WO2021037242A1

WO2021037242A1 - Pyrrhotite mineral processing method using low-alkali process of magnetic separation followed by flotation

Info

Publication number: WO2021037242A1
Application number: PCT/CN2020/112256
Authority: WO
Inventors: 邱廷省; 陈江安; 方夕辉; 匡敬忠; 余文; 艾光华
Original assignee: 江西理工大学
Priority date: 2019-08-29
Filing date: 2020-08-28
Publication date: 2021-03-04
Also published as: CN110586336A; KR20220033518A

Abstract

A pyrrhotite mineral processing method, comprising the following steps: performing a coarse copper particle flotation process on pyrrhotite ores; performing a secondary fine copper particle flotation process on the obtained copper flotation concentrate; performing a copper flotation scavenging process on tailings obtained from the coarse copper particle flotation process; performing a magnetic separation process on tailings obtained from the copper flotation scavenging process; performing a coarse sulfur particle flotation process on tailings obtained from the magnetic separation process; performing a sulfur flotation scavenging process on tailings obtained from the coarse sulfur particle flotation process; and performing a secondary desulfurization process on concentrate obtained from the magnetic separation process, so as to obtain iron ore concentrate. The method applies in particular to pyrrhotite having low copper content and high ferrous sulfide content, and uses a process of low-alkali magnetic separation followed by flotation; valuable metals such as copper, iron, sulfur and pyrrhotite in copper-iron ores can be fully recovered.

Description

Beneficiation method of low-alkali pyrrhotite containing magnetic first and then floating

Technical field

The invention relates to the fields of chemical industry and metallurgy, in particular to the beneficiation process of mixed ore of chalcopyrite, pyrite, magnetite and pyrrhotite.

Background technique

The Xinqiao copper-pyrite deposit is a very important deposit in the Tongling ore concentration area in the middle and lower reaches of the Yangtze River in my country. This type of deposit has rich sulfur reserves, mainly containing chalcopyrite, pyrite, magnetite, and magnetite. Ores such as pyrite, and a small amount of ores such as galena and sphalerite. There are also many mines with similar deposits in my country, such as Tongling Dongguashan Copper Mine, Anqing Copper Mine in Anhui, and Tongling Zijin Mining.

Xinqiao Mine has a mining and dressing production capacity of 1.5 million tons per year, including 600,000 tons of underground mines and 900,000 tons of open-pit mines. It has now become an annual output of 1.4 million tons of sulfur concentrates, 40,000 tons of copper concentrates and 100,000 tons of iron ore. Tons of large-scale polymetallic mines. After years of production practice, the process flow is smooth and the production index is good. However, there are also some problems. First, affected by market conditions, it is difficult to sell low-sulfur sulfur concentrates with a sulfur content of about 40%, and the price is low. The second is that the sulfur content of iron concentrates is seriously exceeding the standard. Generally, the sulfur content of iron concentrates is more than 3 to 4%, and sometimes even can reach more than 10%, and the iron recovery rate is not high.

At present, there are not many reports on the beneficiation process of copper-pyrite containing pyrrhotite, and a single beneficiation process or a combined beneficiation process with magnetic separation is mainly used. Zhao Guanfei and others recovered high-sulfur copper-iron ore in Anhui and other places, but iron concentrates contain high sulfur and are difficult to comprehensively utilize.

Summary of the invention

(1) Technical problems to be solved

In order to improve the separation efficiency of copper, sulfur, iron valuable metal iron and quartz, garnet and other gangues in copper pyrite ore, the present invention is specially proposed.

(2) Technical solution

The pyrrhotite-containing ore is subjected to the copper flotation roughing process, the collector uses ethyl thiourethane Z-200, the dosage is: 15-25g/t and the ethylxanthate B03, the dosage is: 40-60g/ t;; The foaming agent is No. 2 oil: 15-25g/t; the obtained copper flotation concentrate is subjected to a secondary copper flotation process; the tailings obtained from the copper flotation roughing process are carried out Copper flotation sweeping process, ethyl thiourethane Z-200, the dosage is 5-10g/t and ethyl xanthate B03, the dosage: 20-30g/t; the foaming agent is No. 2 oil: 5～ 10g/t; the tailings obtained by the copper flotation sweeping process are subjected to a magnetic separation process with a magnetic field strength of 111.4KA/M; the tailings obtained by the magnetic separation process are subjected to a sulfur flotation roughing process, using coke Sodium sulfite 1400～1600g/t+copper sulfate 55～60g/t, ethyl xanthate 30～70g/t, No. 2 oil 15～25g/t, flotation time 13 minutes; obtained by the rough flotation process of sulfur Sulfur flotation sweeping process for tailings, using sodium metabisulfite 950～1050g/t + copper sulfate 25～35g/t, ethyl xanthate 20～30g/t, No. 2 oil 10～20g/t, flotation time 5 minutes ; The concentrate obtained by the magnetic separation process is subjected to a secondary desulfurization process to obtain iron concentrate.

Preferably, the foaming agent used in the copper flotation roughing process of the pyrrhotite-containing ore is No. 2 oil. The amount is 21 g/t.

Preferably, the second copper flotation beneficiation process is divided into a first copper flotation beneficiation process and a second copper flotation beneficiation process, and the second copper flotation beneficiation process also obtains the first The middle ore, the first middle ore is returned to the first copper flotation beneficiation process.

Preferably, the first copper flotation beneficiation process also obtains a second middle ore, and the second middle ore is returned to the copper flotation roughing process.

Preferably, the third medium ore obtained by the copper flotation sweeping process is returned to the copper flotation roughing process.

Preferably, the concentrate obtained by the magnetic separation process is subjected to the first desulfurization process, using sodium metabisulfite 1000g/t + copper sulfate 50g/t, ethyl xanthate 20-40g/t, and No. 2 oil 15-25g/t , The flotation time is 9 minutes, and the fourth medium ore and flotation tailings are obtained.

Preferably, the flotation tailings are subjected to the second desulfurization process, using the chemicals sodium pyrosulfate 300g/t + copper sulfate 20g/t, ethyl xanthate 5-15g/t, and No. 2 oil 10-20g/t, The flotation time is 5 minutes, and the foam product obtained is the fifth medium ore and iron concentrate.

Preferably, the sulfur concentrate is obtained by the rough sulfur flotation process.

Preferably, the sixth medium ore obtained by the sulfur flotation sweeping is returned to the sulfur flotation roughing.

Preferably, the copper concentrate is obtained by the secondary copper flotation beneficiation process.

(3) Beneficial effects

① In the present invention, equipment with a combination of multiple force fields is used on the equipment, such as a flotation machine and a magnetic separator, which are important support points for realizing the method, and the new beneficiation equipment brings a good separation effect.

② In the separation process of the present invention, a new type of pyrrhotite agent activator (A1+A2) is used. Compared with the activation of the sulfuric acid activator, the sulfur grade in the iron concentrate can be reduced, which is also another important support point for the realization of the invention.

③In the sorting process of the present invention, low alkali is adopted, which reduces the consumption of lime during the formation process, improves the subsequent dehydration process, reduces production costs, and increases economic benefits.

④Compared with the known technology, this method more comprehensively recovers the valuable elements in the copper-iron ore, including the metals copper, iron, sulfur, pyrrhotite, etc., and has good economic benefits.

Description of the drawings

Fig. 1 is a process flow diagram of the beneficiation method of pyrrhotite-containing ore of the present invention.

detailed description

In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings.

Fig. 1 is a process flow diagram of the beneficiation method of pyrrhotite-containing ore of the present invention. As shown in Figure 1, the process includes the following steps:

S1. The pyrrhotite-containing ore is subjected to a copper flotation roughing process, and the obtained copper flotation concentrate is subjected to a secondary copper flotation beneficiation process.

In specific implementation, raw iron ore can be crushed and ground. For example, after crushing the raw materials into -2mm copper pyrite, use a ball mill to grind the ore, add lime before the grinding starts, and finally make the PH value of 9±0.5, and the particle size of the product should be controlled by overflow. The particle size -0.074mm accounts for 75%.

The overflow product undergoes a rough copper flotation process, and the copper flotation process can use suitable collectors and foaming agents. The preferably used collector is Z-200+B03, Z-200: 15-25g/t, B03: 40-60g/t (the B03 is ethyl xanthate, the unit g/t is gram/ton), The foaming agent is No. 2 oil: 15-25g/t.

After copper flotation roughing, the product copper flotation roughing concentrate and copper flotation roughing tailings are obtained. The copper flotation roughing concentrate is controlled at the pH value of 11-12 for the first copper flotation selection. , The concentration time is between 5 and 15 minutes, such as 10 minutes, to obtain the product copper flotation concentrate and the second middle ore. The obtained copper flotation concentrate can be selected for the second copper flotation. Similarly, the PH value is controlled at 11-12, the concentration time is about 10 minutes, and the products obtained are copper concentrate and the first middle ore.

The product obtained from the first copper flotation concentration, the second medium ore is returned to the copper flotation rough selection, and the copper flotation is performed again, and the product obtained from the second copper flotation concentrate is returned to the first copper flotation selection. Copper flotation beneficiation is performed again in the middle, and the copper flotation roughing tailings produced by the copper flotation roughing will be subjected to copper flotation sweeping operations.

S2. The tailings obtained by the copper flotation roughing process are subjected to a copper flotation sweeping process.

The process of copper flotation and sweeping in this step also uses suitable collectors and foaming agents. In the present invention, it is preferred that the collector used is Z-200+B03, the dosage is: Z-200: (5-10) g/t, B03: (20-30) g/t; foaming agent is 2 No. oil: 5～10g/t. Copper flotation scavenging will obtain the third medium ore and copper flotation scavenging tailings. The third medium ore will return to copper flotation roughing and flotation again, and the obtained copper flotation scavenging tailings will be subjected to magnetic separation operations .

S3, subjecting the tailings obtained by the copper flotation sweeping process to a magnetic separation process.

In this step, a rough magnetic separation process is performed. The magnetic field strength can be 90-130 KA/M, and the magnetic field strength is preferably 111.4 KA/M. Obtain the magnetic separation roughing concentrate and magnetic separation roughing tailings. The magnetic separation roughing tailings is subjected to a sulfur flotation roughing process.

S4. The tailings obtained by the magnetic separation process are subjected to a rough sulfur flotation process.

In this step, sulfur flotation is carried out. The medicament used is preferably A1+A2: 1500+60g/t, ethyl xanthate 30-70g/t, No. 2 oil 15-25g/t, flotation time is generally 10-15 minutes, preferably 13 minutes, The product sulfur flotation roughing sulfur concentrate and sulfur flotation roughing tailings are obtained. (The A1 is sodium pyrosulfate; A2 is copper sulfate, the unit g/t is gram/ton)

S5, subjecting the tailings obtained from the sulfur flotation roughing process to a sulfur flotation sweeping process.

The crude sulfur flotation tailings will be subjected to a sulfur flotation sweeping. The sulfur flotation sweeping is preferably A1+A2: 1000+30g/t, ethyl xanthate 20-30g/t, No. 2 oil 10 ~20g/t, the flotation time can be about 5 minutes. The obtained foam product is the second sulfur flotation roughing operation of the No. 6 Middle Mine returning to the sulfur flotation roughing operation.

S6, subjecting the concentrate obtained by the magnetic separation process to a secondary desulfurization process to obtain iron concentrate.

This step will carry out two desulfurization processes. Carry out the first desulfurization operation of the magnetic separation coarse concentrate, using agent A1+A2: 1000+60g/t, ethyl xanthate 20-40g/t, No. 2 oil 15-25g/t, flotation time Preferably, it takes 9 minutes to obtain the fourth middle ore and flotation tailings of the product. The flotation tailings are subjected to the second desulfurization operation, using agent A1+A2: 300+20g/t, ethyl xanthate 5-15g/t, No. 2 oil 10-20g/t, and the flotation time can be within It takes about 5 minutes to obtain foam products as the fifth medium ore and iron concentrate.

In the steps S1 to S6, the fourth middle mine, the fifth middle mine and the sulphur concentrate are combined into a comprehensive sulphur concentrate.

Example 1: The raw material is a certain copper-sulfur iron in Anhui, in which the raw ore contains 0.366% Cu, S32.54%, and Fe39.85%. The composition of ore minerals is relatively complex, among which metal minerals include chalcopyrite, magnetite, hematite, pyrrhotite, pyrite, galena and siderite. The non-metallic minerals are mainly carbonate minerals. The ore is dominated by massive structure and disseminated structure. The mineral intercalation is more complicated. The magnetite cracks are divided into many particles by calcite, and the intercalation particle size is mainly fine particles. The content of copper minerals is sparse and relatively dispersed. Pyrite has porphyritic metamorphic crystals, unequal-grained metamorphic structure, and the grain size is extremely unequal grained. The main reason is that the particle size of the inlay is fine, and the calcite mesh veins are cut through, which makes it more difficult for the monomer to dissociate. Using the process flow shown in Figure 1, the specific process parameters are:

(1) After crushing the raw materials into -2mm copper-pyrite ore, grind the ore in a ball mill (the product particle size is controlled by overflow so that the particle size -0.074mm accounts for 74%), and the lime agent is added before the grinding starts. Finally, the pH value is 11±0.5.

(2) The overflow product is first subjected to the first copper flotation rough selection (the collector uses butyl xanthate, the dosage is: 50～70g/t; the foaming agent is No. 2 oil: 21g/t), The beneficiation concentrate is subjected to a copper flotation beneficiation (pH value is controlled so that the pH value is 11-12). The flotation tailings products are returned to the first roughing operation of copper flotation. The tailings of the first copper flotation roughing are carried out for the first copper flotation sweeping operation (the collector uses butyl xanthate, the dosage is: 20-30g/t; the foaming agent is No. 2 oil: 7g /t), the flotation concentrate is returned to the first copper flotation roughing operation, and the flotation tailings is subjected to the next magnetic separation operation.

(3) After the copper flotation operation, the magnetic separation operation is carried out, and the operation adopts the primary magnetic separation rough separation and the secondary magnetic separation selection desulfurization operation. The specific operation is as follows, iron ore magnetic separation roughing operation (magnetic field strength is 111.4KA/M), magnetic separation concentrate for desulfurization operation 1 (A1+A2: 1500+60g/t, B03 medicine 30g/t, No. 2 oil 21g/t, flotation time 9 minutes), to obtain sulfur concentrate product one. The flotation tailings of the first desulfurization operation are subjected to the second desulfurization operation (A1+A2: 500+10g/t, B03 drug 10g/t, No. 2 oil 14g/t, flotation time 5 minutes), and the foam product obtains the sulfur concentrate product Second, the tailings are iron concentrates.

(4) Magnetic separation roughing tailings is used for one roughing and one sweeping operation of sulphur concentrate. The specific operation is as follows, the magnetic tailings are subjected to sulfur roughing operation (A1+A2: 1500+60g/t, B03 medicine: 50g/t, No. 2 oil: 21g/t, flotation time 13 minutes) to obtain sulfur concentrate Product three. The flotation tailings of the rough sulfur separation operation are subjected to sulfur sweeping operation (A1+A2: 1000+30g/t, B03 medicine: 30g/t, No. 2 oil: 14g/t, flotation time 5 minutes), and the foam product is returned When it comes to sulfur roughing operation, the flotation tailings are the final tailings.

(5) Sulfur product one, sulfur product two, and sulfur concentrate are combined into a comprehensive sulfur concentrate.

In summary, the products after flotation are as follows:

It can be seen from the above examples that, in the separation process of the present invention, a new type of process flow is adopted, the beneficiation process is shortened, and low alkali is adopted, which reduces the consumption of lime during the production process, improves the subsequent dehydration process, and reduces Cost of production. A new type of pyrrhotite agent activator (A1+A2) is used. In this way, compared with the activation of sulfuric acid activator, the grade of sulfur in the iron concentrate can be reduced, and the use of equipment with a combination of various force fields brings a good separation effect.

At the same time, in the sorting process of the present invention, the valuable metals in the copper-iron ore, including the metals copper, iron, sulfur, pyrrhotite, etc., are recovered more comprehensively, which reduces production costs and increases economic benefits.

The specific embodiments described above further describe the purpose, technical solutions and beneficial effects of the present invention in further detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Within the spirit and principle of the present invention, any modification, equivalent replacement, improvement, etc., shall be included in the protection scope of the present invention.

Claims

A method for beneficiating pyrrhotite, which is characterized in that it comprises the following steps:

The pyrrhotite-containing ore is subjected to the copper flotation roughing process, the collector uses ethyl thiourethane Z-200, the dosage is: 15-25g/t and the ethylxanthate B03, the dosage is: 40-60g/ t;; The foaming agent is No. 2 oil: 15-25g/t; the obtained copper flotation concentrate is subjected to a secondary copper flotation beneficiation process;

The tailings obtained by the copper flotation roughing process are subjected to the copper flotation sweeping process, ethyl thiourethane Z-200, the dosage is 5-10g/t and ethyl xanthate B03, the dosage is: 20-30g /t; Foaming agent is No. 2 oil: 5～10g/t;

Subjecting the tailings obtained by the copper flotation sweeping process to a magnetic separation process, the magnetic field intensity is 111.4KA/M;

The tailings obtained by the magnetic separation process are subjected to a rough sulfur flotation process, using sodium metabisulfite 1400-1600g/t + copper sulfate 55-60g/t, ethyl xanthate 30-70g/t, No. 2 oil 15-25g /t, the flotation time is 13 minutes;

The tailings obtained by the sulfur flotation roughing process are subjected to a sulfur flotation sweeping process, using sodium metabisulfite 950～1050g/t + copper sulfate 25～35g/t, ethyl xanthate 20～30g/t, No. 2 oil 10～20g/t, flotation time 5 minutes;

The concentrate obtained by the magnetic separation process is subjected to a secondary desulfurization process to obtain iron concentrate.
The method for beneficiation of pyrrhotite-containing ore according to claim 1, wherein the foaming agent used in the copper flotation roughing process of the pyrrhotite-containing ore is No. 2 oil. The amount is 21g/t. .
The method for beneficiation of pyrrhotite-containing ore according to claim 1, wherein the secondary copper flotation and beneficiation process is divided into a first copper flotation and beneficiation process and a second copper flotation and beneficiation process. Process, the second copper flotation beneficiation process also obtains a first middle ore, and the first middle ore is returned to the first copper flotation beneficiation process.
The method for beneficiating pyrrhotite according to claim 1, characterized in that: the first copper flotation process also obtains a second middle ore, and the second middle ore is returned to the copper flotation process. In the roughing process.
The pyrrhotite-containing ore beneficiation method according to claim 1, wherein the third medium ore obtained by the copper flotation sweeping process is returned to the copper flotation roughing process.
The method for beneficiating pyrrhotite according to claim 1, characterized in that: the concentrate obtained by the magnetic separation process is subjected to the first desulfurization process, using the chemical sodium sulfate 1000g/t + copper sulfate 50g/t , Ethyl xanthate 20-40g/t, No. 2 oil 15-25g/t, flotation time is 9 minutes, get the product fourth middle ore and flotation tailings.
The method for beneficiation of pyrrhotite-containing ore according to claim 8, characterized in that: the flotation tailings are subjected to the second desulfurization process, using sodium metabisulfite 300g/t + copper sulfate 20g/t, ethyl xanthate 5～15g/t, No. 2 oil 10～20g/t, flotation time is 5 minutes, the foam product obtained is the fifth medium ore and iron concentrate.
The method for beneficiation of pyrrhotite-containing ore according to claim 1, characterized in that the sulfur concentrate is obtained by the rough sulfur flotation process.
The method for beneficiating pyrrhotite according to claim 1, wherein the sixth middle ore obtained by the sulfur flotation sweeping is returned to the sulfur flotation roughing.
The method for beneficiating pyrrhotite according to claim 1, wherein the secondary copper flotation and beneficiation process obtains copper concentrate.