CN117399159A - Method for separating low-grade complex copper-sulfur ore and application thereof - Google Patents

Abstract

The invention relates to the technical field of mineral processing, and specifically relates to a method and application for sorting low-grade complex copper-sulfur ores. The invention first selects different pre-selection and discarding processes according to the particle size of the copper-sulfur ores, and adopts "intelligent optical separation + heavy "Separation" combined technology achieves refined tailing of gangue minerals of different sizes in the ore, improves the copper grade of the selected ore, and reduces the amount of ore entering the ore dressing plant for grinding; then, through multi-component inhibitor DR and combined capture The combined effect of agent CR achieves selective flotation separation of copper and sulfur under low alkalinity; finally, the copper tailings can achieve comprehensive recovery of sulfur resources by combining the effective effects of activator AR and double xanthate. The invention has good adaptability to the sorting of low-grade complex copper-sulfur ores, can comprehensively recover copper and sulfur valuable elements in the ores, and has outstanding advantages in that the process flow is stable, reliable, clean, environmentally friendly and energy-saving.

Description

A method for separating low-grade complex copper-sulfur ores and its application

Technical Field

The present invention relates to the technical field of ore dressing, and in particular to a method and application for sorting low-grade complex copper-sulfur ores.

Background Art

The industrial types of copper ore deposits in my country are relatively complete, among which copper sulfide ore is the main one. Copper-sulfur ore is the most common ore type among copper sulfide ores and is widely distributed. In the mining process of copper-sulfur ore resources, surrounding rocks and intercalated stones will inevitably be mixed in, resulting in a decrease in the grade of the ore; on the other hand, the increasingly prominent resource characteristics of copper-sulfur ore, such as "poor, fine, mixed, difficult, and oxygen", have caused a natural increase in mining production costs, a large amount of land resources occupied by tailings storage, and a reduction in the service life of tailings ponds. Therefore, the economic and efficient development and utilization of low-grade, complex and difficult-to-select copper-sulfur ore resources has become increasingly urgent.

The copper grade in low-grade copper-sulfur ore is usually lower than the minimum boundary grade required for copper sulfide mining (i.e. 0.2-0.3%), so it cannot be directly sent to the ore dressing plant for sorting, resulting in many low-grade copper sulfide ores not being mined and utilized. On the other hand, with the continuous development of the domestic economy, my country's demand for copper has gradually increased, and the external dependence on copper resources has remained above 80% for a long time. The huge gap in copper resources has posed a serious threat to the security of my country's copper resources. Therefore, the efficient use of low-grade copper-sulfur ore resources is an effective way to improve the domestic self-sufficiency rate of copper metal, which is of great strategic significance for ensuring the security of my country's copper resources.

Chalcopyrite and pyrite are typical sulfide minerals in copper-sulfur ores. Flotation is an important rough processing link for obtaining copper metal and sulfur resources from copper-sulfur ores, and improving the quality of copper products and obtaining concentrates with high recovery rates are the primary tasks of flotation. Due to the complex dense symbiosis and mosaic relationship between minerals in copper-sulfur ores, and the similar natural floatability of iron sulfide and copper sulfide minerals, it is easy to cause serious metal intercontainment in copper and sulfur concentrates. When flotating such ores, whether it is priority flotation, mixed flotation or other processes, the common problem of copper-sulfur separation must be faced. The principle process of copper-sulfur separation generally adopts the sulfur-suppressing copper flotation process. At present, the high-alkali flotation process (pH greater than 12) with lime as a depressant is widely used at home and abroad to achieve copper and sulfur separation. This process is quite mature and has a good separation effect. However, the use of a large amount of lime not only inhibits the floating of some copper minerals and affects the recovery rate of copper concentrate, but also easily causes serious ore mud entrainment, affecting the quality of the concentrate. In addition, the use of large amounts of lime will lead to scaling of equipment and slurry transportation pipelines, affect the comprehensive recovery of valuable associated elements, and cause environmental pollution of mine wastewater.

There are relevant reports on the research of flotation of copper sulfide ores. The invention patent with application number CN 111495788A discloses "a method for intelligently and preferentially selecting copper sulfide ores containing covellite by X-rays". By using X-rays for resolution, some high-grade copper concentrates are first selected, and then the remaining copper concentrates are selected through a matching flotation process, which effectively improves the comprehensive recovery rate of copper mineral resources. This method obtains good indicators when selecting high-grade single covellite sulfide copper ore (containing Cu7.11%), but the enrichment ratio of X-ray selection is limited, and it is difficult to adapt to the selection of low-grade copper-sulfur ores. The invention patent with application number CN112264181A discloses "a method for pre-selection and discarding of low-grade copper sulfide ore", which is pre-selected and discarded by "intelligent ray ore sorting + jigging selection", realizing the pre-separation of copper sulfide ore and a large amount of waste rock, and improving the copper grade of the selected ore. However, this method produces some primary mud (-0.15mm particle size) and does not pre-select tailings. Obviously, this part of the primary mud is prone to over-grinding during the grinding process, which has an adverse effect on subsequent sorting. The invention patent with application number CN110787911A discloses "a flotation method for low-grade copper ore and its associated gold and silver", that is, by combining the foam (concentrate) products of the first group of roughing and scavenging with the raw ore of the second group, the grade of the selected ore is improved, the recovery rate of coarse-grained, intergrown and fine-grained copper minerals, the grade of copper concentrate and the content of associated gold and silver in the copper concentrate are improved, but this method is limited to the sorting of a single sulfide copper ore, and it is difficult to solve the problem of copper and sulfur separation in the sorting of copper-sulfur ore. The invention patent with application number CN116273485A discloses "a pyrite flotation separation combined inhibitor and its application". The invention adopts a branched series flow process to improve the grade of the selected product and the sorting process; the separation of copper and sulfur is achieved through the combined action of gardenia yellow and inhibitor A (lime, sodium sulfite or calcium hypochlorite), but the method produces a large amount of tailings rich in iron sulfide ore, and the sulfur resources therein are not comprehensively recovered. In addition, the method requires fine grinding of the ore, and the cost of tailings disposal is relatively high.

Based on the above analysis, due to the low grade of the original ore and the large amount of waste rock, the selective separation of copper and sulfur is difficult, and the effective sorting of low-grade complex sulfide copper ore is still a comprehensive resource recycling problem that needs to be solved urgently.

Summary of the invention

The purpose of the present invention is to provide a method and application for sorting low-grade complex copper-sulfur ores. For low-grade copper-sulfur ores mainly containing chalcopyrite and pyrite, the present invention is completed through the technical route of "fine pre-selection tailings-low-alkalinity copper-sulfur flotation separation-coupled activation capture". First, coarse, medium and fine-grained minerals are respectively selected by intelligent optical selection, jigging sorting and suspended vibration cone concentrator to achieve fine tailings of different-grained gangue minerals in low-grade copper-sulfur ores, thereby improving the copper grade of the selected ore and reducing the amount of ore entering the concentrator for grinding; then, after the pre-enriched material is crushed and ground, a multi-component inhibitor is added to achieve selective inhibition of pyrite at low alkalinity (pH=8-9) to obtain high-quality copper concentrate; finally, the copper tailings are coupled activated by a combined activator and strongly captured by a dixanthate to obtain high-quality sulfur concentrate, thereby realizing the comprehensive recovery and utilization of copper and sulfur in this type of copper sulfide resources.

In order to achieve the above technical objectives and the above technical effects, the present invention is implemented through the following technical solutions:

A method for separating low-grade complex copper-sulfur ores comprises the following steps:

S1: After the copper-sulfur ore is crushed, it is screened by a double-layer vibrating screen and divided into three particle sizes: +60mm, +10～-60mm and -10mm;

S2: +60mm particle size ore is returned to the crushing operation, +10～-60mm particle size ore is subjected to intelligent X-ray ore sorting, waste rock is discarded and qualified ore 1 is obtained;

S3: -10mm ore is wet screened and divided into two granularity materials: +0.2～-10mm and -0.2mm;

S4: +0.2～-10mm particle size materials are jigged and sorted, waste rocks are discarded and qualified ore 2 is obtained;

S5: -0.2mm particle size materials are sorted by suspended vibration cone concentrator, waste materials are discarded and qualified ore 3 is obtained;

S6: After crushing and screening, qualified ore 1 is crushed to obtain -10mm particle size ore, which is combined with qualified ore 2 and qualified ore 3 as raw materials for grinding;

S7: The raw materials are ground at a concentration of 65-75%, and the fineness is controlled to be -0.074 mm, accounting for 80-85%;

S8: Sodium hydroxide, combined depressant DR, combined collector CR and 2 ^# oil are sequentially added to the pulp to perform copper roughing with priority, and produce foam and in-tank products;

S9: The copper roughing foam product is sequentially processed into copper concentration I and copper concentration II, and the intermediate ore is sequentially returned to produce copper concentrate;

S10: adding sulfuric acid, combined activator AR, double xanthate and 2 ^# oil to the product in the preferred copper roughing tank in sequence to perform sulfur roughing, and produce foam and products in the tank;

S11: sulfur roughing foam is sequentially used for sulfur concentration I, sulfur concentration II and sulfur concentration III, and the intermediate ore is returned in sequence to produce sulfur concentrate;

S12: sulfur scavenging is performed on the sulfur roughing tank products, sulfuric acid, combined activator AR, double xanthate and 2 ^# oil in sequence, and the sulfur scavenging foam is combined with the product in the sulfur concentration tank I and returned to the sulfur roughing, and the product in the sulfur scavenging tank is the final tailings;

Furthermore, in step S1, the copper grade of the copper-sulfur ore is less than 0.3%, the sulfur content is greater than 6%, and chalcopyrite and pyrite are the main sulfide minerals in the copper-sulfur ore.

Furthermore, the conditions for intelligent X-ray ore sorting in step S2 include: the speed of the feeding belt is 3 m/s, the voltage of the ray source is 180 kV, and the current is 3-5 mA;

Furthermore, the jigging separation conditions in step S4 include: a stroke of 5 to 20 mm, a stroke of 150 to 320 times/min, and a bed thickness of 19 to 25 mm;

Further, the separation by the suspended vibration cone concentrator in step S5 includes: a rotation frequency of 8 to 20 Hz and a vibration frequency of 10 to 20 Hz;

Furthermore, in step S8, the amount of sodium hydroxide added is 400-800 g/t (based on the mass of the original ore), and the pH of the slurry is controlled to be 8-9;

Furthermore, in step S8, the combined inhibitor DR is a mixture containing lime (40 parts), calcium hypochlorite (30 parts), carboxymethyl chitosan (20 parts) and calcium lignin sulfonate (10 parts); the addition amount of DR is 600-1200 g/t (based on the mass of the original ore);

Furthermore, in step S8, the combined collector CR is a mixture of ethyl xanthate (60 parts) and BK916 (40 parts), and the addition amount of CR is 30-70 g/t (based on the mass of the original ore);

Furthermore, the amount of 2 ^# oil added in step S8 is 30-60 g/t (based on the mass of the original ore);

Furthermore, in step S10, the amount of sulfuric acid added is 300-800 g/t (based on the mass of the original ore), and the pH of the slurry is controlled to be 8-9;

Furthermore, in step S10, the combined activator AR is a mixture containing ammonium bicarbonate (50 parts), copper sulfate (30 parts) and ferrous sulfate (20 parts); the addition amount of AR is 200-400 g/t (based on the mass of the original ore);

Furthermore, the addition amounts of the double xanthate and 2 ^# oil in step S10 are 40-80 g/t and 30-60 g/t respectively (based on the mass of the original ore);

Furthermore, the addition amounts of sulfuric acid, AR, dixanthate and 2 ^# oil in step S12 (based on the mass of the original ore) are: 200-400 g/t (control the pH of the slurry = 8-9), 100-200 g/t, 20-40 g/t and 15-20 g/t respectively.

On the other hand, the present invention proposes the application of the above method in the separation of low-grade copper-sulfur ores.

Beneficial effects of the present invention:

The present invention selects different pre-selection and discarding processes according to the particle size of low-grade complex copper sulfide ore, that is, coarse, medium and fine-grained minerals are respectively selected by intelligent optical selection, jig separation and suspended vibration cone concentrator separation to pre-discard gangue minerals of different particle sizes. Intelligent optical selection uses X-rays in a medical sense to distinguish coarse-grained ores based on the differences in refractive power of chalcopyrite-containing ores. Jigging separation targets medium-grained ores with large density differences, and uses vertical alternating water flow caused by strong vibration to stratify the ore particles according to relative density to achieve the purpose of separation. Suspended vibration cone concentrator separation has a particularly obvious enrichment effect on fine-grained copper minerals, and fine-grained gangue minerals are removed, effectively avoiding the adverse effects of over-grinding of minerals on subsequent separation. The pre-selection and discarding combined technology of "intelligent optical selection + gravity separation" improves the copper grade of the selected ore, reduces the amount of ore entering the concentrator for grinding, and has reasonable process technology and is easy to realize industrial production.

The multi-component inhibitor DR promotes the passivation modification of the pyrite surface by means of oxidation modification and characteristic adsorption, resulting in the covering of multi-component hydrophilic species of calcium, iron and sulfur on the mineral surface, which significantly reduces the floatability of pyrite, thus creating good conditions for the selective flotation separation of copper and sulfur under low alkalinity (pH=8-9).

The combined collector CR has good selectivity for chalcopyrite, can reduce the entrainment of pyrite in the copper-preferred foam during the copper-sulfur separation process, and can increase the copper concentrate grade by 1-2% or the copper recovery rate by 3-4%.

The combined activator AR promotes the desorption of calcium, iron and sulfur multi-component hydrophilic species on the surface of suppressed pyrite in a low alkalinity (pH=8-9) slurry system through coupled activation effects such as precipitation, desorption and copper component adsorption, effectively activates pyrite, and the pH adjustment range of the slurry is small, saving the amount of adjusting agent.

The flotation mechanism of pyrite in the xanthate system is mainly based on the adsorption of dixanthate, that is, xanthate is converted into dixanthate through electrochemical action, and adsorbs on the surface of pyrite to promote the hydrophobic floating of the mineral. In the present invention, the flotation performance of pyrite is improved by directly adding dixanthate collector, pyrite is strongly collected, and the recovery rate of sulfur concentrate is increased by 1-2%.

In summary, the present invention has good adaptability to the separation of low-grade complex copper-sulfur ores, can effectively and comprehensively recover the valuable elements copper and sulfur in the ores, and the process flow has outstanding advantages of being stable, reliable, clean, environmentally friendly and energy-saving.

Of course, any product implementing the present invention does not necessarily need to achieve all of the above-mentioned advantages at the same time.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for describing the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

FIG1 is a process flow chart of a method for efficiently separating low-grade complex copper-sulfur ores according to the present invention;

Figure 2 is a schematic diagram of a separation and flotation verification test;

Figure 3 is a schematic diagram of a separation and flotation comparison test;

FIG4 is a schematic diagram of a reagent comparison flotation test.

DETAILED DESCRIPTION

The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Example 1

As shown in Figure 1

The method for separating low-grade complex copper-sulfur ores described in this embodiment comprises the following steps:

S1: After the copper-sulfur ore is crushed, it is screened by a double-layer vibrating screen and divided into three particle sizes: +60mm, +10～-60mm and -10mm;

S2: +60mm particle size ore is returned to the crushing operation, +10～-60mm particle size ore is subjected to intelligent X-ray ore sorting, waste rock is discarded and qualified ore 1 is obtained;

S3: -10mm ore is wet screened and divided into two granularity materials: +0.2～-10mm and -0.2mm;

S4: +0.2～-10mm particle size materials are jigged and sorted, waste rocks are discarded and qualified ore 2 is obtained;

S5: -0.2mm particle size materials are sorted by suspended vibration cone concentrator, waste materials are discarded and qualified ore 3 is obtained;

S6: After crushing and screening, qualified ore 1 is crushed to obtain -10mm particle size ore, which is combined with qualified ore 2 and qualified ore 3 as raw materials for grinding;

S7: The raw materials are ground at a concentration of 65-75%, and the fineness is controlled to be -0.074 mm, accounting for 80-85%;

S8: Sodium hydroxide, combined depressant DR, combined collector CR and 2 ^# oil are sequentially added to the pulp to perform copper roughing with priority, and produce foam and in-tank products;

S9: The copper roughing foam product is sequentially processed into copper concentration I and copper concentration II, and the intermediate ore is sequentially returned to produce copper concentrate;

S10: adding sodium hydroxide, combined activator AR, double xanthate and 2 ^# oil to the product in the preferred copper roughing tank in sequence to perform sulfur roughing, and produce foam and the product in the tank;

S11: sulfur roughing foam is sequentially used for sulfur concentration I, sulfur concentration II and sulfur concentration III, and the intermediate ore is returned in sequence to produce sulfur concentrate;

S12: Sodium hydroxide, combined activator AR, double xanthate and 2 ^# oil are sequentially added to the product in the sulfur roughing tank for sulfur scavenging. The sulfur scavenging foam is combined with the product in the sulfur concentration tank I and returned to the sulfur roughing. The product in the sulfur scavenging tank is the final tailings;

In this embodiment, the copper grade of the copper-sulfur ore in step S1 is less than 0.3%, the sulfur content is greater than 6%, and chalcopyrite and pyrite are the main sulfide minerals in the copper-sulfur ore.

In this embodiment, the conditions for intelligent X-ray ore sorting in step S2 include: the speed of the feeding belt is 3 m/s, the voltage of the ray source is 180 kV, and the current is 3-5 mA;

In this embodiment, the jigging separation conditions in step S4 include: a stroke of 5 to 20 mm, a stroke of 150 to 320 times/min, and a bed thickness of 19 to 25 mm;

In this embodiment, the suspended vibration cone concentrator separation in step S5 includes: rotation frequency: 8 to 20 Hz, vibration frequency: 10 to 20 Hz;

In this embodiment, the amount of sodium hydroxide added in step S8 is 400-800 g/t (based on the mass of the original ore), and the pH of the slurry is controlled to be 8-9;

In this embodiment, the combined inhibitor DR in step S8 is a mixture containing lime (40 parts), calcium hypochlorite (30 parts), carboxymethyl chitosan (20 parts) and calcium lignin sulfonate (10 parts); the addition amount of DR is 600-1200 g/t (based on the mass of the original ore);

In this embodiment, the combined collector CR in step S8 is a mixture of ethyl xanthate (60 parts) and BK916 (40 parts), and the addition amount of CR is 30-70 g/t (based on the mass of the original ore);

In this embodiment, the amount of 2 ^# oil added in step S8 is 30-60 g/t (based on the mass of the original ore);

In this embodiment, the amount of sulfuric acid added in step S10 is 300-800 g/t (based on the mass of the original ore), and the pH of the slurry is controlled to be 8-9;

In this embodiment, the combined activator AR in step S10 is a mixture of ammonium bicarbonate (50 parts), copper sulfate (30 parts) and ferrous sulfate (20 parts); the addition amount of AR is 200-400 g/t (based on the mass of the original ore);

In this embodiment, the amount of double yellow medicine added in step S10 is 40-80 g/t, and the amount of 2 ^# oil added is 30-60 g/t (based on the mass of the original ore);

In this embodiment, the addition amounts of sulfuric acid, AR, dixanthate and 2 ^# oil in step S12 (based on the mass of the original ore) are: 200-400 g/t (control the slurry pH=8-9), 100-200 g/t, 20-40 g/t and 15-20 g/t respectively.

Example 2

As shown in Figure 1-4

A low-grade copper-sulfur ore from Yunnan was selected. The original ore contained 0.25% copper, with chalcopyrite being the main copper mineral. The original ore contained 9.5% sulfur, and the content of pyrite was 23.5%.

After the copper-sulfur ore is crushed, it is screened through a double-layer vibrating screen and divided into three particle sizes of +60mm, +10 to -60mm and -10mm.

The +60mm particle size ore is returned to the crushing operation, and the +10 to -60mm particle size ore is subjected to intelligent X-ray ore sorting, the waste rock is discarded and qualified ore 1 is obtained.

The -10mm particle size ore is wet screened and divided into two particle size materials: +0.2 to -10mm and -0.2mm.

The materials with particle size of +0.2～-10mm are jigged and sorted, the waste rocks are discarded and qualified ore 2 is obtained.

-0.2mm particle size materials are sorted by suspended vibration cone concentrator, waste materials are discarded and qualified ore 3 is obtained.

After crushing and screening, qualified ore 1 is crushed to obtain -10mm particle size ore, which is combined with qualified ore 2 and qualified ore 3 as the raw material for grinding.

The above raw materials are ground, the grinding concentration is 65%, and the fineness is controlled to be -0.074mm, accounting for 80%.

Sodium hydroxide, combined depressant DR, combined collector CR and 2 ^# oil are sequentially added to the pulp to perform copper roughing with priority, and foam and in-tank products are produced.

The copper roughing foam product is sequentially processed into copper concentration I and copper concentration II, and the intermediate ore is returned in sequence to produce copper concentrate.

Sodium hydroxide, combined activator AR, double yellow medicine and 2 ^# oil are sequentially added to the product in the copper roughing tank for sulfur roughing to produce foam and tank products.

The sulfur roughing foam is sequentially subjected to sulfur concentration I, sulfur concentration II and sulfur concentration III, and the intermediate ore is returned in sequence to produce sulfur concentrate.

Sodium hydroxide, combined activator AR, double yellow medicine and 2 ^# oil are added to the product in the sulfur roughing tank in turn for sulfur scavenging. The sulfur scavenging foam is combined with the product in the sulfur concentration I tank and returned to the sulfur roughing. The product in the sulfur scavenging tank is the final tailings.

In this embodiment, the conditions for the intelligent X-ray ore sorting are: the speed of the feeding belt is 3 m/s, the voltage of the ray source is 180 kV, and the current is 3 mA.

In this embodiment, the jigging separation conditions are: a stroke of 10 mm, a stroke frequency of 150 times/min, and a bed thickness of 19 mm.

In this embodiment, the separation conditions of the suspended vibration cone concentrator are: rotation frequency: 15 Hz, vibration frequency: 12 Hz.

In this embodiment, the amount of sodium hydroxide added is 700 g/t (based on the mass of the original ore), and the pH of the slurry is controlled to be 8.5.

In this embodiment, the step combined inhibitor DR is a mixture containing lime (40 parts), calcium hypochlorite (30 parts), carboxymethyl chitosan (20 parts) and calcium lignin sulfonate (10 parts); the addition amount of DR is 800g/t (based on the mass of the original ore).

In this embodiment, the combined collector CR in step S8 is a mixture of ethyl xanthate (60 parts) and BK916 (40 parts), and the added amount of CR is 50 g/t (based on the mass of the original ore).

In this embodiment, the addition amount of the 2 ^# oil is 60 g/t (based on the mass of the original ore).

In this embodiment, the amount of sulfuric acid added is 400 g/t (based on the mass of the original ore), and the pH value of the slurry is controlled to be 8.5.

In this embodiment, the combined activator AR is a mixture containing ammonium bicarbonate (50 parts), copper sulfate (30 parts) and ferrous sulfate (20 parts); the addition amount of AR is 300g/t (based on the mass of the original ore).

In this embodiment, the amount of double yellow medicine added is 50 g/t, and the amount of 2 ^# oil added is 40 g/t (based on the mass of the original ore).

In this embodiment, the addition amounts of sulfuric acid, AR, dixanthate and 2 ^# oil (based on the mass of the original ore) are 300 g/t (controlling the pH value of the slurry = 8.5), 150 g/t, 25 g/t and 20 g/t respectively.

The sorting indicators of this case are shown in Table 1.

Example 3

A low-grade copper-sulfur ore from Yunnan was selected. The original ore contained 0.18% copper, with chalcopyrite being the main copper mineral. The original ore contained 6.5% sulfur, and the content of pyrite was 14.5%.

After the copper-sulfur ore is crushed, it is screened through a double-layer vibrating screen and divided into three particle sizes of +60mm, +10 to -60mm and -10mm.

The +60mm particle size ore is returned to the crushing operation, and the +10 to -60mm particle size ore is subjected to intelligent X-ray ore sorting, the waste rock is discarded and qualified ore 1 is obtained.

The -10mm particle size ore is wet screened and divided into two particle size materials: +0.2 to -10mm and -0.2mm.

The materials with particle size of +0.2～-10mm are jigged and sorted, the waste rocks are discarded and qualified ore 2 is obtained.

-0.2mm particle size materials are sorted by suspended vibration cone concentrator, waste materials are discarded and qualified ore 3 is obtained.

After crushing and screening, qualified ore 1 is crushed to obtain -10mm particle size ore, which is combined with qualified ore 2 and qualified ore 3 as the raw material for grinding.

The above raw materials are ground with a grinding concentration of 75% and a controlled fineness of -0.074 mm accounting for 85%.

Sodium hydroxide, combined depressant DR, combined collector CR and 2 ^# oil are sequentially added to the pulp to perform copper roughing with priority, and foam and in-tank products are produced.

The copper roughing foam product is sequentially processed into copper concentration I and copper concentration II, and the intermediate ore is returned in sequence to produce copper concentrate.

Sodium hydroxide, combined activator AR, double yellow medicine and 2 ^# oil are sequentially added to the product in the copper roughing tank for sulfur roughing to produce foam and tank products.

The sulfur roughing foam is sequentially subjected to sulfur concentration I, sulfur concentration II and sulfur concentration III, and the intermediate ore is returned in sequence to produce sulfur concentrate.

Sodium hydroxide, combined activator AR, double yellow medicine and 2 ^# oil are added to the product in the sulfur roughing tank in turn for sulfur scavenging. The sulfur scavenging foam is combined with the product in the sulfur concentration I tank and returned to the sulfur roughing. The product in the sulfur scavenging tank is the final tailings.

In this embodiment, the conditions for the intelligent X-ray ore sorting are: the speed of the feeding belt is 3 m/s, the voltage of the ray source is 180 kV, and the current is 5 mA.

In this embodiment, the jigging separation conditions are: a stroke of 15 mm, a stroke of 300 times/min, and a bed thickness of 22 mm.

In this embodiment, the separation conditions of the suspended vibration cone concentrator are: rotation frequency: 20 Hz, vibration frequency: 18 Hz.

In this embodiment, the amount of sodium hydroxide added is 400 g/t (based on the mass of the original ore), and the pH value of the slurry is controlled to be 8.

In this embodiment, the combined inhibitor DR is a mixture containing lime (40 parts), calcium hypochlorite (30 parts), carboxymethyl chitosan (20 parts) and calcium lignin sulfonate (10 parts); the addition amount of DR is 600g/t (based on the mass of the original ore).

In this embodiment, the combined collector CR is a mixture of ethyl xanthate (60 parts) and BK916 (40 parts), and the addition amount of CR is 40 g/t (based on the mass of the original ore).

In this embodiment, the addition amount of the 2 ^# oil is 50 g/t (based on the mass of the original ore).

In this embodiment, the amount of sulfuric acid added is 300 g/t (based on the mass of the original ore), and the pH value of the slurry is controlled to be 8.

In this embodiment, the combined activator AR is a mixture of ammonium bicarbonate (50 parts), copper sulfate (30 parts) and ferrous sulfate (20 parts); the addition amount of AR is 200g/t (based on the mass of the original ore).

In this embodiment, the amount of double yellow medicine added is 30 g/t, and the amount of 2 ^# oil added is 30 g/t (based on the mass of the original ore).

In this embodiment, the addition amounts of sulfuric acid, AR, dixanthate and 2 ^# oil (based on the mass of the original ore) are 150 g/t (controlling the pH value of the slurry = 8), 100 g/t, 15 g/t and 15 g/t respectively.

The sorting indicators of this case are shown in Table 1.

Example 4

A low-grade copper-sulfur ore from Yunnan was selected. The original ore contained 0.29% copper, with chalcopyrite being the main copper mineral. The original ore contained 12.5% sulfur, and the content of pyrite was 26.5%.

After the copper-sulfur ore is crushed, it is screened through a double-layer vibrating screen and divided into three particle sizes of +60mm, +10 to -60mm and -10mm.

The +60mm particle size ore is returned to the crushing operation, and the +10 to -60mm particle size ore is subjected to intelligent X-ray ore sorting, the waste rock is discarded and qualified ore 1 is obtained.

The -10mm particle size ore is wet screened and divided into two particle size materials: +0.2 to -10mm and -0.2mm.

The materials with particle size of +0.2～-10mm are jigged and sorted, the waste rocks are discarded and qualified ore 2 is obtained.

-0.2mm particle size materials are sorted by suspended vibration cone concentrator, waste materials are discarded and qualified ore 3 is obtained.

After crushing and screening, qualified ore 1 is crushed to obtain -10mm particle size ore, which is combined with qualified ore 2 and qualified ore 3 as the raw material for grinding.

The above raw materials are ground with a grinding concentration of 70% and a controlled fineness of -0.074 mm accounting for 82%.

Sodium hydroxide, combined depressant DR, combined collector CR and 2 ^# oil are sequentially added to the pulp to perform copper roughing with priority, producing foam and in-tank products.

The copper roughing foam product is sequentially processed into copper concentration I and copper concentration II, and the intermediate ore is returned in sequence to produce copper concentrate.

Sodium hydroxide, combined activator AR, double yellow medicine and 2 ^# oil are sequentially added to the product in the copper roughing tank for sulfur roughing to produce foam and tank products.

The sulfur roughing foam is sequentially subjected to sulfur concentration I, sulfur concentration II and sulfur concentration III, and the intermediate ore is returned in sequence to produce sulfur concentrate.

Sodium hydroxide, combined activator AR, double yellow medicine and 2 ^# oil are added to the product in the sulfur roughing tank in turn for sulfur scavenging. The sulfur scavenging foam is combined with the product in the sulfur concentration I tank and returned to the sulfur roughing. The product in the sulfur scavenging tank is the final tailings.

In this embodiment, the conditions for the intelligent X-ray ore sorting are: the speed of the feeding belt is 3 m/s, the voltage of the ray source is 180 kV, and the current is 4 mA.

In this embodiment, the jigging separation conditions are: a stroke of 20 mm, a stroke frequency of 220 times/min, and a bed thickness of 25 mm.

In this embodiment, the separation conditions of the suspended vibration cone concentrator are: rotation frequency: 22 Hz, vibration frequency: 16 Hz.

In this embodiment, the amount of sodium hydroxide added is 800 g/t (based on the mass of the original ore), and the pH value of the slurry is controlled to be 9.

In this embodiment, the combined inhibitor DR is a mixture containing lime (40 parts), calcium hypochlorite (30 parts), carboxymethyl chitosan (20 parts) and calcium lignin sulfonate (10 parts); the addition amount of DR is 1200g/t (based on the mass of the original ore).

In this embodiment, the combined collector CR is a mixture of ethyl xanthate (60 parts) and BK916 (40 parts), and the addition amount of CR is 70 g/t (based on the mass of the original ore).

In this embodiment, the addition amount of the 2 ^# oil is 60 g/t (based on the mass of the original ore).

In this embodiment, the amount of sulfuric acid added is 800 g/t (based on the mass of the original ore), and the pH value of the slurry is controlled to be 9.

In this embodiment, the combined activator AR is a mixture of ammonium bicarbonate (50 parts), copper sulfate (30 parts) and ferrous sulfate (20 parts); the addition amount of AR is 400g/t (based on the mass of the original ore).

In this embodiment, the amount of double yellow medicine added is 80 g/t, and the amount of 2 ^# oil added is 60 g/t (based on the mass of the original ore).

In this embodiment, the addition amounts of sulfuric acid, AR, dixanthate and 2 ^# oil (based on the mass of the original ore) are: 400 g/t (control the slurry pH=9), 200 g/t, 35 g/t and 30 g/t respectively.

The sorting indicators of this case are shown in Table 1.

Example 5

The treatment conditions of this comparative example are the same as those of Example 2, except that: the inhibitor is replaced by lime alone, and its dosage is twice that of Example 2; the collector is replaced by sodium isobutyl xanthate, and its dosage is the same as that of Example 1; the sulfur selection activator is replaced by ammonium bicarbonate alone, and its dosage is the same as that of Example 2; the sulfur selection collector is replaced by ethyl xanthate, and its dosage is 1.5 times that of Example 2. The separation indexes of Example 5 are shown in Table 1.

Example 6

The treatment conditions of this comparative example are the same as those of Example 3, except that the inhibitor is replaced by lime in an amount twice that of Example 3, the collector is replaced by sodium isobutyl xanthate in an amount the same as that of Example 1, the sulfur selection activator is replaced by copper sulfate in an amount the same as that of Example 1, and the sulfur selection collector is replaced by ethyl xanthate in an amount 1.5 times that of Example 3. The separation indexes of Example 6 are shown in Table 1.

Example 7

The processing conditions of this comparative example are the same as those of Example 4, except that: in this comparative example, there is no pre-waste treatment, and the raw ore is directly subjected to crushing and flotation. The separation indexes of Example 7 are shown in Table 1.

Table 1 Sorting indexes of various embodiments

It can be seen from the results of the embodiment in Table 1 that after the low-grade complex copper sulfide ore is treated by the method of the present invention, the copper concentrate grade obtained is greater than 19%, the recovery rate is greater than 66%, the sulfur concentrate grade obtained is greater than 50%, and the recovery rate is greater than 63%, thereby achieving comprehensive flotation recovery of copper sulfide ore and pyrite.

It can be seen from the comparative examples in Table 1 that when copper is selected first, if the inhibitor is replaced by single lime and the collector is replaced by isobutyl sodium xanthate, the grade of the obtained copper concentrate decreases by 1-2% or the copper recovery rate decreases by 3-4%, and the amount of lime and isobutyl sodium xanthate is relatively large; when sulfur is selected from copper tailings, if the activator is replaced by single ammonium bicarbonate or single copper sulfate and the collector is replaced by ethyl xanthate, the recovery rate of the obtained sulfur concentrate decreases by 1-2%. When the raw ore is directly flotated without pre-selection and tailings discarding by "intelligent optical selection + gravity selection", the grade of the obtained copper concentrate and the grade of the sulfur concentrate decrease significantly. Therefore, the combined use of "intelligent optical selection + gravity selection" pre-selection tailings discarding, combined inhibitors, combined collectors and double xanthate has good adaptability to the sorting of low-grade complex copper-sulfur ores, can effectively and comprehensively recover the valuable elements of copper and sulfur in the ore, and the process flow is stable and reliable, clean, environmentally friendly and energy-saving.

In summary, the present invention realizes the refined tailings of gangue minerals of different particle sizes in the ore through the combined technology of "intelligent optical separation + gravity separation", improves the copper grade of the selected ore, and reduces the amount of ore entering the ore dressing plant for grinding and selection; then, the selective flotation separation of copper and sulfur is realized under low alkalinity through the combined action of multi-component depressant DR and combined collector CR; finally, the copper tailings are effectively used to realize the comprehensive recovery of sulfur resources through the combined activator AR and dixanthate. The present invention has good adaptability to the sorting of low-grade complex copper-sulfur ores, can comprehensively recover the copper and sulfur valuable elements in the ore, and the process flow is stable and reliable, clean, environmentally friendly and energy-saving.

The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims (10)

1. A method for sorting low-grade complex copper-sulfur ores, which is characterized by including the following steps: S1: After crushing the copper-sulfur ore, it is screened by a double-layer vibrating screen and divided into three types of ore: +60mm, +10~-60mm and -10mm; S2: +60mm size ore returns to crushing operation, +10~-60mm size ore undergoes intelligent X-ray ore sorting, discards waste rock and obtains qualified ore 1; S3: The -10mm particle size ore is wet screened and divided into two types of materials: +0.2~-10mm and -0.2mm; S4: The +0.2~-10mm particle size materials are jigged and sorted, the waste rocks are discarded and qualified ore 2 is obtained; S5: -0.2mm particle size materials are sorted by a suspended cone concentrator, discarding waste and obtaining qualified ore 3; S6: After the qualified ore 1 is crushed and screened, the -10mm particle size ore is obtained, and is combined with qualified ore 2 and qualified ore 3 as raw materials for grinding; S7: The above-mentioned raw materials are ground for grinding, the grinding concentration is 65-75%, and the controlled fineness is -0.074mm accounting for 80-85%; S8: Add sodium hydroxide, combined inhibitor DR, combined collector CR and 2 ^# oil to the slurry in sequence to conduct rough copper selection to produce foam and tank products; S9: The copper roughing foam products undergo copper concentration I and copper concentration II in sequence, and the medium ore returns in sequence to produce copper concentrate; S10: Add sulfuric acid, combined activator AR, double xanthate and 2 ^# oil to the products in the priority copper roughing tank in sequence to perform sulfur roughing to produce foam and products in the tank; S11: The sulfur roughing foam undergoes sulfur beneficiation I, sulfur beneficiation II and sulfur beneficiation III in sequence, and the medium ore is returned in sequence to produce sulfur concentrate; S12: The products in the sulfur roughing tank are sulfuric acid, combined activator AR, double xanthate and 2 ^# oil in sequence, and the sulfur sweeping foam and the products in the sulfur selection I tank are combined and returned to the sulfur roughing, sulfur sweeping The product in the tank is the final tailings. 2. The method for sorting low-grade complex copper-sulfur ores according to claim 1, wherein the characteristics of the copper-sulfur ores in step S1 are that the copper grade is <0.3% and the sulfur content is >6%. 3. The method for sorting low-grade complex copper-sulfur ores according to claim 1, characterized in that: the conditions for intelligent X-ray ore sorting in step S2 include: the speed of the feeding belt is 3m/s, and the ray The source voltage is 180kV and the current is 3~5mA. 4. The method for sorting low-grade complex copper-sulfur ores as claimed in claim 1, characterized in that: the jig sorting conditions in step S4 include: a stroke of 5 to 20 mm, and a stroke of 150 to 320 times/ The bed thickness is 19~25mm. 5. The method for sorting low-grade complex copper-sulfur ores as claimed in claim 1, characterized in that: the suspended cone concentrator sorting in step S5 includes: a rotation frequency of 8 to 20 Hz and a vibration frequency of 10 ~20Hz. 6. The method for sorting low-grade complex copper-sulfur ores according to claim 1, characterized in that: based on the raw ore mass, the amount of sodium hydroxide added in step S8 is 400-800g/t, and the pH of the slurry is controlled. =8~9. 7. The method for sorting low-grade complex copper-sulfur ores according to claim 1, characterized in that: the combined inhibitor DR in step S8 includes lime, calcium hypochlorite, carboxymethyl chitosan and lignin. Calcium sulfonate, the combined collector CR includes ethyl xanthate and BK916; based on the raw ore mass, the added amount of DR is 600-1200g/t; the added amount of CR is 30-70g/t, 2 ^# oil The addition amount is 30~60g/t. 8. The method for sorting low-grade complex copper-sulfur ores as claimed in claim 1, characterized in that: the combined activator AR in step S10 includes ammonium bicarbonate, copper sulfate and ferrous sulfate; based on raw ore mass, The amount of sulfuric acid added in step S10 is 300-800g/t, and the pH of the slurry is controlled to be 8-9; the amount of AR added is 200-400g/t, and the amount of bixanthate and ^# 2 oil is 40-80g respectively. /t and 30~60g/t. 9. The method for sorting low-grade complex copper-sulfur ores as claimed in claim 1, characterized in that: based on the raw ore mass, the added amounts of sulfuric acid, AR, bixanthate and 2 ^# oil in step S12 are respectively : 200～400g/t, 100～200g/t, 20～40g/t and 15～20g/t. 10. Application of the method according to any one of claims 1 to 9 in the sorting of low-grade copper-sulfur ores.