A method for improving the flotation separation efficiency of malachite and calcite

Abstract

The present invention provides a method for improving malachite and calcite flotation separation efficiency, including: first, calcite and malachite monomineral are subjected to ore grinding treatment, the powder samples of calcite and malachite monomineral are obtained respectively, and calcite and malachite monomineral powder samples are mixed to obtain mixed minerals;Secondly, water is added to the mixed mineral to form the first slurry, and the pH value of the first slurry is adjusted to 6~11;Again, slurry mixing is carried out after adding calcite inhibitor and collector to the first slurry, and the second slurry is obtained, and the calcite inhibitor is naphthalenesulfonic acid formaldehyde condensation product sodium salt, and the collector is a mixture of sodium octylhydroxamate, octanol, hexamethoxy melamine resin and fatty alcohol polyoxyethylene ether AEO 3 composition;Finally, aeration flotation treatment is carried out to the second slurry, and aeration flotation foam is copper concentrate, and product in flotation tank is tailings.The present invention can improve the flotation separation efficiency of malachite and calcite.

Description

Technical Field

[0001] The present invention relates to the technical field of copper ore beneficiation, and in particular to a method for improving the flotation separation efficiency of malachite and calcite. Background Art

[0002] The rapid development of the defense industry, the electronics and electrical industry, and new technologies has led to an increasing demand for copper. The shortage of copper resources and the dwindling availability of copper-bearing sulfide and rich ores have created an urgent need for the development and utilization of refractory copper oxide deposits. Malachite is a common copper oxide ore, and flotation is the most commonly used method for its beneficiation.

[0003] Currently, malachite flotation is generally divided into sulfidation flotation and direct flotation. Sulfidation flotation involves sulfidation with a sulfiding agent followed by collection with a collector. However, the dosage of the sulfiding agent is difficult to control. Excessive sulfidation results in incomplete sulfidation, while excessive amounts inhibit flotation. Direct flotation is effective for collecting malachite containing silicate gangue minerals. High recoveries can be achieved by simply adding fatty acids, phosphonic acids, hydroxamic acids, and other collectors. Compared to sulfidation flotation, direct flotation offers a simpler reagent system and a more streamlined process. However, direct flotation is less effective for malachite containing calcite, primarily due to the relatively small differences in the surface physicochemical properties between malachite and calcite. Research on direct flotation of malachite has largely focused on flotation reagents, surface chemistry, and solution chemistry, with less attention paid to surface physical properties such as roughness.

[0004] Therefore, there is an urgent need for a method to improve the flotation separation efficiency of malachite and calcite to solve the above technical problems. Summary of the Invention

[0005] The purpose of the present invention is to solve the technical problems of low recovery rate and poor separation selectivity of malachite ore whose main gangue mineral is calcite by direct flotation method.

[0006] In order to solve the above technical problems, the present invention provides a method for improving the flotation separation efficiency of malachite and calcite, comprising:

[0007] S10, grinding the single minerals of calcite and malachite respectively, and mixing them in a certain proportion to obtain a mixed mineral;

[0008] S20, adding water to the mixed mineral to form a first slurry, and adjusting the pH value of the first slurry to 6-11;

[0009] S30, adding a calcite inhibitor and a collector to the first slurry and performing slurry adjustment to obtain a second slurry, wherein the calcite inhibitor is sodium salt of naphthalenesulfonic acid formaldehyde condensation polymer, and the collector is a mixture of sodium octylhydroxamate, octanol, hexamethoxymelamine resin, and fatty alcohol polyoxyethylene ether AEO-3;

[0010] S40, performing aeration flotation treatment on the second slurry, wherein the aeration flotation foam is copper concentrate, and the product in the aeration flotation tank is tailings.

[0011] Preferably, in step S10, the mass ratio of calcite to malachite in the raw ore is (1-5):1.

[0012] Preferably, in step S10: the -0.074 mm particle size content of the mixed mineral is 65-85%, the average surface roughness of the mixed mineral is 12-96 nm, and the average root mean square roughness of the mixed mineral is 15-116 nm.

[0013] Preferably, in step S10: the grinding method for the single minerals of calcite and malachite is one of wet rod milling and wet ball milling.

[0014] Preferably, in step S20: the concentration of solid mineral particles in the first slurry is 10% to 40%.

[0015] Preferably, in step S20: the pH value of the first slurry is adjusted to 6-11 by a pH adjuster, and the pH adjuster includes sodium hydroxide and hydrochloric acid.

[0016] Preferably, in step S30: the mass ratio of sodium octylhydroxamate, octanol, hexamethoxymelamine resin and fatty alcohol polyoxyethylene ether AEO-3 in the collector is (46-78): (7-20): (8-14): (7-20).

[0017] Preferably, in step S30: the concentration range of the collector in the second slurry is greater than 0 and less than or equal to 240 mg / L.

[0018] Preferably, in step S40: the second pulp is subjected to aeration flotation treatment by a hanging trough flotation machine.

[0019] Preferably, in step S40: the Cu recovery rate of the copper concentrate is 80.56% to 88.47%.

[0020] The beneficial effects of the present invention are as follows: different from the prior art, the present invention provides a method for improving the flotation separation efficiency of malachite and calcite, comprising: first, grinding single minerals of calcite and malachite separately, and mixing them in a certain proportion to obtain a mixed mineral; second, adding water to the mixed mineral to form a first slurry, and adjusting the pH value of the first slurry to 6-11; third, adding a calcite inhibitor and a collector to the first slurry and performing slurry adjustment to obtain a second slurry, wherein the calcite inhibitor is sodium salt of naphthalenesulfonic acid formaldehyde condensation product, and the collector is a mixture of sodium octylhydroxamate, octanol, hexamethoxymelamine resin and fatty alcohol polyoxyethylene ether AEO-3; and finally, performing aeration flotation treatment on the second slurry, wherein the aeration flotation foam is copper concentrate, and the product in the aeration flotation tank is tailings. The present invention firstly performs wet rod grinding on single minerals of calcite and malachite to reduce the average surface roughness of the minerals, then selects a special compound collector to capture the malachite in the first slurry, integrates physical and chemical methods, expands the difference in hydrophilicity and hydrophobicity between malachite and calcite, thereby improving the flotation separation efficiency of malachite and calcite, and ultimately improving the copper recovery rate and copper grade of the flotation concentrate of the single mineral mixed ore of calcite and malachite. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 A flow chart of a method for improving the flotation separation efficiency of malachite and calcite provided in an embodiment of the present invention;

[0022] Figure 2 This is a process flow chart for improving the flotation separation efficiency of malachite and calcite provided by an embodiment of the present invention;

[0023] Figure 3 This is a graph showing the relationship between collector concentration and flotation rate in improving the flotation separation efficiency of malachite and calcite provided in Example 1 of the present invention;

[0024] Figure 4 This is a relationship diagram between the pH value of the first pulp and the flotation rate in improving the flotation separation efficiency of malachite and calcite provided in Example 2 of the present invention. DETAILED DESCRIPTION

[0025] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0026] The present invention addresses the technical problem of low recovery rate in the existing direct flotation method for single minerals of calcite and malachite, and provides a method for improving the flotation separation efficiency of malachite and calcite. The method can improve the flotation separation efficiency of malachite and calcite, thereby improving the copper recovery rate and copper grade in the flotation concentrate of malachite-type copper ore.

[0027] See also Figure 1 as well as Figure 2 , Figure 1 A flow chart of a method for improving the flotation separation efficiency of malachite and calcite provided in an embodiment of the present invention; wherein the above-mentioned preparation method specifically includes:

[0028] S10, grinding the single minerals of calcite and malachite separately, and mixing them in a certain proportion to obtain a mixed mineral.

[0029] Specifically, step S10 further includes:

[0030] First, single minerals of calcite and malachite are provided. Calcite is a calcium carbonate mineral, and malachite is a carbonate mineral, the main component of which is Cu2(OH)2CO3. Among them, the surface physical and chemical properties of malachite and calcite are slightly different.

[0031] Preferably, in step S10: the mass ratio of calcite to malachite in the mixed mineral is (1-5):1.

[0032] Subsequently, the calcite and malachite minerals are ground separately and mixed in a certain proportion to obtain a mixed mineral. The grinding method for the calcite and malachite minerals is any one of wet rod milling, dry ball milling, and wet ball milling. Preferably, the grinding method is wet rod milling to obtain malachite and calcite samples with less roughness.

[0033] In this step, the surface roughness of calcite and malachite can be manipulated by grinding them separately. Surface roughness affects the adsorption of the reagent. Furthermore, the surface microstructure of the minerals influences their surface hydrophobicity and the breakdown of the liquid film between the particles and bubbles, significantly impacting the particle-bubble interaction process. Due to the unique molecular structure of the octylhydroxamic acid reagent, malachite surfaces with less roughness adsorb more octylhydroxamic acid molecules, while calcite surfaces with less roughness adsorb fewer octylhydroxamic acid molecules. Therefore, the combination of chemical (octylhydroxamic acid) and physical (surface roughness) methods can maximize the difference in surface hydrophilicity between malachite and calcite, achieving efficient flotation separation of calcite and malachite.

[0034] Preferably, in step S10: the -0.074 mm particle size content of malachite and calcite single minerals is 65-85%, the average surface roughness Ra is 12-96 nm, and the average root mean square roughness Rq is 15-116 nm.

[0035] S20, adding water to the mixed minerals to form a first slurry, and adjusting the pH value of the first slurry to 6-11.

[0036] Specifically, step S20 further includes:

[0037] First, water is added to the mixed minerals to form a primary slurry. The concentration of solid mineral particles in the primary slurry is between 10% and 40%. Within this concentration range, the solid particles in the primary slurry have relatively more opportunities to come into contact with the flotation reagents, which is beneficial for improving flotation efficiency. When the concentration of solid mineral particles in the primary slurry exceeds 40%, the stability of the foam product decreases, affecting flotation selectivity. When the concentration of solid mineral particles in the primary slurry is less than 10%, the processing capacity decreases, requiring more equipment and time to process the same amount of mineral.

[0038] Secondly, the pH value of the first slurry is adjusted to 6-11 by a pH adjuster, which includes sodium hydroxide and hydrochloric acid. Among them, the appropriate pH value can enable the flotation agent to better interact with the mineral surface, making the target mineral surface more hydrophobic after interaction with the agent, thereby enhancing the capture ability and selectivity of the agent, thereby making the target mineral more easily captured by the flotation agent and improving the flotation efficiency; while non-target minerals remain hydrophilic at this pH value and are not easily adsorbed by the flotation agent, thereby achieving the separation of malachite and calcite minerals.

[0039] S30, adding a calcite inhibitor and a collector to the first slurry and then performing slurry adjustment to obtain a second slurry, wherein the calcite inhibitor is sodium salt of naphthalenesulfonic acid formaldehyde condensation polymer, and the collector is a mixture of sodium octylhydroxamate, octanol, hexamethoxymelamine resin and fatty alcohol polyoxyethylene ether AEO-3.

[0040] Specifically, step S30 further includes:

[0041] A calcite inhibitor and a collector are added to the first slurry and slurry conditioning is performed to obtain a second slurry. The calcite inhibitor is sodium salt of naphthalenesulfonic acid formaldehyde condensation polymer; the collector is a mixture of sodium octylhydroxamate, octanol, hexamethoxymelamine resin, and fatty alcohol polyoxyethylene ether AEO-3.

[0042] Specifically, sodium naphthalenesulfonic acid formaldehyde condensation polymer is an anionic agent that ionizes into negatively charged ionic groups in solution. It has a certain selective adsorption effect on calcite. After adsorption on the calcite surface, the polar groups face outward, making the calcite surface more hydrophilic. Furthermore, the polymer has a larger molecular structure. After adsorption on the surface of calcite particles, it forms a steric barrier, which prevents the adsorption of the collector and further enhances the inhibitory effect.

[0043] Specifically, sodium octylhydroxamate, as the primary collector, has a stronger capture performance for malachite than for calcite. Sodium octylhydroxamate adsorbs more on malachite surfaces with less roughness than on malachite surfaces with greater roughness, whereas sodium octylhydroxamate adsorbs less on calcite surfaces with less roughness than on calcite surfaces with greater roughness. Therefore, sodium octylhydroxamate more easily forms stable chelates with metal ions on the surface of malachite with less roughness, rendering the surface hydrophobic. In particular, at low concentrations, sodium octylhydroxamate can selectively render the malachite surface hydrophobic, while calcite remains hydrophilic. Adding auxiliary collectors further enhances the hydrophobicity of the malachite surface, widening the difference in hydrophilicity and hydrophobicity between malachite and calcite. Ultimately, malachite is more easily captured and floated by bubbles, while calcite remains hydrophilic. These auxiliary agents primarily adsorb on the malachite surface where sodium octylhydroxamate has adsorbed, without interacting with calcite. Consequently, sorting performance can be enhanced.

[0044] Specifically, octanol, as an auxiliary collector, has foaming properties, producing stable foam that helps the mineral particles carrying malachite to float. It can also co-adsorb with sodium octylhydroxamate on the malachite surface, enhancing its surface hydrophobicity and creating a synergistic effect, thereby increasing the recovery rate of malachite.

[0045] Specifically, hexamethoxymelamine resin is a colorless or pale yellow viscous liquid that is soluble in alcohols and partially soluble in water. In this flotation system, it can coat the mixed adsorption layer of octylhydroxamic acid and octanol, enhancing the hydrophobicity of the malachite surface, strengthening its synergistic effect with sodium octylhydroxamate, and improving the floatability of malachite. Compared to commonly used agents such as non-polar oils, hexamethoxymelamine resin has better adaptability to this system, easily spreading over the mixed adsorption layer of octylhydroxamic acid and octanol, forming a multi-component mixed adsorption layer.

[0046] Specifically, fatty alcohol polyoxyethylene ether AEO-3 has excellent emulsifying and dispersing properties, enabling sodium octylhydroxamate to be better dispersed in the first slurry, increasing the contact between sodium octylhydroxamate and malachite. It also reduces the surface tension of the first slurry, forming a mixed adsorption layer at the gas-liquid interface and promoting the adhesion of mineral particles and bubbles.

[0047] Furthermore, in step S30: the mass ratio of sodium octylhydroxamate, octanol, hexamethoxymelamine resin and fatty alcohol polyoxyethylene ether AEO-3 in the collector is (46-78): (7-20): (8-14): (7-20);

[0048] Among them, when the mass ratio of sodium octylhydroxamate in the collector is less than 46, it may not be able to fully exert its collecting effect, reducing the mineral recovery rate; when the mass ratio of sodium octylhydroxamate in the collector is greater than 78, it may lead to a decrease in selectivity for gangue minerals and reduce the mineral recovery rate; when the mass ratio of octanol in the collector is less than 7, the foaming effect is not obvious, affecting the carrying and floating of minerals; when the mass ratio of octanol in the collector is greater than 20, it may cause excessive foaming, affecting subsequent treatment; when the mass ratio of hexamethoxytrimer in the collector is greater than 10, the foaming effect is not obvious, affecting the ... When the mass ratio of cyanamide resin is less than 8, it cannot fully exert its effect of strengthening the hydrophobicity of the malachite surface; when the mass ratio of hexamethoxymelamine resin in the collector is greater than 14, it may increase the cost and have adverse effects on other minerals; when the mass ratio of fatty alcohol polyoxyethylene ether AEO-3 in the collector is less than 7, it cannot fully exert its dispersing and foaming effects; when the mass ratio of fatty alcohol polyoxyethylene ether AEO-3 in the collector is greater than 20, it may cause excessive foaming and reduce the selectivity of the collector.

[0049] In this step, the collector concentration in the second slurry is between 0 and 240 mg / L. Within this concentration range, the collector can fully interact with the surface of the mineral particles, making them hydrophobic and thus improving the floatability of the mineral. Excessively high concentrations increase reagent costs and reduce flotation selectivity, and may also lead to excessive foaming and instability, complicating subsequent processing.

[0050] S40, performing aeration flotation treatment on the second slurry, wherein the aeration flotation foam is copper concentrate, and the product in the aeration flotation tank is tailings.

[0051] Specifically, step S40 further includes:

[0052] The second pulp is subjected to aeration flotation treatment by a hanging trough flotation machine. The aeration flotation foam is copper concentrate, and the product in the aeration flotation tank is tailings. The Cu recovery rate of the copper concentrate is 80.56% to 88.47%.

[0053] Specifically, in a flotation cell, minerals are separated based on differences in surface hydrophobicity. Under the action of the collector, the surface of malachite becomes hydrophobic, while the surface of calcite in the tailings remains hydrophilic. When aeration is added to the secondary slurry, the hydrophobic malachite particles readily attach to the bubbles and rise to the surface of the secondary slurry, forming a frothy copper concentrate product. The hydrophilic calcite, however, remains in the secondary slurry, forming the tailings.

[0054] The technical solution of the present invention will now be further described with reference to specific embodiments.

[0055] Example 1:

[0056] Example 1 of the present invention provides a method for improving the flotation separation efficiency of malachite and calcite, and the specific operating steps are as follows:

[0057] Step 1: Wet-rod milling is performed on calcite and malachite single minerals to obtain malachite and calcite single minerals with a -0.074 mm particle size content of 65% to 85%; wherein the average surface roughness Ra of malachite is 25 nm, and the average root mean square roughness Rq is 36 nm; the average surface roughness Ra of calcite is 16 nm, and the average root mean square roughness Rq is 19 nm.

[0058] Step 2: 2 g of the above single mineral was mixed with 50 mL of distilled water and added to a 70 mL hanging tank flotation machine. The mixture was stirred at a speed of 1500 r / min to obtain a first slurry. Sodium hydroxide was added to the first slurry to adjust the pH of the first slurry to 9.

[0059] Step 3: Add a calcite inhibitor and a collector to the first slurry and stir for 2 minutes to perform slurry adjustment to obtain a second slurry; the calcite inhibitor is sodium salt of naphthalenesulfonic acid formaldehyde condensation polymer, and the collector is a mixture of sodium octylhydroxamate, octanol, hexamethoxymelamine resin and fatty alcohol polyoxyethylene ether AEO-3, with a mass ratio of 56:15:10:19. The concentrations of the collector in the second slurry are 0, 30, 50, 70, 90, 120, 180, and 240 mg / L, respectively.

[0060] Step 4: The second pulp is subjected to aeration flotation treatment. The foam product and the product in the tank are filtered, dried, and weighed respectively. The flotation rate is calculated. The results are as follows: Figure 3 .

[0061] Example 2:

[0062] Example 2 of the present invention provides a method for improving the flotation separation efficiency of malachite and calcite, and the specific operating steps are as follows:

[0063] Step 1: Wet-rod milling is performed on calcite and malachite single minerals to obtain malachite with a -0.074 mm particle size content of 65% to 85% and calcite single minerals; wherein the average surface roughness Ra of malachite is 25 nm, and the average root mean square roughness Rq is 36 nm; the average surface roughness Ra of calcite is 16 nm, and the average root mean square roughness Rq is 19 nm.

[0064] Step 2: 2 g of the mixed mineral was mixed with 50 mL of distilled water, and the mixture was added to a 70 mL hanging trough flotation machine. The mixture was stirred and slurried at a speed of 1500 r / min to obtain a first slurry. Sodium hydroxide and hydrochloric acid were added to the first slurry to adjust the pH value of the first slurry. The pH values ​​of the first slurry were adjusted to 6.2, 7.1, 8.0, 9.2, 9.9, and 11.0 (±0.2), respectively.

[0065] Step 3: Add a calcite inhibitor and a collector to the first slurry and stir for 2 minutes to perform slurry adjustment to obtain a second slurry; the calcite inhibitor is sodium salt of naphthalenesulfonic acid formaldehyde condensation polymer, and the collector is a mixture of sodium octylhydroxamate, octanol, hexamethoxymelamine resin, and fatty alcohol polyoxyethylene ether AEO-3, with a mass ratio of 56:15:10:19. The concentration of the collector in the second slurry after slurry adjustment is 70 mg / L.

[0066] Step 4: The second pulp is subjected to aeration flotation treatment, and the foam product and the product in the tank are filtered, dried, and weighed respectively, and the flotation rate is calculated. Figure 4 .

[0067] Example 3:

[0068] Example 3 of the present invention provides a method for improving the flotation separation efficiency of malachite and calcite, and the specific operating steps are as follows:

[0069] Step 1: wet-rod milling calcite and malachite single minerals, and uniformly mixing calcite and malachite single minerals with a -0.074 mm particle size content of 65% to 85% in a ratio of 1:3 to obtain mixed minerals of calcite and malachite single minerals; wherein the average surface roughness Ra of malachite is 25 nm, and the average root mean square roughness Rq is 36 nm; the average surface roughness Ra of calcite is 16 nm, and the average root mean square roughness Rq is 19 nm.

[0070] Step 2: 2 g of the mixed minerals were mixed with 50 mL of distilled water and added to a 70 mL hanging trough flotation machine. The mixture was stirred at a speed of 1500 r / min to obtain a first slurry. Sodium hydroxide was added to the first slurry to adjust the pH of the first slurry to 9.1.

[0071] Step 3: Add a calcite inhibitor and a collector to the first slurry and stir for 2 minutes to perform slurry adjustment to obtain a second slurry; the calcite inhibitor is sodium salt of naphthalenesulfonic acid formaldehyde condensation polymer, and the collector is a mixture of sodium octylhydroxamate, octanol, hexamethoxymelamine resin, and fatty alcohol polyoxyethylene ether AEO-3, with a mass ratio of 56:15:10:19. The concentration of the collector in the second slurry after slurry adjustment is 50 mg / L.

[0072] In step 4, the second pulp is subjected to aeration flotation treatment, the aeration flotation foam is copper concentrate, and the product in the aeration flotation tank is tailings; then, the copper concentrate and tailings are filtered and dried separately, weighed and the Cu content in the copper concentrate is tested, and the copper concentrate yield and the recovery rate of Cu in the copper concentrate are calculated. The experimental results are shown in Table 1 below:

[0073] Table 1 Test results of Example 3

[0074]

[0075] Comparative Example 1:

[0076] Comparative Example 1 provides a method for improving the flotation separation efficiency of malachite and calcite, and its specific operating steps are as follows:

[0077] The method for improving the flotation separation efficiency of malachite and calcite provided in Comparative Example 1 is substantially the same as the method for improving the flotation separation efficiency of malachite and calcite provided in Example 3, except that:

[0078] Step 1: dry ball milling the calcite and malachite single minerals, and uniformly mixing the calcite and malachite single minerals with a -0.074 mm particle size content of 65% to 85% in a ratio of 1:3 to obtain mixed minerals of calcite and malachite single minerals; wherein the average surface roughness Ra of malachite is 70 nm, and the average root mean square roughness Rq is 88 nm; the average surface roughness Ra of calcite is 66 nm, and the average root mean square roughness Rq is 92 nm.

[0079] In step 4, the second pulp is subjected to aeration flotation treatment, the aeration flotation foam is copper concentrate, and the product in the aeration flotation tank is tailings; then, the copper concentrate and tailings are filtered and dried separately, weighed and the Cu content in the copper concentrate is tested, and the copper concentrate yield and the recovery rate of Cu in the copper concentrate are calculated. The experimental results are shown in Table 2 below:

[0080] Table 2 Test results of comparative example 1

[0081]

[0082] Comparative Example 2:

[0083] Comparative Example 2 provides a method for improving the flotation separation efficiency of malachite and calcite, and its specific operating steps are as follows:

[0084] The method for improving the flotation separation efficiency of malachite and calcite provided in Comparative Example 2 is substantially the same as the method for improving the flotation separation efficiency of malachite and calcite provided in Example 3, except that:

[0085] Step 1: wet ball milling the calcite and malachite single minerals, and uniformly mixing the calcite and malachite single minerals with a -0.074 mm particle size content of 65% to 85% in a ratio of 1:3 to obtain mixed minerals of calcite and malachite single minerals; wherein the average surface roughness Ra of malachite is 49 nm, and the average root mean square roughness Rq is 66 nm; the average surface roughness Ra of calcite is 42 nm, and the average root mean square roughness Rq is 71 nm.

[0086] In step 4, the second pulp is subjected to aeration flotation treatment, the aeration flotation foam is copper concentrate, and the product in the aeration flotation tank is tailings; then, the copper concentrate and tailings are filtered and dried separately, weighed and the Cu content in the copper concentrate is tested, and the copper concentrate yield and the recovery rate of Cu in the copper concentrate are calculated. The experimental results are shown in Table 3 below:

[0087] Table 3 Test results of comparative example 2

[0088]

[0089] Comparative Example 3:

[0090] Comparative Example 3 provides a method for improving the flotation separation efficiency of malachite and calcite, and its specific operating steps are as follows:

[0091] The method for improving the flotation separation efficiency of malachite and calcite provided in Comparative Example 3 is substantially the same as the method for improving the flotation separation efficiency of malachite and calcite provided in Example 3, except that:

[0092] Step three, adding a calcite inhibitor and a collector to the first slurry and stirring for 2 minutes to perform slurry adjustment to obtain a second slurry; the calcite inhibitor is sodium salt of naphthalenesulfonic acid formaldehyde condensation product, and the collector is a mixture of sodium oleate, octanol, hexamethoxymelamine resin and fatty alcohol polyoxyethylene ether AEO-3, and the mass ratios thereof are 56:15:10:19 respectively; the concentration of the collector in the second slurry after slurry adjustment is 50 mg / L.

[0093] In step 4, the second pulp is subjected to aeration flotation treatment, the aeration flotation foam is copper concentrate, and the product in the aeration flotation tank is tailings; then, the copper concentrate and tailings are filtered and dried separately, weighed and the Cu content in the copper concentrate is tested, and the copper concentrate yield and the recovery rate of Cu in the copper concentrate are calculated. The experimental results are shown in Table 4 below:

[0094] Table 4 Test results of Comparative Example 3

[0095]

[0096] Comparative Example 4:

[0097] Comparative Example 4 provides a method for improving the flotation separation efficiency of malachite and calcite, and its specific operating steps are as follows:

[0098] The method for improving the flotation separation efficiency of malachite and calcite provided in Comparative Example 4 is substantially the same as the method for improving the flotation separation efficiency of malachite and calcite provided in Example 3, except that:

[0099] Step three, adding a calcite inhibitor and a collector to the first slurry and stirring for 2 minutes to perform slurry adjustment to obtain a second slurry; the calcite inhibitor is sodium salt of naphthalenesulfonic acid formaldehyde condensation product, and the collector is a mixture of sodium octylhydroxamate, octanol, hexamethoxymelamine resin and fatty alcohol polyoxyethylene ether AEO-3, and the mass ratios thereof are 80:15:3:2 respectively; the concentration of the collector in the second slurry after slurry adjustment is 50 mg / L.

[0100] In step 4, the second pulp is subjected to aeration flotation treatment, the aeration flotation foam is copper concentrate, and the product in the aeration flotation tank is tailings; then, the copper concentrate and tailings are filtered and dried separately, weighed and the Cu content in the copper concentrate is tested, and the copper concentrate yield and the recovery rate of Cu in the copper concentrate are calculated. The experimental results are shown in Table 5 below:

[0101] Table 5 Test results of Comparative Example 4

[0102]

[0103] Comparative Example 5:

[0104] Comparative Example 5 provides a method for improving the flotation separation efficiency of malachite and calcite, and its specific operating steps are as follows:

[0105] The method for improving the flotation separation efficiency of malachite and calcite provided in Comparative Example 5 is substantially the same as the method for improving the flotation separation efficiency of malachite and calcite provided in Example 3, except that:

[0106] Step three, adding a calcite inhibitor and a collector to the first slurry and stirring for 2 minutes to perform slurry adjustment to obtain a second slurry; the calcite inhibitor is sodium salt of naphthalenesulfonic acid formaldehyde condensation product, and the collector is a mixture of sodium octylhydroxamate and octanol, with a mass ratio of 79:21; the concentration of the collector in the second slurry after slurry adjustment is 50 mg / L.

[0107] In step 4, the second pulp is subjected to aeration flotation treatment, the aeration flotation foam is copper concentrate, and the product in the aeration flotation tank is tailings; then, the copper concentrate and tailings are filtered and dried separately, weighed and the Cu content in the copper concentrate is tested, and the copper concentrate yield and the recovery rate of Cu in the copper concentrate are calculated. The experimental results are shown in Table 6 below:

[0108] Table 6 Test results of Comparative Example 5

[0109]

[0110] See also Figure 3 , Figure 3 The graph is a relationship between collector concentration and flotation rate in improving the flotation separation efficiency of malachite and calcite provided in Example 1 of the present invention; wherein, Figure 3 It can be seen that when the concentration of the collector in the second slurry after slurry adjustment is 30 mg / L~60 mg / L, the difference between the flotation rate of malachite and the flotation rate of calcite is the largest.

[0111] See also Figure 4 , Figure 4 The relationship between the pH value and the flotation rate of the first pulp in improving the flotation separation efficiency of malachite and calcite provided in Example 2 of the present invention is shown; wherein, Figure 4 It can be seen that when the pH value in the first slurry is about 9, the difference between the floating rates of malachite and calcite is the largest.

[0112] Specifically, by comparing Comparative Example 1 with Example 3, it can be seen that the average surface roughness of malachite and calcite obtained by dry ball milling is greater. Under the same reagent conditions, the grade of the copper concentrate product obtained is 9.00% lower and the recovery rate is 6.65% lower.

[0113] Specifically, by comparing Comparative Example 2 with Example 3, it can be seen that the average surface roughness of malachite and calcite obtained by wet rod grinding is greater. Under the same reagent conditions, the grade of the copper concentrate product obtained is 4.52% lower and the recovery rate is 7.91% lower.

[0114] Specifically, by comparing Comparative Example 3 with Example 3, it can be seen that the octylhydroxamic acid in the collector is replaced with sodium oleate, and when other conditions remain unchanged, the flotation separation efficiency is greatly reduced, and the concentrate product grade obtained is low by 22.22%, and the recovery rate is low by 16.3%. This is because the adsorption characteristics of sodium oleate on malachite and calcite surfaces are different. First, the selective adsorption capacity of sodium oleate to malachite and calcite is worse. Secondly, the adsorption capacity of sodium oleate on the surface of malachite with little roughness is smaller, and the adsorption capacity on the surface of malachite with big roughness is larger, and the same pattern is shown on the calcite surface. Therefore, when using sodium oleate as the main collector, the hydrophilicity difference on the surface of malachite and calcite can not be expanded by grinding and regulating the surface roughness.

[0115] Specifically, by comparing Comparative Example 4 with Example 3, it can be seen that when the proportion of the mixture of sodium octylhydroxamate, octanol and fatty alcohol polyoxyethylene ether AEO-3 in the collector exceeds a certain range and other conditions remain unchanged, the flotation separation efficiency decreases, the grade of the obtained concentrate product is 5.86% lower, and the recovery rate is 5.36% lower.

[0116] Specifically, by comparing Comparative Example 5 with Example 3, it can be seen that when the mixed collector lacks fatty alcohol polyoxyethylene ether AEO-3 and hexamethoxymelamine resin, and other conditions remain unchanged, the flotation separation efficiency is reduced, the grade of the obtained concentrate product is 9.04% lower, and the recovery rate is 9.81% lower.

[0117] Adjusting surface wettability is crucial to flotation performance. Surface wettability can be adjusted by modifying the surface chemical composition and roughness. Currently, adding flotation agents to modify the surface chemical composition is the most common method for adjusting surface wettability. Research on adjusting surface wettability using average surface roughness is less common, as roughness has a significant impact on surface wettability. The present invention, by combining flotation agents with the adjustment of average surface roughness, integrates physical and chemical methods. This approach is expected to further enhance the surface hydrophilicity and hydrophobicity differences between malachite and calcite, significantly improving the flotation separation efficiency of malachite and calcite, and reducing flotation costs.

[0118] In summary, compared with the prior art, the present invention has the following beneficial effects:

[0119] 1. Compared with the use of chemicals to control the hydrophilicity and hydrophobicity of the mineral surface, the present invention combines physical methods (controlling the average surface roughness of the mineral) with chemical methods (special compound collectors) to expand the difference in hydrophilicity and hydrophobicity between malachite and calcite, improve the flotation separation efficiency, and thus enhance the malachite enrichment effect;

[0120] 2. The combined collector used in the present invention has a small dosage and strong selectivity, and the reagents used are non-toxic, environmentally friendly and relatively safe, providing a new option for green and economical mineral processing technology.

[0121] It should be noted that the above embodiments all belong to the same inventive concept, and the description of each embodiment has its own focus. For any details not described in individual embodiments, reference may be made to the description in other embodiments.

[0122] The above embodiments merely illustrate the implementation methods of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art could make various modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A method for improving the flotation separation efficiency of malachite and calcite, characterized in that: include: S10, grinding the single minerals of calcite and malachite separately, and mixing them in a certain proportion to obtain a mixed mineral; S20, adding water to the mixed mineral to form a first slurry, and adjusting the pH value of the first slurry to 6-11; S30, adding a calcite inhibitor and a collector to the first slurry and performing slurry adjustment to obtain a second slurry, wherein the calcite inhibitor is naphthalenesulfonic acid formaldehyde condensation polymer sodium salt, and the collector is a mixture of sodium octylhydroxamate, octanol, hexamethoxymelamine resin, and fatty alcohol polyoxyethylene ether AEO-3; S40, performing aeration flotation treatment on the second slurry, wherein the aeration flotation foam is copper concentrate, and the product in the aeration flotation tank is tailings.

2. The method for improving the flotation separation efficiency of malachite and calcite according to claim 1, characterized in that: In the step S10, the mass ratio of calcite to malachite in the mixed mineral is (1-5):

1.

3. The method for improving the flotation separation efficiency of malachite and calcite according to claim 1, characterized in that: In step S10, the -0.074 mm particle size content of the mixed mineral is 65-85%, the average surface roughness of the mixed mineral is 12-96 nm, and the average root mean square roughness of the mixed mineral is 15-116 nm.

4. The method for improving the flotation separation efficiency of malachite and calcite according to claim 1, characterized in that: In the step S10, the single minerals of calcite and malachite are ground by a grinding method selected from wet rod milling and wet ball milling.

5. The method for improving the flotation separation efficiency of malachite and calcite according to claim 1, characterized in that: In the step S20, the concentration of solid mineral particles in the first slurry is 10% to 40%.

6. The method for improving the flotation separation efficiency of malachite and calcite according to claim 1, characterized in that: In the step S20, the pH value of the first slurry is adjusted to 6-11 by a pH adjuster, wherein the pH adjuster includes sodium hydroxide and hydrochloric acid.

7. The method for improving the flotation separation efficiency of malachite and calcite according to claim 1, characterized in that: In the step S30, the mass ratio of sodium octylhydroxamate, octanol, hexamethoxymelamine resin and fatty alcohol polyoxyethylene ether AEO-3 in the collector is (46-78): (7-20): (8-14): (7-20).

8. The method for improving the flotation separation efficiency of malachite and calcite according to claim 1, characterized in that: In the step S30, the concentration of the collector in the second slurry is greater than 0 and less than or equal to 240 mg / L.

9. The method for improving the flotation separation efficiency of malachite and calcite according to claim 1, characterized in that: In the step S40, the second pulp is subjected to aeration flotation treatment by a hanging trough flotation machine.

10. The method for improving the flotation separation efficiency of malachite and calcite according to claim 1, characterized in that: In the step S40, the Cu recovery rate of the copper concentrate is 80.56% to 88.47%.

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