Composite collector and its use in flotation of zinc oxide ore

Abstract

The composite collector includes a mixed amine, a mixed alcohol, hydrocarbon oil, and an emulsifier. The mixed amine includes laurylamine and N-lauryldiethanolamine. The mixed alcohol includes glycerol and n-octanol. The hydrocarbon oil includes kerosene oil and diesel oil. The emulsifier includes sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, and dodecylphenol ethoxylate. Taking the composite collector as 100 parts, mixed amine accounts for 30 to 40 parts, mixed alcohol accounts for 20 to 30 parts, hydrocarbon oil accounts for 5 to 15 parts, emulsifier accounts for 25 to 35 parts. A process for the flotation of the zinc oxide ore using the composite collector may include roughing twice, scavenging once, cleaning twice, and cleaning-scavenging once, where a middling is not recycled to the roughing and the cleaning, the ore is crushed and ground, and then added with agents to obtain a blended pulp, and the blended pulp is subjected to flotation to obtain a zinc concentrate and a flotation tailing.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a composite collector and its use in flotation of a zinc oxide ore, and belongs to the technical field of mineral processing. BACKGROUND

[0002] Flotation is a main method for enriching zinc oxide ore, including fatty acid direct flotation, chelation flotation, sulfidization-amine flotation, sulfidization-xanthate flotation and the like. Fatty acid collectors could recover zinc oxide ore through flotation, but are easily affected by metal ions in a pulp. Moreover, the fatty acid collectors have poor selectivity, and could allow the flotation of calcareous minerals and minerals activated by metal ions when used in the flotation of zinc oxide ore. Chelating collectors could be selectively combined with zinc ions on surfaces of zinc oxide ore through specific functional groups to form stable metal chelates, thereby allowing the separation of zinc oxide ore from ores. However, the chelating collectors have high prices, and immature applications in industrial production. The sulfidization-amine flotation is a common enrichment process for zinc oxide ore with an advantage of relatively-excellent flotation indexes, but is easily affected by a slime in the pulp. When a slime content in an ore is high, a flotation froth is “armored” with the combination of a slime and an amine collector, resulting in that the froth is extremely difficult to be defoamed, such that the flotation environment and indexes are deteriorated and the production cannot be conducted smoothly. The sulfidization-xanthate flotation has excellent selectivity and allows stable flotation. However, the sulfidization-xanthate flotation has high requirements for sulfidization of the surface of a zinc oxide ore, and undesirable flotation recovery rates when treating a zinc oxide ore with a high slime content.

[0003] Therefore, it is urgent to develop new efficient collectors and flotation methods to maximize the utilization of zinc oxide ore resources, thereby providing a technical support for the economical and efficient recovery of complicated and difficult-to-separate zinc resources. SUMMARY

[0004] In view of the technical problems existing in traditional collectors for zinc oxide ore, such as poor selectivity, a weak collecting capacity, a large amount of a flotation froth with poor fluidity, and an unstable process, the present disclosure provides a composite collector and use of the same in flotation of a zinc oxide ore. The composite collector comprises a mixed amine, a mixed alcohol, hydrocarbon oil, and an emulsifier. By a process flow of performing roughing twice (i.e., first roughing and second roughing), scavenging once, cleaning twice (first cleaning and second cleaning), cleaning-scavenging once, and making a middling be not recycled to the roughing and the cleaning, the influence of a slime on indexes of roughing and cleaning could be avoided, and the stability and viscosity of a froth layer could be improved, thereby significantly improving the flotation recovery index for a zinc oxide ore, and economically and effectively allowing the clean utilization of complicated and difficult-to-separate zinc ore resources.

[0005] The present disclosure provides a composite collector, including a mixed amine, a mixed alcohol, hydrocarbon oil, and an emulsifier, where the mixed amine includes laurylamine and N-lauryldiethanolamine, the mixed alcohol includes glycerol and n-octanol, the hydrocarbon oil includes kerosene oil and diesel oil, and the emulsifier includes sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, and dodecylphenol ethoxylate; and

[0006] taking a mass of the composite collector as 100 parts, the mixed amine accounts for 30 to 40 parts, the mixed alcohol accounts for 20 to 30 parts, the hydrocarbon oil accounts for 5 to 15 parts, and the emulsifier accounts for 25 to 35 parts.

[0007] In some embodiments, taking a mass of the mixed amine as 100%, the laurylamine accounts for 65% to 75% and the N-lauiyldiethanolamine accounts for 25% to 35%.

[0008] In some embodiments, taking a mass of the mixed alcohol as 100%, the glycerol accounts for 75% to 85% and the n-octanol accounts for 15% to 25%.

[0009] In some embodiments, taking a mass of the hydrocarbon oil as 100%, the kerosene oil accounts for 50% to 60% and the diesel oil accounts for 40% to 50%.

[0010] In some embodiments, taking a mass of the emulsifier as 100%, the sodium dodecyl sulfonate accounts for 55% to 65%, the sodium dodecylbenzene sulfonate accounts for 20% to 30%, and the dodecylphenol ethoxylate accounts for 10% to 20%.

[0011] The present disclosure further provides a method for preparing the composite collector as described in the above solutions, including the following steps:

[0012] SI. mixing glycerol and n-octanol according to a mass ratio to be uniform to obtain the mixed alcohol; mixing laurylamine and N-lauryldiethanolamine according to a mass ratio to be uniform, and then heating a resulting mixture under a water bath condition until complete dissolution to obtain the mixed amine; and adding the mixed alcohol into the mixed amine, and stirring to be uniform to obtain mixture I;

[0013] S2. mixing kerosene oil and diesel oil according to a mass ratio to be uniform to obtain the hydrocarbon oil; and adding the hydrocarbon oil into the mixture I under a water bath condition and then stirring to be uniform to obtain mixture II; and

[0014] S3, mixing sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, and dodecylphenol ethoxylate according to a mass ratio to be uniform to obtain the emulsifier; adding the emulsifier into mixture II under a water bath condition, fully stirring to obtain a mixed system, subjecting the mixed system to ultrasonic treatment, and then cooling a resulting system to room temperature to obtain the composite collector.

[0015] In some embodiments, a temperature of the water bath condition is in a range of 45°C to 65°C.

[0016] The present disclosure further provides use of the composite collector as described in the above solutions in flotation of a zinc oxide ore, including the following steps:

[0017] (1) crushing and grinding the zinc oxide ore, and adding water to prepare a pulp; and

[0018] (2) adding flotation agents to the pulp to obtain a blended pulp, and subjecting the blended pulp to roughing twice (i.e., first roughing and second roughing), scavenging once, cleaning twice (i.e., first cleaning and second cleaning), and cleaning-scavenging once in sequence to obtain a zinc concentrate and a flotation tailing, where a middling is not recycled to the roughing and the cleaning, and a cleaning-scavenging tailing is recycled to the scavenging; in terms of each ton of the zinc oxide ore, an agent for the first roughing consists of 8 kg to 10 kg of sodium sulfide, 1,000 g to 1,400 g of a regulator, and 350 g to 550 g of the composite collector, an agent for the second roughing consists of 500 g to 700 g of the regulator and 150 g to 250 g of the composite collector, an agent for the first cleaning consists of 200 g to 300 g of the regulator and 80 g to 120 g of the composite collector, and an agent for the cleaning-scavenging consists of 300 g to 400 g of the regulator and 80 g to 120 g of the composite collector.

[0019] In some embodiments, in step (1), a mass percentage content of zinc in the zinc oxide ore is in a range of 6.2% to 9.6%.

[0020] In some embodiments, in step (1), a water content of the pulp is in a range of 65 wt.% to 75 wt.%.

[0021] In some embodiments, in step (2), the regulator is a mixture of sodium carbonate, sodium hexametaphosphate, and water glass; and taking a mass of the regulator as 100%, the sodium carbonate accounts for 35% to 45%, the sodium hexametaphosphate accounts for 30% to 40%, and the water glass accounts for 20% to 30%.

[0022] In some embodiments, in step (2), the middling includes cleaning tailings from the first cleaning and the second cleaning and a scavenging concentrate from the scavenging.

[0023] The present disclosure has the following beneficial effects:

[0024] (1) In the present disclosure, an amine cationic agent and a sulfonate anionic agent are combined and result in an intermolecular association effect, which reduces a critical micelle concentration, enhances the reactivity of a collector, and weaken a mutual repulsion effect between liquid films, facilitating to thin the liquid film, improve the stability and viscosity of a flotation froth layer, and improve the fluidity of a flotation froth.

[0025] (2) In the present disclosure, the mixed alcohol could reduce a surface tension of the composite collector system and increase the solubility of agents; the hydrocarbon oil could change a structure of a flotation froth, promote the thinning of a liquid film, and promote the rapid bursting of bubbles to reduce an amount of froths; and the emulsifier could promote the effective dispersion of the other agents, increase a discharge rate of a froth liquid film and a diffusion rate of a gas, and reduce a life of a flotation froth.

[0026] (3) In the present disclosure, the middling produced during the flotation process is not recycled to the roughing and the cleaning, which could avoid the accumulation and circulation of a slime in a flotation system, eliminate the deterioration of roughing and cleaning indexes caused by slimes, reduce the consumption of flotation agents, and optimize a structure and mineral-carrying capacity of flotation froths, thereby solving the problem of froth control and slime depression during a flotation process for a zinc oxide ore and greatly improving a utilization rate of a zinc oxide ore.

[0027] (4) In the present disclosure, the composite collector could be prepared by a simple process, is easy to use, and has a strong controllability, thus reducing the cost of separation, and allowing desirable flotation indexes. Therefore, the technical problems existing in the traditional collectors for zinc oxide ore could be economically and efficiently solved, such as a poor selectivity, a weak collecting capacity, a large amount of flotation froths with poor fluidity, and an unstable process, and the eco-friendly and efficient recovery of complicated and difficult-to-separate zinc resources could be achieved. BRIEF DESCRIPTION OF THE DRAWING

[0028] FIG. 1 shows a flotation process for a zinc oxide ore according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0029] The present disclosure will be further described in detail below in conjunction with examples, but the scope of the present disclosure is not limited thereto.

[0030] The composite collector of the present disclosure includes (or consists of) a mixed amine, a mixed alcohol, hydrocarbon oil, and an emulsifier. The mixed amine includes (or consists of) laurylamine and N-lauryldiethanolamine, the mixed alcohol includes (or consists of) glycerol and n-octanol, the hydrocarbon oil includes (or consists of) kerosene oil and diesel oil, and the emulsifier includes (or consists of) sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, and dodecylphenol ethoxylate.

[0031] The composite collector is prepared as follows:

[0032] SI. Glycerol and n-octanol are mixed according to a mass ratio to be uniform to obtain the mixed alcohol. Laurylamine and N-lauryldiethanolamine are mixed according to a mass ratio to be uniform, and then heated under a water bath (45°C to 65°C) condition until complete dissolution to obtain the mixed amine. The mixed alcohol is added to the mixed amine and then stirred to be uniform to obtain mixture I.

[0033] S2. Kerosene oil and diesel oil are mixed according to a mass ratio to be uniform to obtain the hydrocarbon oil. Under a water bath (45°C to 65°C) condition, the hydrocarbon oil is added to mixture I, and then stirred to be uniform to obtain mixture II.

[0034] S3. Sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, and dodecylphenol ethoxylate are mixed according to a mass ratio to be uniform to obtain the emulsifier. Under a water bath (45°C to 65°C) condition, the emulsifier is added to mixture II and then thoroughly stirred, a resulting mixed system was subjected to ultrasonic treatment and then cooled to room temperature to obtain the composite collector.

[0035] Example 1

[0036] In this example, taking a mass of a composite collector as 100 parts, a mixed amine accounted for 30 parts, a mixed alcohol accounted for 30 parts, hydrocarbon oil accounted for 5 parts, and an emulsifier accounted for 35 parts; taking a mass of the mixed amine as 100%, lauryl amine accounted for 65% and N-lauryldiethanolamine accounted for 35%; taking a mass of the mixed alcohol as 100%, glycerol accounted for 75% and n-octanol accounted for 25%; taking a mass of the hydrocarbon oil as 100%, kerosene oil accounted for 50% and diesel oil accounted for 50%; and taking a mass of the emulsifier as 100%, sodium dodecyl sulfonate accounted for 55%, sodium dodecylbenzene sulfonate accounted for 25%, and dodecylphenol ethoxylate accounted for 20%.

[0037] A flotation process for a zinc oxide ore (as shown in FIG. 1) was performed as follows:

[0038] (1) Zinc oxide ore was crushed and ground, and then water was added thereto to prepare a pulp, where a mass percentage content of zinc in the zinc oxide ore was 6.2%, and a water content of the pulp was 75 wt.%.

[0039] (2) Sodium sulfide, a regulator, and the composite collector were added to the pulp, and a resulting mixture was subjected to first roughing to obtain a first roughing concentrate and a first roughing tailing. The first roughing tailing was added with the regulator and the composite collector, and a resulting mixture was then subjected to second roughing to obtain a second roughing concentrate and a second roughing tailing. The second roughing tailing was subjected to scavenging to obtain a scavenging concentrate and a flotation tailing. The first roughing concentrate and the second roughing concentrate were combined, and added with the regulator and the composite collector, and a resulting mixture was then subjected to first cleaning to obtain a first cleaning concentrate and a first cleaning tailing. The first cleaning concentrate was directly subjected to second cleaning to obtain zinc concentrate I and a second cleaning tailing. The first cleaning tailing, the second cleaning tailing, and the scavenging concentrate were combined, and added with the regulator and the composite collector, and a resulting mixture was then subjected to cleaningscavenging to obtain zinc concentrate II and a cleaning-scavenging tailing. The zinc concentrate I and the zinc concentrate II were combined to obtain a zinc concentrate product. In terms of each ton of the zinc oxide ore, agents for the first roughing were 8 kg of the sodium sulfide, 1,000 g of the regulator, and 350 g of the composite collector, agents for the second roughing were 500 g of the regulator and 150 g of the composite collector, agents for the first cleaning were 200 g of the regulator and 80 g of the composite collector, and agents for the cleaning-scavenging were 300 g of the regulator and 80 g of the composite collector. The regulator was a mixture of sodium carbonate, sodium hexametaphosphate, and water glass, taking a mass of the regulator as 100%, the sodium carbonate accounted for 35%, the sodium hexametaphosphate accounted for 35%, and the water glass accounted for 30%.

[0040] In this example, a middling was not recycled to the roughing and the cleaning, the cleaningscavenging tailing was recycled to the scavenging, and finally the zinc concentrate product and the flotation tailing were obtained.

[0041] In this example, a flotation recovery of zinc is 84.7%.

[0042] Example 2

[0043] In this example, taking a mass of a composite collector as 100 parts, a mixed amine accounted for 35 parts, a mixed alcohol accounted for 25 parts, hydrocarbon oil accounted for 15 parts, and an emulsifier accounted for 25 parts; taking a mass of the mixed amine as 100%, laurylamine accounted for 70% and N-lauryldiethanolamine accounted for 30%; taking a mass of the mixed alcohol as 100%, glycerol accounted for 80% and n-octanol accounted for 20%; taking a mass of the hydrocarbon oil as 100%, kerosene oil accounted for 55% and diesel oil accounted for 45%; and taking a mass of the emulsifier as 100%, sodium dodecyl sulfonate accounted for 60%, sodium dodecylbenzene sulfonate accounted for 30%, and dodecylphenol ethoxylate accounted for 10%.

[0044] A flotation process for a zinc oxide ore (as shown in FIG. 1) was performed as follows:

[0045] (1) Zinc oxide ore was crushed and ground, and then water was added thereto to prepare a pulp, where a mass percentage content of zinc in the zinc oxide ore was 7.9%, and a water content of the pulp was 70 wt.%.

[0046] (2) Sodium sulfide, a regulator, and the composite collector were added to the pulp, and a resulting mixture was subjected to first roughing to obtain a first roughing concentrate and a first roughing tailing. The first roughing concentrate was added with the regulator and the composite collector, and a resulting mixture was then subjected to second roughing to obtain a second roughing concentrate and a second roughing tailing. The second roughing tailing was subjected to scavenging to obtain a scavenging concentrate and a flotation tailing. The first roughing concentrate and the second roughing concentrate were combined, and added with the regulator and the composite collector, and a resulting mixture was then subjected to first cleaning to obtain a first cleaning concentrate and a first cleaning tailing. The first cleaning concentrate was directly subjected to second cleaning to obtain zinc concentrate I and a second cleaning tailing. The first cleaning tailing, the second cleaning tailing, and the scavenging concentrate were combined, and added with the regulator and the composite collector, and a resulting mixture was then subjected to cleaning-scavenging to obtain zinc concentrate II and a cleaning-scavenging tailing. The zinc concentrate I and the zinc concentrate II were combined to obtain a zinc concentrate product. In terms of each ton of the zinc oxide ore, agents for the first roughing were 9 kg of the sodium sulfide, 1,200 g of the regulator, and 450 g of the composite collector, agents for the second roughing were 600 g of the regulator and 200 g of the composite collector, agents for the first cleaning were 250 g of the regulator and 100 g of the composite collector, and agents for the cleaning-scavenging were 350 g of the regulator and 100 g of the composite collector. The regulator was a mixture of sodium carbonate, sodium hexametaphosphate, and water glass, taking a mass of the regulator as 100%, the sodium carbonate accounted for 40%, the sodium hexametaphosphate accounted for 40%, and the water glass accounted for 20%.

[0047] In this example, a middling was not recycled to the roughing and the cleaning, the cleaningscavenging tailing was recycled to the scavenging, and finally the zinc concentrate product and the flotation tailing were obtained.

[0048] In this example, a flotation recovery of zinc is 86.1%.

[0049] Examples

[0050] In this example, taking a mass of a composite collector as 100 parts, a mixed amine accounted for 40 parts, a mixed alcohol accounted for 20 parts, hydrocarbon oil accounted for 10 parts, and an emulsifier accounted for 30 parts; taking a mass of the mixed amine as 100%, laurylamine accounted for 75% and N-lauryldiethanolamine accounted for 25%; taking a mass of the mixed alcohol as 100%, glycerol accounted for 85% and n-octanol accounted for 15%; taking a mass of the hydrocarbon oil as 100%, kerosene oil accounted for 60% and diesel oil accounted for 40%; and taking a mass of the emulsifier as 100%, sodium dodecyl sulfonate accounted for 65%, sodium dodecylbenzene sulfonate accounted for 20%, and dodecylphenol ethoxylate accounted for 15%.

[0051] A flotation process for a zinc oxide ore (as shown in FIG. 1) was performed as follows:

[0052] (1) Zinc oxide ore was crushed and ground, and then water was added thereto to prepare a pulp, where a mass percentage content of zinc in the zinc oxide ore was 6.2%, and a water content of the pulp was 65 wt.%.

[0053] (2) Sodium sulfide, a regulator, and the composite collector were added to the pulp, and a resulting mixture was subjected to first roughing to obtain a first roughing concentrate and a first roughing tailing. The first roughing tailing was added with the regulator and the composite collector, and a resulting mixture was then subjected to second roughing to obtain a second roughing concentrate and a second roughing tailing. The second roughing tailing was subjected to scavenging to obtain a scavenging concentrate and a flotation tailing. The first roughing concentrate and the second roughing concentrate were combined, and added with the regulator and the composite collector, and a resulting mixture was then subjected to first cleaning to obtain a first cleaning concentrate and a first cleaning tailing. The first cleaning concentrate was directly subjected to second cleaning to obtain zinc concentrate I and a second cleaning tailing. The first cleaning tailing, the second cleaning tailing, and the scavenging concentrate were combined, and added with the regulator and the composite collector, and a resulting mixture was then subjected to cleaningscavenging to obtain zinc concentrate II and a cleaning-scavenging tailing. The zinc concentrate I and the zinc concentrate II were combined to obtain a zinc concentrate product. In terms of each ton of the zinc oxide ore, agents for the first roughing were 10 kg of the sodium sulfide, 1,400 g of the regulator, and 550 g of the composite collector, agents for the second roughing were 700 g of the regulator and 250 g of the composite collector, agents for the first cleaning were 300 g of the regulator and 120 g of the composite collector, and agents for the cleaning-scavenging were 400 g of the regulator and 120 g of the composite collector. The regulator was a mixture of sodium carbonate, sodium hexametaphosphate, and water glass, taking a mass of the regulator as 100%, the sodium carbonate accounted for 45%, the sodium hexametaphosphate accounted for 30%, and the water glass accounted for 25%.

[0054] In this example, a middling was not recycled to the roughing and the cleaning, the cleaningscavenging tailing was recycled to the scavenging, and finally the zinc concentrate product and the flotation tailing were obtained.

[0055] In this example, a flotation recovery of zinc is 88.3%.

[0056] The specific embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the above embodiments. Various changes can be made without departing from the concept of the present disclosure within the range of knowledge possessed by those of ordinary skill in the art.

Claims

1. A composite collector, comprising a mixed amine, a mixed alcohol, hydrocarbon oil, and an emulsifier, whereinthe mixed amine comprises laurylamine and N-lauryl di ethanol ami ne, the mixed alcohol comprises glycerol and n-octanol, the hydrocarbon oil comprises kerosene oil and diesel oil, and the emulsifier comprises sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, and dodecylphenol ethoxylate; andtaking a mass of the composite collector as 100 parts, the mixed amine accounts for 30 to 40 parts, the mixed alcohol accounts for 20 to 30 parts, the hydrocarbon oil accounts for 5 to 15 parts, and the emulsifier accounts for 25 to 35 parts.

2. The composite collector according to claim 1, wherein taking a mass of the mixed amine as 100%, the laurylamine accounts for 65% to 75% and the N-lauryldiethanolamine accounts for 25% to 35%.

3. The composite collector according to claim 1, wherein taking a mass of the mixed alcohol as 100%, the glycerol accounts for 75% to 85% and the n-octanol accounts for 15% to 25%.

4. The composite collector according to claim 1, wherein taking a mass of the hydrocarbon oil as 100%, the kerosene oil accounts for 50% to 60% and the diesel oil accounts for 40% to 50%.

5. The composite collector according to claim 1, wherein taking a mass of the emulsifier as 100%, the sodium dodecyl sulfonate accounts for 55% to 65%, the sodium dodecylbenzene sulfonate accounts for 20% to 30%, and the dodecylphenol ethoxylate accounts for 10% to 20%.

6. Use of the composite collector according to any one of claims 1 to 5 in flotation of a zinc oxide ore, comprising the following steps:(1) crushing and grinding the zinc oxide ore, and adding water to prepare a pulp; and(2) adding flotation agents to the pulp to obtain a blended pulp, and subjecting the blended pulp to roughing twice (i.e., first roughing and second roughing), scavenging once, cleaning twice (i.e., first cleaning and second cleaning), and cleaning-scavenging once in sequence to obtain a zinc concentrate and a flotation tailing, wherein a middling is not recycled to the roughing and the cleaning, and a cleaning-scavenging tailing is recycled to the scavenging; and in terms of each ton of the zinc oxide ore, an agent for the first roughing consists of 8 kg to 10 kg of sodium sulfide,1,000 g to 1,400 g of a regulator, and 350 g to 550 g of the composite collector, an agent for the second roughing consists of 500 g to 700 g of the regulator and 150 g to 250 g of the composite collector, an agent for the first cleaning consists of 200 g to 300 g of the regulator and 80 g to 120 g of the composite collector, and an agent for the cleaning-scavenging consists of 300 g to 400 g of the regulator and 80 g to 120 g of the composite collector.

7. The use according to claim 6, wherein in step (1), a mass percentage content of zinc in the zinc oxide ore is in a range of 6.2% to 9.6%.

8. The use according to claim 6, wherein in step (2), the regulator is a mixture of sodium carbonate, sodium hexametaphosphate, and water glass; and taking a mass of the regulator as 100%, the sodium carbonate accounts for 35% to 45%, the sodium hexametaphosphate accounts for 30% to 40%, and the water glass accounts for 20% to 30%.11

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