Inhibitor, flotation reagent and method for flotation separation of molybdenite-other metal sulfide ore

Abstract

The invention belongs to the field of mineral flotation, and particularly discloses an inhibitor, a flotation reagent and a method for flotation separation of molybdenite and other metal sulfide ores, and the flotation inhibitor is a compound with a formula 1 # imgabs0 # structure; r1 is a substituted alkyl group with an active group; r2 is H, a sulfonic group or a substituent which is the same as R1; the active group comprises at least one of hydroxyl, amino, carboxyl and sulfonic group. The inhibitor in the formula 1 can selectively inhibit metal sulfide ores such as copper, lead and iron, but basically does not inhibit molybdenite, so that selective flotation separation of the molybdenite and the sulfide ores such as copper, lead and iron can be realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of mineral flotation, and specifically relates to the field of flotation separation of molybdenite and other metal sulfide ores. Background Art

[0002] Sulfide ores such as copper, lead, zinc, and iron (collectively referred to as other metal sulfide ores in the present invention) and molybdenite often occur together, and the difficulty of flotation separation is great.

[0003] The prior art has also disclosed some solutions for inhibiting other metal sulfide ores to achieve the separation of molybdenite. For example, Chinese document with publication number CN119634055A discloses a method for flotation separation of copper-molybdenum bulk concentrate and a combined inhibitor used therefor, wherein the combined inhibitor for inhibiting copper sulfide ore includes dithionite and thiobarbituric acid. Chinese patent document with publication number CN119608401A discloses an inhibitor for copper-molybdenum separation, its preparation method and application, wherein the inhibitor is a graft copolymer DG-1 obtained by grafting chitosan and sodium thioglycolate.

[0004] In addition, Chinese patent document with publication number CN115445779A discloses a method for selective flotation separation of molybdenite and galena. The ore to be selected containing molybdenite and galena is floated in a flotation reagent containing an inhibitor (R1-X1-CO-C(X)-CO-X2-R2) to selectively inhibit galena therein, obtaining a concentrate enriched with molybdenite and a tailing enriched with galena. Chinese patent document with publication number CN117960392A discloses a combined inhibitor for inhibiting flavonoid ore, which is composed of oxalyl dihydrazide + mercaptobenzoic acid organic matter.

[0005] In summary, although the prior art has disclosed some solutions for inhibiting other sulfide ores to achieve the selective flotation separation of molybdenite, the types of existing inhibitors are still relatively scarce, and most of them require the combination of multiple components to achieve the expected inhibition effect. The industry needs to further expand the types of inhibitors with strong affinity, low toxicity, and high stability. Summary of the Invention

[0006] Aiming at the problems faced in the flotation separation of molybdenite - other metal sulfide ores, the first object of the present invention is to provide a flotation inhibitor, aiming to provide a flotation inhibitor that can highly selectively inhibit other sulfide ores and at the same time take into account excellent strong affinity, low toxicity, and high stability.

[0007] The second object of the present invention is to provide a preparation method of the flotation inhibitor and its application in the flotation separation of molybdenite and other metal sulfide ores.

[0008] A flotation inhibitor is a compound having the structure of Formula 1;

[0009]

[0010] The described R1 is a substituted alkyl group with an active group; the described R2 is H, a sulfonic acid group, or a substituent the same as R1; the active group includes at least one of a hydroxyl group, an amino group, a carboxyl group, and a sulfonic acid group.

[0011] The described M1 and M2 are H, Na, K, or NH4.

[0012] The innovative research of the present invention shows that the combination of the parent structure of the compound of formula 1 and the functionalized R1 and / or R2 can achieve synergy, can selectively target and inhibit other metal sulfide ores, and basically does not affect the flotation of molybdenite. Thus, the selective flotation separation of molybdenite and other metal sulfide ores can be effectively achieved. The inhibitor of formula 1 can achieve good flotation selectivity based on a single reagent. Moreover, this reagent also has advantages such as low toxicity and high stability.

[0013] In the present invention, the substituted alkyl group is a group with the active group on the alkyl carbon chain of C1 - C4.

[0014] Preferably, R1 is -CH2OH, -CH2CH2OH, -CH2CH2CH2OH, -CH2COOX, -CH2CH2COOX, -CH2SO3X, or -CH2CH2SO3X.

[0015] R2 can be H, -CH2OH, -CH2CH2OH, -CH2CH2CH2OH, -CH2COOX, -CH2CH2COOX, -CH2SO3X, or -CH2CH2SO3X.

[0016] X is H, Na, or K.

[0017] Preferably, both R1 and R2 are the substituted alkyl groups with the active group; among them, the active group can further be a hydroxyl group or a carboxyl group. The research of the present invention shows that by using this preferred formula 1, the combination of the structures can be further strengthened, which helps to further improve the selective separation effect of other metal sulfide ores and molybdenite.

[0018] In the present invention, the flotation inhibitor can be obtained by subjecting the compound of formula 2 and the compound of formula 3 to an ammoniation reaction, and then subjecting the product to a mercaptanization reaction with a sulfide.

[0019]

[0020] Among them, during the ammoniation reaction, the molar ratio of Formula 2 to Formula 3 can be 1:1 to 1.1. And during the ammoniation reaction, an acid-binding agent is also allowed to be added, and the addition equivalent of the acid-binding agent can be 1 to 5 times.

[0021] In the present invention, the sulfiding agent for the mercaptanization reaction can be a sulfide and / or a hydrosulfide of Na, K or NH4. For example, it can be NaHS, or a complex of NaHS and Na2S, etc.

[0022] The molar ratio of the sulfiding agent to Formula 2 during the mercaptanization reaction can be 2 to 3:1. For example, when the sulfide contains a hydrosulfide and a sulfide, the addition equivalent of the hydrosulfide can be 2 to 2.2 eqv. The addition equivalent of the Na2S can be 0.5 to 0.7 eqv.

[0023] The present invention also provides a flotation reagent for separating molybdenite - other metal sulfide ores, which comprises a molybdenite collector and an inhibitor, and the inhibitor comprises the flotation inhibitor described above.

[0024] In the present invention, the molybdenite collector can be a reagent well-known in the industry that can be used to collect molybdenite. For example, it can include hydrocarbon collectors (such as kerosene, diesel, etc.), mercapto collectors (such as xanthate collectors, etc.) and other collectors well-known in the industry that can be used to collect molybdenite.

[0025] In the present invention, the flotation reagent is also allowed to contain at least one of a pH regulator, a foaming agent, and other inhibitors.

[0026] In the flotation reagent of the present invention, except for the inhibitor described in the present invention, other reagent components and ratios can be reasonably adjusted based on known principles and ideas.

[0027] The present invention also provides a method for separating molybdenite - other metal sulfide ores by flotation. The ore to be selected containing other metal sulfide ores and molybdenite is mixed with the flotation reagent of the present invention for flotation treatment to obtain a molybdenite concentrate.

[0028] Thanks to the innovative use of the inhibitor of Formula 1 in the flotation method of the present invention, it can target other metal sulfide ores with high affinity and basically does not inhibit molybdenite, so that the selective separation of other metal sulfide ores and molybdenite can be achieved.

[0029] In the present invention, the other metal sulfide ores include sulfide minerals of at least one metal among copper, lead, and iron, and further include at least one of chalcopyrite, galena, pyrite, and marcasite.

[0030] In the present invention, based on known flotation means and equipment, the flotation reagent containing the inhibitor of Formula 1 can be used to achieve the selective separation of other metal sulfides and molybdenite. In addition, the dosage of the reagent in the flotation process can be reasonably adjusted as needed.

[0031] For example, as an alternative, based on the weight of the flotation feed ore, the dosage of the inhibitor is 50 - 1500 g / t, and further can be 200 - 600 g / t; the dosage of the collector is 50 - 1500 g / t, and further can be 50 - 200 g / t.

[0032] Preferably, the pulp pH of the flotation is 3 - 12; further can be 6 - 8. The method of the present invention has excellent pH tolerance and can obtain excellent flotation separation selectivity in a wide pH range. Especially under the conditions more favorable for industrial production, such as neutral and slightly alkaline conditions, excellent flotation separation selectivity can still be obtained.

[0033] Beneficial effects

[0034] (1) The present invention provides a flotation inhibitor for other metal sulfides with the structure of Formula 1. Based on the combination of the parent nucleus structure and R1, R2, it can achieve synergy, target and inhibit other metal sulfides with high affinity, and basically does not inhibit molybdenite, so as to achieve the flotation separation of molybdenite and sulfide minerals such as copper, lead, and iron.

[0035] (2) Traditional inhibitors, such as sodium sulfide, sodium hydrosulfide, and phosphonox, have large dosages, are prone to oxidation and deterioration, are highly toxic, and cause serious pollution when separating molybdenite from sulfide minerals such as copper, lead, and iron. The inhibitor of Formula 1 of the present invention has low toxicity and is not easily oxidized and deteriorated, and can achieve good flotation separation effect of molybdenite at low dosages. These characteristics make the inhibitor of the present invention have broad application prospects in the field of mineral processing. Description of the drawings

[0036] Figure 1 For Formula 1A 1 HNMR;

[0037] Figure 2 For Formula 1A 13 CNMR;

[0038] Figure 3 For Formula 1B 1 HNMR;

[0039] Figure 4 For Formula 1B 13 CNMR;

[0040] Figure 5 For Formula 1C 1 HNMR;

[0041] Figure 6 For formula 1C 13 CNMR;

[0042] Figure 7 For the flotation results of chalcopyrite and molybdenite with formula 1A;

[0043] Figure 8 For the flotation results of chalcopyrite and molybdenite with formula 1B;

[0044] Figure 9 For the flotation results of chalcopyrite and molybdenite with formula 1C. Detailed implementation mode

[0045] The following examples are intended to further illustrate the content of the present invention, but the protection scope of the claims of the present invention is not limited by these examples.

[0046] In the present invention, as a typical example, the formula 1 inhibitor has the following formula 1A, formula 1B and formula 1C as typical implementation schemes:

[0047]

[0048] In formula 1A to formula 1C, M1 and M2 are optionally H or Na. Among them, M1 and M2 can be reasonably changed according to the pH of the pulp in flotation. For example, when the pH of the pulp in flotation is acidic, M1 and M2 can be H, and when the pH of the pulp is alkaline, M1 and M2 can be Na.

[0049] In the present invention, the formula 1 agent can be prepared based on known ammoniation and sulfide substitution. For example, it is obtained by ammoniating a compound of formula 2, a compound of formula 3, and an acid-binding agent (such as an alkaline component such as sodium hydroxide and potassium hydroxide), and then performing a mercapto group reaction with a sulfide (such as at least one of Na2S and NaHS); among them, in the ammoniation reaction process, the molar ratio of formula 2 to formula 3 can be 1:1 to 1.1. The molar ratio of the sulfiding agent to formula 2 in the mercapto group reaction process can be 2 to 2.2:1.

[0050] For example, as an example that can be cited, the specific synthesis method of formula 1B can be, for example:

[0051] In a 250 mL three-necked flask equipped with a thermometer, a dropping funnel and a reflux condenser, 50 mmol of formula 2 and 40 mL of ethanol are added, stirring is started and the temperature is maintained at about 0 °C. 50 mmol of formula 3 (in this case, formula 3A, the structure is After mixing evenly with 5 mL of ethanol, it was added to the reaction system through a constant-pressure dropping funnel. After the dropping was completed, 20% sodium carbonate solution (25 mmol) was added, and the mixture was continuously stirred and reacted for 1 h. Subsequently, 30% sodium hydrosulfide solution (107.5 mmol) was added for the second mercapto substitution reaction, and then 15% sodium sulfide solution (50 mmol) was added. After the feeding was completed, the temperature was raised in stages. First, it was raised to 20 °C and stirred and reacted for 1 h. Subsequently, it was raised to 50 °C and reacted for another 2 h. After the mercapto reaction was completed, the temperature was lowered below 20 °C to obtain the product of formula 1B. Optionally, the mercapto reaction product was acidified for easy structural identification of the product. When used in flotation applications, the product of the mercapto reaction can also be used for flotation treatment without separation or acidification.

[0052] For the synthesis of other optional formula 1A and formula 1C, reference can be made to formula 1B, with the only difference being that the corresponding raw materials of formula 3 are changed. For example, the raw material of formula 3 for synthesizing formula 1A is formula 3B, and the structure is The raw material of formula 3 for synthesizing formula 1C is formula 3C, and the structure is

[0053] In the following examples that can be cited, there is no special requirement for the flotation temperature. For example, it can be room temperature (25 ± 5 °C).

[0054] Example 1 Flotation separation of chalcopyrite and molybdenite with formula 1A

[0055] At a concentration of formula 1A of 5×10 -6 mol·L -1 , with the concentration of the foaming agent methyl isobutyl carbinol (MIBC) being 1×10 - 5 mol / L, the concentration of kerosene being 20 mg / L, the N2 gas flow rate being 200 mL / min, a mixed ore of chalcopyrite with a particle size of 38 - 74 μm and molybdenite < 38 μm (mass ratio 1:1) was flotated for 3 minutes, and the flotation results are shown in Figure 7 . It shows that in the range of pH 3 - 11, the flotation recovery rate of molybdenite is significantly higher than that of chalcopyrite, and formula 1A has achieved excellent molybdenite / chalcopyrite separation efficiency.

[0056] Example 2 Flotation separation of chalcopyrite and molybdenite with formula 1B

[0057] At a concentration of formula 1B of 4×10 -6 mol·L -1 , with the concentration of the foaming agent methyl isobutyl carbinol (MIBC) being 1×10 - 5mol / L, the kerosene concentration is 20 mg / L, the N2 gas flow rate is 200 mL / min, and the mixed ore of chalcopyrite with a particle size of 38 - 74 μm and molybdenite with a particle size of < 38 μm (mass ratio 1:1) is flotated for 3 minutes. The flotation results are shown in Figure 8 . It shows that in the range of pH 3 - 11, the flotation recovery rate of molybdenite is higher than 80%, while the recovery rate of chalcopyrite is lower than 20%. Equation 1B achieves excellent molybdenite / chalcopyrite separation efficiency and also confirms that Equation 1B is an excellent depressant for chalcopyrite.

[0058] Example 3: Flotation separation of chalcopyrite and molybdenite by Equation 1C

[0059] At a concentration of Equation 1C of 6×10 -6 mol·L -1 , the concentration of the foaming agent methyl isobutyl carbinol (MIBC) is 1×10 - 5 mol / L, the kerosene concentration is 20 mg / L, the N2 gas flow rate is 200 mL / min, and the mixed ore of chalcopyrite with a particle size of 38 - 74 μm and molybdenite with a particle size of < 38 μm (mass ratio 1:1) is flotated for 3 minutes. The flotation results are shown in Figure 9 . In the range of pH 3 - 11, the flotation recovery rate of molybdenite is significantly higher than that of chalcopyrite, and Equation 1C achieves excellent molybdenite / chalcopyrite separation efficiency.

[0060] Example 4: Flotation separation of galena and molybdenite by Equation 1B

[0061] At pH = 7.0, the concentration of Equation 1B is 3×10 -6 mol·L -1 , the concentration of the foaming agent methyl isobutyl carbinol (MIBC) is 1×10 -5 mol / L, the kerosene concentration is 20 mg / L, the N2 gas flow rate is 200 mL / min, and the mixed ore of galena and molybdenite with a particle size of < 38 μm (mass ratio 1:1) is flotated for 3 minutes. The recovery rate of molybdenite in the flotation concentrate obtained is 88.4%, and the recovery rate of galena is 14.5%. Therefore, Equation 1B is a highly efficient depressant for the flotation separation of molybdenite / galena, and it shows excellent inhibitory ability for galena.

[0062] Example 5: Flotation separation of molybdenite from copper concentrate by Equation 1B

[0063] The main sulfide minerals in a certain flotation copper concentrate are chalcopyrite and pyrite, and it also contains molybdenite, as well as a small amount of chalcocite, bornite, and enargite. The concentration of this flotation copper concentrate is 24%. After drying, the copper content is measured to be 23.4%, the molybdenum content is 0.45%, and the sulfur content is 34.8%. Take 1 liter of copper concentrate pulp, add an inhibitor (stir for 5 minutes) and 100 g / t of kerosene (stir for 3 minutes) respectively, and then carry out a flotation test. The flotation time is 3 minutes, and the flotation pH = 7.0. The flotation conditions and results are shown in Table 1. Table 1 shows that compared with 2000 g / t of sodium sulfide, 300 g / t of Formula 1B can achieve a better flotation separation effect of molybdenite.

[0064] Table 1 Conditions and Results for Flotation Separation of Molybdenite from Copper Concentrate

[0065]

[0066] From the above case, it can be seen that Formula 1 described in the present invention can effectively inhibit other metal sulfide ores and basically does not inhibit molybdenite. In this way, selective flotation separation of other metal sulfide ores and molybdenite can be achieved. In addition, from Examples 1 to 3, it can be seen that Formula 1 described in the present invention can adapt to the application requirements of a wide pH range. It can obtain good collecting selectivity at a lower dosage. Especially for Formula 1B and inhibitors with similar structures, a better flotation separation effect of other metal sulfide ores and molybdenite can be obtained.

Claims

1. A flotation depressant, characterized in that: is a compound having a structure of Formula 1; The R1 is a substituted alkyl group with an active group; the R2 is H, a sulfonic acid group or a substituent group identical to R1; the active group includes at least one of a hydroxyl group, an amino group, a carboxyl group and a sulfonic acid group; The M1 and M2 are H, Na, K or NH4.

2. The flotation depressant according to claim 1, characterized in that The substituted alkyl group is a group having the active group on the C1-C4 alkyl carbon chain; Preferably, R1 is -CH2OH, -CH2CH2OH, -CH2CH2CH2OH, -CH2COOX, -CH2CH2COOX, -CH2SO3X or -CH2CH2SO3X; Preferably, R2 is H, -CH2OH, -CH2CH2OH, -CH2CH2CH2OH, -CH2COOX, -CH2CH2COOX or -CH2SO3X or -CH2CH2SO3X; X is H, Na or K.

3. The flotation depressant according to claim 2, characterized in that The R1 and R2 are both substituted alkyl groups with active groups, wherein the active groups are preferably hydroxyl groups or carboxyl groups.

4. The flotation depressant according to any one of claims 1 to 3, characterized in that: The compound of formula 2 and the compound of formula 3 are subjected to an amination reaction, followed by a thiolation reaction with a sulfide to obtain the compound; 5. A flotation agent for flotation separation of molybdenite and other metal sulfide ores, comprising a molybdenite collector and a depressant, characterized in that: The depressant comprises the flotation depressant according to any one of claims 1 to 4.

6. The flotation reagent according to claim 5, characterized in that: The flotation reagent is also allowed to contain at least one of a pH regulator, a frother, and other inhibitors.

7. A method for flotation separation of molybdenite and other metal sulfide ores, characterized in that: The minerals to be selected including other metal sulfide ores and molybdenite are mixed with the flotation agent described in any one of claims 5 to 6 for flotation treatment to obtain molybdenite concentrate.

8. The method for flotation separation of molybdenite and other metal sulfide ores according to claim 7, characterized in that: The other metal sulfide ores are sulfide minerals of at least one metal selected from copper, lead and iron, and further selected from at least one selected from chalcopyrite, galena, pyrite and marcasite.

9. The method for flotation separation of molybdenite and other metal sulfide ores according to claim 7 or 8, characterized in that: Based on the weight of the flotation feed ore as the calculation standard, the dosage of the inhibitor is 50-1500 g / t.

10. The method for flotation separation of molybdenite and other metal sulfide ores according to claim 7 or 8, characterized in that: The pH of the flotation pulp is 3-12.

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