Multi-metal resource comprehensive recovery method

Abstract

The invention provides a method for comprehensively recovering multi-metal resources, which comprises the following steps: grinding raw ore, and then carrying out copper-zinc bulk flotation, sulfur flotation, magnetic iron separation, cyclone desliming and tungsten-tin bulk flotation to obtain sulfide ore bulk concentrate, tungsten-tin bulk concentrate and tailings; and the sulfide ore bulk concentrate is subjected to copper-zinc separation and zinc-sulfur separation flotation, and sulfur concentrate, copper concentrate and zinc concentrate are obtained. Sulphide minerals such as copper and zinc are recycled firstly, cassiterite and wolframite are subjected to flotation through a full-flotation process and a novel efficient collecting agent, and the recovery rate of tin, tungsten and the like is increased.

Description

Technical Field

[0001] The invention belongs to the technical field of metal recovery, and specifically relates to a method for comprehensive recovery of multi-metal resources. Background Art

[0002] Tin has the characteristics of fine particle size, concentrated distribution, many types of associated minerals, and complex inter-mineral distribution relationships. Due to the high density of cassiterite, most tin ores are mainly processed by gravity separation technology, but the comprehensive recovery rate of cassiterite is extremely low.

[0003] Low-grade copper, tin, and tungsten complex polymetallic resources contain a variety of metals, and comprehensive recovery is difficult. Cassiterite, as the main element, is generally recovered by gravity separation or gravity-flotation combined processes, and the recovery rate is low. If the recovery of copper, zinc and other minerals is considered first, the copper, zinc and other minerals can be dissociated into monomers, but the particle size of cassiterite is relatively fine, and the gravity separation recovery rate is low, especially the fine particles are very easy to lose. If the gravity separation recovery of cassiterite is considered first, the degree of monomer dissociation of copper, zinc and other minerals is not enough, and the copper and zinc recovery rate is reduced. Summary of the invention

[0004] The purpose of the present invention is to provide a method for comprehensive recovery of multi-metal resources, which adopts a process flow of copper-zinc mixed flotation-sulfur flotation-magnetic iron separation-cyclone desludging-tungsten-tin mixed flotation, and the mixed concentrate of sulfide ore is then subjected to copper-zinc separation and zinc-sulfur separation. By first recovering sulfide minerals such as copper and zinc, and adopting a full flotation process and a new high-efficiency collector to float cassiterite and wolframite, the recovery rate of tin and tungsten is improved.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] A method for comprehensive recovery of multi-metal resources comprises the following steps:

[0007] S1: After grinding, the raw ore is subjected to copper-zinc mixed flotation, sulfur flotation, magnetic separation of iron, cyclone desludging, and tungsten-tin mixed flotation to obtain sulfide ore mixed concentrate, tungsten-tin mixed concentrate and tailings;

[0008] S2: The mixed concentrate of sulfide ore is then subjected to copper-zinc separation and zinc-sulfur separation flotation to obtain sulfur concentrate, copper concentrate and zinc concentrate.

[0009] Furthermore, the grinding fineness of the raw ore in step S1 is -0.074 mm ≥ 75%.

[0010] Furthermore, in step S1, 200-300 g / t of ethyl xanthate and 8-15 kg / t of lime are added to the copper-zinc mixed flotation, and the scavenging is performed for 3-5 minutes.

[0011] Furthermore, in step S1, 3-5 kg / t of concentrated sulfuric acid and 80-100 g / t of butyl xanthate are added during sulfur flotation, and the flotation is carried out for 1-3 minutes.

[0012] Furthermore, the field intensity of the magnetic separator in the step S1 magnetic separation of iron is 4000-30000e.

[0013] Furthermore, in step S1, 200-500 g / t oxalic acid, 150-400 g / t butyl xanthate, 150-400 g / t salicylic hydroxamic acid, 200-600 g / t water glass and 100-500 g / t sodium fluorosilicate are added to the mixed flotation of tungsten and tin, and the scavenging is carried out for 2-6 minutes.

[0014] Furthermore, in step S2, 200-300 g / t of butyl xanthate, 60-80 g / t of isopropyl ethylthiocarbamate, 10-30 g / t of polyoxyethylene polyoxypropylene glycerol ether, 20-50 g / t of copper sulfate and 15-45 g / t of sodium sulfide are added to the copper-zinc separation flotation, and the flotation is performed for 3-5 min.

[0015] Furthermore, in step S2, 10-30 g / t of ammonium persulfate, 30-60 g / t of ethyl thiocyanate, 5-10 g / t of methyl amyl alcohol, 100-300 g / t of zinc sulfate and 200-350 g / t of sodium sulfite are added to the zinc-sulfur separation flotation, and the flotation is carried out for 2-5 min.

[0016] Compared with the prior art, the advantages and beneficial effects of the present invention are:

[0017] 1. The present invention takes into account the efficient utilization of resources and first recovers sulfide minerals such as copper and zinc, and then uses a full flotation process and a new type of efficient collector to float cassiterite and black tungsten. According to the characteristics of the ore, the process of copper-zinc mixed flotation-sulfur flotation-magnetic iron selection-cyclone desludging-tungsten-tin mixed flotation is adopted, and the sulfide ore mixed concentrate is then subjected to copper-zinc separation and zinc-sulfur separation. A new collector is used as the collection method for tin-tungsten minerals, and a full flotation process is used to float cassiterite and black tungsten to produce tin-tungsten mixed concentrate, thereby improving the recovery rate of tin and tungsten. The process has relatively fewer interference factors in mineral processing, stable operation, and mature and reliable technology; it has strong adaptability to ores, is not affected by large fluctuations in mineral proportions, and has stable tin-tungsten separation indicators; in the tin-tungsten flotation operation, a large amount of combined inhibitors with strong inhibitory effect on fluorite are not added, which creates favorable conditions for subsequent fluorite recovery; it is conducive to the comprehensive recovery of mineral resources.

[0018] 2. Through industrial tests, the copper recovery rate of copper concentrate reached 82.23%; the zinc recovery rate of zinc concentrate reached 37.79%; the tin recovery rate of tin-tungsten mixed concentrate reached 63.76%; and the tungsten recovery rate of tin-tungsten mixed concentrate reached 34.34%. The new process has greatly improved the recovery rate of multiple metals, and the comprehensive utilization level of multiple metal resources has been greatly improved. This achievement can also be applied and promoted in other similar mines. DETAILED DESCRIPTION

[0019] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] Example 1

[0021] This embodiment provides a method for comprehensive recovery of multi-metal resources, comprising the following steps:

[0022] S1: Grind the raw ore to a grinding fineness of -0.074mm≥75%; then add 200-300g / t ethyl xanthate and 8-15kg / t lime, scavenging for 3-5min, and carry out copper-zinc mixed flotation; then add 3-5kg / t concentrated sulfuric acid and 80-100g / t butyl xanthate, scavenging for 1-3min, and carry out sulfur flotation; enter the magnetic separator to select iron at an airport strength of 4000-30000e, and desludging through a cyclone; then add 200-500g / t oxalic acid, 150-400g / t butyl xanthate, 150-400g / t salicylic hydroxamic acid, 200-600g / t water glass and 100-500g / t sodium fluorosilicate, scavenging for 2-6min, and carry out tungsten-tin mixed flotation; obtain sulfide ore mixed concentrate, tungsten-tin mixed concentrate and tailings;

[0023] S2: Add 200-300g / t butyl xanthate, 60-80g / t isopropyl ethylthiocarbamate, 10-30g / t polyoxyethylene polyoxypropylene glycerol ether, 20-50g / t copper sulfate and 15-45g / t sodium sulfide to the mixed concentrate of sulfide ore, scavenging for 3-5min, and then flotation separation of copper and zinc; then add 10-30g / t ammonium persulfate, 30-60g / t ethylthiocyanate, 5-10g / t methyl amyl alcohol, 100-300g / t zinc sulfate and 200-350g / t sodium sulfite, scavenging for 2-5min, and flotation separation of zinc and sulfur to obtain sulfur concentrate, copper concentrate and zinc concentrate.

[0024] Example 2

[0025] This embodiment provides a method for comprehensive recovery of multi-metal resources, comprising the following steps:

[0026] S1: Grind the raw ore to a grinding fineness of -0.074mm≥75%; then add 200-300g / t ethyl xanthate and 8-15kg / t lime, scavenging for 3-5min, and carry out copper-zinc mixed flotation; then add 3-5kg / t concentrated sulfuric acid and 80-100g / t butyl xanthate, scavenging for 1-3min, and carry out sulfur flotation; enter the magnetic separator to select iron at an airport strength of 4000-30000e, and desludging through a cyclone; then add 200-500g / t oxalic acid, 150-400g / t butyl xanthate, 150-400g / t salicylic hydroxamic acid, 200-600g / t water glass and 100-500g / t sodium fluorosilicate, scavenging for 2-6min, and carry out tungsten-tin mixed flotation; obtain sulfide ore mixed concentrate, tungsten-tin mixed concentrate and tailings;

[0027] S2: Add 200-300g / t butyl xanthate, 60-80g / t isopropyl ethylthiocarbamate, 10-30g / t polyoxyethylene polyoxypropylene glycerol ether, 20-50g / t copper sulfate and 15-45g / t sodium sulfide to the mixed concentrate of sulfide ore, scavenging for 3-5min, and then flotation separation of copper and zinc; then add 10-30g / t ammonium persulfate, 30-60g / t ethylthiocyanate, 5-10g / t methyl amyl alcohol, 100-300g / t zinc sulfate and 200-350g / t sodium sulfite, scavenging for 2-5min, and flotation separation of zinc and sulfur to obtain sulfur concentrate, copper concentrate and zinc concentrate.

[0028] Example 3

[0029] This embodiment provides a method for comprehensive recovery of multi-metal resources, comprising the following steps:

[0030] S1: Grind the raw ore to a grinding fineness of -0.074mm≥75%; then add 200-300g / t ethyl xanthate and 8-15kg / t lime, scavenging for 3-5min, and carry out copper-zinc mixed flotation; then add 3-5kg / t concentrated sulfuric acid and 80-100g / t butyl xanthate, scavenging for 1-3min, and carry out sulfur flotation; enter the magnetic separator to select iron at an airport strength of 4000-30000e, and desludging through a cyclone; then add 200-500g / t oxalic acid, 150-400g / t butyl xanthate, 150-400g / t salicylic hydroxamic acid, 200-600g / t water glass and 100-500g / t sodium fluorosilicate, scavenging for 2-6min, and carry out tungsten-tin mixed flotation; obtain sulfide ore mixed concentrate, tungsten-tin mixed concentrate and tailings;

[0031] S2: Add 200-300g / t butyl xanthate, 60-80g / t isopropyl ethylthiocarbamate, 10-30g / t polyoxyethylene polyoxypropylene glycerol ether, 20-50g / t copper sulfate and 15-45g / t sodium sulfide to the mixed concentrate of sulfide ore, scavenging for 3-5min, and then flotation separation of copper and zinc; then add 10-30g / t ammonium persulfate, 30-60g / t ethylthiocyanate, 5-10g / t methyl amyl alcohol, 100-300g / t zinc sulfate and 200-350g / t sodium sulfite, scavenging for 2-5min, and flotation separation of zinc and sulfur to obtain sulfur concentrate, copper concentrate and zinc concentrate.

[0032] Comparative Example 1

[0033] The difference between this comparative example and Example 1 is that the sulfur flotation process is not performed in step S1, and the other steps are the same.

[0034] Comparative Example 2

[0035] The difference between this comparative example and Example 1 is that the magnetic separation process is not performed in step S1, and the other steps are the same.

[0036] Comparative Example 3

[0037] The difference between this comparative example and Example 1 is that salicylic hydroxamic acid is not added in step S1 of tungsten-tin mixed flotation, and the other steps are the same.

[0038] Comparative Example 4

[0039] The difference between this comparative example and Example 1 is that sodium fluorosilicate is not added in step S1 of tungsten-tin mixed flotation, and the other steps are the same.

[0040] Comparative Example 5

[0041] The difference between this comparative example and Example 1 is that isopropyl ethyl thiocarbamate and polyoxyethylene polyoxypropylene glycerol ether are not added in the copper-zinc separation flotation in step S2, and the other steps are the same.

[0042] Comparative Example 6

[0043] The difference between this comparative example and Example 1 is that ammonium persulfate and zinc sulfate are not added in the zinc-sulfur separation flotation in step S2, and the other steps are the same.

[0044] The copper recovery rate of copper concentrate, the zinc recovery rate of zinc concentrate, the tin recovery rate of tin-tungsten mixed concentrate, and the tungsten recovery rate of tin-tungsten mixed concentrate were calculated for each embodiment and comparative example.

[0045]

[0046] From the above results, it can be seen that the recovery rates of Examples 1-3 are good. However, since Comparative Examples 1-5 do not adopt the necessary technical solutions, their corresponding performance tests are significantly worse than those of the embodiments. The above experimental results further prove the importance of the technical solutions defined in the present invention for its technical effects.

[0047] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for comprehensive recovery of multi-metal resources, characterized in that: The steps include: S1: After grinding, the raw ore is subjected to copper-zinc mixed flotation, sulfur flotation, magnetic separation of iron, cyclone desludging, and tungsten-tin mixed flotation to obtain sulfide ore mixed concentrate, tungsten-tin mixed concentrate and tailings; S2: The mixed concentrate of sulfide ore is then subjected to copper-zinc separation and zinc-sulfur separation flotation to obtain sulfur concentrate, copper concentrate and zinc concentrate.

2. A method for comprehensive recovery of multi-metal resources according to claim 1, characterized in that: The grinding fineness of the raw ore in step S1 is -0.074mm≥75%.

3. The method for comprehensive recovery of multi-metal resources according to claim 1, characterized in that: In step S1, 200-300 g / t of ethyl xanthate and 8-15 kg / t of lime are added to the copper-zinc mixed flotation, and the flotation is performed for 3-5 minutes.

4. The method for comprehensive recovery of multi-metal resources according to claim 1, characterized in that: In step S1, 3-5 kg / t of concentrated sulfuric acid and 80-100 g / t of butyl xanthate are added during sulfur flotation, and the flotation is performed for 1-3 minutes.

5. The method for comprehensive recovery of multi-metal resources according to claim 1, characterized in that: The field intensity of the magnetic separator in the step S1 magnetic separation of iron is 4000-30000e.

6. The method for comprehensive recovery of multi-metal resources according to claim 1, characterized in that: In step S1, 200-500 g / t oxalic acid, 150-400 g / t butyl xanthate, 150-400 g / t salicylic hydroxamic acid, 200-600 g / t water glass and 100-500 g / t sodium fluorosilicate are added to the tungsten-tin mixed flotation, and the mixture is scavenged for 2-6 minutes.

7. The method for comprehensive recovery of multi-metal resources according to claim 1, characterized in that: In step S2, 200-300 g / t of butyl xanthate, 60-80 g / t of isopropyl ethylthiocarbamate, 10-30 g / t of polyoxyethylene polyoxypropylene glycerol ether, 20-50 g / t of copper sulfate and 15-45 g / t of sodium sulfide are added to the copper-zinc separation flotation, and the flotation is performed for 3-5 minutes.

8. The method for comprehensive recovery of multi-metal resources according to claim 1, characterized in that: In step S2, 10-30 g / t of ammonium persulfate, 30-60 g / t of ethyl thiocyanate, 5-10 g / t of methyl amyl alcohol, 100-300 g / t of zinc sulfate and 200-350 g / t of sodium sulfite are added to the zinc-sulfur separation flotation, and the flotation is performed for 2-5 min.

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