CN112916210B - Application method of novel triphenylamine olefin compound in zinc oxide ore flotation - Google Patents
Application method of novel triphenylamine olefin compound in zinc oxide ore flotation Download PDFInfo
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- CN112916210B CN112916210B CN202110300890.8A CN202110300890A CN112916210B CN 112916210 B CN112916210 B CN 112916210B CN 202110300890 A CN202110300890 A CN 202110300890A CN 112916210 B CN112916210 B CN 112916210B
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Abstract
The invention discloses an application method of a novel triphenylamine olefin compound in zinc oxide ore flotation, wherein the novel triphenylamine olefin compound shown as a formula I is used as a collecting agent in the zinc oxide ore flotation. When the novel triphenylamine olefin compound is used as a flotation collector, the molecule of the novel triphenylamine olefin compound has two different mineral-philic groups, the action capacity with the surface of a mineral is stronger, and the selectivity to a target mineral is better; the collecting agent has the characteristics that the collecting agent has two benzene ring hydrophobic groups, the hydrophobic capacity of the collecting agent is improved, the collecting capacity of the collecting agent on target minerals is stronger, and the flotation efficiency and the recovery rate can be effectively improved compared with those of common flotation collecting agents in the prior art; meanwhile, because the molecules contain unsaturated double bonds, the critical micelle concentration of the ionic surfactant is lower. Compared with the common flotation collector in the prior art, the flotation collector has the characteristics that the flotation efficiency and the recovery rate of minerals can be effectively improved, the flotation collector can be used at low temperature, and the like.
Description
Technical Field
The invention belongs to the technical field of mineral separation, and particularly relates to an application method of a novel triphenylamine olefin compound in zinc oxide ore flotation.
Background
Zinc is an important strategic resource in China and plays an important role in the nonferrous metal industry. By 2019, the zinc resource amount is over 19 hundred million tons, the zinc storage amount is over 25000 million tons, and the total zinc concentrate yield is 1289.5 million tons all over the world. Zinc ore resources are mainly distributed in seven countries of Australia, China, Mexico, Russia, America, Peru and Kazakhstan. As the first world zinc concentrate producing country and the second world zinc ore resource country, the yield and the reserve respectively account for 44.7 percent and 25.0 percent of the 7 country-based yield and the total reserve. The reserves of zinc ore resources in China are relatively rich, and the quantity of the zinc resources is about 13737.7 ten thousand tons by 2019. The zinc ore resources in China are mainly distributed in Yunnan, Gansu, inner Mongolia, Guangdong, Guangxi, Hunan and other provinces. However, nearly one fourth of zinc ores in China are oxidized ores, and the zinc metal storage capacity of the oxidized ores is over 4000 million tons. Due to the reasons of high ore oxidation rate, large mud content, more ore pulp interfering ions and the like, the beneficiation index of the zinc oxide ore is not ideal, and a large amount of ores cannot be effectively utilized. Currently, flotation is the primary method of treating zinc oxide ore. In the flotation process, the flotation collector is the key and directly determines the quality of the flotation index. At present, the flotation of zinc oxide ore mainly adopts aliphatic amine collectors, but the common aliphatic amine collectors, such as octadecylamine and dodecylamine, have the defects of poor selectivity, large using amount, and poor solubility and dispersibility at low temperature. Therefore, in the concentrating mill of China, the dosage of the aliphatic amine collecting agent is very large due to poor solubility of the aliphatic amine collecting agent in winter, and indexes such as grade and recovery rate of zinc oxide concentrate are poor. Therefore, in order to solve the technical problem of poor flotation index of zinc oxide concentrate in zinc oxide ore at low temperature, the novel efficient zinc oxide ore flotation collector with strong collecting capacity and good selectivity is researched and developed, and the novel efficient zinc oxide ore flotation collector has great significance for development and utilization of zinc oxide ore resources and sustainable development of related industries.
At present, the application of the novel triphenylamine alkene compound 1-amino-styryl-triphenylamine shown in the formula I as a flotation collector in the zinc oxide ore flotation is not reported. The present invention has been made in view of this situation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an application method of a novel surfactant in zinc oxide ore flotation, and solves the problems that the existing aliphatic amine collecting agent has poor selectivity and large using amount on zinc oxide ore, has poor solubility and dispersibility at low temperature, causes poor zinc oxide concentrate grade and recovery rate, and particularly has poor zinc oxide ore flotation effect at low temperature.
In order to solve the technical problems, the invention adopts the technical scheme that:
an application method of a novel triphenylamine olefin compound in zinc oxide ore flotation is characterized in that 1-amino-styryl-triphenylamine with a structural formula shown in a formula I is used as a collecting agent in the zinc oxide ore flotation, sodium sulfide is used as an activating agent, sodium thioglycolate is used as an inhibitor, and No. 2 oil is used as a foaming agent; the structural formula of formula I is as follows:
further, the invention explains that the pH value range of the ore pulp subjected to flotation is 7.5-12; the flotation temperature is 0-30 ℃; the granularity of the zinc oxide ore is-400 meshes and accounts for 60-90%.
The invention further discloses that the dosage of the 1-amino-styryl-triphenylamine is 50-300 g/t.
The invention further discloses that the dosage of the sodium sulfide is 4000-8000 g/t.
The invention further discloses that the dosage of the sodium thioglycolate is 150-350 g/t.
The invention further discloses that the dosage of the No. 2 oil is 50-100 g/t.
After the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects.
(1) The molecules of the novel triphenylamine alkene compound have two mineral-philic amino groups, so that the novel triphenylamine alkene compound has stronger binding capacity with the surface of a mineral and better selectivity on a target mineral;
(2) the molecule of the collector has two hydrophobic benzene rings, so that the hydrophobic capacity of the collector is improved, and the sorting capacity of the collector on target minerals is stronger;
(3) because molecules contain unsaturated alkenyl, the critical micelle concentration of the ionic surfactant is lower, and the ionic surfactant has good solubility and dispersibility at low temperature;
(4) the novel triphenylamine olefin compound provided by the invention is used as a zinc oxide flotation collector, has strong sorting capability and good selectivity on zinc oxide ores at low temperature, improves the grade and recovery rate of zinc oxide concentrates, and has good popularization and application values.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention to its proper form. In the drawings:
FIG. 1 is a flow chart of the process for flotation of pure zinc oxide mineral using amino-styryl-triphenylamine according to example 1;
FIG. 2 is a flow diagram of an example of a process for the flotation of zinc oxide ores using amino-styryl-triphenylamine;
FIG. 3 is a flow diagram of another example of a process for the flotation of zinc oxide ore using 1-amino-styryl-triphenylamine;
fig. 4 is a flow diagram of another example of the use of 1-amino-styryl-triphenylamine in the flotation of zinc oxide ores.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a novel triphenylamine alkene compound 1-amino-styryl-triphenylamine for zinc oxide ore flotation, which has a structure shown in a formula I:
the application of the novel triphenylamine olefin compound as a flotation collector of zinc oxide ores is described in the following with reference to specific examples.
Example 1: application of 1-amino-styryl-triphenylamine in flotation of pure zinc oxide ore minerals (the flotation temperature is 18 ℃)
10.0g of zinc oxide pure mineral with the granularity of-400 meshes is placed in a 200mL flotation tank, 150mL of distilled water is added, the mixture is stirred and mixed uniformly, the flotation is carried out under the condition that the using amount of a collecting agent is 70g/t, and the flow chart of the flotation process is shown in attached figure 1. The results of the flotation comparative test of the collector in the invention and the commonly used two collectors, namely dodecylamine and hexadecylamine, are shown in table 1.
As can be seen from table 1, the collecting ability of the collector of the present invention to zinc oxide pure mineral is significantly stronger than that of the two collectors commonly used.
TABLE 1 comparative experimental results of collector flotation pure minerals
| Species of collector | Collecting agent | The recovery rate is high |
| Common collecting agent | Dodecyl amine | 71.94 |
| Common collecting agent | Hexadecyl amine | 77.21 |
| Collector in the invention | 1-amino-styryl-triphenylamine | 96.81 |
Putting 10.0g of zinc oxide pure mineral with the granularity of-400 meshes into a 200mL flotation tank, adding 150mL of distilled water, stirring and mixing uniformly, carrying out flotation under the condition that the using amount of a collecting agent is 70g/t, and changing the flotation temperature to be 8 ℃, 18 ℃, 28 ℃, 30 ℃ and 35 ℃. The results of the flotation comparative test of the collector in the invention and the commonly used two collectors, namely dodecylamine and hexadecylamine, are shown in table 2.
As can be seen from the table 2, the collecting capacity of the collecting agent of the invention to the pure zinc oxide mineral is more than 95% in the range of 8-30 ℃. It can also be seen from the table that the recovery was only 91.24% in the experiments when the flotation temperature exceeded 30 ℃, i.e. at 35 ℃, demonstrating that the flotation temperature using the collector of the invention performed well in the range of 8 ℃ to 30 ℃ and the capacity of the collector of the invention decreased significantly when it exceeded 30 ℃. Therefore, the collecting capacity of the collecting agent in the invention to the zinc oxide pure mineral is not influenced by the temperature in the range of 8-30 ℃. The later experiments were carried out with a temperature of 28 ℃ for the optimum flotation. Under the condition of 8 ℃, the recovery rates of two common collecting agents are far lower than those of the collecting agent in the invention, and are both about 40%; the fact that the molecules of the collector contain unsaturated alkenyl groups shows that the critical micelle concentration of the ionic surfactant is lower, and the ionic surfactant has good solubility and dispersibility at low temperature, so that the recovery rate in flotation is effectively improved.
TABLE 2 temperature comparison of pure minerals for collector flotation
Example 2: application of 1-amino-styryl-triphenylamine in flotation of zinc oxide minerals (the flotation temperature is 28 ℃)
The method comprises the steps of grinding ores of certain zinc oxide raw ore in Yunnan, wherein the raw ore contains 6.56% of Zn, grinding the ores to 75% of-400 meshes, adding water to adjust the pulp to have a mass concentration of 20%, adjusting the pH value of the pulp to 9, adding 130g/t of sodium thioglycolate, 5000g/t of sodium sulfide, 105g/t of 1-amino-styryl-triphenylamine and 75g/t of foaming agent No. 2 oil, performing rough flotation on the zinc oxide ore, adding 1000g/t of sodium sulfide and 70g/t of 1-amino-styryl-triphenylamine in scavenging, adding 60g/t of sodium thioglycolate in first concentration, adding 60g/t of sodium thioglycolate in second concentration, and adopting a flotation process flow of primary rough flotation, primary scavenging and secondary concentration, wherein the flotation process flow chart is shown in figure 2.
Example 3: application of 1-amino-styryl-triphenylamine in flotation of zinc oxide minerals (the flotation temperature is 28 ℃)
The method comprises the steps of grinding ores of certain zinc oxide raw ores in Yunnan, wherein the raw ores contain 6.56% of Zn, grinding the ores to 60% of-400 meshes, adding water to adjust the pulp to 20% of mass concentration, adjusting the pH value of the pulp to 7.5, adding 100g/t of sodium thioglycolate, 3000g/t of sodium sulfide, 25g/t of 1-amino-styryl-triphenylamine and 50g/t of foaming agent No. 2 oil, performing rough flotation on the zinc oxide ores, adding 1000g/t of sodium sulfide and 25g/t of 1-amino-styryl-triphenylamine in scavenging, adding 25g/t of sodium thioglycolate in first concentration and 25g/t of sodium thioglycolate in second concentration, and adopting a flotation process flow of primary roughing, primary scavenging and secondary concentration, wherein a flotation process flow chart is shown in figure 3.
Example 4: application of 1-amino-styryl-triphenylamine in flotation of zinc oxide minerals (the flotation temperature is 28 ℃)
The method comprises the following steps of grinding a certain zinc oxide raw ore in Yunnan, wherein the raw ore contains 6.56% of Zn, grinding the ore until the ore is 90% of-400 meshes, adding water to adjust the pulp to have a mass concentration of 20%, adjusting the pH value of the pulp to 12, adding 200g/t of sodium thioglycolate, 6000g/t of sodium sulfide, 200g/t of 1-amino-styryl-triphenylamine and 100g/t of foaming agent No. 2 oil, performing rough flotation on the zinc oxide ore, adding 2000g/t of sodium sulfide and 100g/t of 1-amino-styryl-triphenylamine in scavenging, adding 75g/t of sodium thioglycolate in first concentration, adding 75g/t of sodium thioglycolate in second concentration, adopting a flotation process flow of primary rough concentration, primary scavenging and secondary concentration, and taking a flotation process flow chart as shown in an attached figure 4.
The results of comparative flotation tests of 1-amino-styryl-triphenylamine in the present invention with the commonly used collectors dodecylamine and hexadecylamine are shown in tables 3 and 4.
As can be seen from table 3, the collector of the present invention has significantly stronger collecting ability for zinc oxide minerals than the two collectors commonly used.
TABLE 3 comparative experimental results of collector flotation of Yunnan zinc oxide mineral
Aiming at a certain zinc oxide raw ore in Yunnan, the raw ore contains 6.56 percent of Zn, the flotation temperature is changed to be 8 ℃, 18 ℃, 28 ℃, 30 ℃ and 35 ℃, and the results of the flotation comparison test of the collecting agent in the embodiment 2 and the commonly used two collecting agents of dodecylamine and hexadecylamine are shown in the table 4.
As can be seen from Table 4, the excellent recovery rate of the collecting ability of the collector of the invention to minerals is more than 81% in the range of 8-30 ℃. It can also be seen from the table that the recovery was only 77.45% in the experiments when the flotation temperature exceeded 30 ℃, i.e. at 35 ℃, demonstrating that the flotation temperature using the collector of the invention performed well in the range of 8 ℃ to 30 ℃ and the capacity of the collector of the invention decreased significantly when it exceeded 30 ℃. Therefore, the collecting capacity of the collecting agent in the invention to the zinc oxide pure mineral is not influenced by the temperature in the range of 8-30 ℃.
TABLE 4 comparative experimental results of collector flotation of Yunnan zinc oxide mineral
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (6)
1. An application method of a novel triphenylamine alkene compound in zinc oxide ore flotation is characterized in that: will have the formula
The 1-amino-styryl-triphenylamine with the structural formula is used as a collecting agent in the flotation of zinc oxide ores, sodium sulfide is used as an activating agent, sodium thioglycolate is used as an inhibitor, and No. 2 oil is used as a foaming agent; formula (II)
The structural formula of (A) is as follows:
2. the method of claim 1, wherein the application of triphenylamine alkene compound in zinc oxide ore flotation is as follows: the pH value range of the ore pulp subjected to flotation is 7.5-12; the flotation temperature is 0-30 ℃; the granularity of the zinc oxide ore is-400 meshes and accounts for 60-90%.
3. The method of claim 1, wherein the application of triphenylamine alkene compound in zinc oxide ore flotation is as follows: the dosage of the 1-amino-styryl-triphenylamine is 50-300 g/t.
4. The method of claim 1, wherein the application of triphenylamine alkene compound in zinc oxide ore flotation is as follows: the dosage of the sodium sulfide is 4000-8000 g/t.
5. The method of claim 1, wherein the application of triphenylamine alkene compound in zinc oxide ore flotation is as follows: the dosage of the sodium thioglycolate is 150-350 g/t.
6. The method of claim 1, wherein the application of triphenylamine alkene compound in zinc oxide ore flotation is as follows: the dosage of the No. 2 oil is 50-100 g/t.
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