Efficient foaming agent suitable for high-cold region argillaceous porphyry copper mine and preparation method thereof

Abstract

The application provides a high-efficiency foaming agent suitable for argillaceous porphyry copper ore in high-cold regions and a preparation method and application thereof. The high-efficiency foaming agent suitable for argillaceous porphyry copper ore in high-cold regions is composed of mixed alcohols, pine oil, sulfur-nitrogen esters, diesel oil, xanthate and a surfactant. The high-efficiency foaming agent suitable for argillaceous porphyry copper ore in high-cold regions is simple in preparation method, does not produce intermediate products, has low irritation, is friendly to the environment, has low dosage of the medicament compared with traditional single foaming agent, has stable foam properties, and can also assist in collecting some chalcopyrite, molybdenite and other sulfide ores. Within the range of the component allocation, the foaming agent can fully exert the synergistic effect of each component. In a high-altitude environment (altitude >= 3500m), the foaming capacity and foaming rate of the foaming agent are obviously superior to those of traditional foaming agents.

Description

Technical Field

[0001] This invention belongs to the field of metallurgical chemical engineering, and further to the field of mineral processing technology. Specifically, it relates to a high-efficiency foaming agent suitable for argillaceous porphyry copper ore in high-altitude and cold regions and its preparation method. Background Technology

[0002] Copper constitutes approximately 0.01% of the Earth's crust on average, often existing as compounds in associated minerals. Due to its excellent electrical and thermal conductivity and ductility, copper has become an indispensable metal in many modern technological and industrial fields. Currently, the most important industrial types of copper deposits include porphyry copper deposits, copper-bearing sandstone copper deposits, copper-bearing pyrite copper deposits, and copper-nickel sulfide deposits. Among these, porphyry copper deposits account for more than half of the world's copper reserves. Many large-scale concentrators with reserves exceeding tens of thousands of tons process porphyry copper ore. These large porphyry copper deposits are mostly located in high-altitude, cold regions, and these ores are generally characterized by low grade, fine grain size, and severe mudification.

[0003] As altitude increases, atmospheric pressure decreases linearly. At 1000m, the pressure drops to 89.88kPa, and at 3500m, it plummets to 66kPa. The maximum aeration capacity of the flotation machine decreases with decreasing pressure, exhibiting a near-linear relationship. Since the amount of air within the device gradually decreases with decreasing pressure, the flotation machine aerates itself, inevitably reducing the aeration capacity. Simultaneously, severe mud formation in the ore, a high concentration of fine particles, slow foaming rates, and unstable foam further exacerbate the deterioration of performance indicators. However, upgrading flotation equipment is a massive and uneconomical undertaking. Adding excessive frother creates numerous sticky, fine bubbles, which can cause gangue minerals to adhere to these bubbles, affecting concentrate grade. If the raw ore contains a high amount of mud, it will generate a large amount of viscous foam, easily leading to "foam overflow" accidents, causing a large amount of concentrate to spill from the foam tank and disrupting production operations. Therefore, developing a frother suitable for muddy porphyry copper deposits in high-altitude, cold regions is of great significance. Summary of the Invention

[0004] The first objective of this invention is to provide a high-efficiency foaming agent suitable for argillaceous porphyry copper deposits in cold regions; the second objective is to provide a method for preparing the aforementioned high-efficiency foaming agent suitable for argillaceous porphyry copper deposits in cold regions.

[0005] The first objective of this invention is achieved by the fact that the high-efficiency foaming agent suitable for argillaceous porphyry copper deposits in cold regions is composed of mixed alcohols, pine oil, sulfur-nitrogen esters, diesel oil, xanthate esters, and surfactants.

[0006] The second objective of this invention is achieved by including the preparation and formulation steps of mixed alcohols, specifically including:

[0007] A. Preparation of mixed alcohols: Butanol and methylpentanol in the formula ratio are stirred and mixed at room temperature to obtain mixed alcohols;

[0008] B. Preparation:

[0009] 1) Add the pine oil in the formula ratio to the mixed alcohols, and stir and mix at room temperature to obtain mixture a;

[0010] 2) The sulfur-nitrogen esters, diesel oil, xanthate esters and surfactants in the formula are added to mixture a in sequence at a stirring speed of 800~1200r / min to obtain the target product, which is a high-efficiency foaming agent suitable for argillaceous porphyry copper deposits in cold regions. The time interval between each material is 3~5min and the stirring time is 35~55min.

[0011] The high-efficiency foaming agent for argillaceous porphyry copper deposits in high-altitude and cold regions of the present invention comprises, by weight, 15-55 parts of mixed alcohols, 30-60 parts of pine oil, 2-10 parts of sulfur-nitrogen esters, 1-10 parts of diesel oil, 1-10 parts of xanthate esters, and 0.5-2 parts of surfactants.

[0012] Furthermore, the mixed alcohol is a mixture of butanol and methylpentanol prepared in a certain proportion; the pine oil is a hydroxy terpene alcohol generated by the reaction of α-pinene with water; the sulfur ester is ethyl thiocyanate, propylene dimethyl dithiocarbamate, propylene N,N-diethyl dithiocarbamate, propylene N,N-diethyl dithiocarbamate, propionitrile N,N-diethyl dithiocarbamate, or propylene N,N-diethyl dithiocarbamate; the xanthate is methyl butyl xanthate, propylene ethyl xanthate, propionitrile n-butyl xanthate, or propylene isopentyl xanthate; the surfactant is one of sodium dodecylbenzene sulfonate, disodium N-octadecyl sulfonated succinate, tetrasodium N-octadecyl-N-sulfonated succinate aspartate, and tetrasodium N-octadecyl-N-1,2-dicarboxyethyl sulfonated succinate.

[0013] Furthermore, the butanol in the mixed alcohols can be other isomers of n-butanol such as n-butanol, sec-butanol, isobutanol, or tert-butanol, or combinations thereof.

[0014] Furthermore, the mixture of alcohols is prepared in the following proportions: 35% butanol and 65% methylpentanol.

[0015] The preparation method involves mixing mixed alcohols, pine oil, sulfur-nitrogen esters, diesel oil, xanthate esters, and surfactants according to the formula ratio to obtain the high-efficiency foaming agent.

[0016] The specific steps are as follows:

[0017] 1) Add butanol and methylpentanol to a stirred tank in the proportions described above, and mix them at room temperature, with a stirring speed of 100-280 r / min and a stirring time of 1-5 min to obtain a mixed alcohol.

[0018] 2) Add pine oil to the mixed alcohols according to the formula ratio, and stir at high speed at room temperature, stirring speed of 300-480 r / min and stirring time of 20-35 min to obtain the stirred mixture a;

[0019] 3) Add sulfur nitrogen esters, diesel oil, xanthate esters and surfactants to the mixture a in sequence according to the formula ratio. Stir at a speed of 800-1200 r / min, with an interval of 3-5 min between each material. Stir for 35-55 min to obtain the high-efficiency foaming agent suitable for argillaceous porphyry copper deposits in cold regions.

[0020] The advantages of this invention are:

[0021] 1. The present invention provides a high-efficiency foaming agent suitable for argillaceous porphyry copper deposits in cold regions. The preparation method is simple, does not produce intermediate products, has low irritation, and is environmentally friendly.

[0022] 2. The dosage of the agent is lower than that of traditional single foaming agents, the foam properties are stable, and it can also assist in the collection of some sulfide ores such as chalcopyrite and molybdenite.

[0023] 3. Within the above-mentioned component ratio range, this foaming agent can fully exert the synergistic effect of each component. In high-altitude environments (altitude ≥ 3500m), the foaming ability and foaming rate of this foaming agent are significantly better than those of traditional foaming agents. Detailed Implementation

[0024] 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.

[0025] The high-efficiency foaming agent for argillaceous porphyry copper deposits in high-altitude and cold regions described in this invention is composed of mixed alcohols, pine oil, sulfur-nitrogen esters, diesel oil, xanthate esters, and surfactants.

[0026] The mass ratio of the mixed alcohols, pine oil, sulfur nitrogen esters, diesel oil, xanthate esters and surfactants is (15~55):(30~60):(2~10):(1~10):(1~10):(0.5~2).

[0027] The mixed alcohols mentioned are a mixture of butanol and methylpentanol.

[0028] The volume ratio of butanol to methylpentanol is (30~40):(60~70).

[0029] The pine oil is a hydroxy compound terpene alcohol produced by reacting α-pinene with water.

[0030] The sulfur-nitrogen esters mentioned are ethyl thiocyanate acrylonitrile, dimethyl dithiocarbamate propylene ester, N,N-diethyl dithiocarbamate propylene ester, N,N-diethyl dithiocarbamate propionitrile ester, or N,N-diethyl dithiocarbamate acrylonitrile.

[0031] The xanthate esters mentioned are methyl butyl xanthate, propylene ethyl xanthate, n-butyl xanthate propionitrile, or propylene isopentyl xanthate.

[0032] The surfactant is sodium dodecylbenzenesulfonate, disodium N-octadecyl sulfonated succinate, tetrasodium N-octadecyl-N-sulfonated succinate aspartate, or tetrasodium N-octadecyl-N-1,2-dicarboxyethyl sulfonated succinate.

[0033] The method for preparing the high-efficiency foaming agent for argillaceous porphyry copper deposits in high-altitude and cold regions, as described in the invention, includes the steps of preparing and formulating mixed alcohols, specifically including:

[0034] A. Preparation of mixed alcohols: Butanol and methylpentanol in the formula ratio are stirred and mixed at room temperature to obtain mixed alcohols;

[0035] B. Preparation:

[0036] 1) Add the pine oil in the formula ratio to the mixed alcohols, and stir and mix at room temperature to obtain mixture a;

[0037] 2) The sulfur-nitrogen esters, diesel oil, xanthate esters and surfactants in the formula are added to mixture a in sequence at a stirring speed of 800~1200r / min to obtain the target product, which is a high-efficiency foaming agent suitable for argillaceous porphyry copper deposits in cold regions. The time interval between each material is 3~5min and the stirring time is 35~55min.

[0038] In step B, the stirring speed is 300-480 r / min, and the time is 20-35 min.

[0039] The invention will be further illustrated below with specific implementation examples:

[0040] Example 1

[0041] In this embodiment, the foaming agent raw material composition is as follows: 35 parts mixed alcohols, 50 parts pine oil, 5 parts N,N-diethyldithiocarbamate acrylonitrile, 6 parts diesel oil, 3 parts methyl butyl xanthate, and 1 part sodium dodecylbenzene sulfonate.

[0042] The specific weight parts of the mixed alcohol are 12.25 parts of n-butanol and 22.75 parts of methylpentanol.

[0043] The foaming rate and flotation effect of the foaming agent were determined using the following method:

[0044] In a laboratory at an altitude of 3500m, a porphyry copper ore deposit in a high-altitude, cold region of Yunnan Province with a Cu content of 0.32% was processed. A single roughing process was used, with 60% of the ore being ground to a fineness of -0.074mm. 300g / t of lime, 90g / t of ethyl thiocyanate, and 38g / t of the frother were added. Timing was started after opening the aeration valve, and the time required to form a uniform and stable froth layer was recorded. After 5 minutes of flotation and frothing, the Cu content in the concentrate and tailings products was analyzed. The results are shown in Table 1.

[0045] Table 1. Test Results of Example 1

[0046]

[0047] Comparative Example 1 (Compared with Example 1, the foaming agent in this comparative example is methyl isobutyl alcohol)

[0048] In a laboratory at an altitude of 3500m, a porphyry copper ore deposit in a high-altitude, cold region of Yunnan Province with a Cu content of 0.32% was processed. A single roughing process was used, with 60% of the ore being ground to a fineness of -0.074mm. Lime (300g / t), ethyl thiocyanate (90g / t), and methyl isobutyl methanol (38g / t) were added. Timing was started after the aeration valve was opened, and the time required to form a uniform and stable froth layer was recorded. After 5 minutes of flotation and frothing, the Cu content in the concentrate and tailings products was analyzed. The results are shown in Table 2.

[0049] Table 2 Results of Comparative Example 1

[0050]

[0051] As can be seen from Table 2, when methyl isobutyl methanol was used as the foaming agent, the time to form uniform bubbles was extended by 32 seconds compared with Example 1, and the Cu recovery rate was 3.28% lower.

[0052] Comparative Example 2 (Compared to Example 1, the foaming agent in this comparative example is No. 2 oil, specifically referring to flotation oil in the art)

[0053] In a laboratory at an altitude of 3500m, a porphyry copper ore deposit in a high-altitude, cold region of Yunnan Province with a Cu content of 0.32% was processed. A single roughing process was used, with 60% of the ore having a grinding fineness of -0.074mm. 300g / t of lime, 90g / t of ethyl thiocyanate, and 38g / t of No. 2 oil were added. Timing was started after the aeration valve was opened, and the time required to form a uniform and stable froth layer was recorded. After 5 minutes of flotation and frothing, the Cu content in the concentrate and tailings products was analyzed. The results are shown in Table 3.

[0054] Table 3. Results of Comparative Example 2

[0055]

[0056] As can be seen from Table 3, when No. 2 oil was used as the foaming agent, the time to form uniform bubbles was extended by 25 seconds compared with Example 1, and the Cu recovery rate was 2.55% lower.

[0057] Example 2

[0058] In this embodiment, the foaming agent raw material composition is as follows: 30 parts mixed alcohols, 55 parts pine oil, 6 parts N,N-diethyldithiocarbamate acrylonitrile, 5 parts diesel oil, 2 parts methyl butyl xanthate, and 2 parts dodecylbenzene sulfonic acid.

[0059] The specific weight parts of the mixed alcohol are 10.50 parts of n-butanol and 19.50 parts of methylpentanol.

[0060] The foaming rate and flotation effect of the foaming agent were determined using the following method:

[0061] In a laboratory at an altitude of 1800m, a porphyry copper ore deposit in a high-altitude, cold region of Tibet with a Cu content of 0.51% was processed. A single roughing process was used, with a grinding fineness of -0.074mm accounting for 65%. 500g / t of lime, 40g / t of ethyl thiocyanate, and 28g / t of the frother were added. Timing was started after opening the aeration valve, and the time required to form a uniform and stable froth layer was recorded. After flotation and frothing for 3 minutes, the Cu content in the concentrate and tailings products was analyzed. The results are shown in Table 4.

[0062] Table 4. Experimental Results of Example 2

[0063]

[0064] Comparative Example 3 (Compared to Example 2, the foaming agent in this comparative example is methyl isobutyl alcohol)

[0065] In a laboratory at an altitude of 1800m, a porphyry copper ore deposit in a high-altitude, cold region of Tibet with a Cu content of 0.51% was processed. A single roughing process was used, with a grinding fineness of -0.074mm accounting for 65%. 500g / t of lime, 40g / t of ethyl thiocyanate, and 28g / t of methyl isobutyl methanol were added. Timing was started after opening the aeration valve, and the time required to form a uniform and stable froth layer was recorded. After 3 minutes of flotation and frothing, the Cu content in the concentrate and tailings products was analyzed. The results are shown in Table 5.

[0066] Table 5. Results of Comparative Example 3

[0067]

[0068] As can be seen from Table 5, when methyl isobutyl methanol was used as the foaming agent, the time to form uniform bubbles was extended by 5 seconds compared with Example 2, and the Cu recovery rate was 2.95% lower.

[0069] Comparative Example 4 (Compared to Example 2, the foaming agent in this comparative example is No. 2 oil, specifically referring to flotation oil in the art)

[0070] In a laboratory at an altitude of 1800m, a porphyry copper ore deposit in a high-altitude, cold region of Tibet with a Cu content of 0.51% was processed. A single roughing process was used, with a grinding fineness of -0.074mm accounting for 65%. 500g / t of lime, 40g / t of ethyl thiocyanate, and 28g / t of No. 2 oil were added. Timing was started after opening the aeration valve, and the time required to form a uniform and stable froth layer was recorded. After 5 minutes of flotation and frothing, the Cu content in the concentrate and tailings products was analyzed. The results are shown in Table 3.

[0071] Table 6. Results of Comparative Example 4

[0072]

[0073] As can be seen from Table 6, when No. 2 oil was used as the foaming agent, the time to form uniform bubbles was extended by 3 seconds compared with Example 2, and the Cu recovery rate was 1.45% lower.

Claims

1. A high-efficiency foaming agent suitable for argillaceous porphyry copper deposits in high-altitude and cold regions, characterized in that, The high-efficiency foaming agent suitable for argillaceous porphyry copper deposits in cold regions is composed of mixed alcohols, pine oil, sulfur-nitrogen esters, diesel oil, xanthate esters, and surfactants. The mass ratio of the mixed alcohols, pine oil, sulfur-nitrogen esters, diesel oil, xanthate esters, and surfactants is (15~55):(30~60):(2~10):(1~10):(1~10):(0.5~2); The mixed alcohols mentioned are a mixture of butanol and methylpentanol; The volume ratio of butanol to methylpentanol is (30~40):(60~70); The xanthate esters mentioned are methyl butyl xanthate, propylene ethyl xanthate, n-butyl xanthate propionitrile, or propylene isopentyl xanthate. The surfactant is sodium dodecylbenzenesulfonate, disodium N-octadecyl sulfonated succinate, tetrasodium N-octadecyl-N-sulfonated succinate aspartate, or tetrasodium N-octadecyl-N-1,2-dicarboxyethyl sulfonated succinate.

2. The high-efficiency foaming agent for argillaceous porphyry copper deposits in high-altitude and cold regions according to claim 1, characterized in that, The pine oil is a hydroxy compound terpene alcohol produced by reacting α-pinene with water.

3. The high-efficiency foaming agent for argillaceous porphyry copper deposits in high-altitude and cold regions according to claim 1, characterized in that, The sulfur-nitrogen esters mentioned are ethyl thiocyanate acrylonitrile, dimethyl dithiocarbamate propylene ester, N,N-diethyl dithiocarbamate propylene ester, N,N-diethyl dithiocarbamate propionitrile ester, or N,N-diethyl dithiocarbamate acrylonitrile.

4. A method for preparing a high-efficiency foaming agent suitable for argillaceous porphyry copper deposits in high-altitude and cold regions, as described in any one of claims 1 to 3, characterized in that, This includes the preparation and formulation steps of mixed alcohols, specifically including: A. Preparation of mixed alcohols: Butanol and methylpentanol in the formula ratio are stirred and mixed at room temperature to obtain mixed alcohols; B. Preparation: 1) Add the pine oil in the formula ratio to the mixed alcohols in the formula ratio, and stir and mix at room temperature to obtain mixture a; 2) The sulfur-nitrogen esters, diesel oil, xanthate esters and surfactants in the formula are added to mixture a in sequence at a stirring speed of 800~1200r / min to obtain the target product, which is a high-efficiency foaming agent suitable for argillaceous porphyry copper deposits in cold regions. The time interval between each material is 3~5min and the stirring time is 35~55min.

5. The preparation method according to claim 4, characterized in that, In step B, the stirring speed is 300-480 r / min, and the time is 20-35 min.

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