 18 Total dosage of each example

[0165]

[0166] From the comparison results, it can be seen that the flotation index obtained by the new method is better, and the fluorite concentrate obtained by the traditional process has high CaCO3 and SiO2 contents and low concentrate quality.

[0167] Example 4

[0168] The flotation separation method of Example 4 was used to conduct a flotation test on a high calcium carbonate type fluorite ore (the CaF2 content in the original ore was 35.78%, the CaCO3 content was 22.04%, and the SiO2 content was 7.31%).

[0169] The specific process is as follows:

[0170] (1) Grinding: Grind the high calcium carbonate fluorite ore in an XMQ ball mill at a grinding concentration of 67%. After grinding to a particle size of 80% or less of 0.074 mm, flush the ore pulp with clean water to obtain the selected ore pulp for flotation;

[0171] (2) Fluorite roughing: The pulp is placed in a flotation machine, and then a pH adjuster, a calcium carbonate combination inhibitor, and oleic acid are added in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is performed for 4 minutes to obtain fluorite rough concentrate and fluorite rough tailings;

[0172] (3) When selecting fluorite coarse concentrate, inhibitors are added in the first, third and fifth selections, and no reagents are added in the second, fourth and sixth selections. The tailings of the first and second selections are combined and then two fine sweeping operations are performed. Inhibitors and collectors are added in the first fine sweeping, and only collectors are added in the second fine sweeping. The remaining selected middlings are returned to the previous operation in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is 2 minutes to obtain fluorite concentrate.

[0173] (4) Sweeping and selection of fluorite coarse tailings. Collectors are added in sequence during the first sweep, the second sweep and the third sweep. The stirring time for each addition is 1 min, and the sweeping time for each sweep is 2 min. The scavenged concentrate is returned to the previous operation in sequence.

[0174] See the process flow adopted Figure 1The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by 2,3-dihydroxysuccinic acid: water glass according to a mass ratio of 15:85, the calcium carbonate strengthening inhibitor is a sulfonated phenolic resin from Shandong Nice Chemical Co., Ltd., and the capture agent is a mixed capture agent mixed by sodium oleate: diesel according to a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 19. The test results obtained are shown in Table 21.

[0175] Table 19 Example 4 Medicament dosage

[0176]

[0177] Comparative Example 11:

[0178] The conventional flotation separation process and the patented reagent system of the present invention were used to carry out a flotation test on a high calcium carbonate type fluorite ore (the original ore has a CaF2 content of 26.9%, a CaCO3 content of 5.11%, and a SiO2 content of 25.25).

[0179] The test steps are as follows:

[0180] (1) Grinding: Grind the high calcium carbonate fluorite ore in an XMQ ball mill at a grinding concentration of 67%. After grinding to a particle size of 50% or less than 0.074 mm, flush the ore pulp with clean water to obtain the selected ore pulp for flotation;

[0181] (2) Fluorite roughing: The pulp is placed in a flotation machine, and then a pH adjuster, a calcium carbonate combination inhibitor, and oleic acid are added in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is performed for 4 minutes to obtain fluorite rough concentrate and fluorite rough tailings;

[0182] (3) When selecting fluorite coarse concentrate, inhibitors are added in the first, third and fifth selections, and no reagents are added in the second, fourth and sixth selections. The selected middlings are returned to the previous operation in sequence. The stirring time for each addition of reagents is 2 minutes, and the flotation is 2 minutes to obtain fluorite concentrate.

[0183] (4) Sweeping and selection of fluorite coarse tailings. Collectors are added in sequence during the first sweep, the second sweep and the third sweep. The stirring time for each addition is 1 min, and the sweeping time for each sweep is 2 min. The scavenged concentrate is returned to the previous operation in sequence.

[0184] See the process flow adopted Figure 2The inhibitors used are acidified water glass and calcium carbonate strengthening inhibitor, the acidified water glass is a complex prepared by sulfuric acid: water glass according to a mass ratio of 50:50, the calcium carbonate strengthening inhibitor is tannin extract, and the capture agent is a mixed capture agent mixed by sodium oleate: diesel according to a mass ratio of 95:5. The actual addition amount during the flotation operation is shown in Table 20. The test results obtained are shown in Table 21.

[0185] Table 20 Comparative Example 10 Medicament Dosage

[0186]

[0187] Table 21 Ore dressing results of each embodiment Ore dressing process

[0188]

[0189] Table 22 Dosage of each example

[0190]

[0191] From the comparison results, it can be seen that the flotation index obtained by the new method is better. The CaF2 grade in the fluorite concentrate obtained by the traditional process is only 95.35%, and the CaCO3 grade exceeds 0.8%, which seriously affects the sales price.

Claims

1. A high-calcium fluorite ore inhibitor, characterized in that: The invention comprises modified water glass and a calcium carbonate strengthening inhibitor, wherein the modified water glass is a complex of an organic acid and water glass, wherein the organic acid is one or more of 3-carboxy-3-hydroxyglutaric acid, 2-hydroxysuccinic acid, and 2,3-dihydroxysuccinic acid; the calcium carbonate strengthening inhibitor is one or two of sulfonated asphalt powder or sulfonated phenolic resin, and the structural formula of the sulfonated phenolic resin is shown in formula (III); Wherein, n is an integer.

2. The inhibitor of high-calcium fluorite ore according to claim 1, characterized in that: The organic acid is 3-carboxy-3-hydroxyglutaric acid.

3. The inhibitor of high-calcium fluorite ore according to claim 1, characterized in that: The ratio of organic acid to water glass ranges from 5-20:80-95.

4. The inhibitor of high-calcium fluorite ore according to claim 1, characterized in that: The water-soluble components in the sulfonated asphalt powder are not less than 70%.

5. A flotation method for high-calcium fluorite ore, characterized in that: The following steps are involved: (1) grinding high calcium fluorite ore to obtain slurry; flotation of the slurry, sequentially adding sodium carbonate, the inhibitor according to any one of claims 1 to 4, and the collector, stirring for 1 to 3 minutes, and flotation for 2.5 to 5 minutes to obtain fluorite coarse concentrate and fluorite coarse tailings; (2) The fluorite rough concentrate is beneficiated, and the above inhibitor is added in the first beneficiation, the third beneficiation, and the fifth beneficiation process, respectively, and no reagent is added in the second beneficiation, the fourth beneficiation, and the sixth beneficiation process. After six beneficiations, the fluorite concentrate is obtained, and the beneficiation time for each time is 1.5-4 minutes; The obtained fluorite rough tailings are scavenged by adding a collector, and each scavenging time is 2-4 minutes; the obtained medium ore is returned to the previous operation; The tailings from the first and second concentrations are supplemented with inhibitors and collectors for fine scavenging. The fine scavenging foam obtained is returned to the previous operation as the middlings. The fine scavenging tailings are combined with the rough scavenging tailings as the final tailings. The tailings from the third, fourth, fifth and sixth concentrations are returned to the previous level of operation as middlings in sequence; The CaF2 content in the high-calcium fluorite ore is 12-45%, and the CaCO3 content is 2-50%.

6. The flotation method of high-calcium fluorite ore according to claim 5, characterized in that: The added amount of the inhibitor is 1200-3300 g / t; preferably, the total amount of modified water glass is 800-2500 g / t, and the total amount of calcium carbonate strengthening inhibitor is 400-800 g / t.

7. The flotation method of high-calcium fluorite ore according to claim 5, characterized in that: The collector is a complex of fatty acid, soap thereof and diesel oil, and the total dosage of the collector is 400-1000 g / t.

8. The flotation method of high-calcium fluorite ore according to claim 7, characterized in that: The fatty acid and soap thereof include one or more of oleic acid, sodium oleate, oxidized paraffin soap and tall oil.

9. The flotation method of high-calcium fluorite ore according to claim 8, characterized in that: The fatty acid and soap thereof are oleic acid or sodium oleate.

10. The flotation method of high-calcium fluorite ore according to claim 7, characterized in that: The ratio of fatty acids and their soaps to diesel in the collector is 5:95.

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