Composite flotation reagent, composite collector and application thereof in flotation of refractory nickel sulfide ore

Abstract

The present application belongs to the field of mineral flotation, and particularly relates to a composite collector, which comprises compound A, compound B and compound C; wherein the compound A is a compound with the structure of formula 1, the compound B is a compound with the structure of formula 2, and the compound C is a sulfide ore collector. The present application also comprises a flotation reagent comprising the composite collector and the application thereof. Researches of the present application show that the composite collector can improve the mineral collecting effect, and particularly for the refractory nickel sulfide ore, the composite collector still has excellent collecting capacity.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of mineral processing, and particularly relates to a collector for nickel sulfide ore. BACKGROUND

[0002] Nickel is an important non-ferrous metal. With the rapid development of industries that consume a large amount of nickel, such as alloy, electroplating, catalysis, battery, and national defense equipment, the global demand for nickel is increasing. Nickel sulfide ore is an important source of nickel resources in China. More than two-thirds of industrial nickel raw materials in China come from nickel sulfide ore.

[0003] The annual consumption of nickel sulfide in China is increasing, resulting in a decrease in the reserves of easily selected nickel sulfide ore. The proportion of lean ore in the raw ore of nickel sulfide ore flotation is increasing year by year. In the process of ore rock formation, mining, crushing, transportation, and grinding, the nickel-containing minerals in the lean nickel sulfide ore are easily oxidized to form hydroxides and sulfates, etc. Therefore, the floatability of the ore and the adsorption of the collector on the mineral surface decrease, making it difficult to float. At present, the traditional flotation collector (such as ammonium black drug) for nickel sulfide ore is used for the flotation process of lean nickel sulfide ore, which is difficult to achieve efficient flotation of nickel sulfide ore with high surface oxidation. Due to the difficulty of traditional flotation reagents to efficiently collect high-oxidation difficult nickel sulfide ore, acid method and sulfidation flotation process have also been applied on a large scale. Acid flotation adjusts the pH value of the ore slurry to below 4 by adding strong acid to dissolve the oxidation film on the surface of the nickel sulfide ore, which has obvious effect, but also has the defects that are difficult to overcome: the addition of acid leads to the release of toxic hydrogen sulfide gas, corrosion of equipment, and increase in process cost of tailings treatment and wastewater reuse. Sulfidation flotation uses sodium sulfide and other sulfur-containing reagents to generate a hydrophobic sulfide film on the surface of the mineral, improving the floatability of the difficult nickel sulfide ore. The sulfidation method has the following defects: 1. Large consumption of reagents; 2. Significant change in ore slurry properties; 3. A large amount of gangue minerals are activated after addition, and a large amount of sulfides are generated in the slurry, which enter the concentrate in the concentration process, affecting the nickel grade of the concentrate.

[0004] In summary, changing the flotation process cannot completely solve the bottleneck problem of the flotation of difficult nickel sulfide ore. Therefore, in order to achieve efficient flotation of difficult nickel sulfide ore, it is urgent to develop a high-efficiency collector for the flotation of difficult nickel sulfide ore. SUMMARY

[0005] The first object of the present application is to provide a flotation composite collector, which aims to provide a synergistic collector with excellent collecting ability for sulfide ore, especially difficult nickel sulfide ore.

[0006] The second object of the present application is to provide a flotation reagent containing the flotation composite collector and its application in nickel sulfide ore, especially in difficult nickel sulfide ore.

[0007] The higher the surface oxidation degree of the poor nickel sulfide ore is, the more difficult the flotation is; in view to the problem that the selectivity and recovery rate of the existing flotation reagent for the poor nickel sulfide ore are not high, the application provides the following scheme:

[0008] A composite collector comprises compound A, compound B and compound C.

[0009] The compound A is a compound with the structure of formula 1, the compound B is a compound with the structure of formula 2, and the compound C is a sulfide ore collector.

[0010] The compound C is a sulfide ore collector.

[0011]

[0012] The n is 1-6, and the M1, M2, M3 and M4 are independently H, Na, K or NH4.

[0013] The R1 is H, C1-C6 alkyl or C1-C6 alkoxy.

[0014] The R2 is C1-C6 alkyl.

[0015] The alkyl or alkoxy alkyl chain can be provided with a substituent, and the substituent is a hydroxyl, halogen, alkoxy, phenyl, ester group or amide group.

[0016] The researches of the application show that the component A with the structure of formula 1 and the component B with the structure of formula 2 are combined in the conventional sulfide ore collector (component C), so that the synergistic effect can be unexpectedly achieved, the collecting effect can be significantly strengthened, and excellent collecting capacity can be obtained for the poor nickel sulfide ore which is difficult to be floated in the industry.

[0017] In the application, the combination of the component A, the component B and the component C is the key to solve the collecting capacity of the poor nickel sulfide ore.

[0018] In the application, in the formula 1, the n is 2-4, preferably 3. The researches show that the preferred compound A can have a more suitable synergistic effect with other components, and is helpful to further improve the flotation capacity of the poor nickel sulfide ore.

[0019] In the application, in the formula 2, the R1 is at the para position of P.

[0020] Preferably, the R1 is C1-C6 alkoxy.

[0021] Preferably, the R2 is C1-C6 alkyl.

[0022] In the present application, the compound C can be a collector for sulfide ore known in the industry, and in an embodiment of the present application, the compound C is a collector for nickel sulfide ore.

[0023] Preferably, the compound C is a compound having the structure of formula 3:

[0024]

[0025] M5 is H, Na, K or NH4; R3 and R4 are independently C2-C8 alkyl.

[0026] The weight ratio of the compound A, the compound B and the compound C in the composite collector of the present application is 15-40:40-70:10-25; preferably 20-36:40-70:10-25; and further preferably 22-32:44-64:14-20.

[0027] The present application shows that, under the combination of the compounds A-C, and further in combination with the joint control of the component ratio, the synergy can be unexpectedly achieved, which helps to further improve the collecting ability of the mineral, especially the refractory nickel sulfide ore.

[0028] In the present application, the compound A, the compound B and the compound C can be mixed based on the conventional composite mode.

[0029] The present application also provides a flotation reagent comprising the composite collector.

[0030] The flotation reagent of the present application further comprises a frother;

[0031] In the present application, the type of the frother is not particularly limited, and for example, at least one of sec-octyl alcohol, methyl isobutyl propyl alcohol, pine oil, dimethyl benzyl alcohol can be included.

[0032] In the composite flotation reagent of the present application, the mass ratio of the composite flotation collector to the frother can be 1.5:1-5:1; and further preferably 2.5:1-3.5:1.

[0033] In the present application, the flotation reagent further comprises a pH adjusting agent and other components allowed to be added in the flotation process. The amount of the pH adjusting agent can be controlled according to the flotation condition, for example, it can control the pH of the flotation stage under the conditions of allowed acidity, neutrality and alkalinity.

[0034] The present application also provides a flotation method for nickel sulfide ore, which uses the composite collector of the present application or the flotation reagent comprising the composite collector of the present application.

[0035] The composite collector can be applied to the flotation of any nickel sulfide ore, but considering the excellent synergistic effect of the composite collector, it is particularly suitable for the refractory nickel sulfide ore which is difficult to float in the industry, so that greater economic value can be obtained.

[0036] In the present application, the refractory nickel sulfide ore can be further a surface-oxidized nickel-containing sulfide mineral. Further, it refers to the mineral that the surface of the nickel sulfide ore generates hydrophilic hydroxide and sulfate under the action of oxygen and water.

[0037] In the present application, the amount of the composite collector used in the flotation stage can be reasonably adjusted according to the mineral grade, for example, it can be 100-300 g / t.

[0038] Preferably, the pH in the flotation stage is 3-12, preferably 4-11, and further preferably 6.5-7.5. The composite collector described in the present application can obtain good flotation effect under different flotation pH conditions, especially in the neutral system which is difficult to effectively float in the industry, and still can obtain excellent flotation effect.

[0039] In the present application, the flotation collector described in the present application can be used for flotation based on conventional means and principles. For example, the mineral to be selected can be slurried, and the reagent containing the composite collector can be added before, during or after the slurry, and the slurry flotation treatment can be carried out.

[0040] In the present application, the rotation speed of the flotation machine is in the range of 1800-2000 r / min.

[0041] Advantages

[0042] The flotation composite collector of the combination of compound A, compound B and compound C can effectively improve the flotation performance of nickel sulfide ore, especially the refractory nickel sulfide ore. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 It is the flotation flowchart of Example 5. DETAILED DESCRIPTION

[0044] The present application will be described in detail below in combination with examples.

[0045] The present application can be applied to any nickel sulfide ore, but in order to further prove the advantages of the scheme described in the present application in the difficult-to-treat nickel sulfide ore, the present application takes the refractory nickel sulfide ore (such as surface-oxidized sulfide ore) as an illustrative embodiment for research. In the following cases, unless otherwise stated, the refractory nickel sulfide ore mineral refers to the nickel sulfide ore which is naturally oxidized for more than 20 hours (specifically for 20-30 hours in the following cases) at normal temperature and pressure.

[0046] Example 1

[0047] This example uses a composite flotation reagent for single mineral flotation of refractory nickel sulfide lean ore;

[0048] The composite collector in this example includes compound A, compound B and compound C, which are floated with different composite collectors 1#-4#, the conditions of each group of flotation process are the same, the only difference is the proportion of the composition of the compound, and the difference in the flotation ability of the composite collector with different proportion is investigated.

[0049] Compound A

[0050] Compound B

[0051] Collector C: butyl ammonium black

[0052] Composite collector 1#: compound A 22 parts, compound B 64 parts, compound C 14 parts.

[0053] Composite collector 2#: compound A 24 parts, compound B 60 parts, compound C 16 parts.

[0054] Composite collector 3#: compound A 28 parts, compound B 54 parts, compound C 18 parts.

[0055] Composite collector 4#: compound A 32 parts, compound B 48 parts, compound C 20 parts.

[0056] The single mineral flotation of refractory nickel sulfide lean ore is carried out by the following steps: 2g of high surface oxidation degree nickel sulfide ore is put into a 45mL flotation tank, 40mL of deionized water is added, stirring at 1900r / min for 3min, adjusting the pH to 7, adding collector 200mg / L, stirring for 3min, adding frother 67mg / L, stirring for 3min, and then floating for 3min. The froth product after flotation is filtered, dried and weighed.

[0057] Table 1 is the flotation results of refractory nickel sulfide lean ore under different component proportions of composite collector

[0058] Table 1

[0059]

[0060] As can be seen from Table 1, different proportions of composite collector can achieve high flotation recovery rate for refractory nickel sulfide lean ore. Considering comprehensively, 3# flotation is better, and the component proportion of 3# composite collector is used as the subsequent experiment.

[0061] Example 2

[0062] This embodiment uses different types of compound A in the composite collector to float the refractory nickel sulfide lean ore. The same experimental procedure as in Example 1 (specifically, Group 3) is used, and the only difference is that the type of compound A is different, so as to investigate the optimal type of compound A in the composite collector.

[0063]

[0064] Table 2 is the flotation results of the refractory nickel sulfide lean ore under different types of compound A in the composite collector

[0065] Table 2

[0066]

[0067] As can be seen from Table 2, different types of compound A can achieve good flotation results for the refractory nickel sulfide lean ore, and the recovery rate is more than 80%. It shows that different types of compound A can efficiently float the refractory nickel sulfide lean ore, and the type of compound A has little effect on the flotation performance of the composite collector. Considering comprehensively, the compound of formula 1-b is preferred for subsequent experiments.

[0068] Example 3

[0069] This embodiment uses different proportions of composite collectors and frothers in the composite flotation reagent to float the refractory nickel sulfide lean ore. The same experimental procedure as in Example 1 (specifically, Group 3) is used, and the only difference is that the proportion of composite collectors and frothers is 2.5:1, 3.0:1 and 3.5:1 respectively. Thus, the flotation effect under different proportions of composite collectors and frothers is investigated.

[0070] Table 3 is the recovery rate of the refractory nickel sulfide lean ore under different proportions of composite collectors and frothers

[0071]

[0072] As can be seen from Table 3, when the proportion of composite collectors and frothers is 3.0:1, the highest flotation recovery rate can be achieved, and increasing or decreasing the proportion of the two will reduce the recovery rate of the concentrate. The appropriate proportion is more conducive to the flotation of the refractory nickel sulfide lean ore. Considering comprehensively, the proportion of 3.0:1 of the composite collector and the frother is preferred, which is used for subsequent experiments.

[0073] Example 4

[0074] This embodiment uses different pH values of the flotation slurry to float the refractory nickel sulfide lean ore. The same experimental procedure as in Example 1 (3#) is used, and the only difference is that the flotation pH is different, so as to investigate the flotation effect of the composite collector under different pH values.

[0075] Table 4 Recovery of refractory nickel sulphide lean ore using composite collector at different pH

[0076]

[0077] As can be seen from Table 4, the composite collector has strong collecting ability for the refractory nickel sulphide lean ore in a large pH range, and does not depend on acidic conditions. In order to reduce the amount of reagent used and harm to the environment, a pH of 7 is preferred for subsequent experiments.

[0078] Example 5

[0079] In this example, the composite collector (3# of Example 1) was used for the flotation of a refractory nickel sulphide lean ore actual mine.

[0080] Figure 1 The flotation experiment process is shown in Figure 1. The specific implementation is as follows:

[0081] The raw ore was first broken and ball milled to 75% passing 0.074 mm. In the first stage of flotation, 100 g / t of copper sulphate was added, stirred for 2 min, 150 g / t of composite collector was added, stirred for 2 min, 50 g / t of frother was added, stirred for 2 min, and then roughing, cleaning and scavenging were carried out for 10 min, 8 min and 8 min respectively to obtain concentrate 1. In the second stage of flotation, the ore slurry from the first stage was re-ground for about 5 min to make 95% of the mineral particles less than 0.074 mm, and then the reagents were added in turn. 80 g / t of copper sulphate was added, stirred for 2 min, and 100 g / t of composite collector was added, stirred for 2 min. After the addition of reagents was completed, roughing, cleaning and scavenging were carried out for 10 min, 6 min and 3 min respectively to obtain concentrate 2, and for 6 min and 4 min respectively to obtain tailings.

[0082] The examples were all closed-circuit floated to equilibrium, and the closed-circuit experimental results are as follows:

[0083] Table 5 Closed-circuit experimental results using composite flotation reagents:

[0084]

[0085] The total concentrate Ni, Cu grade was 6.38%, 4.91% respectively, the total concentrate Ni, Cu recovery was 77.23%, 79.66% respectively; the total concentrate MgO grade was 6.55%; the tailings Ni, Cu grade was 0.15%, 0.10% respectively.

[0086] Comparative Example 1

[0087] The process flow is the same as that of Example 1 #3, except that the composite collector is changed to a single compound C (the amount is the same as that of the composite collector of Example 1 #3). The single mineral flotation process of the refractory nickel sulfide lean ore is the same as that of the example. The experimental results are shown in Table 6.

[0088] Comparative Example 2

[0089] The process flow is the same as that of Example 1 #3, except that the composite collector is changed to a single compound B (the amount is the same as that of the composite collector of Example 1 #3). The single mineral flotation process of the refractory nickel sulfide lean ore is the same as that of the example. The experimental results are shown in Table 6.

[0090] Comparative Example 3

[0091] The process flow is the same as that of Example 1 #3, except that the composite collector is changed to a single compound A (the amount is the same as that of the composite collector of Example 1 #3). The single mineral flotation process of the refractory nickel sulfide lean ore is the same as that of the example. The experimental results are shown in Table 6.

[0092] Comparative Example 4

[0093] The process flow is the same as that of Example 1 #3, except that the composite collector is changed to a single compound A (the amount is the same as that of the composite collector of Example 1 #3). The single mineral flotation process of the refractory nickel sulfide lean ore is the same as that of the example. The experimental results are shown in Table 6.

[0094] Comparative Example 5

[0095] The process flow is the same as that of Example 1 #3, except that the composite collector is changed to a single compound A (the amount is the same as that of the composite collector of Example 1 #3). The single mineral flotation process of the refractory nickel sulfide lean ore is the same as that of the example. The experimental results are shown in Table 6.

[0096] Comparative Example 6

[0097] The process flow is the same as that of Example 1 #3, except that the composite collector is changed to a single compound A (the amount is the same as that of the composite collector of Example 1 #3). The single mineral flotation process of the refractory nickel sulfide lean ore is the same as that of the example. The experimental results are shown in Table 6.

[0098] Table 6 Experimental results of Comparative Examples 1-6

[0099]

[0100] As can be seen from Table 6, only the conventional collector of compound C, i.e. nickel sulfide concentrate, is used in Comparative Example 1, and only a recovery rate of 43.13% can be obtained, which indicates that the conventional collector of nickel sulfide concentrate cannot realize the flotation recovery of the high oxidation degree nickel sulfide lean ore.

[0101] When the different component allocation ratios of the composite collector are changed, the results are as follows:

[0102] 1. Comparative Examples 1-3 all use single collectors, and only a recovery rate of 40%-50% can be obtained, which cannot meet the development demand for nickel metal.

[0103] 2. When a component in the composite collector is removed (Comparative Examples 4-6), a recovery rate of 63%-71% can be obtained, which is lower than the recovery rate of more than 80% obtained by using the composite collector in Example 1, which indicates that the remaining components are difficult to achieve a relatively ideal recovery rate.

[0104] The components of the composite collector in the present application have a synergistic effect, and are suitable for different regions of the high oxidation degree nickel sulfide lean ore, i.e. the characteristic region of the completely oxidized sulfide ore and the characteristic region of the oxidized ore, and the collectors on the mineral surface interact with each other, so that the reagent can be adsorbed in the sulfidation region and the oxidation region, thereby improving the flotation recovery rate of the high oxidation degree nickel sulfide lean ore.

[0105] Comparative Example 7

[0106] The process flow is the same as that of Example 4, and the only difference is that the composite collector is changed.

[0107] The collector of the present comparative example is a conventional nickel sulfide concentrate mixed collector; according to weight, 66 parts of ethyl xanthate and 33 parts of butyl ammonium black medicine are mixed.

[0108] The single mineral flotation process of the refractory nickel sulfide lean ore is the same as that of the example. The experimental results are shown in Table 7.

[0109] Table 7 Recovery rate of the refractory nickel sulfide lean ore using the conventional nickel sulfide concentrate mixed collector under different pH

[0110]

[0111] As can be seen from Table 7, the conventional nickel sulfide concentrate mixed collector can only achieve a relatively high recovery rate under acidic conditions, and with the increase of pH, the recovery rate of nickel sulfide is significantly reduced, and only a recovery rate of 43.76% can be obtained under neutral conditions. In order to achieve the required recovery rate, the flotation can only be carried out under acidic conditions, which brings risks to the equipment and environment and the operating personnel.

[0112] Comparative Example 8

[0113] Except that the composite flotation reagent is replaced by the site reagent, the rest is consistent with Example 5. Figure 1 The flotation experiment is carried out according to the flotation experiment procedure, and the results are shown in Table 8

[0114] Table 8: Closed-circuit experiment results obtained using site flotation reagents

[0115]

[0116] The total concentrate Ni and Cu grades are 6.2% and 4.72% respectively, the total concentrate Ni and Cu recovery rates are 75.66% and 77.51% respectively, the total concentrate MgO grade is 7.06%, and the tailings Ni and Cu grades are 0.16% and 0.11% respectively.

[0117] During the transportation, crushing and flotation process of the actual mine, the actual mine is oxidized to different degrees. According to the flotation results obtained in Example 5 and Comparative Example 7, under the condition that the dosage of the collector is the same, compared with the site reagent group, the total concentrate nickel and copper grades are increased by 0.18 and 0.19 percentage points respectively, the total concentrate MgO grade is reduced by 0.51 percentage points, the nickel and copper recovery rates are increased by 1.57 and 2.15 percentage points respectively, and the tailings nickel and copper contents are reduced by 0.01 percentage points respectively. It is proved that the composite flotation reagent of the present application can be well applied in the actual mine.

[0118] In summary, the composite flotation reagent of the present application can exhibit good collecting capacity for refractory nickel sulfide lean ore, and can achieve better flotation separation effect under neutral conditions. It can efficiently and greenly float the nickel sulfide lean ore.

Claims

1. A composite collector, characterized in that: Including compound A, compound B and compound C; Wherein, the compound A is a compound having a structure of formula 1, the compound B is a compound having a structure of formula 2, and the compound C is a sulfide ore collector; Formula 1 Formula 2 Said n is 2-4, said M1, M2, M3, M4 are independently H, Na, K or NH4; The R1 is H, C1~C6 alkyl or C1~C6 alkoxy; The R2 is a C1~C6 alkyl group; The alkyl or alkoxy alkyl carbon chain is allowed to have a substituent, and the substituent is a hydroxyl group, a halogen group, an alkoxy group, a phenyl group, an ester group or an amide group; The weight ratio of compound A, compound B and compound C is 20-36:40-70:10-25.

2. The composite collector according to claim 1, wherein In the formula 1, n is 3.

3. The composite collector according to claim 1, wherein In the formula 2, the R1 is in the para position.

4. The composite collector according to claim 3, wherein In the formula 2, R1 is a C1~C6 alkoxy group.

5. The composite collector according to claim 4, wherein In the formula 2, R2 is a C1~C6 alkyl group.

6. The composite collector according to claim 1, wherein Compound C is a collector for nickel sulfide ores.

7. The composite collector according to claim 6, wherein The compound C is a compound having a structure of formula 3: Formula 3 The M5 is H, Na, K or NH4; and the R3 and R4 are each a C2-C8 alkyl group.

8. The composite collector according to any one of claims 1 to 7, wherein The weight ratio of compound A, compound B and compound C is 22-32:44-64:14-20.

9. A flotation reagent comprising the composite collector according to any one of claims 1 to 8.

10. The flotation reagent according to claim 9, characterized in that Also contains a foaming agent.

11. The flotation reagent according to claim 10, characterized in that The foaming agent comprises at least one of octanol, methyl isobutyl propanol, pine oil and dimethyl benzyl alcohol.

12. The flotation reagent according to claim 10, characterized in that The mass ratio of the composite collector to the foaming agent is (1.5:1)~(5:1).

13. The flotation reagent according to claim 12, wherein The mass ratio of the composite collector to the foaming agent is (2.5:1)~(3.5:1).

14. The flotation reagent according to claim 9, characterized in that The flotation reagent also contains a pH regulator.

15. A flotation method for nickel sulfide ore, characterized in that: Flotation is carried out using the composite collector according to any one of claims 1 to 8 or the flotation reagent according to any one of claims 9 to 14.

16. The flotation method of nickel sulfide ore according to claim 15, characterized in that: The nickel sulfide ore is a difficult-to-select nickel sulfide lean ore.

17. The flotation method for nickel sulfide ore according to claim 15 or 16, characterized in that: In the flotation stage, the dosage of the composite collector is 100-300 g / t.

18. The flotation method of nickel sulfide ore according to claim 17, wherein: The pH value in the flotation stage is 3~12.

19. The flotation method of nickel sulfide ore according to claim 18, wherein: The pH value in the flotation stage is 4~11.

20. The flotation method of nickel sulfide ore according to claim 18, wherein: The pH value in the flotation stage is 6.5~7.5.

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