High-calcium zinc oxide ore flotation collecting agent and preparation method and application thereof

Abstract

The invention discloses a high-calcium zinc oxide ore flotation collector as well as a preparation method and application thereof. The high-calcium zinc oxide ore flotation collector is prepared from the following raw materials: 3-(dodecyloxy) propyl-1-amine, 3-(tetradecyloxy) propyl-1-amine, glacial acetic acid and di (2-ethylhexyl) phosphate. The collecting agent has the advantages that the surface tension of ore pulp is effectively reduced, separation of zinc oxide minerals and calcium-containing gangue minerals is enhanced, and therefore the collecting agent has the advantages of being good in selectivity, high in collecting capacity, low in agent dosage, resistant to low temperature and the like, is especially suitable for low-grade zinc oxide ores rich in easily-argillized calcium-containing minerals and has good zinc oxide flotation indexes.

Description

Technical Field

[0001] This invention belongs to the field of metallurgical technology, specifically relating to a high-calcium zinc oxide ore flotation collector, its preparation method, and its application. Background Technology

[0002] Zinc is a strategic mineral resource, holding a vital position in the non-ferrous metals industry. It is the fourth most consumed metal after iron, aluminum, and copper, and is widely used in various sectors of production and daily life. Domestic demand for zinc is projected to increase by approximately 5.3% annually until 2030, but the supply-demand imbalance in zinc resources is becoming increasingly prominent, leading to a significant dependence on imports. With the large-scale development of easily beneficiated sulfide zinc ore resources, the global average grade of zinc ore is decreasing, ore composition is becoming more complex, and the proportion of zinc oxide ore is gradually increasing. Carbonate rock-type zinc deposits are the main type, accounting for approximately 33% of the national proven reserves. These deposits are characterized by a predominance of carbonate gangue minerals (calcite, dolomite, gypsum, etc.), and the surface of these zinc oxide ores contains Ca. 2+ or Zn 2+ The presence of active sites leads to poor selectivity of traditional anionic collectors (such as fatty acids). Furthermore, fine-grained calcareous gangue easily coats the surface of zinc oxide minerals, hindering collector adsorption. Additionally, the presence of Ca in the pulp... 2+ High ion concentrations can interfere with the directional adsorption of collectors on the surface of target minerals. This leads to poor pre-enrichment effects and low resource utilization. Therefore, there is an urgent need for technological innovation in the beneficiation of high-calcium, low-grade zinc oxide ores to provide technical support for the development and utilization of this type of resource.

[0003] The primary method for separating zinc oxide ore is flotation. Currently, the most commonly used method is the sulfide-amine process, which employs a combination of sodium sulfide and dodecylamine as collectors. However, this reagent system suffers from problems such as high annual flotation froth, process instability, poor low-temperature resistance, poor selectivity, large reagent consumption, high flotation costs, and low concentrate grades. Therefore, developing economical and efficient zinc oxide collectors is of great significance. Summary of the Invention

[0004] The first objective of this invention is to provide a high-calcium zinc oxide ore flotation collector; the second objective is to provide a method for preparing the high-calcium zinc oxide ore flotation collector; and the third objective is to provide the application of the high-calcium zinc oxide ore flotation collector.

[0005] The first objective of this invention is achieved by the high-calcium zinc oxide ore flotation collector being prepared from the raw materials 3-(dodecyloxy)prop-1-amine, 3-(tetradecyloxy)prop-1-amine, glacial acetic acid, and di(2-ethylhexyl) phosphate.

[0006] The 3-(dodecyloxy)prop-1-amine and 3-(tetradecyloxy)prop-1-amine have the following structures:

[0007] In this case, R- represents a straight-chain hydrocarbon group consisting of 12 and 14 carbon atoms.

[0008] The di(2-ethylhexyl) phosphate has the following structure:

[0009] The drug molecule contains phosphate groups precisely linked to two alkyl chains.

[0010] The second objective of this invention is achieved by including the synthesis of mixed alkoxyamine acetates and synergistic reaction steps, specifically including: A. Synthesis of mixed alkoxyamine acetates: 1) Mixing raw materials 3-(dodecyloxy)prop-1-amine and 3-(tetradecyloxy)prop-1-amine yields mixture a; 2) Add glacial acetic acid to mixture a and stir at room temperature to obtain mixed alkoxyamine acetate b; B. Synergistic reaction: Di(2-ethylhexyl) phosphate is added to mixed alkoxyamine acetate b and stirred at room temperature to obtain the target high-calcium zinc oxide ore flotation collector.

[0011] The third objective of this invention is achieved by the application of the high-calcium zinc oxide ore flotation collector in the flotation process of low-grade zinc oxide ore rich in easily muddy calcium-bearing minerals; specifically, the high-calcium low-grade zinc oxide ore is ground and then sent to a flotation cell, where a flotation activator, gangue inhibitor, and the high-calcium zinc oxide ore flotation collector of this invention are added in sequence to obtain zinc oxide concentrate flotation froth and tailings in the flotation cell.

[0012] To address various problems encountered in the zinc oxide flotation process, current research on zinc oxide flotation reagents mainly focuses on two directions: firstly, actively developing novel and highly efficient collectors and depressants using modern new technologies, especially computer simulation technology; and secondly, finding effective reagent combinations to further improve the flotation effect of zinc oxide and reduce reagent dosage and usage costs by utilizing the positive synergistic effect between reagents. Compared to the high cost of developing and promoting novel and highly efficient collectors, which makes them difficult to apply in actual production, the combined use of reagents can alleviate the problem of reagent usage costs to a certain extent. Therefore, this invention will be based on modified reagents and reagent combinations, aiming to achieve a "1+1>2" effect.

[0013] The beneficial effects of this invention on high-calcium, low-grade zinc oxide ore are achieved as follows: (1) The mixed alkylamine acetates synthesized using 3-(dodecyloxy)prop-1-amine and 3-(tetradecyloxy)prop-1-amine and glacial acetic acid have excellent water solubility and can be adsorbed on the surface of negatively charged calcareous gangue minerals. By neutralizing the charge, the covering of zinc oxide by the ore slime is reduced, thereby increasing the zinc oxide mineral Zn. 2+ Exposure provides favorable conditions for the action of the collector, and the -NH2 and -COO in the agent molecule - Functional groups can interact with Zn on the surface of zinc oxide minerals. 2+ Strong chemical adsorption occurs, thus being collected by flotation; (2) The mixed alkylamine acetate obtained by synthesizing 3-(dodecyloxy)prop-1-amine and 3-(tetradecyloxy)prop-1-amine and glacial acetic acid, combined with di(2-ethylhexyl) phosphate, can effectively reduce the surface tension of the pulp, realize the flotation-enhanced separation of zinc oxide minerals and gangue minerals, thereby improving the selectivity of the collector. At the same time, the active group -PO(OH)2 of di(2-ethylhexyl) phosphate can form stable five-membered or six-membered ring chelates with metal ions on the mineral surface, and with Zn 2+ The stability constant of the chelate formed is much higher than that of Ca. 2+ The resulting chelate can both collect and selectively chemically adsorb Zn on the surface of zinc oxide minerals. 2+ At the active site, it exhibits better selectivity and achieves efficient harvesting of zinc oxide minerals compared to the traditional dodecylamine and fatty acid method. Attached Figure Description

[0014] Figure 1 This is a process flow diagram for preparing the zinc oxide ore flotation collector of the present invention; Figure 2 This is a flowchart of the flotation test of the zinc oxide ore flotation collector of the present invention. Detailed Implementation

[0015] The present invention will be further described below with reference to embodiments, but this is not intended to limit the present invention in any way. Any modifications or substitutions made based on the teachings of the present invention shall fall within the protection scope of the present invention.

[0016] The high-calcium zinc oxide ore flotation collector of the present invention is prepared from raw materials 3-(dodecyloxy)prop-1-amine, 3-(tetradecyloxy)prop-1-amine, glacial acetic acid and di(2-ethylhexyl) phosphate.

[0017] The preparation method of the high-calcium zinc oxide ore flotation collector of the present invention includes the steps of synthesizing mixed alkoxyamine acetate and synergistic reaction, specifically including: A. Synthesis of mixed alkoxyamine acetates: 1) Mixing raw materials 3-(dodecyloxy)prop-1-amine and 3-(tetradecyloxy)prop-1-amine yields mixture a; 2) Add glacial acetic acid to mixture a and stir at room temperature to obtain mixed alkoxyamine acetate b; B. Synergistic reaction: Di(2-ethylhexyl) phosphate is added to mixed alkoxyamine acetate b and stirred at room temperature to obtain the target high-calcium zinc oxide ore flotation collector.

[0018] In step A, the mass ratio of 3-(dodecyloxy)prop-1-amine to 3-(tetradecyloxy)prop-1-amine is (40~55):(10~20).

[0019] In step 2), the mass ratio of mixture a to glacial acetic acid is (75~80):(20~25).

[0020] In step B, the mass ratio of mixed alkoxyamine acetate b to di(2-ethylhexyl) phosphate is (85~90):(10~15).

[0021] The application of the high-calcium zinc oxide ore flotation collector of the present invention is its application in the flotation process of low-grade zinc oxide ore containing easily muddy calcium minerals.

[0022] The present invention will be further described below with reference to specific embodiments: Example 1

[0023] Mix 3-(dodecyloxy)prop-1-amine and 3-(tetradecyloxy)prop-1-amine in a mass ratio of 3:1 to obtain mixture a.

[0024] Glacial acetic acid was added to mixture a and stirred at room temperature for 2 hours to obtain an acidic pale yellow colloidal mixture b. The mass ratio of mixture a to glacial acetic acid was 4:1. Di(2-ethylhexyl) phosphate was added to reactant b, and the mixture was stirred at room temperature for 1 hour to obtain the target collector. The mass ratio of reactant b to di(2-ethylhexyl) phosphate was 8:1.

[0025] Example 2

[0026] Mix 3-(dodecyloxy)prop-1-amine and 3-(tetradecyloxy)prop-1-amine in a mass ratio of 2:1 to obtain mixture a.

[0027] Glacial acetic acid was added to mixture a and stirred at room temperature for 2 hours to obtain an acidic pale yellow colloidal mixture b. The mass ratio of mixture a to glacial acetic acid was 3:1. Di(2-ethylhexyl) phosphate was added to reactant b, and the mixture was stirred at room temperature for 1 hour to obtain the target collector. The mass ratio of reactant b to di(2-ethylhexyl) phosphate was 7:1.

[0028] Example 3

[0029] Take a zinc oxide mine in Sichuan as an example.

[0030] Properties of the raw ore: The raw material contains 6.39% Zn and 42.11% CaO, with a zinc oxidation rate of 88%. The main gangue mineral is calcite, followed by quartz.

[0031] Experimental Procedure: A single roughing test was conducted, with 80% of the ore being ground to a fineness of -0.074 mm. The activator consisted of 2000 g / t sodium carbonate and 6000 g / t sodium sulfide, and the gangue inhibitor was sodium hexametaphosphate at 800 g / t. The collector invented in Example 1 was used at a dosage of 300 g / t. The process flow is as follows: Figure 2 As shown.

[0032] Mineral processing parameters: Zn content of zinc concentrate is 18.74%, and Zn recovery rate is 83.55%.

[0033] Example 4

[0034] Take a zinc oxide mine in Yunnan as an example.

[0035] Properties of the raw ore: The raw material contains 5.78% Zn and 39.11% CaO, with a zinc oxidation rate of 90%. The main gangue minerals are calcite and dolomite, followed by quartz.

[0036] Experimental Procedure: A single roughing test was conducted, with grinding fineness of -0.074mm accounting for 85%. The activator consisted of 3000g / t sodium carbonate + 6000g / t sodium sulfide, and the gangue inhibitor sodium hexametaphosphate was 1000g / t. The collector invented in Example 2 was used at a dosage of 250g / t. The process flow is as follows: Figure 2 As shown.

[0037] Mineral processing parameters: Zn content in zinc concentrate is 17.49%, and Zn recovery rate is 81.26%.

Claims

1. A high-calcium zinc oxide ore flotation collector, characterized in that, The high-calcium zinc oxide ore flotation collector is prepared from raw materials 3-(dodecyloxy)prop-1-amine, 3-(tetradecyloxy)prop-1-amine, glacial acetic acid and di(2-ethylhexyl) phosphate.

2. A method for preparing the high-calcium zinc oxide ore flotation collector according to claim 1, characterized in that, This includes the synthesis and synergistic reaction steps of mixed alkoxyamine acetates, specifically including: A. Synthesis of mixed alkoxyamine acetates: 1) Mixing raw materials 3-(dodecyloxy)prop-1-amine and 3-(tetradecyloxy)prop-1-amine yields mixture a; 2) Add glacial acetic acid to mixture a and stir at room temperature to obtain mixed alkoxyamine acetate b; B. Synergistic reaction: Di(2-ethylhexyl) phosphate is added to mixed alkoxyamine acetate b and stirred at room temperature to obtain the target high-calcium zinc oxide ore flotation collector.

3. The preparation method according to claim 2, characterized in that, In step A, the mass ratio of 3-(dodecyloxy)prop-1-amine to 3-(tetradecyloxy)prop-1-amine is (40~55):(10~20).

4. The preparation method according to claim 2, characterized in that, In step 2), the mass ratio of mixture a to glacial acetic acid is (75~80):(20~25).

5. The preparation method according to claim 2, characterized in that, In step B, the mass ratio of mixed alkoxyamine acetate b to di(2-ethylhexyl) phosphate is (85~90):(10~15).

6. The application of the high-calcium zinc oxide ore flotation collector according to claim 1, characterized in that, The application of the high-calcium zinc oxide ore flotation collector in the flotation process of low-grade zinc oxide ore rich in easily muddy calcium-containing minerals.

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