CN114471958A - Combined inhibitor for separating pyrite from complex molybdenite and separation method thereof - Google Patents
Combined inhibitor for separating pyrite from complex molybdenite and separation method thereof Download PDFInfo
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- CN114471958A CN114471958A CN202111533398.1A CN202111533398A CN114471958A CN 114471958 A CN114471958 A CN 114471958A CN 202111533398 A CN202111533398 A CN 202111533398A CN 114471958 A CN114471958 A CN 114471958A
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Abstract
A combined inhibitor for separating pyrite from complex molybdenite and a separation method thereof relate to the technical field of mineral processing, and comprise polyaspartic acid, calcium hypochlorite and sodium humate, wherein the mass ratio of the polyaspartic acid to the calcium hypochlorite to the sodium humate is as follows: (1-3): (3-6): (3-6); the combined inhibitor is added by respectively preparing the components into aqueous solution, wherein: the mass concentration of the polyaspartic acid aqueous solution is 0.5-1.0%; the mass concentration of the calcium hypochlorite aqueous solution is 3.0-6.0%; the mass concentration of the sodium humate aqueous solution is 3.0-6.0%; the addition mass ratio of the three aqueous solutions is (2-3): 1: 1; the combined inhibitor is applied to ore grinding and flotation processes, the invention realizes the high-efficiency separation of molybdenite and pyrite, and overcomes the problems that the traditional lime method influences the recovery rate of molybdenite and the cyanide method generates great harm to the ecological environment.
Description
Technical Field
The invention relates to the technical field of mineral processing, in particular to a combined inhibitor for separating pyrite in complex molybdenite and a separation method thereof.
Background
It is known that pyrite is one of the main minerals affecting polymetallic sulphidic ores, usually associated with useful minerals such as chalcopyrite, galena and blende, but in some cases also associated with molybdenite and possesses good floatability; therefore, the inhibition of pyrite with better floatability in molybdenite plays an important role in improving the grade and the recovery rate of the molybdenite. In the polymetallic sulphide ore, pyrite is generally inhibited first, target minerals such as molybdenite are preferentially floated, and mineral ions inevitably cause unnecessary activation of pyrite. How to effectively inhibit pyrite and improve the flotation index of molybdenite becomes the problem to be faced in the first flotation of polymetallic sulphide ores. At present, the inhibitors for pyrite are mainly divided into two main classes of inorganic inhibitors and organic inhibitors, such as inorganic inhibitors like lime, sodium thiosulfate, calcium peroxide and sodium sulfite; fulvic acid, polyaspartic acid, sodium carboxymethylcellulose and other organic inhibitors.
The pyrite inhibitor that is currently most commonly used in industrial applications is the lime process; the method has good selectivity in separating pyrite from other sulfide ores, but the lime contains a large amount of calcium ions, and a large number of researches show that the lime has a strong inhibition effect on molybdenite, so that the method is not beneficial to further improving wood indexes and can cause resource waste of the molybdenite; in addition, the industrial application process of a large amount of lime has many problems, namely, the scale is easy to form to cause pipeline blockage, and the high alkalinity can corrode equipment; in addition, the method can cause the pH value of the backwater of the tailing pond to be high, and the flotation of molybdenite is not facilitated due to the higher pH value. Therefore, it is imperative to provide a separation inhibitor for pyrite in molybdenite, which is highly efficient, clean and safe.
Disclosure of Invention
In order to overcome the defects in the background art, the invention discloses a combined inhibitor for separating pyrite in complex molybdenite and a separation method thereof.
In order to realize the purpose, the invention adopts the following technical scheme:
a combined inhibitor for separating pyrite from complex molybdenite comprises polyaspartic acid, calcium hypochlorite and sodium humate in a mass ratio of: (1-3): (3-6): (3-6).
The combined inhibitor for separating the pyrite in the complex molybdenite is characterized in that the combined inhibitor is added by respectively preparing an aqueous solution from each component, wherein: the mass concentration of the polyaspartic acid aqueous solution is 0.5-1.0%; the mass concentration of the calcium hypochlorite aqueous solution is 3.0-6.0%; the mass concentration of the sodium humate aqueous solution is 3.0-6.0%; the addition mass ratio of the three aqueous solutions is (2-3): 1: 1.
the combined inhibitor for pyrite in complex molybdenite comprises the following chemical structural formula of polyaspartic acid:
wherein: m is 5-20; n is 5 to 20; the relative molecular mass is 1000-5000.
A separation method for separating pyrite in complex molybdenite specifically comprises the following steps:
(1) grinding ore
In the rough concentration, the molybdenite is ground to obtain ore pulp with the fineness of-200 meshes accounting for 53 percent; grinding the pre-concentration concentrate during concentration to obtain ore pulp with the fineness of-400 meshes accounting for 95%;
(2) flotation
Adding a flotation inhibitor and other agents into the ore pulp, and sequentially carrying out flotation operations of roughing, scavenging, concentrating and fine scavenging on the ore pulp to finally obtain molybdenite concentrate, fine scavenging tailings and tailings;
other agents include the collector kerosene, the frother terpineol, the inhibitor TGA (sodium thioglycolate), the inhibitor P-Nos (phosphoenolics);
in the flotation step, the addition amount of collecting agent kerosene is 40-150g/t, and the addition amount of foaming agent terpineol is 10-50g/t, calculated according to the mass of the inhibitor in the molybdenum-sulfur raw ore; the addition amount of inhibitor TGA (sodium thioglycolate) is 2-50g/t, and the addition amount of P-Nokes (phosphoinosis) is 2-50 g/t.
In the separation method for separating the pyrite in the complex molybdenite, in the flotation step, the rougher concentrate is subjected to pre-concentration, and only 20g/t of collecting agent kerosene is added in the pre-concentration process for eliminating foams in a flotation system.
The separation method for separating the pyrite in the complex molybdenite comprises the steps of performing primary rough concentration in the flotation step, and adding a combined inhibitor, a collector kerosene and a foaming agent terpineol in the rough concentration process, wherein the use amounts of the combined inhibitor, the collector kerosene and the foaming agent terpineol are 100g/t, 100g/t and 30g/t respectively;
scavenging the rougher tailings obtained in the flotation step for two times, adding collecting kerosene in the scavenging process, wherein the adding amount of the collecting kerosene in the first scavenging and the second scavenging is 1/5 and 1/20 of the using amount of the collecting kerosene in the rougher; only in the first sweep was terpineol added as blowing agent in an amount of 2/15 rougher.
According to the separation method for separating the pyrite in the complex molybdenite, in the flotation step, the obtained rough concentrate is subjected to pre-concentration, and only 20g/t of collecting agent kerosene is added in the pre-concentration process to eliminate foams in a flotation system.
In the flotation step, the obtained pre-concentration concentrate is subjected to four times of concentration and two times of fine scavenging, and a combined inhibitor is required to be added in each concentration process, namely, the first concentrate: adding 3g/t of each of inhibitor TGA and P-Nokes, 200g/t of combined inhibitor and 20g/t of collecting agent kerosene; refined II: adding 2g/t of each of inhibitor TGA and P-Nokes, and combining 100g/t of inhibitor; and (3) refining: adding 2g/t of each of inhibitor TGA and P-Nokes, and combining 100g/t of inhibitor; and C, fine IV: adding 2g/t of each of inhibitor TGA and P-Nokes, and combining 50g/t of inhibitor; fine sweeping: adding 20g/t of collecting agent and 4g/t of foaming agent; the second fine powder is not added with any medicament.
The invention will be further explained and illustrated below, and the technical principle of the invention lies in that:
firstly, calcium hypochlorite is a strong oxidant and can cause a series of oxidation reactions of pyrite, wherein the most important thing is to oxidize on the surface of pyrite to generate Fe (OH)2And which is further oxidized to Fe (OH)3Attached to the surface of pyrite because of Fe (OH)3Is a compound with small solubility product, so that Fe (OH) is greatly deposited on the surface of the pyrite3Is one of the main reasons for its inhibition.
Secondly, sodium humate is a natural polyelectrolyte and chelating agent, can be chelated or complexed with various metal ions, and is capable of being combined with Fe3+、Fe2+、Cu2+Very strong chelation can occur. Cu is well known2+The pyrite can be greatly activated, so that the pyrite is difficult to inhibit, and the addition of the sodium humate can greatly weaken the activation influence of other metal ions on the pyrite, so that the floatability of the pyrite is reduced, and the aim of inhibiting the pyrite is fulfilled.
And finally, mixing the organic macromolecular inhibitor polyaspartic acid and the inorganic micromolecular inhibitor calcium hypochlorite according to a certain proportion for use, and having a synergistic inhibition effect, so that the selective inhibition effect on the pyrite is enhanced, and the aim of flotation separation of the pyrite and the molybdenite is fulfilled.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
compared with the existing molybdenum-sulfur separation technology, the combined inhibitor for separating the pyrite from the complex molybdenite and the separation method thereof have good selectivity and inhibition capability on the pyrite; the method has the characteristics of small using amount and convenient addition, not only can realize the high-efficiency separation of the molybdenite and the pyrite, but also overcomes the problems that the traditional lime method influences the recovery rate of the molybdenite and the cyanide method generates great harm to the ecological environment.
Drawings
FIG. 1 is a flow chart of a beneficiation process employed in examples 1-3 of the present invention.
Detailed Description
The present invention will be explained in detail by the following examples, which are disclosed for the purpose of protecting all technical improvements within the scope of the present invention.
The molecular weight m of the polyaspartic acid adopted in the embodiment is 5-20; n is 5 to 20; the relative molecular mass is 1000-5000.
Example 1
The invention separates molybdenite and pyrite in a mineral processing plant of Fuyingyang Limited company of molybdenum industry in gold heap City. The-200 meshes of the raw ore account for about 53 percent, wherein the grade of molybdenum in the raw ore is about 0.115 percent, the grade of Fe is about 4.83 percent, the occurrence fineness of part of pyrite is finer, so that the pyrite and molybdenite are not dissociated yet, and the separation difficulty is increased due to the residual medicament on the surface of the ore in a concentration section.
Grinding the raw ore molybdenite to obtain ore pulp with the fineness of 53 percent of minus 200 meshes, and adding 100g/t of combined inhibitor, 100g/t of collecting agent kerosene and 30g/t of foaming agent terpineol for stirring in the rough concentration process; grinding the pre-concentration concentrate during concentration to obtain ore pulp with the fineness of-400 meshes accounting for 95%; carrying out four times of concentration and two times of fine scavenging on the obtained pre-concentration concentrate, adding a combined inhibitor for stirring in each concentration process, adding 3g/t of each of the inhibitors TGA and P-Nokes in the fine process, 200g/t of the combined inhibitor and 20g/t of collecting agent kerosene; 2g/t of each of inhibitor TGA and P-Nokes is added in the second refining process, and 100g/t of inhibitor is combined; adding 2g/t of each of inhibitor TGA and P-Nokes in the third refining process, and combining 100g/t of inhibitor; 2g/t of each of inhibitor TGA and P-Nokes is added in the process of the extract IV, and 50g/t of combined inhibitor is added; adding 20g/t of collecting agent and 4g/t of foaming agent in the fine sweeping process; no medicament is added in the second fine sweeping process; performing scavenging twice on the roughed tailings, wherein the adding amount of the collecting agent kerosene in the first scavenging and the second scavenging is 20g/t and 5g/t respectively, and adding 4g/t of foaming agent terpineol in the first scavenging;
the combined inhibitor is prepared from 0.5 wt% of polyaspartic acid aqueous solution, 3.0 wt% of calcium hypochlorite aqueous solution and 3.0 wt% of sodium humate aqueous solution in a mass ratio of (2: 1: 1, mixing; the combined inhibitor added by 100g/t in the embodiment refers to that 100g of the combined inhibitor is added into 1 ton of raw ore; as shown in table 1 below, a final molybdenum concentrate having an Fe grade of 3.28%, a recovery rate of 0.14%, an Mo grade of 46.98%, and a recovery rate of 85.56% was finally obtained.
TABLE 1 test results of flotation separation
Comparative example 1
In this comparative example, the same flotation scheme as in example 1 was used, and the same recipes were used for the flotation reagents except that the combination depressant was replaced with polyaspartic acid.
TABLE 2 test results of flotation separation
As can be seen from table 2, the effect of using a single polyaspartic acid as an inhibitor for pyrite was significantly inferior to that of using a combination inhibitor, and the recovery rate of molybdenite was also 4.36% lower than that of example 1.
Comparative example 2
In this comparative example, the same flotation flow as in the example was used, and the chemical system was the same in the flotation chemicals except that the combined depressant was changed to calcium hypochlorite.
TABLE 3 test results of flotation separation
As can be seen from table 3, a single calcium hypochlorite has a certain inhibitory effect on pyrite, and calcium hypochlorite inhibits pyrite by oxidation. Because calcium hypochlorite also has a certain amount of calcium ions, a large number of studies show that the calcium ions have a certain inhibiting effect on molybdenite.
Comparative example 3
The same flotation procedure was used in this comparative example, and the same recipe was used for the flotation reagent except that the combined depressant was changed to sodium humate.
TABLE 4 test results of flotation separation
As can be seen from table 4, the inhibition ability of sodium humate alone on pyrite is very limited, and in general, the use amount of sodium humate is relatively large, so that the strong inhibition on pyrite can be shown.
Comparative example 4
The same flotation scheme was used in this comparative example as in the example, but without any pyrite depressant being added, except that the amount and location of all other chemicals were the same as in example 1.
TABLE 5 test results of flotation separation
As can be seen from table 5, the Fe grade in the mo concentrate was high and the mo grade and recovery were low without any pyrite inhibitor.
Example 2
The method is adopted to separate molybdenite and pyrite in a mineral processing factory of Fuzz limited liability company of molybdenum industry of gold heap city. The-200 meshes in the raw ore account for 53 percent, wherein the grade of molybdenum in the raw ore is about 0.121 percent, and the grade of Fe is about 4.96 percent.
The grinding and flotation steps were the same as in example 1, and the combined depressant was prepared from 1.0 wt% aqueous polyaspartic acid, 6.0 wt% aqueous calcium hypochlorite, 6.0 wt% aqueous sodium humate in a mass ratio of 3: 1: 1, mixing; the combined inhibitor added by 100g/t in the embodiment refers to that 100g of the combined inhibitor is added into 1 ton of raw ore; as shown in table 1 below, a final molybdenum concentrate having an Fe grade of 3.25%, a recovery rate of 0.14%, an Mo grade of 47.13%, and a recovery rate of 85.49% was finally obtained.
TABLE 6 test results of flotation separation
Example 3
The method is adopted to separate molybdenite and pyrite in a mineral processing factory of Fuzz limited liability company of molybdenum industry of gold heap city. The-200 meshes in the raw ore account for 53 percent, wherein the grade of molybdenum in the raw ore is about 0.115 percent, and the grade of Fe is about 4.89 percent.
The grinding and flotation steps were the same as in example 1, and the combined depressant was prepared from 0.7 wt% aqueous polyaspartic acid, 5.0 wt% aqueous calcium hypochlorite, 4.0 wt% aqueous sodium humate in a mass ratio of 3: 1: 1, mixing; the combined inhibitor added by 100g/t in the embodiment refers to that 100g of the combined inhibitor is added into 1 ton of raw ore; as shown in table 7 below, a final molybdenum concentrate having an Fe grade of 3.74%, a recovery rate of 0.16%, an Mo grade of 46.98%, and a recovery rate of 85.50% was finally obtained.
TABLE 7 test results of flotation separation
The present invention is not described in detail in the prior art.
The embodiments selected for the purpose of disclosing the invention, are presently considered to be suitable, it being understood, however, that the invention is intended to cover all variations and modifications of the embodiments which fall within the spirit and scope of the invention.
Claims (9)
1. A combined inhibitor for separating pyrite in complex molybdenite is characterized in that: comprises polyaspartic acid, calcium hypochlorite and sodium humate, and the mass ratio is as follows: (1-3): (3-6): (3-6).
2. The combined inhibitor for the separation of pyrite in complex molybdenite of claim 1, wherein: the combined inhibitor is added by respectively preparing the components into aqueous solution, wherein: the mass concentration of the polyaspartic acid aqueous solution is 0.5-1.0%; the mass concentration of the calcium hypochlorite aqueous solution is 3.0-6.0%; the mass concentration of the sodium humate aqueous solution is 3.0-6.0%; the addition mass ratio of the three aqueous solutions is (2-3): 1: 1.
3. the combination inhibitor for pyrite in complex molybdenite of claim 1, wherein: the chemical structural formula of the polyaspartic acid is as follows:
wherein: m is 5-20; n is 5 to 20; the relative molecular mass is 1000-5000.
4. The separation process of a combined inhibitor for the separation of pyrite in complex molybdenite according to any one of claims 1 to 3, wherein: the method specifically comprises the following steps:
(1) grinding ore
In the rough concentration, the molybdenite is ground to obtain ore pulp with the fineness of-200 meshes accounting for 53 percent; grinding the pre-concentration concentrate during concentration to obtain ore pulp with the fineness of-400 meshes accounting for 95%;
(2) flotation
Adding a flotation inhibitor and other agents into the ore pulp, and sequentially carrying out flotation operations of roughing, scavenging, concentrating and fine scavenging on the ore pulp to finally obtain molybdenite concentrate, fine scavenging tailings and tailings;
other agents include kerosene, which is a collector, terpineol, TGA (sodium thioglycolate), which is an inhibitor, P-Nokes (Phosphonocks).
5. The method of claim 4, wherein the separation of the combined inhibitors for pyrite in the complex molybdenite comprises: calculating according to the mass of the inhibitor in the molybdenum-sulfur raw ore, wherein the addition amount of the collecting agent kerosene is 40-150g/t, and the addition amount of the foaming agent terpineol is 10-50 g/t; the addition amount of inhibitor TGA (sodium thioglycolate) is 2-50g/t, and the addition amount of P-Nokes (phosphoinosis) is 2-50 g/t.
6. The method of claim 4, wherein the separation of the combined inhibitors for pyrite in the complex molybdenite comprises: in the flotation step, the rougher concentrate is subjected to pre-concentration, and only 20g/t of collecting agent kerosene is added in the pre-concentration process for eliminating foam in the flotation system.
7. The method of claim 4, wherein the separation of the combined inhibitors for pyrite in the complex molybdenite comprises: in the flotation step, carrying out primary roughing, and adding a combined inhibitor, a collecting agent kerosene and a foaming agent terpineol in the roughing process, wherein the use amounts of the combined inhibitor, the collecting agent kerosene and the foaming agent terpineol are 100g/t, 100g/t and 30g/t respectively;
scavenging the rougher tailings obtained in the flotation step for two times, adding collecting kerosene in the scavenging process, wherein the adding amount of the collecting kerosene in the first scavenging and the second scavenging is 1/5 and 1/20 of the using amount of the collecting kerosene in the rougher; only in the first sweep was terpineol added as blowing agent in an amount of 2/15 rougher.
8. The method of claim 4, wherein the separation of the combined inhibitors for pyrite in the complex molybdenite comprises: in the flotation step, the obtained rough concentrate is subjected to pre-concentration, and only 20g/t of collecting agent kerosene is added in the pre-concentration process to eliminate foam in the flotation system.
9. The method of claim 4, wherein the separation of the combined inhibitors for pyrite in the complex molybdenite comprises: in the flotation step, the obtained pre-concentration concentrate is subjected to four times of concentration and two times of scavenging, and a combined inhibitor is required to be added in each concentration process, namely, the first concentrate: adding 3g/t of each of inhibitor TGA and P-Nokes, 200g/t of combined inhibitor and 20g/t of collecting agent kerosene; refined II: adding 2g/t of each of inhibitor TGA and P-Nokes, and combining 100g/t of inhibitor; and (3) refining: adding 2g/t of each of inhibitor TGA and P-Nokes, and combining 100g/t of inhibitor; and C, fine IV: adding 2g/t of each of inhibitor TGA and P-Nokes, and combining 50g/t of inhibitor; fine sweeping: adding 20g/t of collecting agent and 4g/t of foaming agent; the second fine powder is not added with any medicament.
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