A combined collector for high-arsenic chalcopyrite flotation and application thereof

Abstract

The application relates to a combined collector for high-arsenic chalcopyrite flotation and application thereof, and belongs to the technical field of mineral flotation separation. ‑ The combined collector is prepared by combining a flotation reagent with R-OCSS functional groups and a flotation reagent with R-NCS functional groups, wherein R is a hydrocarbon group with 2-4 carbon atoms. Meanwhile, the application also provides an application method of the combined collector in high-arsenic chalcopyrite flotation. Under the condition of the same amount of reagent, the combined collector has better selectivity and separation efficiency, can greatly improve the recovery grade and recovery rate of chalcopyrite, can better utilize mineral resources, improve the benefit, and reduce the pollution to the environment.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of mineral flotation, and particularly relates to a combined collector for high-arsenic chalcopyrite flotation and application thereof in high-arsenic chalcopyrite flotation. BACKGROUND

[0002] As one of the common and closely related non-ferrous metals to human, copper has excellent properties such as electrical conductivity, thermal conductivity, ductility and corrosion resistance, and is an indispensable metal material in the fields of electronic technology, construction, mechanical processing and light industry. With the rapid development of China's national economy, the demand for copper is increasing day by day. However, with the large-scale development of copper resources in recent years, rich ores are becoming less and less, and the overall resources are becoming increasingly lean, leading to an increasingly prominent contradiction between supply and demand of high-quality copper concentrates.

[0003] Most of the copper mines are mainly based on sulfide ores, among which the copper sulfide minerals mainly include chalcopyrite, parasympathy, chalcocite, arsenic covellite, bornite and blue copper, etc. Chalcopyrite (CuFeS2) is an important and abundant copper ore, accounting for 70% of the copper resources on earth. Copper ions are activators of arsenic-containing sulfide minerals, and the presence of copper ions increases the floatability of arsenic-containing sulfide minerals and improves the arsenic content in copper concentrates, thereby making the arsenic content in copper concentrates exceed the standard. Although various smelting processes of copper sulfide are relatively mature, they are mostly suitable for materials with low arsenic content (0.3-0.5%), which can be directly smelted without treatment. If the arsenic content exceeds the standard, it will be converted into arsenic trioxide, arsine, arsenite and organic arsenic compounds during the smelting process, which will corrode equipment, pollute the environment and seriously affect the quality of copper smelting products.

[0004] Therefore, in order to solve the contradiction between supply and demand of domestic mineral resources, improve the technical level of utilization of mineral resources in China and reduce the content of harmful impurities, it is the key to the separation of copper-arsenic sulfide ore to develop a new type of combined collector which is efficient, non-toxic, low in cost and environmentally friendly for efficient separation of copper-arsenic flotation, as well as an effective separation method and process. SUMMARY

[0005] The primary object of the present application is to provide a combined collector for copper-arsenic separation, which can not only achieve effective separation of gangue minerals and copper minerals, but also reduce the arsenic content while ensuring high copper grade and recovery rate in the concentrate.

[0006] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0007] A combined collector for high-arsenic chalcopyrite flotation, comprising R-OCSS -The functional group and the flotation reagent with R-NCS functional group are combined to be formulated, wherein R is a hydrocarbon group with 2-4 carbon atoms.

[0008] Further, the high arsenic chalcopyrite has an arsenic content of greater than 3%.

[0009] Further, the flotation reagent with R-OCSS - The flotation reagent with the functional group is one or more of ethyl xanthate, butyl xanthate and isobutyl xanthate, and preferably sodium butyl xanthate.

[0010] Further, the flotation reagent with R-NCS functional group is thiocyanate, and preferably 3-(methylthio) propyl isothiocyanate.

[0011] As a general inventive idea, the application further provides a method for applying the combined collector to high-arsenic chalcopyrite flotation, comprising the following steps:

[0012] (1) grinding the raw ore to obtain a slurry with a certain concentration;

[0013] (2) adding a depressant to depress the minerals including pyrite, and then adding the combined collector and a frother to fully mix the slurry, and then performing roughing flotation to obtain a roughing concentrate and a roughing tailing;

[0014] (3) performing blank cleaning on the obtained roughing concentrate to obtain a copper concentrate; and adding the combined collector and the frother to the obtained roughing tailing to perform scavenging to obtain a copper tailing.

[0015] Further, the flotation particle size of the slurry in step (1) is 75% of -0.074 mm, and the flotation slurry concentration is 30%, which can achieve the purpose of selective dissociation of the flotation sample.

[0016] Further, the depressant in step (2) is CaO, and the combined collector is composed of the flotation reagent with R-OCSS - functional group and the flotation reagent with R-NCS functional group in a mass ratio of 1:1 to 1:3; the frother is No. 2 oil; the CaO agent amount is 500-800 g·t -1 ; the combined collector agent amount is 100-300 g·t -1 ; and the frother No. 2 oil agent amount is 40 g·t -1 . The frother can increase the froth in the slurry and make the froth more stable, and interact with the combined collector to drive the useful minerals to float.

[0017] Furthermore, in step (3), the blank refining refers to flotation without adding additional flotation reagents. The blank refining is performed twice, with the tailings from each refining being the middlings of their respective refining processes. The concentrate obtained from the final refining is copper concentrate. The scavenging is performed three times, with the concentrate from each scavenging being the middlings of their respective scavenging processes. The tailings from the final scavenging are copper tailings. During each scavenging process, the dosage of the combined collector is 10-50 g / t. -1 The dosage of the foaming agent is 5-20 g / t. -1 The middlings from the first fine selection and the middlings from the first scavenging are combined and returned to the roughing process for further selection; the middlings from the second fine selection are returned to the first fine selection process for further selection; the middlings from the second and third scavenging processes are returned to the first and second scavenging processes for further selection, respectively.

[0018] The beneficial effects of this invention are:

[0019] In this invention, the R-OCSS is used. - Flotation reagents with functional groups can form biflavonoids on the surface of sulfide minerals, resulting in a strong collecting effect. They have a long history of application, are widely available, and are inexpensive. The flotation reagents with R-NCS functional groups have a strong selective effect, are less likely to interact with arsenopyrite, and are more likely to adsorb onto the surface of chalcopyrite, making the surface hydrophobic. They are also natural extracts, suitable for use in the food industry. Compared to most organic flotation reagents currently available, they are less toxic and have a simpler production process.

[0020] The combined collector of the present invention uses R-OCSS - Flotation reagents with functional groups and those with R-NCS functional groups are compounded in a specific mass ratio and combined with a reasonable application process. This allows the flotation reagents with R-NCS functional groups to adsorb onto the copper sites on the surface of chalcopyrite, and these reagents possess R-OCSS functional groups. - The functional groups in the flotation reagents increase the number of iron adsorption sites, resulting in a higher adsorption density and stronger surface hydrophobicity. The formulated combined collector exhibits strong collecting ability and selectivity. At the same dosage, the combined collector of this invention can effectively improve copper grade and recovery rate, while reducing arsenic content, thus maximizing the utilization of mineral resources and increasing mine profitability. Attached Figure Description

[0021] Figure 1 This is a process flow diagram for the flotation of high-arsenic chalcopyrite using the combined collector described in this invention.

[0022] Reference numerals: a-CaO; b-The combined collector described in this invention; c-Foaming agent No. 2 oil Detailed Implementation

[0023] For the convenience of understanding the present application, the following will make a more comprehensive and detailed description of the present application in combination with the drawings of the specification and the preferred embodiments, but it should be noted that the protection scope of the present application is not limited to the following specific embodiments.

[0024] Unless otherwise defined, all the professional terms used in the following have the same meaning as generally understood by those skilled in the art. The professional terms used in the present application are only for the purpose of describing the specific embodiments and are not intended to limit the protection scope of the present application.

[0025] Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by existing methods.

[0026] Ore raw material: a certain polymetallic copper ore in Liaoning, wherein the copper content is 0.854%, the arsenic content is 3.574%, and the sulfur content is 6.65%. The main metal mineral components in the ore are chalcopyrite, pyrite, and arsenopyrite, and the non-metallic gangue minerals are mainly quartz and calcite, etc.

[0027] Example 1

[0028] A combined collector for high-arsenic chalcopyrite flotation, which is composed of sodium butyl xanthate and 3-(methylthio) propyl isothiocyanate with a mass ratio of 1:3.

[0029] A method for applying the combined collector in high-arsenic chalcopyrite flotation, as shown in the accompanying Figure 1 , the specific operation is as follows:

[0030] (1) The raw ore is added to the ball mill for grinding, and the grinding fineness is controlled at 75% of -0.074mm, and the grinding concentration is 60%;

[0031] (2) After adding CaO, the combined collector and the foaming agent No. 2 oil into the flotation sample of step (1) to fully mix, air is filled for roughing to obtain rough concentrate and rough tailings; the combined collector used is composed of three parts of 3-(methylthio) propyl isothiocyanate and one part of sodium butyl xanthate, which is added into water at room temperature and used after being dissolved uniformly by ultrasonic; the CaO dosage is 800g·t -1 , the combined collector dosage is 100g·t -1 , and the foaming agent No. 2 oil dosage is 40g·t -1 ;

[0032] (3) The rough concentrate is subjected to two blank cleaning, and the tailings of each cleaning are the respective cleaning middlings, and the concentrate obtained by the last cleaning is the copper concentrate. The rough tailings are subjected to three times of scavenging, and the concentrate of each scavenging is the respective scavenging middling, and the tailings of the last scavenging is the copper tailings;

[0033] The combined collector dosage of the first scavenging is 50 g·t -1 The frother No. 2 oil dosage is 20 g·t -1 ; The combined collector dosage of the second scavenging is 25 g·t -1 The frother No. 2 oil dosage is 10 g·t -1 ; The combined collector dosage of the third scavenging is 10 g·t -1 The frother No. 2 oil dosage is 5 g·t -1 ;

[0034] The middlings of the first cleaning and the middlings of the first scavenging are combined and returned to the roughing process for reselection; the middlings of the second cleaning are returned to the first cleaning process for reselection; the middlings of the second scavenging and the middlings of the third scavenging are returned to the first scavenging and the second scavenging processes for reselection, respectively.

[0035] Example 2

[0036] A combined collector for high-arsenic chalcopyrite flotation, which is composed of sodium butyl xanthate and 3-(methylthio) propyl isothiocyanate in a mass ratio of 1:2.

[0037] A method for applying the combined collector in high-arsenic chalcopyrite flotation, as shown in the accompanying drawings, the specific operation is as follows: Figure 1

[0038] (1) The raw ore is added to the ball mill for grinding, and the grinding fineness is controlled at 75% of -0.074 mm, and the grinding concentration is 60%;

[0039] (2) After adding CaO, the combined collector and the frother No. 2 oil to the flotation sample of step (1) to fully condition, air is filled for roughing to obtain a roughing concentrate and a roughing tailings; the combined collector used is composed of two portions of 3-(methylthio) propyl isothiocyanate and one portion of sodium butyl xanthate. It is used after being dissolved uniformly in water at room temperature by ultrasonic treatment; the CaO dosage for roughing is 800 g·t -1 , the combined collector dosage is 100 g·t -1 , and the frother No. 2 oil dosage is 40 g·t -1 ;

[0040] (3) The roughing concentrate is subjected to two blank cleanings, and the tailings of each cleaning are the respective cleaning middlings, and the concentrate obtained by the last cleaning is a copper concentrate; the roughing tailings are subjected to three scavengings, and the concentrate of each scavenging is the respective scavenging middling, and the tailings of the last scavenging are a copper tailings;

[0041] The combined collector dosage of the first scavenging is 50 g·t -1 , and the frother No. 2 oil dosage is 20 g·t​-1 ; the combined collector dosage of the third scavenging is 10 g·t -1 , the frother No. 2 oil dosage is 10 g·t -1 ; the combined collector dosage of the third scavenging is 10 g·t -1 , the frother No. 2 oil dosage is 5 g·t -1 ;

[0042] The middlings of the first cleaning and the middlings of the first scavenging are combined and returned to the roughing process for reselection; the middlings of the second cleaning are returned to the first cleaning process for reselection; the middlings of the second scavenging and the middlings of the third scavenging are returned to the first scavenging and the second scavenging processes for reselection, respectively.

[0043] Example 3

[0044] A combined collector for high-arsenic chalcopyrite flotation, which is composed of sodium butyl xanthate and 3-(methylthio) propyl isothiocyanate in a mass ratio of 1:1.

[0045] A method for applying the combined collector in high-arsenic chalcopyrite flotation, as shown in the accompanying drawings, and the specific operation is as follows: Figure 1

[0046] (1) The raw ore is added to a ball mill for grinding, and the grinding fineness is controlled at 75% of -0.074 mm, and the grinding concentration is 60%;

[0047] (2) After adding CaO, the combined collector and the frother No. 2 oil to the flotation sample of step (1) to fully condition the pulp, air is charged for roughing to obtain a roughing concentrate and a roughing tailings; the combined collector used is composed of one part of 3-(methylthio) propyl isothiocyanate and one part of sodium butyl xanthate. The combined collector is used after being dissolved in water at room temperature by ultrasonic treatment until each component is uniformly dissolved; the CaO dosage for roughing is 800 g·t -1 , the combined collector dosage is 100 g·t -1 , and the frother No. 2 oil dosage is 40 g·t -1 ;

[0048] (3) The roughing concentrate is subjected to two blank cleanings, and the tailings of each cleaning are the respective cleaning middlings, and the concentrate obtained by the last cleaning is a copper concentrate; the roughing tailings are subjected to three scavengings, and the concentrate of each scavenging is the respective scavenging middling, and the tailings of the last scavenging are a copper tailings;

[0049] The combined collector dosage of the first scavenging is 50 g·t -1 , the frother No. 2 oil dosage is 20 g·t -1 ; the combined collector dosage of the second scavenging is 25 g·t -1 , the frother No. 2 oil dosage is 10 g·t​-1 ; the dosage of the 3-(methylthio)propyl isothiocyanate in the third scavenging is 10 g·t -1 ; the dosage of the frother No. 2 oil in the third scavenging is 5 g·t -1 ;

[0050] The middlings of the first cleaning and the first scavenging are combined and returned to the roughing process for reselection; the middlings of the second cleaning are returned to the first cleaning process for reselection; the middlings of the second scavenging and the third scavenging are returned to the first scavenging and the second scavenging processes, respectively, for reselection.

[0051] Comparative Example 1

[0052] A high-arsenic chalcopyrite flotation method using 3-(methylthio)propyl isothiocyanate as a collector is specifically operated as follows:

[0053] (1) The raw ore is added to a ball mill for grinding, and the grinding fineness is controlled at 75% of -0.074 mm, and the grinding concentration is 60%;

[0054] (2) After CaO, the collector and the frother No. 2 oil are added to the flotation sample of step (1) to fully condition the pulp, air is charged for roughing to obtain a roughing concentrate and a roughing tailing. Different from Example 1-3, the collector used only contains 3-(methylthio)propyl isothiocyanate. The components are dissolved uniformly in water at room temperature by ultrasonic and then used; the dosage of CaO in the roughing is 800 g·t -1 , the dosage of 3-(methylthio)propyl isothiocyanate is 100 g·t -1 , and the dosage of the frother No. 2 oil is 40 g·t -1 ;

[0055] (3) The roughing concentrate is subjected to two blank cleanings, and the tailings of each cleaning are the middlings of the respective cleanings, and the concentrate obtained by the last cleaning is a copper concentrate. The roughing tailing is subjected to three scavengings, and the concentrate of each scavenging is the middling of the respective scavenging, and the tailing of the last scavenging is a copper tailing;

[0056] The dosage of 3-(methylthio)propyl isothiocyanate in the first scavenging is 50 g·t -1 , the dosage of the frother No. 2 oil is 20 g·t -1 ; the dosage of 3-(methylthio)propyl isothiocyanate in the second scavenging is 25 g·t -1 , the dosage of the frother No. 2 oil is 10 g·t -1 ; the dosage of 3-(methylthio)propyl isothiocyanate in the third scavenging is 10 g·t -1 , the dosage of the frother No. 2 oil is 5 g·t -1 ;

[0057] The first cleaning middlings and the first scavenging middlings are combined and returned to the roughing process for reselection; the second cleaning middlings are returned to the first cleaning process for reselection; the second scavenging middlings and the third scavenging middlings are returned to the first scavenging process and the second scavenging process for reselection, respectively.

[0058] Comparative Example 2

[0059] A high-arsenic chalcopyrite flotation method using sodium butyl xanthate as a collector is specifically operated as follows:

[0060] (1) The raw ore is added to a ball mill for grinding, and the grinding fineness is controlled at 75% of -0.074 mm, and the grinding concentration is 60%;

[0061] (2) After CaO, a collector, and a frother No. 2 oil are added to the flotation sample in step (1) to fully condition the pulp, air is charged for roughing to obtain a roughing concentrate and a roughing tailings; different from Examples 1-3, the collector used only contains sodium butyl xanthate. The components are dissolved uniformly in water at room temperature by ultrasonic, and then used; the CaO dosage for roughing is 800 g·t -1 , the sodium butyl xanthate dosage is 100 g·t -1 , and the frother No. 2 oil dosage is 40 g·t -1 ;

[0062] (3) The roughing concentrate is subjected to two blank cleanings, and the tailings of each cleaning are the respective cleaning middlings, and the concentrate obtained by the last cleaning is a copper concentrate. The roughing tailings are subjected to three scavengings, and the concentrates of each scavenging are the respective scavenging middlings, and the tailings of the last scavenging are a copper tailings.

[0063] The sodium butyl xanthate dosage for the first scavenging is 50 g·t -1 , the frother No. 2 oil dosage is 20 g·t -1 ; the sodium butyl xanthate dosage for the second scavenging is 25 g·t -1 , the frother No. 2 oil dosage is 10 g·t -1 ; the sodium butyl xanthate dosage for the third scavenging is 10 g·t -1 , and the frother No. 2 oil dosage is 5 g·t -1 ;

[0064] The first cleaning middlings and the first scavenging middlings are combined and returned to the roughing process for reselection; the second cleaning middlings are returned to the first cleaning process for reselection; the second scavenging middlings and the third scavenging middlings are returned to the first scavenging process and the second scavenging process for reselection, respectively.

[0065] The experimental results of the above Examples 1-3 and Comparative Examples 1-2 are shown in Table 1 below.

[0066] Table 1 Experimental results of Examples 1-3 and Comparative Examples 1-2

[0067]

[0068]

[0069] The above merely shows the preferred examples of the present application, and cannot limit the scope of the present application. Any equivalent changes and modifications made according to the scope of the present application and the specification should be within the scope of the present application.

Claims

1. A combined collector for high arsenic type of chalcopyrite flotation, characterized by, a flotation reagent having a functional group of R-OCSS - and a flotation reagent having a functional group of R-NCS, wherein R is a hydrocarbon group having 2-4 carbon atoms; wherein the flotation reagent having a functional group of R-OCSS - is sodium butyl xanthate, the flotation reagent having a functional group of R-NCS is 3-(methylthio)propyl isothiocyanate; and the high-arsenic chalcopyrite has an arsenic content of greater than 3%.

2. Use of the combination collector of claim 1 in the flotation of high arsenopyrite ores, characterized by, The application method comprises the following steps: (1) grinding the raw ore to obtain an ore slurry with a certain concentration; (2) adding the depressant, combined collector and frother in turn and fully mixing, and then performing roughing flotation to obtain roughing concentrate and roughing tailings; the depressant is CaO, the reagent dosage is 500-800 g·t -1 ; the combined collector is composed of sodium butyl xanthate and 3-(methylthio) propyl isothiocyanate, the mass ratio of the two is 1:1-1:3, and the reagent dosage is 100-300 g·t -1 ; the frother is No. 2 oil, and the reagent dosage is 40 g·t -1 ; (3) the obtained roughing concentrate is subjected to blank concentration to obtain copper concentrate; the obtained roughing tailings are added with combined collector and frother to perform scavenging to obtain copper tailings; the number of blank concentration is twice concentration, the tailings of each concentration are the respective concentration middlings, and the concentrate obtained by the last concentration is copper concentrate; the number of scavenging is three times, the concentrate of each scavenging is the respective scavenging middlings, and the tailings of the last scavenging is copper tailings; the reagent dosage of the combined collector is 10-50 g·t -1 , and the reagent dosage of the frother is 5-20 g·t -1 .

3. Use according to claim 2, characterized in that, The flotation particle size of the ore slurry in step (1) is 75% of -0.074 mm, and the concentration of the flotation ore slurry is 30%.

4. Use according to claim 2, characterized in that, The first-time cleaning middlings and the first-time scavenging middlings are combined and returned to the roughing process for reselection; the second-time cleaning middlings are returned to the first-time cleaning process for reselection; the second-time scavenging middlings and the third-time scavenging middlings are respectively returned to the first-time scavenging process and the second-time scavenging process for reselection.

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