Collector, flotation reagent and method for flotation of nickel sulfide ore

Abstract

The present invention belongs to the field of mineral flotation, and specifically discloses a collector, a flotation agent and a method for the flotation of nickel sulfide ore, wherein the steps of the method for the flotation of nickel sulfide ore are as follows: using a flotation agent containing a collector to flotate the ore to be selected containing nickel sulfide ore to obtain a nickel sulfide concentrate; the collector includes at least one of collector a (), collector b (), and collector c (). The collector of the present invention has an excellent collection effect on nickel sulfide ore, especially in terms of low-grade nickel sulfide ore, and can still show excellent collection ability.

Description

Technical Field

[0001] The invention belongs to the flotation reagent technology in the field of mineral processing, and specifically relates to the flotation field of nickel sulfide ore, especially low-grade nickel sulfide ore. Background Art

[0002] Low-grade nickel ore has a high degree of alteration and uneven embedded particle size. Nickel is closely associated with pyrrhotite, pyrite and other minerals, making it difficult to dissociate the monomers. In addition, magnesium silicate gangue minerals have a significant effect on the flotation of nickel, making it a difficult-to-treat nickel sulfide ore.

[0003] At present, the commonly used flotation collectors for nickel sulfide ores are mainly xanthates. For example, the domestic Jinchuan ore dressing plant uses butyl xanthate, while foreign countries mostly use amyl xanthate or isopropyl xanthate. However, the existing collectors have poor flotation effects on low-grade nickel sulfide ores, and it is difficult to effectively improve the nickel recovery rate and concentrate grade. In particular, in the flotation of Jinchuan high-magnesium low-grade nickel sulfide ores, there are problems such as low recovery rate and high magnesium oxide content. It is urgent to develop efficient flotation agents for low-grade nickel sulfide ores.

[0004] There are also some flotation methods for low-grade nickel sulfide ores in the prior art. For example, the Chinese patent document with publication number CN105834006A discloses a beneficiation method for low-grade nickel sulfide ores, which specifically records a scheme for flotation in a system including a pH adjuster, an inhibitor, a collector, and a frother, and further records that the pH adjuster is sodium carbonate, the inhibitor is xanthan gum, the collector is one of ethyl xanthate, butyl xanthate, pentyl xanthate, and Y89 xanthate, and the frother is oil No. 2. For another example, the Chinese patent document with publication number CN114042536A discloses a sulfide ore flotation combination reagent and method, which specifically records that the flotation reagent includes a collector and an adjuster, the collector is a thiol-containing cationic surfactant dodecylamine acetate (Armac C), and the adjuster is ethylenediamine di-o-phenylacetic acid (EDDHA).

[0005] In summary, there is still a lack of efficient and highly selective collectors for low-grade nickel ores in the existing flotation industry. Continuing to use traditional xanthate collectors often makes it difficult to significantly improve the nickel recovery rate, resulting in unsatisfactory flotation effects for nickel sulfide ores and insufficient development and utilization of nickel resources. Summary of the invention

[0006] In view of the technical difficulty that existing collectors are difficult to meet the flotation requirements of low-grade nickel sulfide ores, the present invention provides a method for flotation of nickel sulfide ores, aiming to improve the capture capacity and selectivity of nickel sulfide based on a new collector.

[0007] The second object of the present invention is to provide a collector and a flotation agent for the flotation of nickel sulfide ore.

[0008] For high-grade nickel sulfide ores, effective selective flotation can be achieved through traditional xanthate collectors, while low-grade nickel sulfide ores not only have low nickel content, but also have complex symbiosis with gangue minerals (such as serpentine), which greatly increases the complexity and difficulty of flotation separation. To solve this problem, the present invention has been studied in depth and provides the following solutions:

[0009] A method for flotation of nickel sulfide ore, comprising flotation of the ore to be selected containing the nickel sulfide ore using a flotation reagent containing a collector to obtain a nickel sulfide concentrate;

[0010] The collector includes at least one of collector a, collector b and collector c, wherein collector a is a compound having formula 1, collector b is a compound having formula 2, and collector c is a compound having formula 3 and a salt thereof;

[0011] Formula 1

[0012] Formula 2

[0013] Formula 3

[0014] The R1 is an electron-withdrawing group; the R2 is H, a C1-C6 alkyl group or a C1-C6 alkoxy group;

[0015] The R3 is a C3-C8 alkyl group; the R4 is a C3-C8 alkyl group; and the M is H, Na, K or NH4.

[0016] The research of the present invention shows that the compounds of formula 1 to formula 3 show excellent targeted recognition and capture capabilities for nickel sulfide ore, and can effectively improve the capture efficiency and selectivity of nickel sulfide ore, especially for low-grade nickel sulfide ore, which can show greater flotation advantages compared with conventional collectors.

[0017] In Formula 1 of the present invention, the combination of the benzene ring and the special group at the meta position of the benzene ring (such as the α-electron-withdrawing R1 amide group and CONCSS-) is the key to achieving intramolecular synergy and improving the capture capacity of nickel sulfide ore.

[0018] Furthermore, in Formula 1 of the present invention, R1 is a conventional electron-withdrawing group, such as cyano, nitro or trifluoromethyl. R2 can further be H.

[0019] In the present invention, the combination of Formula 2, Formula 3 and their special coupling groups is the key to synergistically improving the capture capacity and selectivity of nickel sulfide. Furthermore, the alkyl group in R2 and R3 can be a straight chain or branched chain alkyl group with the carbon number.

[0020] In the present invention, the formula 3 may be a free compound of the structure and a salt thereof, and the salt may be at least one of a hydrochloride, a sulfate, and an organic acid salt.

[0021] In the present invention, the collector at least comprises collector a. Among them, the optional schemes include: Scheme a, the collector is a binary composite collector comprising collector a and collector b. Scheme b, the collector is a binary composite collector comprising collector a and collector c. Scheme c, the collector is a ternary composite collector comprising collector a, collector b, and collector c.

[0022] The binary or ternary composite collector formed by the combination of the present invention, especially the ternary collector, can further enhance the molecular synergy between the collectors, and can obtain better capture capacity and selectivity of nickel sulfide ore at the same or even lower dosage.

[0023] In the present invention, in scheme a, the weight ratio of collector a to collector b can be 1:0.5 to 5, and further can be 1:1 to 3. In the preferred scheme b, the weight ratio of collector a to collector c can be 1:0.5 to 5, and further can be 1:1 to 3.

[0024] In the preferred scheme c of the present invention, the collector comprises collector a, collector b and collector c in a weight ratio of 1-3:1-3:1-3.

[0025] In the present invention, the amount of the collector used in the flotation stage is 40-240 g / t, further 50-200 g / t, and further 60-180 g / t.

[0026] The flotation reagent of the present invention, in addition to the collector of the present invention, other components and dosages thereof can be adjusted based on conventional principles and means.

[0027] In the present invention, the flotation reagent further comprises at least one flotation aid selected from the group consisting of an activator, an inhibitor and a frother.

[0028] In the present invention, the activator includes at least one of oxalic acid, calcium oxide, sodium sulfide, copper sulfate and calcium chloride.

[0029] In the present invention, the inhibitor includes at least one of carboxymethyl cellulose, sodium hexametaphosphate, dextrin, citric acid, water glass, lignin, guar gum, and causticized starch.

[0030] In the present invention, the foaming agent includes at least one of terpineol, methyl isobutyl carbinol, polyethylene glycol ether and cresol oil.

[0031] In the present invention, the flotation aid may optionally include a depressant and an activator, wherein the depressant is used in an amount of 50-500 g / t, further 100-300 g / t, and further 150-250 g / t; the activator is used in an amount of 100-1200 g / t, further 150-300 g / t.

[0032] The flotation method of the present invention benefits from the use of the collector, which not only has an excellent targeting effect on nickel sulfide ores, but also has a certain foaming property, and can obtain a good flotation effect without using an additional foaming agent.

[0033] In the present invention, there is no particular requirement for the pH value in the flotation stage, and the pH value may be, for example, 6 to 10, which is particularly suitable for industrial use, or may be 7.5 to 9.5.

[0034] In the present invention, the flotation method can be applied to any nickel grade of the selected minerals, but in order to maximize the flotation value, the selected minerals are particularly selected from low-grade nickel sulfide ores with a nickel content of less than 0.7 Wt.% (for example, 0.1-0.7 Wt.%, and further 0.5-0.7 Wt.%).

[0035] In the present invention, the gangue of the mineral to be selected may be magnesium-containing gangue, for example, may further be serpentine.

[0036] In the present invention, based on the flotation method, the flotation separation of nickel sulfide ore and magnesium-containing gangue can be achieved.

[0037] In the present invention, in addition to selecting the collector of the present invention, the other operations, parameters and equipment of the flotation method can be reasonably adjusted according to conventional principles and methods.

[0038] The present invention also provides a collector for flotation of nickel sulfide ore, wherein the collector comprises at least one of the collector a, collector b and collector c. Preferably, the collector comprises at least collector a; more preferably, a binary composite collector comprising collector a and collector b; or a binary composite collector comprising collector a and collector c; or a ternary composite collector comprising collector a, collector b and collector c. When the weight ratio of collector a to collector b in the binary composite collector is 1:0.5~5, further can be 1:1~3; or, the weight ratio of collector a to collector c is 1:0.5~5, further can be 1:1~3. In the ternary collector, the weight ratio of collector a, collector b and collector c is 1~3:1~3:1~3.

[0039] The present invention also provides a flotation reagent for flotation of nickel sulfide ore, wherein the flotation reagent comprises the collector of the present invention.

[0040] Beneficial Effects

[0041] The present invention shows that the special functional structural units of formula 1 to formula 3 (such as the benzene ring, the α-electron-withdrawing R1 amide group at the meta position of the benzene ring and the functional structural unit of CONCSS in formula 1, the functional structural unit of CSNCSS in formula 2, and the functional structural unit of OCSNCON in formula 3) can achieve intramolecular synergy and optimize the targeting ability and selectivity of nickel sulfide ore. In particular, the combination of binary and ternary compounds of formula 1 to formula 3 can further enhance the capture ability and selectivity of nickel sulfide ore based on the multiple targeting effects of different functional structural units of various collectors.

[0042] The present invention has mild flotation conditions, simple flotation procedures, and low flotation reagent dosage, thus meeting the requirements for industrial flotation applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is the flotation flow chart of Example 1. DETAILED DESCRIPTION

[0044] In the present invention, the compound of formula 1 is typically exemplified by formula 1-A, and its specific structure is:

[0045] Formula 1-A

[0046] The compound of formula 2 is typically exemplified by formula 2-A, and its specific structure is:

[0047] Formula 2-A

[0048] The compound of formula 3 is typically exemplified by formula 3-A, and its specific structure is:

[0049] Formula 3-A

[0050] Comparative structural compounds, the specific structure is:

[0051] Formula 1-a

[0052] Formula 1-b

[0053] Formula 1-c

[0054] Formula 2-a

[0055] Formula 2-b

[0056] Formula 3-a

[0057] The flotation ore described in the present invention can be any grade of nickel sulfide ore, but in order to further verify the flotation effect of the collector of the present invention, low-grade nickel sulfide ore is specially selected for experiment. For example, as an optional scheme, this study uses the lean ore of Jinchuan No. 2 Mining Area, and its composition is listed in the case described below.

[0058] In the following cases, the dosage unit of the reagent is g / t, which refers to the gram weight of the flotation reagent added per ton of the mineral to be selected.

[0059] The present invention is based on conventional flotation methods and principles, and uses the collector of the present invention to carry out flotation experiments on ore. As one of the optional implementation schemes, the specific flotation operation process is as follows:

[0060] The effect of the collector of the present invention was verified by using a two-stage closed-circuit flotation process. Figure 1 This is a closed-circuit flotation flow chart. The specific operation steps are:

[0061] Step 1, grinding: 500 g of low-grade nickel sulfide ore (Ni grade of 0.67 ± 0.009 wt.%) was weighed for each closed-circuit flotation experiment, and the ore was ground to a particle size of -0.074 mm for 70%.

[0062] Step 2: In a flotation process, add sodium hexametaphosphate inhibitor, copper sulfate activator and collector in sequence (see specific case). The dosage and slurry mixing time are as follows: Figure 1 After the addition of chemicals, 12 minutes of scavenging, 7 minutes of concentration and 4 minutes of concentration were carried out to obtain concentrate 1.

[0063] Step 3: In the second stage flotation operation, the pulp obtained from the first stage flotation is re-grinded to make 85% of the particles have a particle size of -0.074 mm, and then the dosing operation is repeated, and the order is the same as that of sodium hexametaphosphate inhibitor, copper sulfate activator and collector. The dosage and pulping time are as follows: Figure 1 After the dosing is completed, two concentrations of 6 minutes and 3 minutes are carried out to obtain concentrate 2; and two scavengings of 6 minutes and 4 minutes are carried out to obtain tailings. The closed-circuit flotation finally obtains concentrate 1, concentrate 2 and tailings.

[0064] Step 4: Result analysis:

[0065] Each closed-circuit flotation group reaches equilibrium after 2 cycles, and the results of the embodiment are the average values ​​of 3-5 cycles. Two groups of flotation experiments were conducted in each case, with the same conditions and only different collectors. The effect of the collector of the present invention was evaluated by comparing the nickel grade and recovery rate of concentrate 1 and concentrate 2.

[0066] The pH value in the flotation stage is a neutral condition which is more practical in industrialization, and as an option, it can be 9±0.3.

[0067] In the above Figure 1 Based on the flotation of the samples, the collectors and conditions of each case were adjusted. The steps and results were as follows:

[0068] Example 1 - Single Collector Solution

[0069] The collector is a single collector, and the experimental groups are:

[0070] Group A: The collector is of formula 1-A;

[0071] Group B: Collector is Formula 2-A;

[0072] Group C: The collector is Formula 3-A;

[0073] Comparative group a: the collector is formula 1-a;

[0074] Comparative group b: the collector is formula 1-b;

[0075] Comparative group c: the collector is formula 1-c;

[0076] Comparative group d: the collector is formula 2-a;

[0077] Comparative group e: the collector is formula 2-b;

[0078] Comparative group f: the collector is formula 3-a;

[0079] Comparative group g: the collector is sodium butyl xanthate;

[0080] The results of each group are shown in Table 1 and Table 2:

[0081]

[0082]

[0083] It can be seen from the results of Example 1 that the use of the collectors of Formula 1-Formula 3 of the present invention can effectively adapt to the characteristics of low-grade nickel sulfide ores and significantly improve the collection effect. Further, by comparing Group A in Example 1 with Comparative Group ac, it is shown that the functional structural units of the α-electron-withdrawing R1 amide group and CONCSS- in the benzene ring and the meta-position of the benzene ring in the collector of Formula 1 can enhance the performance of the collector. By comparing Group B in Example 1 with Comparative Group de, it is shown that the functional structural unit of CSNCSS in the collector of Formula 2 helps to enhance the collection capacity of nickel sulfide ores. In addition, by comparing Group C in Example 1 with Comparative Group f, it is shown that the OCSNCON functional unit in the collector of Formula 3 can enhance the collection capacity of nickel sulfide ores.

[0084] Example 2 - Binary Collector Solution

[0085] Compared with Example 1, the only difference is that the collector is changed to a binary composite collector. The experimental groups are:

[0086] Group A: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:1;

[0087] Group B: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:2;

[0088] Group C: The collectors are Formula 1-A and Formula 3-A in a weight ratio of 1:1;

[0089] D: Collectors are Formula 2-A and Formula 3-A in a weight ratio of 1:1;

[0090] The results of each group are shown in Table 3:

[0091]

[0092] From the comparison between Example 1 and Example 2, it is found that the combination of Formula 1 to Formula 3, especially the combined use of Formula 1 and Formula 2, can further exert a synergistic effect, is more suitable for the characteristics of low-grade nickel sulfide ore, and can achieve better capture performance.

[0093] Example 3-Ternary Collector Solution

[0094] Compared with Example 1, the only difference is that the collector is changed to a ternary composite collector. The experimental groups are:

[0095] Group A: Collectors are Formula 1-A, Formula 2-A and Formula 3-A in a weight ratio of 1:1:1;

[0096] Group B: Collectors are Formula 1-A, Formula 2-A and Formula 3-A in a weight ratio of 2:1:1;

[0097] Group C: Collectors are Formula 1-A, Formula 2-A and Formula 3-A in a weight ratio of 1:2:1;

[0098] Group D: Collectors are Formula 1-A, Formula 2-A and Formula 3-A in a weight ratio of 1:1:2;

[0099] The results of each group are shown in Table 4:

[0100]

[0101] The experimental results of Examples 1 to 3 show that the combined use of Formula 1, Formula 2, and Formula 3 can significantly enhance the synergistic effect and further improve the capture effect of low-grade nickel sulfide ore.

[0102] Example 4

[0103] Compared with Example 3B, the difference is that the dosage of the collector is changed, and the experimental groups are:

[0104] Group A: The collectors are Formula 1-A, Formula 2-A and Formula 3-A in a weight ratio of 2:1:1, and the dosage of the collectors in the first and second roughing is 60 g / t and 80 g / t respectively;

[0105] Group B: The collectors are Formula 1-A, Formula 2-A and Formula 3-A in a weight ratio of 2:1:1, and the dosage of the collectors in the first and second roughing is 100 g / t and 80 g / t respectively;

[0106] Group C: The collectors are Formula 1-A, Formula 2-A and Formula 3-A in a weight ratio of 2:1:1, and the amounts of collectors used in the first and second roughing are 120 g / t and 80 g / t respectively;

[0107] The results of each group are shown in Table 5:

[0108]

[0109] The results of Examples 3 and 4 show that even under the condition of lower collector dosage, the combined use of Formula 1, Formula 2 and Formula 3 can still show excellent collection ability for low-grade nickel sulfide ore.

Claims

1. A method for flotation of nickel sulfide ore, wherein a flotation agent containing a collector is used to flotate the ore to be selected containing nickel sulfide ore to obtain a nickel sulfide concentrate; characterized in that: The collector includes at least one of collector a, collector b and collector c, wherein collector a is a compound having formula 1, collector b is a compound having formula 2, and collector c is a compound having formula 3 and a salt thereof; Formula 1; Formula 2; Formula 3; The R1 is an electron-withdrawing group; the R2 is H, a C1-C6 alkyl group or a C1-C6 alkoxy group; The R3 is a C3-C8 alkyl group; the R4 is a C3-C8 alkyl group; and the M is H, Na, K or NH4.

2. The method according to claim 1, characterized in that The collector at least comprises collector a.

3. The method according to claim 2, characterized in that The collector comprises collector a and collector b in a weight ratio of 1:0.5-5; or comprises collector a and collector c in a weight ratio of 1:0.5-5.

4. The method according to claim 2, characterized in that The collector comprises collector a, collector b and collector c in a weight ratio of 1-3:1-3:1-3.

5. The method according to any one of claims 1 to 4, characterized in that The dosage of collector in the flotation stage is 40~240 g / t.

6. The method according to any one of claims 1 to 4, characterized in that The flotation reagent also includes at least one flotation aid selected from the group consisting of an activator, an inhibitor and a frother.

7. The method according to claim 6, characterized in that The activator comprises at least one of oxalic acid, calcium oxide, sodium sulfide, copper sulfate and calcium chloride; The inhibitor comprises at least one of carboxymethyl cellulose, sodium hexametaphosphate, dextrin, citric acid, water glass, lignin, guar gum, and causticized starch; The foaming agent comprises at least one of terpineol, methyl isobutyl carbinol, polyethylene glycol ether and cresol oil.

8. The method according to claim 7, characterized in that The flotation aid comprises an inhibitor and an activator, wherein the amount of the inhibitor is 50-500 g / t, and the amount of the activator is 100-1200 g / t; The pH value in the flotation stage is 6~10.

9. A collector for flotation of nickel sulfide ore, characterized in that: It is the collector described in the method according to any one of claims 1 to 8.

10. A flotation agent for flotation of nickel sulfide ore, characterized in that: It is the flotation agent described in the method according to any one of claims 1 to 8.

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