CN112517247A - Flotation reagent for high-sulfur magnetite ore and use method thereof - Google Patents

Abstract

The invention provides a flotation reagent for high-sulfur magnetite ore, which comprises: a first flotation reagent, a second flotation reagent, a third flotation reagent, and a fourth flotation reagent; the first flotation reagent comprises copper sulfate, isobutyl xanthate and 2# oil, and the mass ratio of the copper sulfate to the isobutyl xanthate to the 2# oil is (3-5): (4-6): (1-3); the second flotation reagent comprises copper sulfate, FS, isobutyl xanthate and 2# oil, and the mass ratio of the copper sulfate to the FS to the isobutyl xanthate to the 2# oil is (2-3): (12-18): (50-65): (2-4); the third flotation machine comprises concentrated sulfuric acid, FS, isobutyl xanthate and 2# oil, and the mass ratio of the concentrated sulfuric acid to the FS to the isobutyl xanthate to the 2# oil is (7-9): (8-12): (1-5): (1-2), the flotation reagent FS and copper sulfate are reasonably matched for use, so that the beneficiation cost can be effectively reduced, the FS is used when high-sulfur magnetite ore is processed and is combined with sulfuric acid, the desulfurization effect is obviously superior to that of the traditional reagent, and the reagent has great practical significance in desulfurization treatment of iron ore in order to improve the competitiveness of iron ore and the quality of steel products in China.

Description

Flotation reagent for high-sulfur magnetite ore and use method thereof

Technical Field

The invention belongs to the field of ore desulphurization, and particularly relates to a flotation reagent for high-sulfur magnetite ore and a use method thereof.

Background

Along with the continuous mining of mineral resources, limited rich ore and magnetite resources which are easy to select in China are gradually reduced, pyrrhotite is more and more emphasized in the sulfuric acid industry, the selection of high-sulfur magnetite becomes inevitable, and the method has great practical significance for the desulfurization treatment of iron ore in order to improve the competitiveness of iron ore and the quality of steel products in China.

The inventor finds that the pyrite is easy to separate from the magnetite in the magnetic separation process because the pyrite has no magnetism when the iron ore is desulfurized, so that the separation of the pyrite and the magnetite is not difficult; however, the pyrrhotite has strong magnetism, so that the pyrrhotite is easy to enter magnetic concentrate in the magnetic separation process, and the pyrrhotite and magnetite are difficult to separate by single magnetic separation. Therefore, the high-sulfur magnetite is difficult to desulfurize, and the pyrrhotite in the high-sulfur magnetite is mainly difficult to remove.

Disclosure of Invention

In view of the problems of the prior art, the present invention aims to:

in a first aspect: provided is a flotation reagent for high-sulfur magnetite ore, comprising: a first flotation reagent, a second flotation reagent, a third flotation reagent, and a fourth flotation reagent; the first flotation reagent comprises copper sulfate, isobutyl xanthate and 2# oil, and the mass ratio of the copper sulfate to the isobutyl xanthate to the 2# oil is (3-5): (4-6): (1-3); the second flotation reagent comprises copper sulfate, FS, isobutyl xanthate and 2# oil, and the mass ratio of the copper sulfate to the FS to the isobutyl xanthate to the 2# oil is (2-3): (12-18): (50-65): (2-4); the third flotation machine comprises concentrated sulfuric acid, FS, isobutyl xanthate and 2# oil, and the mass ratio of the concentrated sulfuric acid to the FS to the isobutyl xanthate to the 2# oil is (7-9): (8-12): (1-5): (1-2); the fourth flotation machine comprises concentrated sulfuric acid, FS, isobutyl xanthate and 2# oil, and the mass ratio of the concentrated sulfuric acid to the FS to the isobutyl xanthate to the 2# oil is (9-10): (1-2): (3-4): (1-2).

In a second aspect: provided is a method for preparing a flotation reagent for high-sulfur magnetite ore, which comprises the following steps:

1) the high-sulfur magnetite ore is divided into four types according to the content of pyrite less than 1.5 percent, between 1.5 percent and 2.5 percent, between 2.5 percent and 3.5 percent and more than 3.5 percent;

2) use of a first flotation agent according to any one of claims 1 to 3 on high sulfur magnetite ores having a pyrite content of less than 1.5%;

3) use of a second flotation agent according to any one of claims 1 to 3 for high sulfur magnetite ores having a pyrite content of between 1.5% and 2.5%;

4) use of a third flotation agent according to any one of claims 1 to 3 for high sulfur magnetite ores having a pyrite content of between 2.5% and 3.5%;

5) use of a fourth flotation agent according to any one of claims 1 to 3 for high sulfur magnetite ores having a pyrite content greater than 3.5%.

Has the advantages that:

the FS and the copper sulfate are reasonably matched for use, so that the beneficiation cost can be effectively reduced, the FS is used when the high-sulfur magnetite ore is processed and is combined with the sulfuric acid, the desulfurization effect is obviously superior to that of the traditional medicament, and the FS and the sulfuric acid have great practical significance for desulfurization treatment of the iron ore in order to improve the competitiveness of the iron ore and the quality of steel products in China.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.

FIG. 1 is a flow chart of a process for selecting minerals according to an embodiment of the present invention;

FIG. 2 is a line graph showing the results of a dose test of a collector in accordance with an embodiment of the present invention;

FIG. 3 is a line graph illustrating the effect of FS usage on the test in an embodiment of the present invention;

FIG. 4 is a line graph illustrating the effect of FS usage on the test in an embodiment of the present invention;

FIG. 5 is a line graph of the effect of AO dosage on the test in an embodiment of the present invention;

FIG. 6 is a line graph showing the effect of copper sulfate to AO ratio on the test in an embodiment of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the test, an activating agent FS is sequentially added and stirred for 10min (other activating agents are stirred for 3min), a collecting agent isobutyl xanthate or other xanthates are stirred for 3min, and a foaming agent 2# oil is stirred for 2 min; the foam scraping time is 3 min.

The flow is shown in figure 1

FIG. 1 is a flow chart of a beneficiation process

Collector species test

The xanthate is an anion collector, has good collecting performance and is a commonly used sulfide ore collector. In the test, four xanthate collecting agents are selected, namely butyl xanthate, isobutyl xanthate and pentaxanthate, the dosage of the four xanthate collecting agents is 200g/t, the dosage of FS is 2000g/t, the dosage of 2# oil used as a foaming agent is 30g/t, and the flotation is carried out for 3 min. The test results are shown in table 1.

Table 1 collector species test results

The data in table 1 show that from the sulfur grade in the tailings, isobutyl xanthate < butyl xanthate < amyl xanthate, and the desulfurization effect is the best when isobutyl xanthate is used, but the desulfurization capacities of the three collectors are equivalent; from the yield of tailings, the butyl xanthate is more than the isobutyl xanthate is more than the amyl xanthate, the loss of iron ore concentrate is minimum when the butyl xanthate is used, and the isobutyl xanthate is second. Therefore, the collector is determined to be isobutyl xanthate by comprehensive consideration.

Collector usage test

The using amount of the collecting agent can directly influence the index of the test, and in a certain collecting agent concentration range, the adsorption amount is increased along with the increase of the concentration of the medicament, and the flotation recovery rate is obviously increased; after the concentration reaches a certain value, the recovery rate is reduced along with the increase of the concentration and the adsorption quantity; when the concentration of the collecting agent is too high, the adsorption quantity can be continuously increased, but the flotation recovery rate is not increased any more, and even is reduced. Therefore, the amount of collector used is to be properly controlled during the flotation process to achieve the best efficiency. To determine the appropriate amount of collector, a collector dose test was performed. The dosage of isobutyl xanthate is variable and is respectively 60g, 100g, 200g and 300g, the dosage of activating agent FS is 2000g/t, the dosage of foaming agent 2# oil is 30g/t, and the flotation is carried out for 3 min. The process flow is shown in FIG. 1, and the test results are shown in Table 2 and FIG. 2.

TABLE 2 test results of collector usage

FIG. 2-Effect of collector dosage on the test

As shown in table 2 and fig. 2, the grade of sulfur in the tailings gradually decreases with the increase of the usage amount of the collector isobutyl xanthate, and tends to be flat when the usage amount of the collector is greater than 200g/t, while the yield of the tailings gradually decreases. Comprehensively considering, the dosage of the isobutyl xanthate is determined to be 200 g/t.

Test for activator species

The sulfur (usually pyrrhotite and pyrite) in the iron ore concentrate is easy to be oxidized, a hydrophilic film is formed on the surface of the iron ore concentrate, the floating of the sulfur is inhibited, and therefore the iron ore concentrate needs to be activated firstly and then collected by using xanthate in the desulfurization flotation process. The activation of sulfur is generally carried out in three ways: dissolving a mineral surface inhibitory film; secondly, an insoluble activated film is formed on the surface of the mineral by adopting a chemical reaction of exchange adsorption or replacement; and thirdly, eliminating the harmful effect of the inhibitory ions in the ore pulp. Therefore, sulfuric acid, novel activators FS, AO, ACD and copper sulfate are selected as test activators, and the dosage of the test activators is 3000g/t, 2000g/t, 400g/t and 500g/t respectively; the collecting agent adopts isobutyl xanthate, and the dosage is 200 g/t; foaming agent No. 2 oil 30g/t, and flotation for 3 min. The test results are shown in Table 3.

TABLE 3 test results for activator species

The data in table 3 show that the grade of sulfur in the tailings after the FS is used is obviously lower than that of other activators, reaches 0.24%, the desulfurization effect is obvious, and the industrial requirements are met. Although the tailings yield is the lowest and the iron concentrate loss is the greatest, the tailings yield does not change significantly. Therefore, the best activator was determined to be FS.

Dosage test of novel activator FS

The amount of the activating agent directly influences the effect of the flotation desulfurization. The use amount of the activating agent is too much, so that the iron concentrate floats upwards, and the iron loss is increased; the use amount of the activating agent is not enough, so that the sulfur activation is not sufficient, and the good separation effect of the sulfur and the iron ore concentrate cannot be achieved. In order to refine the amount of activator FS used, an amount test of activator FS was performed. The test was performed with two collectors.

FS dosage test using isobutylxanthate

The using amounts of FS are 1000g/t, 1500g/t, 2000g/t and 3000g/t respectively, the using amount of isobutyl xanthate for collecting agent is 200g/t, the using amount of 2# oil for foaming agent is 30g/t, and the flotation is carried out for 3 min. The process flow is shown in FIG. 2-1, and the test results are shown in Table 4 and FIG. 3.

TABLE 3

As can be seen from Table 4 and FIG. 3, the grade of sulfur in the tailings gradually decreases with the increase of the dosage of the novel activating agent FS, and tends to be flat after the dosage of FS is more than 2000g/t, while the yield of the tailings does not change obviously. Therefore, the optimum amount of FS was determined to be 2000 g/t.

FS dosage test using Penhuang

The using amounts of the activating agent FS are 1000g/t, 1500g/t, 2000g/t and 3000g/t respectively, the collecting agent is pentoxanthin, the using amount is 200g/t, the foaming agent is 2# oil, the using amount is 30g/t, and the flotation is carried out for 3 min. The test results are shown in Table 5 and FIG. 4.

TABLE 5

As shown in Table 5 and FIG. 4, the grade of sulfur in the tailings gradually decreases with the increase of the dosage of the novel activating agent FS, and tends to be flat when the dosage of FS is more than 2000g/t, while the yield of the tailings gradually decreases. Therefore, the optimum amount of FS was determined to be 2000 g/t.

When the dosage of FS is 2000g/t, compared with the test results of two different collectors, when the isobutyl xanthate is used, the grade of sulfur in the tailings is lower, and the yield of the tailings is higher, so that the isobutyl xanthate not only has better desulfurization effect than that of a pentaxanthate, but also has less loss of iron ore concentrate. During the course of the subsequent experiments, the use of isobutyl xanthate was determined.

Combined activator test

From the above test results, it is found that the desulfurization effect of the novel activator FS is remarkable. However, the amount of FS is large, and in order to reduce the amount of the active agent and to exert a synergistic effect of the combination of the active agents, it is attempted to reduce the amount of FS in combination with other active agents or use other combination agents in place of FS. Four combinations of FS + AO, copper sulfate + sulfuric acid + AO and copper sulfate + sulfuric acid + ACD were used in the test.

Activator FS and AO combination test

The dosage of an activating agent FS is 1000g/t, the dosage of an activating agent AO is variable and is respectively 100g/t, 200g/t and 300g/t, isobutyl xanthate is used as a collecting agent, the dosage is 200g/t, 2# oil is used as a foaming agent, the dosage is 30g/t, and flotation is carried out for 3 min. The process flow is shown in FIG. 2-1, and the test results are shown in Table 6 and FIG. 5.

TABLE 6

As can be seen from table 6 and fig. 5, the increase of the dosage of the activator AO, the increase of the sulfur grade in the tailings and the increase of the yield of the tailings are both increased, decreased and increased, and the fluctuation trend is shown. When the dosage of AO is 200g/t, the grade of sulfur in the tailings reaches the lowest when the combined medicament is used, but the desulfurization effect of the tailings is obviously lower than that of a single activating agent FS. The addition of AO greatly reduces the collecting property of isobutyl xanthate, so that the yield of sulfur concentrate is obviously lower.

Combination test of activator copper sulfate and AO

The total amount of activating agent copper sulfate and AO is 500g/t, copper sulfate: AO is variable, 3: 2. 1: 1 and 2: 3. the collecting agent adopts isobutyl xanthate with the dosage of 200g/t, the foaming agent adopts 2# oil with the dosage of 30g/t, and the flotation is carried out for 3 min. The test results are shown in table 7 and fig. 6.

TABLE 7

As shown in table 7 and fig. 6, as the ratio of copper sulfate to AO activator was gradually decreased, the sulfur grade in the tailings increased first and then decreased, while the yield of the tailings decreased first and then increased. When the copper sulfate: AO is 3: and 2, the grade of sulfur in the tailings is the lowest, which reaches 0.34%, and the yield of the tailings is 94.88%. The iron concentrate desulfurization effect is slightly poor, and the loss is larger than that when FS is used.

Economic analysis

Basis of calculation

(1) The treatment capacity of the selected factory is 6000t/d, the total yield of the iron is 55 percent and the total recovery rate is 84 percent according to the sulfur content of the fine iron powder (the CUSO4 is used as an activating agent).

(2) According to the current price measurement in a 4-month company, the price of iron ore concentrate with iron grade of 65 percent (sulfur grade of 0.6 percent) is 630 yuan/t, the sulfur content per liter (reduction) is 0.1 percent, and 10 yuan is reduced (added).

Difference of production

CuSO4 is used as a desulfurization activator, the iron concentrate S is approximately equal to 0.8 percent, the operation yield of the flotation desulfurization iron is 98.53 percent, and the total yield of the iron concentrate is 55 percent. After FS is used as a desulfurization activator instead of CuSO4, when the iron concentrate S is less than 0.6%, the operation yield of the flotation desulfurization iron is 97.76%, and the total yield of the iron concentrate is as follows: (97.76% ÷ 98.53% × 55%) -54.57%; when the iron concentrate S is less than 0.3%, the operation yield of the flotation desulphurization iron is 96.57%, and the total yield of the iron concentrate is as follows: (96.57% ÷ 98.53% × 55%) -53.91%. The sale values of the fine iron powder products with different sulfur contents are shown in a table 8, and the cost estimation result of the activating agent is shown in a table 9.

Other costs remained unchanged after replacing CuSO4 with FS. Calculated by taking the sulfur content of the iron concentrate powder as the standard of 0.8 percent when CuSO4 is used as an activator.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (4)

1. A flotation reagent for high-sulfur magnetite ore, comprising:

a first flotation reagent, a second flotation reagent, a third flotation reagent, and a fourth flotation reagent;

the first flotation reagent comprises copper sulfate, isobutyl xanthate and 2# oil, and the mass ratio of the copper sulfate to the isobutyl xanthate to the 2# oil is (3-5): (4-6): (1-3);

the second flotation reagent comprises copper sulfate, FS, isobutyl xanthate and 2# oil, and the mass ratio of the copper sulfate to the FS to the isobutyl xanthate to the 2# oil is (2-3): (12-18): (50-65): (2-4);

the third flotation machine comprises concentrated sulfuric acid, FS, isobutyl xanthate and 2# oil, and the mass ratio of the concentrated sulfuric acid to the FS to the isobutyl xanthate to the 2# oil is (7-9): (8-12): (1-5): (1-2);

the fourth flotation machine comprises concentrated sulfuric acid, FS, isobutyl xanthate and 2# oil, and the mass ratio of the concentrated sulfuric acid to the FS to the isobutyl xanthate to the 2# oil is (9-10): (1-2): (3-4): (1-2).

2. The flotation reagent according to claim 1, wherein the mass ratio of the copper sulfate, the isobutyl xanthate and the 2# oil in the first flotation reagent is 4: 5: 2.

3. the flotation reagent according to claim 1, wherein the mass ratio of the copper sulfate, the FS, the isobutyl xanthate and the No. 2 oil in the second flotation reagent is 5: 40: 160: 6.

4. the method for using the flotation reagent for the high-sulfur magnetite ore is characterized by comprising the following steps:

1) the high-sulfur magnetite ore is divided into four types according to the content of pyrite less than 1.5 percent, between 1.5 percent and 2.5 percent, between 2.5 percent and 3.5 percent and more than 3.5 percent;

2) use of a first flotation agent according to any one of claims 1 to 3 on high sulfur magnetite ores having a pyrite content of less than 1.5%;

3) use of a second flotation agent according to any one of claims 1 to 3 for high sulfur magnetite ores having a pyrite content of between 1.5% and 2.5%;

4) use of a third flotation agent according to any one of claims 1 to 3 for high sulfur magnetite ores having a pyrite content of between 2.5% and 3.5%;

5) use of a fourth flotation agent according to any one of claims 1 to 3 for high sulfur magnetite ores having a pyrite content greater than 3.5%.

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