A flotation separation method for copper-molybdenum mixed concentrate and combined depressant used therein

Abstract

The present invention discloses a flotation separation method for a copper-molybdenum mixed concentrate and a combined depressant used therein. The combined depressant comprises dithionite and thiobarbituric acid. The method involves adding dithionite to the copper-molybdenum mixed concentrate slurry for drug removal, then adding thiobarbituric acid to depress chalcopyrite, and then adding a molybdenite collector and a frother for flotation, thereby obtaining molybdenum and copper concentrates. The combined depressant is non-toxic and environmentally friendly, and the synergistic effect of the two depressants achieves excellent chalcopyrite inhibition at relatively low dosages, significantly improving molybdenum recovery and molybdenum-copper separation efficiency.

Description

Technical Field

[0001] The invention relates to a flotation separation method for a copper-molybdenum mixed concentrate and a combined depressant used therein, belonging to the technical field of copper-molybdenum sulfide mineral separation. Background Art

[0002] Copper and molybdenum are both metallic materials with significant practical value. Copper's high electrical and thermal conductivity make it widely used in electrical, construction, and manufacturing applications. Molybdenum, a key strategic reserve resource, is widely used in the manufacture of high-temperature equipment and electronic components due to its excellent heat and corrosion resistance, providing critical support for aerospace and other fields. However, due to the close association and similar floatability of copper and molybdenum minerals, their separation has long been a major challenge in mineral sorting.

[0003] At present, there are two process flows for the separation of copper-molybdenum mixed concentrates at home and abroad: copper suppression and molybdenum flotation and molybdenum suppression and copper flotation. Since molybdenum ore has good natural floatability, the copper suppression and molybdenum flotation process is basically adopted in practice. Commonly used copper suppression agents can be divided into: (1) Inorganic inhibitors. Commonly used agents include cyanide and Knox agents. The principle of this type of inhibitor is that the ions dissociated after the agent is dissolved in water are adsorbed on the surface of copper minerals, increasing the hydrophilicity of the copper mineral surface, but have no obvious effect on molybdenite. Although this inhibitor has the advantages of good inhibitory effect and low dosage, its application is limited due to its own toxicity and great pollution to the environment. (2) Organic inhibitors. Sodium thioglycolate (HSCH2COONa) is a new organic inhibitor in copper separation in recent years. The -HS group and -COOH group in its molecule are adsorbed on the surface of copper minerals to form a hydrophilic film, which increases the hydrophilicity of the copper mineral surface. However, the high cost of sodium thioglycolate has always restricted its promotion. (3) Oxidants. Commonly used oxidants include hydrogen peroxide, sodium hypochlorite, and potassium permanganate. During the flotation process, the strong reducing properties and easy oxidation properties of xanthates are utilized to oxidize xanthates adsorbed on the surface of copper minerals, generating non-collecting perxanthate Cu(C2H5OCSSO)2, thereby achieving the effect of copper suppression. However, due to its strong oxidizing properties, it is prone to corrosion, the cost of the reagents is also high, and some are toxic. The method and location of adding oxidants also need to be studied.

[0004] Due to many problems in the existing copper-molybdenum separation methods and reagents, the separation effect of copper-molybdenum mixed concentrate in my country is poor. Therefore, there is an urgent need to find a depressant and flotation separation process with fewer types of reagents, low toxicity, low dosage, and strong selectivity. Summary of the Invention

[0005] In response to the shortcomings of the prior art, the first object of the present invention is to provide a combined inhibitor for flotation separation of copper-molybdenum mixed concentrate. The combined inhibitor consists of a small number of reagents and only contains low-toxic and harmless dithionite and thiobarbituric acid. The synergistic effect of the two can achieve excellent inhibition of chalcopyrite at a lower dosage, significantly improving the molybdenum recovery rate and molybdenum-copper separation effect.

[0006] A second object of the present invention is to provide a flotation separation method for a copper-molybdenum mixed concentrate. This process significantly improves the molybdenum recovery rate and the molybdenum-copper separation effect while using a low dosage of reagents by rationally setting the order of adding dithionite and thiobarbituric acid in the combined inhibitor and simultaneously using a hydrocarbon collector with a good capture effect on molybdenite. The entire process is low-toxic, environmentally friendly, and has a simple flow.

[0007] In order to achieve the above-mentioned object, the present invention provides a combined depressant for flotation separation of copper-molybdenum mixed concentrate, wherein the combined depressant comprises dithionite and thiobarbituric acid; the mass ratio of the dithionite to thiobarbituric acid is (0.2-1): (0.5-2).

[0008] In the technical solution of the present invention, dithionite and thiobarbituric acid have good synergistic effects, which are mainly manifested in that: dithionite has strong reducing properties, which can reduce hydrophobic substances such as elemental sulfur and polysulfides on the surface of chalcopyrite, thereby achieving effective desorption of neutral oil collectors used in the flotation separation process of the chalcopyrite surface and copper-molybdenum mixed concentrate; and the molecular structure of thiobarbituric acid is a resonance isomer. Due to the strong electron-pulling effect of the dicarbon group, the double bond between the nitrogen atom and the sulfur atom can be converted into each other, so that thiobarbituric acid has Due to its multiple structural formulas, thiobarbituric acid has both thiol and carbon-nitrogen double bond functional groups, as well as carbon-sulfur double bonds and amino groups. The multiple functional groups work together to selectively form a strong chelate with the surface of chalcopyrite, and its inhibitory effect is significantly stronger than that of traditional inhibitors such as sodium thioglycolate. At the same time, the combination of thiol and amino groups can enhance the adaptability of the agent. More importantly, dithionite can also reduce some of the divalent copper ions present in the ore pulp, eliminating the interaction between the divalent copper ions and thiobarbituric acid, significantly enhancing the inhibitory effect and reducing the dosage of thiobarbituric acid.

[0009] The amounts of dithionite and thiobarbituric acid used in the present invention also have a direct impact on the separation effect. If the mass ratio of dithionite is too low, it will lead to insufficient drug removal, affecting the subsequent inhibitory effect of thiobarbituric acid on chalcopyrite. If the mass ratio is too high, it will cause the surface of chalcopyrite to be excessively reduced, which is also not conducive to the effect of thiobarbituric acid.

[0010] As a preferred embodiment, the combined inhibitor dosage of dithionite and thiobarbituric acid in the flotation separation roughing of the copper-molybdenum mixed concentrate is 0.2-1.0 kg and 0.5-2.0 kg, respectively, per ton of the copper-molybdenum mixed concentrate. The combined inhibitor dosage in the roughing separation of the present invention is low and exhibits a good inhibitory effect.

[0011] As a preferred solution, the dithionite is sodium dithionite and / or potassium dithionite.

[0012] The present invention also provides a flotation separation method for copper-molybdenum mixed concentrate, which comprises adding dithionite to the copper-molybdenum mixed concentrate pulp for drug removal treatment, then adding thiobarbituric acid to inhibit chalcopyrite, and then adding a molybdenite collector and a frother to carry out flotation to obtain molybdenum concentrate and copper concentrate.

[0013] The flotation separation method for a copper-molybdenum mixed concentrate of the present invention first suppresses chalcopyrite and increases its hydrophilicity through the synergistic effect of a combined inhibitor, and then selects a collector and a frother that can increase the surface hydrophobicity of molybdenite and stabilize the foam. Due to the synergistic effect of the combined inhibitor, efficient selective separation of copper ore and molybdenum ore can be achieved under low-alkali conditions, and the recovery rate of the molybdenum concentrate is improved.

[0014] The inventors discovered that in the separation method of the present invention, dithionite must be added first for drug removal, and then thiobarbituric acid is added to achieve the best copper-molybdenum separation effect. If sodium dithionite and thiobarbituric acid are added simultaneously, the inhibitory effect on copper is significantly weakened, resulting in a lower grade of molybdenum concentrate and a higher copper content, while the copper concentrate grade and copper recovery rate are both reduced. If thiobarbituric acid is added first and then dithionite, the adsorption of thiobarbituric acid on the mineral surface is destroyed by dithionite, thereby affecting its inhibitory effect on chalcopyrite. In addition, the drug removal effect of dithionite may affect the adsorption of subsequent flotation reagents, thereby affecting the selectivity and efficiency of flotation.

[0015] As a preferred solution, the flotation includes one roughing process, at least one cleaning process and at least one scavenging process.

[0016] The dosage of the medicament in the present invention is relative to the dosage of the original ore.

[0017] As a preferred solution, the reagent system for the roughing selection is: 0.2-1.0 kg / t of dithionite, 0.5-2.0 kg of thiobarbituric acid, 0.1-1 kg / t of collector, and 50-200 g / t of foaming agent.

[0018] As a preferred solution, the concentrate obtained after the roughing is a molybdenum rough concentrate, and the tailings are a copper rough concentrate; the molybdenum rough concentrate is subjected to beneficiation, and the final beneficiated concentrate is a molybdenum concentrate; the copper rough concentrate is subjected to scavenging, and the scavenging tailings are a copper concentrate.

[0019] As a preferred solution, only a collector is added during the scavenging process, and the amount of the collector is 0.1 to 0.5 times the amount used in the roughing process.

[0020] As a preferred solution, only thiobarbituric acid inhibitor is added during the concentrating process, with the dosage being 0.01 to 0.5 times that of the roughing concentration, and the inhibitor dosage for the Nth concentrating round is less than that for the N-1th concentrating round. Since the primary function of the combined inhibitor of the present invention is drug removal, the addition of dithionite after the roughing concentration can remove the agent from the mineral surface. In subsequent concentrating processes, only thiobarbituric acid needs to be added to further inhibit chalcopyrite and achieve deep flotation. As the number of concentrating rounds increases, the content of impurity minerals in the concentrate decreases, and thus the dosage of the inhibitor gradually decreases.

[0021] As a preferred solution, the copper-molybdenum mixed concentrate is a copper-molybdenum mixed concentrate obtained by flotation of molybdenum-containing copper ore or copper-molybdenum ore using a neutral oil collector; wherein the copper content is 2-30wt%; and the molybdenum content is 0.2-50wt%.

[0022] As a preferred solution, the copper-molybdenum mixed concentrate slurry concentration is 10-40%.

[0023] As a preferred solution, the collector is at least one of diesel and kerosene.

[0024] As a preferred solution, the foaming agent is at least one of No. 2 oil and MIBC.

[0025] In the molybdenite collection process of the present invention, the diesel and kerosene selected are hydrocarbon oil collectors, which can form an oil film on the surface of the molybdenite, increase the hydrophobicity of the molybdenite surface, so that the molybdenite can adhere to the surface of the bubble and be carried by the bubbles to the surface of the slurry to form mineralized foam, and then separate from other minerals; and No. 2 oil can further promote the diffusion of air in the slurry to form foam with suitable size, good toughness and stable performance, provide a carrier for the flotation of the molybdenite, and significantly improve the molybdenite collection effect.

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

[0027] First, through the strong reducing property of dithionite, the elemental sulfur, polysulfide and other hydrophobic substances on the surface of chalcopyrite are reduced, thereby achieving effective desorption of the chalcopyrite surface and the neutral oil collector.

[0028] Secondly, dithionite can also reduce some of the divalent copper ions present in the ore pulp, eliminate the effect of divalent copper ions and thiobarbituric acid, enhance the effect of thiobarbituric acid, and reduce the dosage of thiobarbituric acid.

[0029] Third, thiobarbituric acid contains thiol and amino groups in its molecular structure, which can form a strong chelate with the surface of chalcopyrite. Its inhibitory effect is significantly stronger than traditional inhibitors such as sodium thioglycolate. At the same time, the combination of thiol and amino groups can enhance the adaptability of the agent, and it can flexibly respond to various types of copper-molybdenum mixed concentrates.

[0030] Fourthly, dithionite and thiobarbituric acid have almost no inhibitory effect on molybdenite, and the reagents have good selectivity.

[0031] Fifth, the combined inhibitor is non-toxic and environmentally friendly, which is beneficial to the subsequent wastewater treatment or reuse of the mineral processing plant, and effectively protects the ecological benefits around the processing plant. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The present invention is used to carry out a small-scale closed-circuit test of copper-molybdenum flotation separation. DETAILED DESCRIPTION

[0033] The following specific examples are intended to further illustrate the present invention, but are not intended to limit the scope of protection of the present invention. The pharmaceutical agents used without indicating the manufacturer are all conventional products that can be purchased commercially.

[0034] The dosage of the reagents in the examples of the present invention and the comparative examples is the dosage relative to the original ore, and the slurry concentration is the mass concentration.

[0035] Example 1

[0036] The test raw material was a copper-molybdenum mixed concentrate obtained by flotation using diesel as a collector from a molybdenum-containing copper ore. The copper content was 23.07% and the molybdenum content was 1.19%. Process mineralogy studies showed that the main metallic minerals in this sample were chalcopyrite, molybdenite, and a small amount of pyrite. A small-scale closed-circuit laboratory test was conducted on this ore sample using the combined depressant provided by the present invention for flotation separation of the copper-molybdenum mixed concentrate. The specific test steps were as follows:

[0037] 1) adding 800 g / t of sodium dithionite to the copper-molybdenum mixed concentrate pulp (pulp concentration is 25%) for drug removal, and then sequentially adding 1500 g / t of thiobarbituric acid as an inhibitor, 300 g / t of kerosene as a collector, and 100 g / t of No. 2 oil as a foaming agent to perform a primary roughing;

[0038] 2) The coarse tailings after roughing are subjected to two scavenging processes. In scavenging process 1, 150 g / t of kerosene is added, and in scavenging process 2, 75 g / t of kerosene is added. The scavenging tailings are used as copper concentrate.

[0039] 3) The coarse concentrate after roughing is subjected to three rounds of cleaning, wherein 500 g / t of thiobarbituric acid is added in cleaning 1, 200 g / t of thiobarbituric acid is added in cleaning 2, and 100 g / t of thiobarbituric acid is added in cleaning 3. The clean concentrate is used as molybdenum concentrate.

[0040] The test results are shown in Table 1.

[0041] The test results show that, by using the combined depressant for flotation separation of copper-molybdenum mixed concentrate provided by the present invention, a small-scale closed-circuit laboratory test can obtain a molybdenum concentrate with a molybdenum grade of 49.58%, a copper content of only 1.41%, and a molybdenum recovery rate of 95.07%. A copper concentrate with a copper grade of 23.58%, a molybdenum content of only 0.060%, and a copper recovery rate of 99.86%.

[0042] Table 1

[0043]

[0044] Example 2

[0045] The test raw material was a copper-molybdenum mixed concentrate obtained by flotation using kerosene as a collector from a copper-molybdenum ore. The copper content was 11.20% and the molybdenum content was 22.99%. Process mineralogy studies revealed that the primary metallic minerals in this sample were chalcopyrite, molybdenite, and pyrite. A small-scale laboratory closed-circuit test was conducted on this ore sample using the combined depressant provided in the present invention for flotation separation of the copper-molybdenum mixed concentrate. The specific test steps were as follows:

[0046] 1) adding 500 g / t of sodium dithionite to the copper-molybdenum mixed concentrate pulp (pulp concentration is 20%) for drug removal, and then sequentially adding 1000 g / t of thiobarbituric acid as an inhibitor, 800 g / t of kerosene as a collector, and 150 g / t of MIBC as a foaming agent to perform a primary roughing;

[0047] 2) The coarse tailings after roughing are scavenged twice. In scavenging 1, 400g / t kerosene is added, and in scavenging 2, 200g / t kerosene is added. The scavenged tailings are used as copper concentrate.

[0048] 3) The coarse concentrate after roughing is subjected to three rounds of cleaning, wherein 400 g / t of thiobarbituric acid is added in cleaning 1, 200 g / t of thiobarbituric acid is added in cleaning 2, and 100 g / t of thiobarbituric acid is added in cleaning 3. The clean concentrate is used as molybdenum concentrate.

[0049] The test results are shown in Table 2.

[0050] The test results show that, by using the combined depressant for flotation separation of copper-molybdenum mixed concentrate provided by the present invention, a small-scale closed-circuit laboratory test can obtain a molybdenum concentrate with a molybdenum grade of 50.66%, a copper content of only 0.28%, and a molybdenum recovery rate of 99.50%. A copper concentrate with a copper grade of 20.19%, a molybdenum content of only 0.21%, and a copper recovery rate of 98.87%.

[0051] Table 2

[0052]

[0053]

[0054] Example 3

[0055] The test raw material was a copper-molybdenum mixed concentrate obtained by flotation using heavy oil as a collector from a molybdenum-containing copper ore. The copper content was 21.71% and the molybdenum content was 0.83%. Process mineralogy studies showed that the main metallic minerals in this sample were chalcopyrite, molybdenite, and a small amount of pyrite. A small-scale laboratory closed-circuit test was conducted on this ore sample using the combined depressant provided by the present invention for flotation separation of the copper-molybdenum mixed concentrate. The specific test steps were as follows:

[0056] 1) adding 600 g / t of sodium dithionite to the copper-molybdenum mixed concentrate pulp (pulp concentration is 30%) for drug removal, and then sequentially adding 1200 g / t of thiobarbituric acid as an inhibitor, 200 g / t of kerosene as a collector, and 50 g / t of No. 2 oil as a foaming agent to perform a primary roughing;

[0057] 2) The coarse tailings after roughing are scavenged twice. In scavenging 1, 100g / t kerosene is added, and in scavenging 2, 50g / t kerosene is added. The scavenged tailings are used as copper concentrate.

[0058] 3) The coarse concentrate after roughing is subjected to three rounds of cleaning, wherein 400 g / t of thiobarbituric acid is added in cleaning 1, 200 g / t of thiobarbituric acid is added in cleaning 2, and 100 g / t of thiobarbituric acid is added in cleaning 3. The clean concentrate is used as molybdenum concentrate.

[0059] The test results are shown in Table 3.

[0060] The test results show that, by using the combined depressant for flotation separation of copper-molybdenum mixed concentrate provided by the present invention, a small-scale closed-circuit laboratory test can obtain a molybdenum concentrate with a molybdenum grade of 48.70%, a copper content of only 1.58%, and a molybdenum recovery rate of 94.91%. A copper concentrate with a copper grade of 22.04% contains only 0.043% molybdenum, and a copper recovery rate of 99.88%.

[0061] Table 3

[0062]

[0063]

[0064] Comparative Example 1

[0065] For the ore sample in Example 1, while keeping the process structure and the total dosage of the reagent unchanged, thiobarbituric acid was replaced with sodium thioglycolate, and a small-scale closed-circuit laboratory test was carried out on the ore. The specific steps of the test are as follows:

[0066] 1) adding 800 g / t of sodium dithionite to the copper-molybdenum mixed concentrate pulp (pulp concentration is 25%) for drug removal, and then sequentially adding 1500 g / t of sodium thioglycolate as an inhibitor, 300 g / t of kerosene as a collector, and 100 g / t of No. 2 oil as a foaming agent to perform a primary roughing;

[0067] 2) The coarse tailings after roughing are subjected to two scavenging processes. In scavenging process 1, 150 g / t of kerosene is added, and in scavenging process 2, 75 g / t of kerosene is added. The scavenging tailings are used as copper concentrate.

[0068] 3) The coarse concentrate after roughing is subjected to three rounds of concentration, wherein 500 g / t of sodium thioglycolate is added in concentration 1, 200 g / t of sodium thioglycolate is added in concentration 2, and 100 g / t of sodium thioglycolate is added in concentration 3. The concentrated ore is used as molybdenum concentrate.

[0069] The test results are shown in Table 4.

[0070] The test results show that after removing thiobarbituric acid from the combined inhibitor, a small-scale closed-circuit laboratory test yielded a molybdenum concentrate with a molybdenum grade of 48.44%, a molybdenum recovery of 90.48%, and a copper content of 3.81%. The copper concentrate had a copper grade of 23.51%, a molybdenum content of 0.12%, and a copper recovery of 99.62%. By comparison, replacing thiobarbituric acid with sodium thioglycolate as the inhibitor yielded a lower molybdenum concentrate grade, a higher copper content, and a significantly lower molybdenum recovery.

[0071] Table 4

[0072]

[0073] Comparative Example 2

[0074] For the ore sample in Example 1, while maintaining the process structure and the total dosage of the reagents, the sodium dithionite in the combined inhibitor provided by the present invention was removed, and a small-scale closed-circuit laboratory test was conducted on the ore. The specific steps of the test are as follows:

[0075] 1) Adding 1500 g / t of thiobarbituric acid as an inhibitor, 300 g / t of kerosene as a collector, and 100 g / t of No. 2 oil as a foaming agent to a copper-molybdenum mixed concentrate pulp (pulp concentration of 25%) to perform a primary roughing;

[0076] 2) The coarse tailings after roughing are subjected to two scavenging processes. In scavenging process 1, 150 g / t of kerosene is added, and in scavenging process 2, 75 g / t of kerosene is added. The scavenging tailings are used as copper concentrate.

[0077] 3) The coarse concentrate after roughing is subjected to three rounds of cleaning, wherein 500 g / t of thiobarbituric acid is added in cleaning 1, 200 g / t of thiobarbituric acid is added in cleaning 2, and 100 g / t of thiobarbituric acid is added in cleaning 3. The clean concentrate is used as molybdenum concentrate.

[0078] The test results are shown in Table 5.

[0079] The test results show that after the combined inhibitor removed sodium dithionite, a small-scale closed-circuit laboratory test yielded a molybdenum concentrate with a molybdenum grade of 25.95%, a molybdenum recovery of 81.76%, and a copper content of 7.56%. The copper concentrate had a copper grade of 23.64%, a molybdenum content of 0.22%, and a copper recovery of 98.80%. By comparison, the combined inhibitor's effect on copper was significantly weakened after sodium dithionite was removed, resulting in a lower-grade molybdenum concentrate with a higher copper content. The copper recovery rate in the copper concentrate was also reduced.

[0080] Table 5

[0081]

[0082] Comparative Example 3

[0083] For the ore sample in Example 1, while maintaining the process structure and the total dosage of the reagents, the sodium dithionite in the combined inhibitor provided by the present invention was replaced with sodium sulfide, and a small-scale closed-circuit laboratory test was conducted on the ore. The specific steps of the test are as follows:

[0084] 1) adding 800 g / t of sodium sulfide to the copper-molybdenum mixed concentrate pulp (pulp concentration is 25%) for drug removal, and then sequentially adding 1500 g / t of thiobarbituric acid as an inhibitor, 300 g / t of kerosene as a collector, and 100 g / t of No. 2 oil as a foaming agent to perform a primary roughing;

[0085] 2) The coarse tailings after roughing are subjected to two scavenging processes. In scavenging process 1, 150 g / t of kerosene is added, and in scavenging process 2, 75 g / t of kerosene is added. The scavenging tailings are used as copper concentrate.

[0086] 3) The coarse concentrate after roughing is subjected to three rounds of cleaning, wherein 500 g / t of thiobarbituric acid is added in cleaning 1, 200 g / t of thiobarbituric acid is added in cleaning 2, and 100 g / t of thiobarbituric acid is added in cleaning 3. The clean concentrate is used as molybdenum concentrate.

[0087] The test results are shown in Table 6.

[0088] The test results show that after sodium dithionite was replaced with sodium sulfide, a small-scale closed-circuit laboratory test yielded a molybdenum concentrate with a molybdenum grade of 32.48%, a molybdenum recovery of 86.18%, and a copper content of 4.08%. The copper concentrate had a copper grade of 23.55%, a molybdenum content of 0.16%, and a copper recovery of 99.47%. By comparison, the substitution of sodium dithionite for sodium sulfide significantly weakened the inhibitory effect on copper, resulting in a lower-grade molybdenum concentrate with a higher copper content and a significantly lower molybdenum recovery rate. Both the copper concentrate grade and copper recovery rate were reduced.

[0089] Table 6

[0090]

[0091] Comparative Example 4

[0092] For the ore sample in Example 1, under the condition of maintaining the process structure and the total dosage of the reagents, the sodium dithionite and thiobarbituric acid were added simultaneously instead of sequentially, and a small-scale closed-circuit test was carried out on the ore. The specific steps of the test are as follows:

[0093] 1) adding 800 g / t of sodium dithionite and 1500 g / t of thiobarbituric acid to a copper-molybdenum mixed concentrate slurry (pulp concentration is 25%), then adding 300 g / t of kerosene as a collector and 100 g / t of No. 2 oil as a foaming agent to perform a primary roughing;

[0094] 2) The coarse tailings after roughing are subjected to two scavenging processes. In scavenging process 1, 150 g / t of kerosene is added, and in scavenging process 2, 75 g / t of kerosene is added. The scavenging tailings are used as copper concentrate.

[0095] 3) The coarse concentrate after roughing is subjected to three rounds of cleaning, wherein 500 g / t of thiobarbituric acid is added in cleaning 1, 200 g / t of thiobarbituric acid is added in cleaning 2, and 100 g / t of thiobarbituric acid is added in cleaning 3. The clean concentrate is used as molybdenum concentrate.

[0096] The test results are shown in Table 7.

[0097] The test results show that by switching from sequential to simultaneous addition of sodium dithionite and thiobarbituric acid, a small-scale closed-circuit laboratory test yielded a molybdenum concentrate with a molybdenum grade of 30.82%, a molybdenum recovery of 83.68%, and a copper content of 5.65%. The copper concentrate had a copper grade of 23.70%, a molybdenum content of 0.20%, and a copper recovery of 99.21%. A comparison revealed that switching from sequential to simultaneous addition of sodium dithionite and thiobarbituric acid significantly weakened the inhibitory effect on copper, resulting in a lower molybdenum concentrate with a higher copper content. The copper recovery rate in the copper concentrate was also somewhat reduced.

[0098] Table 7

[0099]

[0100] Comparative Example 5

[0101] For the ore sample in Example 1, under the conditions of maintaining the process structure and the total dosage of the reagents, the mass ratio of sodium dithionite and thiobarbituric acid reagents was changed from 0.8:1.5 to 0.1:2.1, and a small-scale closed-circuit laboratory test was carried out on the ore. The specific steps of the test are as follows:

[0102] 1) adding 100 g / t of sodium dithionite to the copper-molybdenum mixed concentrate pulp (pulp concentration is 25%) for drug removal, and then sequentially adding 2100 g / t of thiobarbituric acid as an inhibitor, 300 g / t of kerosene as a collector, and 100 g / t of No. 2 oil as a foaming agent to perform a primary roughing;

[0103] 2) The coarse tailings after roughing are subjected to two scavenging processes. In scavenging process 1, 150 g / t of kerosene is added, and in scavenging process 2, 75 g / t of kerosene is added. The scavenging tailings are used as copper concentrate.

[0104] 3) The coarse concentrate after roughing is subjected to three rounds of cleaning, wherein 500 g / t of thiobarbituric acid is added in cleaning 1, 200 g / t of thiobarbituric acid is added in cleaning 2, and 100 g / t of thiobarbituric acid is added in cleaning 3. The clean concentrate is used as molybdenum concentrate.

[0105] The test results are shown in Table 8.

[0106] The test results show that by changing the mass ratio of sodium dithionite to thiobarbituric acid from 0.8:1.5 to 0.1:2.1, a small-scale closed-circuit laboratory test can produce a molybdenum concentrate with a molybdenum grade of 40.53%, a molybdenum recovery of 89.39%, and a copper content of 3.06%. The copper concentrate has a copper grade of 23.48%, a molybdenum content of 0.13%, and a copper recovery of 99.65%. By comparison, when the mass ratio of sodium dithionite to thiobarbituric acid is changed from 0.8:1.5 to 0.1:2.1, the inhibitory effect on copper is significantly weakened due to incomplete desulfurization, resulting in a lower molybdenum concentrate grade and a higher copper content. The copper concentrate grade and copper recovery rate are also reduced.

[0107] Table 8

[0108]

[0109] Comparative Example 6

[0110] For the ore sample in Example 1, under the conditions of maintaining the process structure and the total dosage of the reagents, the mass ratio of sodium dithionite and thiobarbituric acid reagents was changed from 0.8:1.5 to 1.6:0.7, and a laboratory small-scale closed-circuit test was carried out on the ore. The specific steps of the test are as follows:

[0111] 1) adding 1600 g / t of sodium dithionite to the copper-molybdenum mixed concentrate pulp (pulp concentration is 25%) for drug removal, and then sequentially adding 700 g / t of thiobarbituric acid as an inhibitor, 300 g / t of kerosene as a collector, and 100 g / t of No. 2 oil as a foaming agent to perform a primary roughing;

[0112] 2) The coarse tailings after roughing are subjected to two scavenging processes. In scavenging process 1, 150 g / t of kerosene is added, and in scavenging process 2, 75 g / t of kerosene is added. The scavenging tailings are used as copper concentrate.

[0113] 3) The coarse concentrate after roughing is subjected to three rounds of cleaning, wherein 500 g / t of thiobarbituric acid is added in cleaning 1, 200 g / t of thiobarbituric acid is added in cleaning 2, and 100 g / t of thiobarbituric acid is added in cleaning 3. The clean concentrate is used as molybdenum concentrate.

[0114] The test results are shown in Table 9.

[0115] The test results show that when the mass ratio of sodium dithionite to thiobarbituric acid is changed from 0.8:1.5 to 1.6:0.7, a small-scale closed-circuit laboratory test can produce a molybdenum concentrate with a molybdenum grade of 31.29%, a molybdenum recovery of 82.94%, and a copper content of 5.22%. The copper concentrate has a copper grade of 23.52%, a molybdenum content of 0.21%, and a copper recovery of 99.28%. By comparison, when the mass ratio of sodium dithionite to thiobarbituric acid is changed from 0.8:1.5 to 1.6:0.7, the inhibition effect on copper is significantly weakened due to the excessive reducing property of the slurry and the reduced dosage of thiobarbituric acid, resulting in a lower molybdenum concentrate grade and a higher copper content. The copper concentrate grade and copper recovery rate are also reduced.

[0116] Table 9

[0117]

Claims

1. A flotation separation method for copper-molybdenum mixed concentrate, characterized by: Adding dithionite to the copper-molybdenum mixed concentrate pulp for drug removal, then adding thiobarbituric acid to inhibit chalcopyrite, and then adding molybdenite collector and frother for flotation to obtain molybdenum concentrate and copper concentrate; The mass ratio of the dithionite to thiobarbituric acid is (0.2-1): (0.5-2); The flotation comprises one roughing selection, at least one cleaning selection and at least one scavenging selection; The concentrate obtained after the roughing is a molybdenum rough concentrate, and the tailings are a copper rough concentrate; wherein the molybdenum rough concentrate is subjected to beneficiation, and the final beneficiated concentrate is a molybdenum concentrate; the copper rough concentrate is subjected to scavenging, and the scavenging tailings are a copper concentrate; During the scavenging process, only the collector is added, and the amount of the collector is 0.1 to 0.5 times the amount used in the roughing process; During the selection process, only thiobarbituric acid inhibitor is added, and the amount used is 0.01 to 0.5 times the amount used in the rough selection, and the amount of the inhibitor used in the Nth selection is less than the amount used in the N-1th selection.

2. The flotation separation method of a copper-molybdenum mixed concentrate according to claim 1, characterized in that: The reagent system for the roughing selection is: 0.2-1.0 kg / t of dithionite, 0.5-2.0 kg / t of thiobarbituric acid, 0.1-1 kg / t of collector, and 50-200 g / t of foaming agent.

3. The flotation separation method of a copper-molybdenum mixed concentrate according to claim 1, characterized in that: The copper-molybdenum mixed concentrate is a copper-molybdenum mixed concentrate obtained by flotation of molybdenum-containing copper ore or copper-molybdenum ore using a neutral oil collector; wherein the copper content is 2-30wt%; and the molybdenum content is 0.2-50wt%.

4. The flotation separation method of a copper-molybdenum mixed concentrate according to claim 3, characterized in that: The copper-molybdenum mixed concentrate slurry concentration is 10-40%.

5. The flotation separation method for a copper-molybdenum mixed concentrate according to claim 1 or 3, characterized in that: The collector is at least one of diesel and kerosene; The foaming agent is at least one of No. 2 oil and MIBC.

Images