A flotation separation method for suppressing molybdenite and galena in the flotation of chalcopyrite

Abstract

The present invention discloses a flotation separation method for inhibiting molybdenite and galena in the flotation of chalcopyrite, realizing the efficient separation of chalcopyrite from molybdenite and galena, and belonging to the technical field of mineral separation. During the flotation separation process, under the conditions of a pH of 4 - 10, an inhibitor dosage of 50 - 200 mg / L, a collector Z-200 dosage of 20 - 40 mg / L, and an MIBC / No. 2 oil dosage of 10 - 20 mg / L, a flotation process of first bulk flotation and then concentrate separation is adopted; Quercetin is widely present in nature and is currently mainly used in the food industry and the clinical industry. It can be obtained by plant extraction and is an ideal inhibitor for molybdenite and galena; Under these process conditions, quercetin inhibits the floatability of molybdenite and galena, realizing the effective separation of copper-molybdenum and copper-lead. This method has advantages such as a wide applicable pH range, good separation effect, and environmental friendliness, and has broad prospects for popularization and application.

Description

Technical Field

[0001] The present invention belongs to the technical field of mineral processing, relates to the separation flotation of sulfide ores, and particularly relates to a flotation separation method for flotation of chalcopyrite to inhibit molybdenite and galena. Background Art

[0002] Molybdenum, copper and lead metals play important roles in national production, life, science and technology, and economic development, and China is a large consumer country of molybdenum, copper and lead metals. With the increasing trend of mineral resources towards "poor, fine and miscellaneous", the washability is continuously decreasing, and the requirements for the comprehensive recovery rate of molybdenum, copper and lead resources, the quality of concentrate products and the separation effect are constantly increasing.

[0003] Under natural conditions, chalcopyrite is often associated with molybdenite and galena, and flotation is the main way for its efficient separation and recovery; however, the natural flotability of the three is good, and the release of metal ions during the grinding process causes the "homogenization effect" on the mineral surface, and these factors bring many difficulties to the flotation separation process.

[0004] At present, there are three flotation separation methods for copper-molybdenum and copper-lead, namely suppressing copper to float molybdenum, suppressing copper to float lead, and suppressing lead to float copper. The processes of suppressing copper to float molybdenum and suppressing copper to float lead often use sodium thioglycolate and sodium cyanide as chalcopyrite inhibitors. Such inhibitors have strong inhibitory ability, but have defects such as strong toxicity and great threats to human body and environment. There are two ways for suppressing lead to float copper, namely oxidation inhibition and selective inhibition. Among them, oxidation inhibition requires adding strong oxidants such as sulfuric acid and potassium dichromate to form insoluble hydrophilic substances on the surface of galena, and it is rarely used on a large scale due to environmental protection and safety issues; selective inhibition often uses adding combined reagents such as zinc sulfate, sodium sulfite, CMC and water glass, and has disadvantages such as large dosage and weak inhibitory ability.

[0005] Therefore, it is very necessary to develop an efficient and environmentally friendly selective inhibitor to achieve the efficient separation of copper-molybdenum and copper-lead, and to provide technical reserves for the comprehensive recovery and utilization of complex low-grade copper-molybdenum and copper-lead sulfide ores. Summary of the Invention

[0006] In order to overcome the above-mentioned flotation separation problems existing in copper-molybdenum and copper-lead sulfide ores, the purpose of the present invention is to provide a flotation separation method for flotation of chalcopyrite to inhibit molybdenite and galena, which effectively realizes the separation of copper-molybdenum and copper-lead.

[0007] The technical solution adopted by the present invention is: under the condition of pH value of 4 - 10, using the principle process of bulk flotation and then cleaning and separating, using quercetin as the inhibitor of molybdenite and galena, using Z-200 as the collector, and using MIBC / No. 2 oil as the frother to realize the separation of copper-lead and copper-molybdenum mixed sulfide ores, and the scraping time is 2 - 3 min.

[0008] Preferably, the inhibitor quercetin of the present invention is formulated into a solution with a mass percentage concentration of 0.1%-0.3% for addition. During the preparation of the solution, sodium hydroxide, sodium carbonate or lime is added to control the pH value to 8-10.

[0009] Preferably, the dosage of quercetin in the present invention is 50-200 mg / L, and the reaction time is 3 min.

[0010] Preferably, the dosage of the collector Z-200 in the present invention is 20-40 mg / L, and the reaction time is 3 min.

[0011] Preferably, the dosage of the frother MIBC / No. 2 oil in the present invention is 10-20 mg / L, and the reaction time is 3 min.

[0012] Principle of the present invention: Quercetin can be adsorbed on the surfaces of molybdenite, chalcopyrite and galena, reducing the natural floatability of the three. The adsorption amount of Z-200 on the surfaces of molybdenite and galena is greatly affected by quercetin, while the adsorption of Z-200 on the surface of chalcopyrite is less affected by quercetin. Therefore, chalcopyrite maintains good floatability during flotation, while molybdenite and galena are strongly inhibited.

[0013] Advantages of the present invention: Compared with traditional inhibitors of molybdenite, chalcopyrite or galena, quercetin has good selectivity, is suitable for a wide range of pulp pH values, and has the advantages of being green, environmentally friendly and widely sourced. Detailed implementation manners

[0014] The following further elaborates on the present invention with reference to specific embodiments, but the protection scope of the present invention is not limited to the content described.

[0015] Example 1

[0016] Mix molybdenite and chalcopyrite. Under natural pH conditions, first add 20 mg / L of Z-200 and stir for 3 min, then add 20 mg / L of MIBC / No. 2 oil and stir for 3 min. After aeration for 1 min, flotation is carried out for 3 min to obtain a copper-molybdenum mixed concentrate. Re-add the copper-molybdenum mixed concentrate to the flotation cell, adjust to the required pH value using hydrochloric acid or sodium hydroxide. First add 0-200 mg / L of quercetin solution and stir for 3 min, then add 20 mg / L of Z-200 and stir for 3 min. After aeration for 1 min, flotation is carried out for 2 min. The foam product is chalcopyrite, and the product in the flotation cell is molybdenite.

[0017] The flotation product indexes under different pH conditions are shown in Table 1. For the pH test, the dosage of the inhibitor quercetin is 100 mg / L.

[0018] Table 1 Flotation product indexes under different pH conditions

[0019]

[0020] As can be seen from Table 1 of the pH condition test results of copper-molybdenum separation, quercetin shows a strong inhibitory effect on molybdenite under acidic, neutral, and alkaline conditions, indicating that the applicable conditions of quercetin are very broad.

[0021] The flotation product indexes under different quercetin dosage conditions are shown in Table 2. The pH 8 close to the natural acidity was selected as the optimal flotation pH for the quercetin dosage test.

[0022] Table 2 Flotation product indexes under different quercetin dosage conditions

[0023]

[0024] From the test results of the quercetin dosage in Table 2, it can be seen that when Z-200 is used as the collector, both molybdenite and chalcopyrite show good floatability without the presence of an inhibitor, indicating that it is difficult to effectively separate molybdenite and chalcopyrite without the action of an inhibitor; when 50 mg / L of quercetin is added, molybdenite begins to be significantly inhibited, but the molybdenum grade and recovery rate in the copper concentrate are relatively high, reaching 8.80% and 14.94%; when the dosage of quercetin gradually increases, the molybdenum grade and recovery rate in the copper concentrate gradually decrease to 3.13% and 4.84%; however, the recovery rate of chalcopyrite remains stable above 86%, and the grade remains at about 31%.

[0025] The pH test and quercetin dosage experiment of copper-molybdenum separation show that when Z-200 is used as the collector and quercetin is used as the inhibitor of molybdenite, it has the advantages of high selectivity, obvious separation effect, and wide application range.

[0026] Example 2

[0027] Galena and chalcopyrite were mixed. Under natural pH conditions, first 20 mg / L of Z-200 was added and stirred for 3 min, then 20 mg / L of MIBC / No. 2 oil was added and stirred for 3 min. After aeration for 1 min, flotation was carried out for 3 min to obtain a copper-lead mixed concentrate. The copper-molybdenum mixed concentrate was re-added to the flotation cell, adjusted to the required pH value using hydrochloric acid or sodium hydroxide. First, 0 - 200 mg / L of quercetin solution was added and stirred for 3 min, then 20 mg / L of Z-200 was added and stirred for 3 min. After aeration for 1 min, flotation was carried out for 2 min. The foam product was chalcopyrite, and the product in the flotation cell was molybdenite.

[0028] The flotation product indexes under different pH conditions are shown in Table 3. The inhibitor dosage of 50 mg / L was selected for the pH test.

[0029] Table 3 Flotation product indexes under different pH conditions

[0030]

[0031] It can be seen from the pH test of copper-lead separation that the inhibitory performance of quercetin on galena is very obvious under acidic, neutral and alkaline conditions, indicating that the applicable conditions of quercetin are more extensive; the pH 8 close to the natural acidity is selected as the optimal flotation pH for the dosage test of quercetin.

[0032] The indexes of flotation products under different dosage conditions are shown in Table 4. The pH for the quercetin dosage test is selected as 8.

[0033] Table 4 Indexes of flotation products under different quercetin dosages.

[0034]

[0035] It can be seen from the results of the quercetin dosage test in Table 4 that when Z-200 is used as the collector, without the inhibitor, both chalcopyrite and galena show good floatability, indicating that it is difficult to effectively separate chalcopyrite and galena without the action of the inhibitor; when 25 mg / L of quercetin is added, galena begins to be significantly inhibited, but the lead grade and recovery rate in copper concentrate are relatively high, reaching 14.80% and 20.69%; when the dosage of quercetin gradually increases, the lead grade and recovery rate in copper concentrate gradually decrease to 3.74% and 4.07%. However, the recovery rate of chalcopyrite is stable above 84%, and the grade remains at about 30%.

[0036] The pH test and quercetin dosage experiment of copper-lead separation show that when Z-200 is used as the collector and quercetin is used as the inhibitor of galena, it has the advantages of high selectivity, obvious separation effect and wide application range.

[0037] Comparative Example 1

[0038] Under conditions similar to those in Examples 1 and 2, when the flotation pH is 8, the inhibitor dosage is 100 mg / L, and 20 mg / L of ethyl xanthate is used as the collector, the flotation results are shown in Table 5.

[0039] Table 5 Flotation indexes using ethyl xanthate as the collector

[0040]

[0041] Using ethyl xanthate as the collector, during the separation of copper and molybdenum, the copper grade in the concentrate reached 25.23%, and the recovery rate was only 49.57%. At the same time, the molybdenum grade in the concentrate was 19.83%, and the recovery rate was 21.72%. During the separation of copper and lead, the copper concentrate grade reached 28.66%, and the recovery rate was 44.48%. At the same time, the lead grade in the concentrate was 10.62%, and the recovery rate was 9.23%. The results show that when using quercetin as the inhibitor of molybdenite or galena, using ethyl xanthate as the collector of chalcopyrite has a certain sorting trend to a certain extent, but does not have good sorting effect. Therefore, it is not feasible to use ethyl xanthate to float and separate chalcopyrite and molybdenite under these conditions.

[0042] Comparative Example 2

[0043] Similar to the conditions of Examples 1 and 2, when the flotation pH is 8, the inhibitor dosage is 100 mg / L, and 20 mg / L of butyl xanthate is used as the collector, the flotation results are shown in Table 6.

[0044] Table 6 Flotation indexes using butyl xanthate as the collector

[0045]

[0046] Using butyl xanthate as the collector, during the separation of copper and molybdenum, the concentrate yield reached 96.83%, and the recovery rates of molybdenite and chalcopyrite were over 96%. During the separation of copper and lead, the concentrate yield reached 95.41%, and the recovery rates of chalcopyrite and galena were over 93%. The results show that when using quercetin as the inhibitor of molybdenite or galena, and using butyl xanthate as the collector of chalcopyrite, all three show good floatability and do not have sorting effect. Therefore, it is not feasible to use butyl xanthate to float and separate chalcopyrite and molybdenite under these conditions.

[0047] The flotation results of Examples 1 and 2 and Comparative Examples 1 and 2 show that: when using quercetin as the inhibitor of molybdenite and galena, and using Z-200 as the collector, molybdenite and galena are strongly inhibited, while chalcopyrite shows good floatability, and the flotation separation effect of copper-molybdenum and copper-lead is good. When using low-grade xanthate such as ethyl xanthate as the collector, it has a certain sorting trend, but high-efficiency separation cannot be achieved. When using high-grade xanthate such as butyl xanthate as the collector, molybdenite, chalcopyrite and galena are all recovered and do not have selectivity.

[0048] It can be seen from the comparison that using the molybdenite and galena inhibitor quercetin of the present invention has a certain compatibility with the selected collector Z-200, and the separation effect is significant.

Claims

1. A flotation separation method for suppressing molybdenite and galena in the flotation of chalcopyrite, characterized in that: Under the condition that the pH value is 4 - 10, the principle process of bulk flotation and then separation is used. Quercetin is used as the depressant for molybdenite and galena, Z - 200 is used as the collector, and MIBC / No. 2 oil is used as the frother to achieve the separation of copper - lead and copper - molybdenum mixed sulfide ores.

2. The flotation separation method for separating chalcopyrite from molybdenite and galena according to claim 1, characterized in that: The inhibitor quercetin is prepared into a solution with a mass percentage concentration of 0.1% - 0.3% for addition. During the process of preparing the solution, sodium hydroxide, sodium carbonate or lime is added to control the pH value to 8 - 10.

3. The flotation separation method for separating chalcopyrite from molybdenite and galena by flotation according to claim 1, characterized in that: The dosage of the quercetin is 50 - 200 mg / L.

4. The flotation separation method for separating chalcopyrite from molybdenite and galena according to claim 1, characterized in that: The dosage of the collector Z - 200 is 20 - 40 mg / L.

5. The flotation separation method for separating chalcopyrite from molybdenite and galena by flotation according to claim 1, characterized in that: The dosage of the frother MIBC / No. 2 oil is 10 - 20 mg / L.

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