A process for recovering carbon dioxide to synthesize chalcopyrite foaming agent and its application

Abstract

This invention discloses a process and application for recovering carbon dioxide to synthesize chalcopyrite frother. The frother synthesis method includes the following steps: (1) synthesizing dimethyl carbonate from carbon dioxide; (2) acidifying and modifying dimethyl carbonate to obtain the target frother; the acid used for acidification includes hydrochloric acid, nitric acid, sulfurous acid, and acetic acid. The acidification and modification process is as follows: dimethyl carbonate and acid are mixed at a mass ratio of (3-2):(1.5-1), stirred at 600 rpm for 30 minutes at 25°C, and then centrifuged. This invention combines the carbon dioxide capture, conversion, and utilization process chain with non-ferrous metal flotation. On the one hand, it utilizes the products after carbon dioxide capture and conversion to promote the flotation of non-ferrous metal ores; on the other hand, it promotes the carbon dioxide capture and conversion industrial chain through flotation, thereby accelerating the carbon dioxide capture and conversion rate, achieving a win-win situation, and contributing to green and sustainable development.

Description

Technical Field

[0001] This invention belongs to the field of mineral processing flotation reagents, specifically, it relates to a process and application for recovering carbon dioxide to synthesize a chalcopyrite frother. Background Technology

[0002] The use of carbon dioxide in flotation has a long history, dating back to 1971 at the Tongguanshan Ore Processing Plant in China. The Tongguanshan Plant utilized waste gas (carbon dioxide) from a lime kiln located near the plant to replace sulfuric acid in the flotation of pyrite, eliminating the old process that required sulfuric acid for sulfur removal. This saved 16,600 tons of sulfuric acid while increasing sulfur recovery by 8.6%. This reduced the plant's economic costs and increased lime kiln production by 50%. Research has found that carbon dioxide can more effectively regulate the pH of the ore pulp, while also promoting a negative shift in the zeta potential on the pyrite surface and creating a layer of nanobubbles on the pyrite surface. These bubbles are more aggregated and stable than air. Bashir Wani Omaretal found that introducing carbon dioxide into nickel ore pulp improved nickel flotation indicators, increasing nickel recovery by 10 percentage points and grade by 4 percentage points. This led to the development of a method for carbon dioxide sequestration during nickel ore flotation.

[0003] In summary, previous studies have primarily used carbon dioxide as a modifier in slurry flotation and to control bubble formation. This aims to improve flotation performance while simultaneously achieving carbon dioxide sequestration. However, this method of sequestering carbon dioxide through flotation has certain limitations. First, it requires convenient spatial proximity between the carbon dioxide supplier and the concentrator; second, it primarily sequesters carbon dioxide generated during current production processes, rather than carbon dioxide already released into the environment.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The technical problem to be solved by this invention is to overcome the shortcomings of the prior art and provide a process and application for recovering carbon dioxide to synthesize chalcopyrite foaming agents. To solve the above technical problem, the basic concept of the technical solution adopted by this invention is as follows:

[0006] A process for recovering carbon dioxide to synthesize chalcopyrite foaming agent and its application, comprising the following steps:

[0007] (1) Use existing synthetic methods to synthesize dimethyl carbonate from carbon dioxide;

[0008] (2) The dimethyl carbonate was subjected to acidification modification treatment;

[0009] (3) The product after acidification and modification of dimethyl carbonate was used in the flotation of chalcopyrite.

[0010] The synthesis methods described in step (1) include existing processes for synthesizing dimethyl carbonate, such as the absorption of carbon dioxide by ammonia and its reaction with methanol, and the reaction between methanol and carbon dioxide, but are not limited to these. This invention uses the direct reaction of methanol and carbon dioxide to synthesize dimethyl carbonate. (The synthesis was carried out using the patented method of Jiang Qi, Lin Qihe, Huang Zhongtao. A direct synthesis method of dimethyl carbonate [P]. Guangdong Province: CN1064346C, 2001-04-11) First, magnesium reacts with methanol to generate magnesium methoxide, and then carbon dioxide reacts with methanol in a gas-liquid reaction under the action of magnesium methoxide to generate dimethyl carbonate. The reaction equation is as follows: The process conditions are as follows: (1) The amount of magnesium accounts for 3 to 9% of the weight percentage of methanol; (2) The reaction temperature of magnesium reacting with methanol is 200℃ and the reaction time is 1 hour; (3) The carbon dioxide gas pressure is 10 to 50 kg / cm2; (4) The reaction temperature of carbon dioxide reacting with methanol in a gas-liquid reaction under the action of magnesium methoxide is 20 to 200℃; (5) The reaction time of carbon dioxide reacting with methanol in a gas-liquid reaction under the action of magnesium methoxide is 1 to 11 hours.

[0011] Step (2) Dimethyl carbonate acidification modification: The acid selected includes strong acids such as hydrochloric acid and nitric acid, medium-strong acids such as sulfurous acid, and weak acids such as acetic acid. Hydrochloric acid is preferred. The two are mixed in a ratio of (3-2):(1.5-1), stirred at 600 rpm for 30 min at 25°C, and then centrifuged to obtain the acidification modification treatment.

[0012] By adopting the above technical solution, the present invention has the following beneficial effects compared with the prior art.

[0013] This invention combines the carbon dioxide capture, conversion, and utilization process chain with non-ferrous metal flotation. On the one hand, it uses the products after carbon dioxide capture and conversion to promote the flotation of non-ferrous metal ores. On the other hand, it promotes the carbon dioxide capture and conversion industrial chain through flotation, thereby accelerating the carbon dioxide capture and conversion rate, achieving a win-win situation, and contributing to green and sustainable development.

[0014] The specific embodiments of the present invention will now be described in further detail with reference to the accompanying drawings. Attached Figure Description

[0015] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments and descriptions of the invention are used to explain the invention, but do not constitute an undue limitation of the invention. Obviously, the drawings described below are merely some embodiments, and those skilled in the art can obtain other drawings based on these drawings without creative effort. In the drawings:

[0016] Figure 1 The infrared spectrum is shown after acidification modification of dimethyl carbonate.

[0017] Figure 2 The infrared spectrum of dimethyl carbonate;

[0018] Figure 3 The results are from flotation tests of dimethyl carbonate, methyl isobutyl methanol, and a blank control.

[0019] Figure 4 The results of flotation tests on dimethyl carbonate acid-modified dimethyl carbonate and modified acid as controls are presented.

[0020] Figure 5 The results of flotation tests are as follows: dimethyl carbonate acidified modified product + methyl isobutyl methanol, dimethyl carbonate acidified modified product and methyl isobutyl methanol as control.

[0021] It should be noted that these accompanying drawings and textual descriptions are not intended to limit the scope of the invention in any way, but rather to illustrate the concept of the invention to those skilled in the art by referring to specific embodiments. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the accompanying drawings. The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0023] Example 1

[0024] The flotation process using dimethyl carbonate as a frother for chalcopyrite includes the following steps:

[0025] (1) Use existing synthetic methods to synthesize dimethyl carbonate from carbon dioxide;

[0026] (2) Apply dimethyl carbonate to chalcopyrite flotation.

[0027] Step (2) Main operation: Using an RK / FDⅢ type 1.5L single-cell flotation machine, 100g of chalcopyrite with a -0.074mm particle size percentage of 80% after grinding is placed into the flotation cell. The pulp is adjusted at a speed of 1900r / min for 2min, and dimethyl carbonate (1500g / t) is added. After a certain period of time, the aeration valve is opened to allow the slurry to flow at 0.1m. 3 Aeration was performed at a flow rate of / min for flotation froth scraping. Froth was scraped every 10s over cumulative time intervals of 1, 3, 6, and 10 min, collecting four concentrates. Due to the high purity of the chalcopyrite samples, the percentage of flotation froth to feed mass was used as the chalcopyrite recovery rate.

[0028] See chalcopyrite flotation parameters Figure 3 .

[0029] Comparative Example 1-1

[0030] Flotation using methyl isobutyl methanol includes the following steps:

[0031] (1) The known flotation frother methyl isobutyl methanol was applied to the flotation of chalcopyrite.

[0032] Step (1) Main operation: Using an RK / FDⅢ type 1.5L single-cell flotation machine, 100g of chalcopyrite with a -0.074mm particle size percentage of 80% after grinding was placed into the flotation cell. The slurry was adjusted at 1900r / min for 2min, and methyl isobutyl methanol (1500g / t) was added. After a certain period of time, the aeration valve was opened and aeration was carried out at a flow rate of 0.1m3 / min for flotation froth removal. During the cumulative time of 1, 3, 6 and 10min, froth was removed every 10s, and 4 concentrates were collected. Due to the high purity of the chalcopyrite sample, the percentage of flotation froth to feed mass was used as the chalcopyrite recovery rate.

[0033] See chalcopyrite flotation parameters Figure 3 .

[0034] Comparative Examples 1-2

[0035] Reagent-free flotation includes the following steps:

[0036] (1) Conduct reagent-free flotation of chalcopyrite.

[0037] Step (1) Main operation: Using an RK / FDⅢ type 1.5L single-cell flotation machine, 100g of chalcopyrite with a -0.074mm particle size percentage of 80% after grinding was placed into the flotation cell. The slurry was adjusted at 1900r / min for 2min, and the aeration valve was opened to aerate at a flow rate of 0.1m3 / min for flotation froth removal. During the cumulative time of 1, 3, 6, and 10min, froth was removed every 10s, and 4 concentrates were collected. Due to the high purity of the chalcopyrite sample, the percentage of flotation froth to feed mass was used as the chalcopyrite recovery rate.

[0038] See chalcopyrite flotation parameters Figure 3 .

[0039] pass Figure 3 It can be seen that dimethyl carbonate alone has a certain foaming property, but it is still somewhat inferior to the traditional foaming agent methyl isobutyl methanol.

[0040] Example 2

[0041] The process of using dimethyl carbonate acid-modified product as a flotation agent for chalcopyrite includes the following steps:

[0042] (1) Use existing synthetic methods to synthesize dimethyl carbonate from carbon dioxide;

[0043] (2) Acidification modification of dimethyl carbonate: Dimethyl carbonate and hydrochloric acid are mixed at a mass ratio of 2:1, stirred at 600 rpm for 30 min at 25℃, and then centrifuged to obtain the acidified product of dimethyl carbonate.

[0044] (3) The product after acidification and modification of dimethyl carbonate was used in the flotation of chalcopyrite.

[0045] The infrared spectrum of dimethyl carbonate after acidification modification in step (2) is shown below. Figure 1 .Depend on Figure 1 and Figure 2 It can be seen that the infrared spectrum of dimethyl carbonate changes significantly after acidification, indicating that acidification causes some chemical bonds in dimethyl carbonate to break.

[0046] Step (3) Main operation: Using an RK / FDⅢ type 1.5L single-cell flotation machine, 100g of chalcopyrite with a -0.074mm particle size percentage of 80% after grinding was placed into the flotation cell. The slurry was adjusted at 1900r / min for 2min, and dimethyl carbonate acidified modification product (1500g / t) was added. After a certain period of action, the aeration valve was opened and aeration was carried out at a flow rate of 0.1m3 / min for flotation froth removal. During the cumulative time of 1, 3, 6 and 10min, froth was removed every 10s, and 4 concentrates were collected. Due to the high purity of the chalcopyrite sample, the percentage of flotation froth to feed mass was used as the chalcopyrite recovery rate.

[0047] See chalcopyrite flotation parameters Figure 4 .

[0048] Comparative Example 2-1

[0049] Flotation using dimethyl carbonate includes the following steps:

[0050] (1) Use existing synthetic methods to synthesize dimethyl carbonate from carbon dioxide;

[0051] (2) Apply dimethyl carbonate to chalcopyrite flotation.

[0052] Step (2) Main operation: Using an RK / FDⅢ type 1.5L single-cell flotation machine, 100g of chalcopyrite with a -0.074mm particle size percentage of 80% after grinding was placed into the flotation cell. The slurry was adjusted at 1900 r / min for 2 min, and dimethyl carbonate (1500g / t) was added. After a certain period of time, the aeration valve was opened and aeration was carried out at a flow rate of 0.1 m3 / min for flotation froth removal. During the cumulative time of 1, 3, 6, and 10 min, froth was removed every 10 s, and 4 concentrates were collected. Due to the high purity of the chalcopyrite sample, the percentage of flotation froth to feed mass was used as the chalcopyrite recovery rate.

[0053] See chalcopyrite flotation parameters Figure 4 .

[0054] Comparative Example 2-2

[0055] Flotation using modified acids includes the following steps:

[0056] (1) Apply modified acid to chalcopyrite flotation.

[0057] Step (2) Main operation: Using an RK / FDⅢ type 1.5L single-cell flotation machine, 100g of chalcopyrite with a -0.074mm particle size percentage of 80% after grinding was placed into the flotation cell. The slurry was adjusted at 1900r / min for 2min, and modified acid (1500g / t) was added. After a certain period of action, the aeration valve was opened and aeration was carried out at a flow rate of 0.1m3 / min for flotation froth removal. During the cumulative time of 1, 3, 6 and 10min, froth was removed every 10s, and 4 concentrates were collected. Due to the high purity of the chalcopyrite sample, the percentage of flotation froth to feed mass was used as the chalcopyrite recovery rate.

[0058] See chalcopyrite flotation parameters Figure 4 .

[0059] pass Figure 4 It can be seen that the foaming properties are greatly improved after the acidification modification of dimethyl carbonate.

[0060] Example 3

[0061] The process of using dimethyl carbonate acid-modified product as a flotation agent for chalcopyrite includes the following steps:

[0062] (1) Use existing synthetic methods to synthesize dimethyl carbonate from carbon dioxide;

[0063] (2) Dimethyl carbonate was acidified and modified. Dimethyl carbonate and hydrochloric acid were mixed at a mass ratio of 2:1 and stirred at 600 rpm for 30 min at 25 °C. Then the mixture was centrifuged to obtain the acidified product of dimethyl carbonate.

[0064] (3) The product after acidification and modification of dimethyl carbonate was used in the flotation of chalcopyrite.

[0065] Step (3) Main operation: Using an RK / FDⅢ type 1.5L single-cell flotation machine, 100g of chalcopyrite with a -0.074mm particle size percentage of 80% after grinding was placed into the flotation cell. The slurry was adjusted at 1900r / min for 2min, and dimethyl carbonate acidified modification product (1500g / t) was added. After a certain period of action, the aeration valve was opened and aeration was carried out at a flow rate of 0.1m3 / min for flotation froth removal. During the cumulative time of 1, 3, 6 and 10min, froth was removed every 10s, and 4 concentrates were collected. Due to the high purity of the chalcopyrite sample, the percentage of flotation froth to feed mass was used as the chalcopyrite recovery rate.

[0066] See chalcopyrite flotation parameters Figure 5 .

[0067] Comparative Example 3-1

[0068] The product modified by acidification with dimethyl carbonate is floated with methyl isobutyl methanol, including the following steps:

[0069] (1) Use existing synthetic methods to synthesize dimethyl carbonate from carbon dioxide;

[0070] (2) The dimethyl carbonate was subjected to acidification modification treatment;

[0071] (3) The product of acidification and modification of dimethyl carbonate and methyl isobutyl methanol were used in the flotation of chalcopyrite.

[0072] Step (3) Main operation: Using an RK / FDⅢ type 1.5L single-cell flotation machine, 100g of chalcopyrite with a -0.074mm particle size percentage of 80% after grinding was placed into the flotation cell. The slurry was adjusted at 1900r / min for 2min, and the product of dimethyl carbonate acidification modification and methyl isobutyl methanol (1500g / t) were added. After a certain period of action, the aeration valve was opened and aeration was carried out at a flow rate of 0.1m3 / min for flotation froth removal. During the cumulative time of 1, 3, 6 and 10min, froth was removed every 10s, and 4 concentrates were collected. Due to the high purity of the chalcopyrite sample, the percentage of flotation froth to feed mass was used as the chalcopyrite recovery rate.

[0073] See chalcopyrite flotation parameters Figure 5 .

[0074] Comparative Example 3-2

[0075] The flotation of methyl isobutyl methanol includes the following steps:

[0076] (1) The known flotation frother methyl isobutyl methanol was applied to the flotation of chalcopyrite.

[0077] Step (1) Main operation: Using an RK / FDⅢ type 1.5L single-cell flotation machine, 100g of chalcopyrite with a -0.074mm particle size percentage of 80% after grinding was placed into the flotation cell. The slurry was adjusted at 1900r / min for 2min, and methyl isobutyl methanol (1500g / t) was added. After a certain period of time, the aeration valve was opened and aeration was carried out at a flow rate of 0.1m3 / min for flotation froth removal. During the cumulative time of 1, 3, 6 and 10min, froth was removed every 10s, and 4 concentrates were collected. Due to the high purity of the chalcopyrite sample, the percentage of flotation froth to feed mass was used as the chalcopyrite recovery rate.

[0078] See chalcopyrite flotation parameters Figure 5 .

[0079] pass Figure 5 It can be seen that the foaming properties of the modified dimethyl carbonate are comparable to those of the traditional foaming agent methyl isobutyl methanol.

[0080] The above examples and comparative studies demonstrate that modified dimethyl carbonate has the potential to act as a foaming agent. Surface tension tests were conducted, primarily measuring the surface tension of deionized water, 10 mg / L MIBC, 15 mg / L MIBC, 10 mg / L LDC, and a mixture of 10 mg / L LDC and 1 mL hydrochloric acid. The surface tensions were 64.0072 mN / m, 62.1874 mN / m, 61.2398 mN / m, 61.0942 mN / m, and 60.4214 mN / m, respectively. Therefore, it is confirmed that acid-modified dimethyl carbonate aqueous solutions can indeed reduce the surface tension of liquids, demonstrating its potential as a foaming agent.

[0081] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-described technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A process for recovering carbon dioxide to synthesize chalcopyrite foaming agent, characterized in that, Includes the following steps: (1) Using existing technology to synthesize dimethyl carbonate from carbon dioxide; (2) Dimethyl carbonate is acidified to obtain the target foaming agent; The acids used for acidification include hydrochloric acid, nitric acid, sulfurous acid, and acetic acid. The acidification and modification process is as follows: dimethyl carbonate and acid are mixed at a mass ratio of (3-2):(1.5-1), stirred at 600 rpm for 30 min at 25°C, and then centrifuged.

2. The application of the foaming agent synthesized by the process described in claim 1 in the flotation of chalcopyrite.

3. The application according to claim 2, characterized in that, The flotation process is as follows: A single-cell flotation machine was used. 100g of chalcopyrite with a -0.074mm particle size percentage of 80% after grinding was put into the flotation cell. The pulp was adjusted at 1900 r / min for 2 min. Dimethyl carbonate acidification modification product was added at a rate of 1500g / t. After a certain period of time, the aeration valve was opened and aeration was carried out at a flow rate of 0.1 m3 / min for flotation frothing. The froth was scraped every 10 seconds at cumulative time intervals of 1, 3, 6 and 10 min, and 4 concentrates were collected.

Images