Efficient foaming agent suitable for argillaceous porphyry copper ore in alpine region and preparation method of efficient foaming agent

Abstract

The invention provides an efficient foaming agent suitable for argillaceous porphyry copper ore in an alpine region and a preparation method and application of the efficient foaming agent. The efficient foaming agent suitable for the argillaceous porphyry copper ore in the alpine region is composed of mixed alcohols, terpenic oil, sulfur-nitrogen esters, diesel oil, xanthates and a surfactant. According to the efficient foaming agent suitable for the argillaceous porphyry copper ore in the alpine region, the preparation method is simple, no intermediate product is generated, irritation is small, and environment friendliness is achieved; the dosage of the agent is lower than that of a traditional single foaming agent, the foam property is stable, and auxiliary collection of sulphide ores such as chalcopyrite and molybdenite is considered; the foaming agent can give full play to the synergistic effect of all the components in the component proportion range, and in the high-altitude environment (the altitude is larger than or equal to 3500 m), the foaming capacity and the foaming rate of the foaming agent are obviously better than those of a traditional foaming agent.

Description

Technical Field

[0001] The invention belongs to the field of metallurgy and chemical industry, and further belongs to the field of mineral processing technology, and specifically relates to a high-efficiency foaming agent suitable for muddy porphyry copper mines in alpine areas and a preparation method thereof. Background Art

[0002] The average content of copper in the earth's crust is about 0.01%. It often exists in the form of compounds in paragenetic ores. Due to its good electrical and thermal conductivity and ductility, copper has become an indispensable metal in many modern scientific and industrial fields. At present, the most important industrial types of copper deposits are porphyry copper, copper-bearing sandstone copper, copper-bearing pyrite copper and sulfide copper-nickel ores. Among them, porphyry copper deposits account for more than half of the world's copper resources. Most of the large-scale ore dressing plants with a capacity of 10,000 tons process porphyry copper. Most of these large-scale porphyry copper mines are located in high-altitude and cold areas, and most of these ores have the characteristics of low grade, fine embedded grain size and severe mud.

[0003] As the altitude increases, the atmospheric pressure decreases linearly. When the altitude is 1000m, the air pressure drops to 89.88kPa. When the altitude is 3500m, the air pressure drops sharply to 66kPa. The maximum air volume of the flotation machine decreases with the decrease of air pressure, and is basically linear with the air pressure. Since the amount of air in the device gradually decreases with the decrease of air pressure, the flotation machine is inflated by self-priming, and the air volume must be reduced. At the same time, the ore is seriously muddy, there are many fine particles, the foaming rate is slow and the foam is unstable, which will aggravate the deterioration of indicators. However, the replacement of flotation equipment is huge and uneconomical. Adding too much foaming agent will cause a large number of sticky and fine bubbles, which will easily cause gangue minerals to adhere to the bubbles and affect the grade of the concentrate. If the original ore contains more mud, a large amount of sticky foam will be formed, which is easy to cause "slot run" accidents. A large amount of concentrate will overflow the foam tank, causing chaos in production operations. Therefore, it is of great significance to develop a foaming agent suitable for muddy porphyry copper mines in high-altitude cold areas. Summary of the invention

[0004] The first purpose of the present invention is to provide a high-efficiency foaming agent suitable for muddy porphyry copper mines in alpine areas; the second purpose is to provide a preparation method of the high-efficiency foaming agent suitable for muddy porphyry copper mines in alpine areas.

[0005] The first object of the present invention is achieved in that the high-efficiency foaming agent suitable for muddy porphyry copper mines in high-cold areas is composed of mixed alcohols, pine oil, thiocyanate, diesel, xanthate and surfactant.

[0006] The second object of the present invention is achieved by comprising the steps of preparing and preparing a mixed alcohol, specifically comprising: A. Preparation of mixed alcohols: Stir and mix butanol and methyl amyl alcohol in a prescribed ratio at room temperature to obtain a mixed alcohol; B. Preparation: 1) adding pine oil in a formulated ratio to the mixed alcohols in a formulated ratio, and stirring and mixing at room temperature to obtain a mixture a; 2) The formulated sulfur nitrogen esters, diesel, xanthate and surfactants are sequentially added into the mixture a at a stirring speed of 800-1200 r / min to obtain the target efficient foaming agent suitable for muddy porphyry copper mines in alpine areas, wherein the time interval for adding each material is 3-5 min, and the stirring time is 35-55 min.

[0007] The high-efficiency foaming agent for muddy porphyry copper mines in alpine areas of the present invention comprises, by weight, 15 to 55 parts of mixed alcohols, 30 to 60 parts of pine oil, 2 to 10 parts of thiocyanate, 1 to 10 parts of diesel, 1 to 10 parts of xanthate and 0.5 to 2 parts of surfactant.

[0008] Furthermore, the mixed alcohols are a mixture of butanol and methylpentanol prepared in a certain proportion; the pine oil is a hydroxy compound terpene alcohol generated by adding water to α-pinene; the thiourea ester is ethylthiourea acrylonitrile or dimethyl dithiocarbamate propionate or N,N-diethyl dithiocarbamate propionitrile or N,N-diethyl dithiocarbamate propionitrile; the xanthate is butyl xanthate methyl formate or ethyl xanthate propionate or n-butyl xanthate propionitrile or isopentyl xanthate; the surfactant is one of sodium dodecylbenzenesulfonate, N-octadecyl sulfosuccinamic acid disodium salt, N-octadecyl-N-sulfosuccinamide aspartic acid tetrasodium salt and N-octadecyl-N-1,2-dicarboxyethyl sulfosuccinamic acid tetrasodium salt.

[0009] Furthermore, the butanol in the mixed alcohols may be other isomers of n-butanol such as n-butanol, sec-butanol, isobutanol or tert-butanol, and combinations thereof.

[0010] Furthermore, the configuration ratio of the mixed alcohols is 35% butanol and 65% methyl amyl alcohol.

[0011] The preparation method comprises the following steps: mixing mixed alcohols, pine oil, thiocyanate, diesel, xanthate and surfactant according to a formula ratio to obtain the high-efficiency foaming agent.

[0012] The specific operations are as follows: 1) adding butanol and methyl amyl alcohol into a stirring kettle in the proportion, stirring and mixing at room temperature, at a stirring speed of 100-280 r / min, and for 1-5 min to obtain a mixed alcohol; 2) adding pine oil to the mixed alcohols according to the formula ratio, stirring at high speed at room temperature, at a stirring speed of 300-480 r / min, and for 20-35 min to obtain a stirred mixture a; 3) Adding sulfur nitrogen esters, diesel, xanthate and surfactants to the stirred mixture a in order according to the formula ratio, stirring at a speed of 800-1200 r / min, adding each material at a time interval of 3-5 minutes, stirring for 35-55 minutes to obtain the high-efficiency foaming agent suitable for muddy porphyry copper mines in alpine areas.

[0013] The advantages of the present invention are: 1. The present invention provides a high-efficiency foaming agent suitable for muddy porphyry copper mines in alpine areas, which has a simple preparation method, does not produce intermediate products, has low irritation, and is environmentally friendly; 2. The dosage of the agent is lower than that of the traditional single foaming agent, the foam property is stable, and it can also assist in the collection of some sulfide ores such as chalcopyrite and molybdenite; 3. Within the above-mentioned component ratio range, the foaming agent can give full play to the synergistic effect of each component. In a high-altitude environment (altitude ≥ 3500m), the foaming ability and foaming rate of the foaming agent are significantly better than those of traditional foaming agents. DETAILED DESCRIPTION

[0014] The present invention is further described below in conjunction with the embodiments, but the present invention is not limited in any way. Any changes or substitutions made based on the teachings of the present invention belong to the protection scope of the present invention.

[0015] The high-efficiency foaming agent suitable for muddy porphyry copper mines in high-cold areas is composed of mixed alcohols, pine oil, thiocyanate, diesel, xanthate and surfactant.

[0016] The mass ratio of the mixed alcohols, pine oil, thiocyanate, diesel, xanthate and surfactant is (15-55): (30-60): (2-10): (1-10): (1-10): (0.5-2).

[0017] The mixed alcohols are mixed alcohols of butanol and methyl amyl alcohol.

[0018] The volume ratio of butanol to methyl amyl alcohol is (30-40): (60-70).

[0019] The pine oil is a terpene alcohol, a hydroxy compound, generated by the reaction of α-pinene with water.

[0020] The thiocarbamates are ethylthiocarbamate acrylonitrile or dimethyl dithiocarbamate acrylonitrile or N,N-diethyl dithiocarbamate acrylonitrile or N,N-diethyl dithiocarbamate propionitrile or N,N-diethyl dithiocarbamate acrylonitrile.

[0021] The xanthate esters are butyl xanthate methyl formate, ethyl xanthate propylene ester, n-butyl xanthate propionitrile ester or isopentyl xanthate propylene ester.

[0022] The surfactant is sodium dodecylbenzenesulfonate, disodium N-octadecyl sulfosuccinamate, tetrasodium N-octadecyl-N-sulfosuccinamide aspartate or tetrasodium N-octadecyl-N-1,2-dicarboxyethyl sulfosuccinamate.

[0023] The method for preparing the high-efficiency foaming agent suitable for argillaceous porphyry copper mines in alpine areas according to the invention comprises the steps of preparing and preparing a mixed alcohol, specifically comprising: A. Preparation of mixed alcohols: Stir and mix butanol and methyl amyl alcohol in a prescribed ratio at room temperature to obtain a mixed alcohol; B. Preparation: 1) adding pine oil in a formulated ratio to the mixed alcohols in a formulated ratio, and stirring and mixing at room temperature to obtain a mixture a; 2) The formulated sulfur nitrogen esters, diesel, xanthate and surfactants are sequentially added into the mixture a at a stirring speed of 800-1200 r / min to obtain the target efficient foaming agent suitable for muddy porphyry copper mines in alpine areas, wherein the time interval for adding each material is 3-5 min, and the stirring time is 35-55 min.

[0024] In step B 1), the stirring speed is 300-480 r / min and the stirring time is 20-35 min.

[0025] The present invention is further described below with specific implementation cases: Example 1 The raw material composition of the foaming agent in this embodiment is as follows: 35 parts of mixed alcohols, 50 parts of pine oil, 5 parts of N,N-diethyldithiocarbamate acrylonitrile, 6 parts of diesel, 3 parts of butyl xanthate methyl formate, and 1 part of sodium dodecylbenzene sulfonate.

[0026] The mixed alcohols specifically include 12.25 parts by weight of n-butanol and 22.75 parts by weight of methyl amyl alcohol.

[0027] The foaming rate and flotation effect of the foaming agent are determined according to the following method: In a laboratory at an altitude of 3500m, a porphyry copper ore in a high-cold area of ​​Yunnan was processed. The Cu content was 0.32%. A primary roughing process was adopted, and the grinding fineness was -0.074mm, accounting for 60%. 300g / t of lime, 90g / t of ethiocarbamate, and 38g / t of the foaming agent were added. After the inflation valve was opened, the timing was started, and the time required to form a uniform and stable foam layer was recorded; after flotation scraping for 5 minutes, the Cu content in the concentrate product and tailings product was tested. The results are shown in Table 1.

[0028] Table 1 Experimental results of Example 1

[0029] Comparative Example 1 (Compared with Example 1, the foaming agent in this comparative example is methyl isobutyl carbinol) In a laboratory at an altitude of 3500m, a porphyry copper ore in a high-cold area of ​​Yunnan was processed. The Cu content was 0.32%. A primary roughing process was adopted, and the grinding fineness was -0.074mm, accounting for 60%. 300g / t of lime, 90g / t of ethiocarbamate, and 38g / t of methyl isobutyl carbinol were added. The timing was started after the inflation valve was opened, and the time required to form a uniform and stable foam layer was recorded; after flotation scraping for 5 minutes, the Cu content in the concentrate product and tailings product was tested. The results are shown in Table 2.

[0030] Table 2 Comparative Example 1 Test results

[0031] It can be seen from Table 2 that when methyl isobutyl carbinol is used as the foaming agent, compared with Example 1, the time for forming uniform bubbles is extended by 32 seconds, and the Cu recovery rate is lowered by 3.28%.

[0032] Comparative Example 2 (Compared with Example 1, the foaming agent in this comparative example is 2# oil, which specifically refers to flotation oil in the art) In a laboratory at an altitude of 3500m, a porphyry copper ore in a high-cold area of ​​Yunnan was processed. The Cu content was 0.32%. A primary roughing process was adopted, and the grinding fineness was -0.074mm, accounting for 60%. 300g / t of lime, 90g / t of ethiocarbamate, and 38g / t of 2# oil were added. The timing was started after the inflation valve was opened, and the time required to form a uniform and stable foam layer was recorded; after flotation scraping for 5 minutes, the Cu content in the concentrate product and tailings product was tested. The results are shown in Table 3.

[0033] Table 3 Comparative Example 2 Test Results

[0034] It can be seen from Table 3 that when 2# oil is used as the foaming agent, the time for forming uniform bubbles is extended by 25 seconds and the Cu recovery rate is lowered by 2.55% compared with Example 1.

[0035] Example 2 The raw material composition of the foaming agent in this embodiment is as follows: 30 parts of mixed alcohols, 55 parts of pine oil, 6 parts of N,N-diethyldithiocarbamate acrylonitrile, 5 parts of diesel, 2 parts of butyl xanthate methyl formate, and 2 parts of dodecylbenzene sulfonic acid.

[0036] The mixed alcohols specifically include 10.50 parts by weight of n-butanol and 19.50 parts by weight of methyl amyl alcohol.

[0037] The foaming rate and flotation effect of the foaming agent are determined according to the following method: In a laboratory at an altitude of 1800m, a porphyry copper ore in a high-cold area of ​​Tibet was processed. The Cu content was 0.51%. A primary roughing process was adopted, and the grinding fineness was -0.074mm, accounting for 65%. 500g / t of lime, 40g / t of ethiocarbamate, and 28g / t of the frother were added. After opening the inflation valve, the timing was started, and the time required to form a uniform and stable foam layer was recorded; after flotation scraping for 3 minutes, the Cu content in the concentrate product and tailings product was tested. The results are shown in Table 4.

[0038] Table 4 Experimental results of Example 2

[0039] Comparative Example 3 (Compared with Example 2, the foaming agent in this comparative example is methyl isobutyl carbinol) In a laboratory at an altitude of 1800m, a porphyry copper ore in a high-cold area of ​​Tibet was processed. The Cu content was 0.51%. A primary roughing process was adopted, and the grinding fineness was -0.074mm, accounting for 65%. 500g / t of lime, 40g / t of ethiocarbamate, and 28g / t of methyl isobutyl carbinol were added. The timing was started after the inflation valve was opened, and the time required to form a uniform and stable foam layer was recorded; after flotation frothing for 3 minutes, the Cu content in the concentrate product and tailings product was tested. The results are shown in Table 5.

[0040] Table 5 Comparative Example 3 Test Results

[0041] It can be seen from Table 5 that when methyl isobutyl carbinol is used as the foaming agent, compared with Example 2, the time for forming uniform bubbles is extended by 5 seconds, and the Cu recovery rate is lowered by 2.95%.

[0042] Comparative Example 4 (Compared with Example 2, the foaming agent in this comparative example is 2# oil, which specifically refers to flotation oil in the art) In a laboratory at an altitude of 1800m, a porphyry copper ore in a high-cold area of ​​Tibet was processed. The Cu content was 0.51%. A primary roughing process was adopted, and the grinding fineness was -0.074mm, accounting for 65%. 500g / t of lime, 40g / t of ethiocarbamate, and 28g / t of 2# oil were added. After opening the inflation valve, the timing was started, and the time required to form a uniform and stable foam layer was recorded; after flotation frothing for 5 minutes, the Cu content in the concentrate product and tailings product was tested. The results are shown in Table 3.

[0043] Table 6 Comparative Example 4 Test Results

[0044] It can be seen from Table 6 that when 2# oil is used as the foaming agent, the time for forming uniform bubbles is extended by 3 seconds and the Cu recovery rate is lower by 1.45% compared with Example 2.

Claims

1. A high-efficiency foaming agent suitable for muddy porphyry copper mines in alpine areas, characterized in that: The high-efficiency foaming agent suitable for muddy porphyry copper mines in high-cold areas is composed of mixed alcohols, pine oil, thiocyanate, diesel, xanthate and surfactant.

2. The high-efficiency foaming agent suitable for argillaceous porphyry copper mines in alpine areas according to claim 1 is characterized in that: The mass ratio of the mixed alcohols, pine oil, thiocyanate, diesel, xanthate and surfactant is (15-55): (30-60): (2-10): (1-10): (1-10): (0.5-2).

3. The high-efficiency foaming agent suitable for argillaceous porphyry copper mines in alpine areas according to claim 1 or 2, characterized in that: The mixed alcohols are mixed alcohols of butanol and methyl amyl alcohol.

4. The high-efficiency foaming agent suitable for argillaceous porphyry copper mines in alpine areas according to claim 4 is characterized in that: The volume ratio of butanol to methyl amyl alcohol is (30-40): (60-70).

5. The high-efficiency foaming agent suitable for argillaceous porphyry copper mines in alpine areas according to claim 1 or 2, characterized in that: The pine oil is a terpene alcohol, a hydroxy compound, generated by the reaction of α-pinene with water.

6. The high-efficiency foaming agent suitable for argillaceous porphyry copper mines in alpine areas according to claim 1 or 2, characterized in that: The thiocarbamates are ethylthiocarbamate acrylonitrile or dimethyl dithiocarbamate acrylonitrile or N,N-diethyl dithiocarbamate acrylonitrile or N,N-diethyl dithiocarbamate propionitrile or N,N-diethyl dithiocarbamate acrylonitrile.

7. The high-efficiency foaming agent suitable for argillaceous porphyry copper mines in alpine areas according to claim 1 or 2, characterized in that: The xanthate esters are butyl xanthate methyl formate, ethyl xanthate propylene ester, n-butyl xanthate propionitrile ester or isopentyl xanthate propylene ester.

8. The high-efficiency foaming agent suitable for argillaceous porphyry copper mines in alpine areas according to claim 1 or 2, characterized in that: The surfactant is sodium dodecylbenzenesulfonate, disodium N-octadecyl sulfosuccinamate, tetrasodium N-octadecyl-N-sulfosuccinamide aspartate or tetrasodium N-octadecyl-N-1,2-dicarboxyethyl sulfosuccinamate.

9. A method for preparing a high-efficiency foaming agent suitable for argillaceous porphyry copper mines in alpine areas according to any one of claims 1 to 8, characterized in that: The method comprises the steps of preparing and formulating mixed alcohols, specifically comprising: A. Preparation of mixed alcohols: Stir and mix butanol and methyl amyl alcohol in a prescribed ratio at room temperature to obtain a mixed alcohol; B. Preparation: 1) adding pine oil in a formulated ratio to the mixed alcohols in a formulated ratio, and stirring and mixing at room temperature to obtain a mixture a; 2) The formulated sulfur nitrogen esters, diesel, xanthate and surfactants are sequentially added into the mixture a at a stirring speed of 800-1200 r / min to obtain the target efficient foaming agent suitable for muddy porphyry copper mines in alpine areas, wherein the time interval for adding each material is 3-5 min, and the stirring time is 35-55 min.

10. The preparation method according to claim 9, characterized in that: In step B 1), the stirring speed is 300-480 r / min and the stirring time is 20-35 min.

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