Flotation collector for zinc ore containing sulphur and oxygen and method for its preparation

Abstract

The application discloses a flotation collector for sulfur-oxygen mixed zinc ore, and a structural general formula of the collector is shown in the following formula: wherein R is a C1-C5 hydrocarbon group; a preparation method of the collector comprises the following steps: adding 0.1 mol of acrylonitrile and 0.1 mol of amine into a reaction bottle, stirring uniformly, slowly and dropwisely adding 0.11 mol of carbon disulfide at 0-20 DEG C, adding 20 mL of water and hydroxylamine sulfate after stirring for 1 h at normal temperature, stirring for 15 min, adding a certain amount of alkali, and synthesizing a reaction for 2-6 h at 30-70 DEG C; and the lower water layer is removed, and the upper organic layer is the sulfur-oxygen mixed zinc ore collector ZJOS-1, which can simultaneously and efficiently float and recover zinc sulfide ore and zinc oxide ore in a same tank, and has the advantages of simplifying a flotation process and reducing equipment investment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mineral processing, in particular to a flotation collector for sulfur-oxygen mixed zinc ore and a preparation method thereof. BACKGROUND

[0002] Zinc is an important industrial raw material next to iron, aluminum and copper, and is one of the key strategic mineral resources in China. It has a wide range of industrial applications, mainly including galvanizing, manufacturing copper alloy, zinc alloy, dry battery, etc. The world's zinc resources are relatively abundant. According to the report of the United States Geological Survey, the global proven zinc resources amount to 1.9 billion tons, and the zinc ore reserves amount to 250 million tons. The zinc ore reserves in China account for 19.2% of the world's reserves, ranking second in the world.

[0003] With the continuous development and depletion of zinc sulfide mineral resources, the efficient development and utilization of zinc oxide ore and sulfur-oxygen mixed zinc ore resources become increasingly important. The known beneficiation methods for complex sulfur-oxygen mixed zinc ore include flotation, roasting-flotation combined process, flotation-hydrometallurgy combined process, and gravity separation-hydrometallurgy process. Among them, flotation is currently the most important method for recovering zinc. This method generally uses the conventional flotation agent of butyl xanthate + benzohydroxamic acid for preferential flotation process, that is, easy-to-select sulfide ore is selected first, and then oxidized ore is selected. However, it is well known in the industry that the preferential flotation process has problems such as long process, multiple equipment investment, etc.

[0004] After searching by the research group, no prior related technical report on the flotation collector and the preparation method thereof was found.

[0005] Therefore, it is of great significance to develop a flotation collector for sulfur-oxygen mixed zinc ore and a preparation method thereof. SUMMARY

[0006] The task of the present application is to overcome the shortcomings of the prior art, and to provide a flotation collector for sulfur-oxygen mixed zinc ore and a preparation method thereof, which can simplify the flotation process and reduce equipment investment.

[0007] The task of the present application is accomplished by the following technical scheme:

[0008] The structure of the flotation collector for sulfur-oxygen mixed zinc ore is as follows:

[0009]

[0010] In the formula, R is a C1-C5 hydrocarbon group

[0011] The collector is named ZJOS-1. Using the collector can effectively optimize the flotation process of sulfur-oxygen mixed zinc ore without the need to separate the flotation of sulfide ore and oxidized ore, and can realize the simultaneous and efficient flotation recovery of zinc sulfide ore and zinc oxide ore in the same tank.

[0012] The preparation method of the collector for the sulfur-oxygen mixed zinc ore flotation comprises the following steps: adding 0.1 mol of acrylonitrile and 0.1 mol of amine into a three-mouth reaction bottle, stirring uniformly, slowly and dropwisely adding 0.11 mol of carbon disulfide at 0-20 DEG C, stirring for 1 h at normal temperature, then adding 20 mL of water and hydroxylamine sulfate, stirring for 15 min, adding a certain amount of alkali, and synthesizing a reaction for 2-6 h at 30-70 DEG C, removing the lower water layer, and the upper organic layer is the sulfur-oxygen mixed zinc ore collector ZJOS-1, and the synthesis reaction formula is as follows:

[0013]

[0014] Compared with the prior art, the present application has the following advantages or effects:

[0015] Because the sulfur-oxygen mixed zinc ore flotation collector contains the thioformyl group -C=S, it has strong collecting capacity for the zinc sulfide ore and certain collecting capacity for the zinc oxide ore, so it is not necessary to separate the sulfide ore and the oxide ore for flotation, the process is simplified and the equipment is reduced, the flotation process is simplified and the equipment investment is reduced; meanwhile, because the sulfur-oxygen mixed zinc ore flotation collector contains the oxime group (-C=N-OH) and the amine group (-NH2), the zinc flotation index can be improved, the zinc sulfide ore and the zinc oxide ore can be simultaneously floated, and the recovery efficiency is improved; in addition, because the preparation method of the collector is simple, the use cost is low. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 The figure is a flotation process schematic diagram of the sulfur-oxygen mixed zinc ore flotation collector ZJOS-1 according to the present application applied to the sulfur-oxygen mixed zinc ore.

[0017] The present application will be further described in detail below with reference to the accompanying drawings. DETAILED DESCRIPTION

[0018] The sulfur-oxygen mixed zinc ore flotation collector is characterized by the following structural general formula:

[0019]

[0020] In the formula, R is a C1-C5 hydrocarbon group

[0021] The collector is named as ZJOS-1, and the use of the collector can effectively optimize the sulfur-oxygen mixed zinc ore flotation process, and it is not necessary to separate the sulfide ore and the oxide ore for flotation, so that the zinc sulfide ore and the zinc oxide ore can be simultaneously and efficiently floated and recovered in the same tank.

[0022] The collector of the present application can be further:

[0023] The R is any one of a methyl group, an ethyl group, a n-propyl group, a n-butyl group and a n-pentyl group.

[0024] R is preferably methyl or ethyl.

[0025] The preparation method of the sulfur-oxygen mixed zinc ore flotation collector comprises the following steps: adding 0.1 mol of acrylonitrile and 0.1 mol of amine into a three-mouth reaction bottle, stirring uniformly, slowly and dropwisely adding 0.11 mol of carbon disulfide at 0-20 DEG C, stirring for 1 h at normal temperature, then adding 20 mL of water and hydroxylamine sulfate, stirring for 15 min, adding a certain amount of alkali, and synthesizing a reaction at 30-70 DEG C for 2-6 h, removing the lower water layer, and the upper organic layer is the sulfur-oxygen mixed zinc ore collector ZJOS-1.

[0026]

[0027] The method of the application can further be:

[0028] The alkali is any one of sodium carbonate and sodium hydroxide.

[0029] The amine is any one of dimethylamine, diethylamine, dipropylamine, dibutylamine and diamylamine.

[0030] The amine is preferably dimethylamine or diethylamine.

[0031] The molar ratio of the acrylonitrile, hydroxylamine sulfate and alkali is 1:0.5:0.55-1.2.

[0032] Referring to Figure 1 The sulfur-oxygen mixed zinc ore flotation collector ZJOS-1 according to the application is applied to the flotation process of the sulfur-oxygen mixed zinc ore, and the process is as follows: the sulfur-oxygen mixed zinc ore is ground by a mill to a fineness of 60% of -0.074 mm, 100 g / t of the sulfur-oxygen mixed zinc ore collector ZJOS-1 and 10 g / t of 2# oil frother are added in turn in the rough flotation of the sulfur-oxygen mixed zinc ore, and the sulfur-oxygen mixed rough concentrate and the sulfur-oxygen mixed rough tailings are obtained through the rough flotation; the sulfur-oxygen mixed rough concentrate is subjected to two times of cleaning to obtain the sulfur-oxygen mixed zinc concentrate; the sulfur-oxygen mixed rough tailings are subjected to two times of scavenging to obtain the tailings, wherein the ZJOS-1 is added at 50 g / t and 25 g / t respectively, and the 2# oil is added at 5 g / t and 2 g / t respectively in the first scavenging and the second scavenging. The middlings produced in the cleaning and scavenging operations are returned to the previous operation in turn. It has been proved in practice that the reagent can effectively optimize the flotation process of the sulfur-oxygen mixed zinc ore, and the sulfide ore and the oxidized ore do not need to be separated for flotation, and the sulfide zinc ore and the oxidized zinc ore can be simultaneously and efficiently recovered in the same tank.

[0033] Example 1

[0034] In a 150 mL three-necked reaction flask, 0.1 mol of acrylonitrile and 0.1 mol of diethylamine were added, stirred uniformly, and then 0.11 mol of carbon disulfide was slowly added dropwise at 0°C. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 h, then 20 mL of water and 0.5 mol of hydroxylamine sulfate were added, stirred for 15 min, and then 0.55 mol of sodium carbonate was added. After the addition was completed, the mixture was reacted at 50°C for 3 h. After the reaction, the lower aqueous layer was removed, and the upper organic layer was the sulfur-oxygen mixed zinc ore collector.

[0035] Example 2

[0036] In a 150 mL three-necked reaction flask, 0.1 mol of acrylonitrile and 0.1 mol of dimethylamine were added, stirred uniformly, and then 0.11 mol of carbon disulfide was slowly added dropwise at 20°C. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 h, then 20 mL of water and 0.5 mol of hydroxylamine sulfate were added, stirred for 15 min, and then 0.6 mol of sodium carbonate was added. After the addition was completed, the mixture was reacted at 30°C for 6 h. After the reaction, the lower aqueous layer was removed, and the upper organic layer was the sulfur-oxygen mixed zinc ore collector.

[0037] Example 3

[0038] In a 150 mL three-necked reaction flask, 0.1 mol of acrylonitrile and 0.1 mol of dibutylamine were added, stirred uniformly, and then 0.11 mol of carbon disulfide was slowly added dropwise at 15°C. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 h, then 20 mL of water and 0.5 mol of hydroxylamine sulfate were added, stirred for 15 min, and then 1.2 mol of sodium hydroxide was added. After the addition was completed, the mixture was reacted at 70°C for 2 h. After the reaction, the lower aqueous layer was removed, and the upper organic layer was the sulfur-oxygen mixed zinc ore collector.

[0039] Example 4

[0040] A certain sulfur-oxygen mixed zinc ore had a raw ore containing 4.60% zinc and an oxidation rate of 40.62%, and the oxidized zinc ore was mainly smithsonite. According to the dry weight of 1 ton of raw ore, the sulfur-oxygen mixed zinc ore was ground to a fineness of 60% passing 0.074 mm, and the flotation slurry concentration was adjusted to 30%. In the flotation of the sulfur-oxygen mixed zinc ore, 100 g / t of the sulfur-oxygen mixed zinc ore collector ZJOS-1 and 10 g / t of 2# oil frother were added in turn in the roughing, and the pulp was stirred for 5 min. In the scavenging 1 and scavenging 2, ZJOS-1 was added at 50 g / t and 25 g / t, respectively, and 2# oil was added at 5 g / t and 2 g / t, respectively. The sulfur-oxygen mixed zinc concentrate was obtained through the process of “one roughing, two cleaning, and two scavenging”. The flotation process is shown in Figure 1 , and the closed-circuit beneficiation results are shown in Table 1.

[0041] Comparative Example

[0042] The raw ore of a certain sulfur-oxygen mixed zinc ore contains 4.60% of zinc, and the oxidation rate is 40.62%, and the oxidized zinc ore is mainly smithsonite. According to the dry weight of each ton of raw ore, the sulfur-oxygen mixed zinc ore is ground to a fineness of 60% passing 0.074 mm by a mill, and the concentration of the flotation slurry is adjusted to 30%. In the flotation of the sulfur-oxygen mixed zinc ore, 100 g / t of butyl xanthate + benzohydroxamic acid combined collector (butyl xanthate: benzohydroxamic acid = 1:3) and 10 g / t of 2# oil frother are added in turn in the roughing, and the pulp is adjusted for 5 minutes; in the scavenging one and the scavenging two, butyl xanthate + benzohydroxamic acid combined collector (butyl xanthate: benzohydroxamic acid = 1:3) is added at 50 g / t and 25 g / t respectively, and 2# oil is added at 5 g / t and 2 g / t respectively, and the sulfur-oxygen mixed zinc concentrate is obtained through the process of "once roughing, twice cleaning, and twice scavenging". The closed-circuit beneficiation results are shown in Table 1. The flotation process of the comparative example is the same as that of Example 4 except that the type of collector is different.

[0043] Table 1 Flotation results of oxidized zinc ore

[0044]

[0045]

[0046] From the flotation results in Table 1, it can be seen that the sulfur-oxygen mixed zinc ore collector provided by the present application has a significant improvement in yield and Zn recovery rate compared to the conventional sulfur-oxygen mixed zinc ore combined collector.

[0047] As described above, the present application can be better implemented. The above examples are only the best implementation of the present application, but the implementation of the present application is not limited by the above examples, and other changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application are equivalent replacement methods, and are all included in the protection scope of the present application.

Claims

1. A sulfur-oxygen mixed zinc ore flotation collector, characterized in that... The general structural formula is as follows: ； In the formula, R is a C1 to C5 hydrocarbon group, named ZJOS-1. Using this collector can effectively optimize the flotation process of sulfur-oxygen mixed zinc ore and eliminate the need to separate the sulfide ore and the oxide ore for flotation. It can enable the simultaneous and efficient flotation recovery of zinc sulfide ore and zinc oxide ore in the same tank. R is any one of methyl, ethyl, n-propyl, n-butyl, and n-pentyl.

2. The sulfur-oxygen mixed zinc ore flotation collector according to claim 1, wherein R is methyl or ethyl.

3. The method for preparing the sulfur-oxygen mixed zinc ore flotation collector according to claim 1, characterized in that... Add 0.1 mol acrylonitrile and 0.1 mol amine to a three-necked reaction flask, stir well, and then slowly add 0.11 mol carbon disulfide dropwise at 0-20℃. Stir at room temperature for 1 h, then add 20 mL of water and hydroxylamine sulfate, stir for 15 min, add a certain amount of alkali, and synthesize at 30-70℃ for 2-6 h. Remove the lower aqueous layer; the upper organic layer is the sulfur-oxygen mixed zinc ore collector ZJOS-1. The synthesis reaction formula is as follows: 。 4. The method according to claim 3, characterized in that: The alkali mentioned is either sodium carbonate or sodium hydroxide.

5. The method according to claim 3, characterized in that: The amine is any one of dimethylamine, diethylamine, dipropylamine, dibutylamine, and dipentylamine.

6. The method according to claim 3 or 4, characterized in that: The amine is dimethylamine or diethylamine.

7. The method according to claim 3, characterized in that: The molar ratio of acrylonitrile, hydroxylamine sulfate and alkali is 1:0.5:0.55 to 1.2.

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