KR101652993B1 - Recovery method of high-grade Tin concentrate by froth flotation - Google Patents
Recovery method of high-grade Tin concentrate by froth flotation Download PDFInfo
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- KR101652993B1 KR101652993B1 KR1020160036121A KR20160036121A KR101652993B1 KR 101652993 B1 KR101652993 B1 KR 101652993B1 KR 1020160036121 A KR1020160036121 A KR 1020160036121A KR 20160036121 A KR20160036121 A KR 20160036121A KR 101652993 B1 KR101652993 B1 KR 101652993B1
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- tin concentrate
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C1/00—Crushing or disintegrating by reciprocating members
- B02C1/02—Jaw crushers or pulverisers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C2/00—Crushing or disintegrating by gyratory or cone crushers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/002—Inorganic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
- B03D1/06—Froth-flotation processes differential
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B1/00—Sieving, screening, sifting, or sorting solid materials using networks, gratings, grids, or the like
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
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- C22B3/0004—
Abstract
Description
The present invention relates to a high-grade tin concentrate recovery method by a floating selection method capable of recovering high-quality tin concentrate from low-grade tin light containing tin.
The present invention relates to a high-grade tin concentrate recovery method by a floating selection method capable of recovering high-quality tin concentrate from low-grade tin light containing tin.
Tin is used in plating, alloying, die casting, metal chemistry, etc. due to its easy-to-alloy characteristics with other metals chemically and is an indispensable metal to prevent corrosion. In addition, the use of tin for electronics, plumbing and PVC safety equipment has increased rapidly, but the tin is not produced in Korea, so the total amount of tin concentrate of about 1,217 tons per year is dependent on imports (Korea Mineral Resources Information Service, 2015). Therefore, it is necessary to develop the tin lamps that are available in Korea and to develop the technology to utilize them.
A typical mineral containing tin is selected from the group consisting of cassiterite (SnO 2 ), stannite (Cu 2 FeSnS 4 ), canfieldite (Ag 8 SnS 6 ), teallite, PbSnS 2 , cylindrite, and Pb 3 Sn 4 FeSb 2 S 14 ). However, it is known that the oxides of stones are the most economical minerals. These grains have a specific gravity of 6.8 ~ 7.1, which is larger than general gangue minerals, so they are mostly treated by specific gravity selection, but only a single gravity selection method is limited to improvement of recovery rate. In addition, because of the high brittleness of the stone, many particles are generated during the wave crushing process. Therefore, in the case of hard rock and disseminated tin deposits, flotation is essential.
On the other hand, the screening studies of tin light by flotation screening have been carried out in a number of basic and applied researches using a trapping agent such as cupferron, sodium cetyl sulphate and oleic acid .
However, tin light produced from domestic deposits is low in tin quality and mixed with various minerals, so it is necessary to select floating tin. However, the process for recovering high-quality tin concentrate, It is not in active mode until. Therefore, it is very urgent to develop a method for recovering high-quality tin concentrate from tin powder produced in domestic deposits.
A related literature related to this is the composite copper photoluminescence method using leaching and precipitation disclosed in Korean Patent No. 1352400 (public announcement: 2014.01.22).
Accordingly, the present invention provides a new floating sorting method capable of recovering tin light produced in domestic ore deposits to high-quality tin concentrate, and is capable of recovering tin by increasing the quality and recovery rate from tin light, Tin concentrate recovery method.
The problems to be solved by the present invention are not limited to the above-mentioned problem (s), and another problem (s) not mentioned can be understood by those skilled in the art from the following description.
In order to solve the above-described problems, the present invention provides a method for crushing an ore obtained from an ore (step 1); Crushing the crushed ore to less than 150 mesh to homogenize the particle size (second step); Adding a reagent to the homogenized ore; adjusting the concentration of the liquid to be stirred; and collecting the shipyard concentrate through the shipbuilding barge (third step); And recovering the tin concentrate by selecting the shipbuilding concentrate to obtain tin concentrate. The fourth aspect of the present invention provides a high-quality tin concentrate recovery method by a floating selection method.
According to the present invention, tin concentrate can be recovered at an optimum quality and recovery rate from tin light generated from domestic ore deposits.
In addition, even when many silicate minerals are contained in the tin light, the kind and amount of the catching agent capable of selecting the most suitable floating stone can be confirmed, and the type and amount of the inhibitor, which is a factor that nourishes the quality and recovery rate of the tin, It is possible to increase the efficiency of the flotation process of tin by checking the addition amount.
1 is a process flow diagram illustrating a high-quality tin concentrate recovery method by a floating selection method according to an embodiment of the present invention.
2 is a graph showing the X-ray diffraction results of the raw ore as a sample in the high-grade tin concentrate recovery method by the floating selection method according to the embodiment of the present invention.
3 is a polarized microscope photograph of a raw ore as a sample in a high-quality tin concentrate recovery method by a floating selection method according to an embodiment of the present invention.
FIG. 4 is a graph showing influences on the flotation selection of stones according to the addition amount of the catching agent in the high-grade tin concentrate recovery method by the floating selection method according to the embodiment of the present invention.
FIG. 5 is a graph comparing flotation results of stones using alkyl-hydroxamic acid trapping agent and flotation results of stones performed using a conventional oleic acid catching agent.
6 is a graph showing the quality and recovering rate of tin recovered according to the flotation selection method according to the type of inhibitor.
FIG. 7 is a graph showing the result of float selection of the stone according to the addition amount of the sodium silico-fluoride inhibitor in the high-grade tin concentrate recovery method by the floating selection method according to the embodiment of the present invention.
FIG. 8 is a graph showing the results obtained when floating and sorting are carried out using oleic acid and alkylhydroxamic acid as a trapping agent and sodium silicate and sodium silico-fluoride inhibitor in the flotation screening method.
FIG. 9 is a graph showing the effect of flotation according to the pH of a light liquid in a high-quality tin concentrate recovery method by a floating selection method according to an embodiment of the present invention.
FIG. 10 is a graph showing the result of floating determination by varying the number of times of cleansing of a cleansing bar in the method of recovering high-quality tin by a floating sorting method according to an embodiment of the present invention.
11 is a graph showing the results of X-ray diffraction analysis of tin concentrate by the high-grade tin concentrate recovery method by the floating selection method according to the embodiment of the present invention.
12 is an electron micrograph (SEM / EDS) photograph of the energy dispersion analysis of a tin concentrate product by a high-grade tin concentrate recovery method by a floating selection method according to an embodiment of the present invention.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving it will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings.
The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.
In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.
1 is a process flow diagram illustrating a high-quality tin concentrate recovery method by a floating selection method according to an embodiment of the present invention.
Referring to the drawings, a high-grade tin concentrate recovery method using floating determination method comprises a step (step 1) of crushing ores recovered from a deposit; Crushing the crushed ore to less than 150 mesh to homogenize the particle size (second step); Adding a reagent to the homogenized ore; adjusting the concentration of the liquid to be stirred; and obtaining a shipbuilding concentrate through a shipbuilding barge (third step); And recovering the tin concentrate by subjecting the shipbuilding concentrate to cleaning (fourth step).
The ores are tin stones which are present in domestic deposits, and may be composed of cassiterite (SnO 2 ) and gangue minerals.
The gangue minerals may be silicate minerals containing one or two or more minerals selected from the group consisting of quartz, muscovite, calcareous stone, chlorite and amphibole, and the ore- It is necessary to select an optimum catcher capable of increasing the recovery rate of tin while maintaining the quality of the recovered tin concentrate since it can prevent the surface of the mineral from being changed to hydrophobic or reduce the trapping power.
The crushing of the first step may be performed by using a jaw crusher or a cone crusher to crush the ore to reduce the average particle size (S100).
In the case of performing the crushing and crushing separately, it is preferable to crush the ore of various diameters preferentially to reduce the average grain size, and then to grind again to uniformize the grain size of the ore, thereby greatly increasing the efficiency of the float sorting process .
The crushed ore can be ground to less than 150 mesh to homogenize the particle size (S200).
The raw ore having been crushed in the first step may be pulverized to have an average particle size of less than 150 mesh using a rod mill.
When the rod mill is used, the grain size of the ore can be homogeneously pulverized.
When the ore is less than 150 mesh, the reaction with the reagent added in the third step can be effectively performed, and the efficiency of the flotation screening process can be increased by increasing the reaction rate.
In the case where the ore having been crushed in the second step is 150 mesh or more, the crushing step is repeated again so that the ore is homogeneously maintained at less than 150 mesh before the shipbuilding of the third step, And the tin recovery rate can also be increased.
The reagent may first be added to the ore having been homogenized in the second step, and the concentration may be controlled to stir the solution.
The reagents include inhibitors, catching agents and foaming agents necessary for the rougher flotation process during the flotation process.
The light-liquid concentration can be adjusted to 20 to 30%.
When the concentration of the light liquid is lower than 20%, the treatment capacity decreases and the change on the surface of the mineral does not occur with the addition of the reagent. When the concentration of the light liquid is higher than 30%, the selectivity is decreased by the excess gangue, An additional process is required to separate the liquid from the flotation stage, thereby reducing the efficiency of the entire process of flotation.
Sulfuric acid and sodium hydroxide may be added as a pH regulator to the optical fluid to maintain the pH of the optical fluid at 5 during the barbishing process.
When the pH of the optical solution is less than 5, the quality and recoverability of the recovered tin concentrate are greatly reduced. When the pH is more than 5, there is no change in the recovery rate, but the quality may be greatly reduced.
The stirring may be performed at 1500 to 1800 rpm.
When the agitation speed is less than 1500, the collision energy between the bubbles and the tin is low due to the low stirring energy. If the stirring speed exceeds 1800 rpm, the gangue minerals are moved to the foam layer due to the strong swirling phenomenon, do.
The vessel concentrate can be harvested through the agitation to obtain a shipyard concentrate (S300).
Since the ore contains a large amount of gangue minerals in addition to the gypsum, the gypsum containing tin can be collected and collected through the shipbuilding process.
In the third step, the addition of the reagent may be carried out in the order of an inhibitor, a pH adjusting agent, a trapping agent, and a foaming agent.
When reagents are added in the order out of the above order, the capturing agent and the inhibitor may interact with each other, resulting in a decrease of the capturing power or a problem of different sorting efficiency.
The inhibitor is added and stirred for 3 to 5 minutes, the catching agent is added, stirring is performed for 1 to 2 minutes, foaming agent is added, and stirring can be performed for 30 seconds.
Stirring for 3 to 5 minutes after the addition of the inhibitor allows the gangue minerals to be sufficiently hydrophilized, and an optimal collection force can be given within 1 to 2 minutes after the addition of the catching agent.
If the agitation time is longer than the above range, there is a problem that the treatment time increases and the trapping agent penetrates into the tin particles, resulting in insufficient collection force.
And the temperature of the light liquid is maintained at 15 to 75 DEG C in the stirring in the third step.
There arises a problem that the trapping agent in the reagent is solidified at a temperature lower than 15 ° C., and when the temperature exceeds 75 ° C., the trapping agent is decomposed and the shipbuilding process may not be performed.
The inhibitor is sodium silicofluoride (Na 2 SiF 6 ) and may be added at 500 to 1500 g / t.
If the amount of the inhibitor is less than 500 g / t, the inhibitory power of the gangue decreases. If the amount of the inhibitor is more than 1500 g / t, some tin may be suppressed and the recovery rate may decrease.
When the inhibitor is selected from sodium silico-fluoride and added in the above-mentioned range and stirred to perform the shipbuilt line, the surface of the gangue is made strong acid hydrophilic and the restraining force is increased.
The catching agent is an alky-lhydroxamic acid, and may be added at 500 to 700 g / t.
When the alkyl-hydroxamic acid is selected as the capturing agent, the recovery is high when 600 g / t is added, which is highly desirable.
However, if the amount of the capturing agent added is less than 500 g / t, the recovery force is weak and the recovery rate is decreased. If the amount of the capturing agent is more than 700 g / t, the quality and the amount of reagent are increased.
When the alkyl-hydroxamic acid is selected as the capturing agent, sodium silico-fluoride may be selected as the inhibitor.
When the sodium silico-fluoride is selected as the inhibitor, the capturing agent exhibits an optimum screening efficiency when it is selected as an alkyl-hydroxamic acid, and thus it is highly desirable that the capturing agent and the inhibitor may interact with each other.
If the added amount of the catching agent is out of the above range, mutual influence with the inhibitor may result in a problem that the screening efficiency is reduced.
The cleaner flotation in the fourth step may be performed three times to recover the tin concentrate.
As the number of times of the regular line line in the fourth step increases, the quality of the recovered tin concentrate increases but the recovery rate decreases. Therefore, the quality and the sorting efficiency can be optimized in the case of three times of selective line flotation.
In the third step, the crude concentrate is obtained, the precipitated product is recovered, the tin concentrate is obtained in the fourth step, and the precipitated product is recovered and treated to produce precipitates such as gangue minerals It is possible to increase the recovery rate of the tin concentrate in the clean line process.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.
< Example 1> Floating sorting Tin concentrate collection
1. Analysis of ore ore
Ore stones were prepared for tin collecting. The ores were collected from Wangpiri area in Uljin-gun, Gyeongbuk province. In the case of Wangpiri tin, the deposits were in the form of quartz veins containing tin originating from acid magma as primary deposit.
Table 1 shows chemical compositions of the raw ore samples.
As shown in Table 1, the content of tin (Sn) in the ore is 1.37%, the contents of SiO 2 and Al 2 O 3 are 76.18% and 13.08%, the contents of Na 2 O and K 2 O are 3.38% and 1.61%, respectively Fe 2 O 3 was 2.24%, indicating that most gangue minerals are composed of silicate minerals and some of Fe minerals.
2 is a graph showing the X-ray diffraction results of the raw ore as a sample in the high-grade tin concentrate recovery method by the floating selection method according to the embodiment of the present invention.
Referring to FIG. 2, the main constituent mineral of tin is cassiterite (SnO 2 ), and other main gangue minerals are silicate minerals such as quartz, muscovite, calcareous stone, chlorite and amphibolite.
3 is a polarized microscope photograph of a raw ore as a sample in a high-quality tin concentrate recovery method by a floating selection method according to an embodiment of the present invention.
Here, (A) and (C) show the results of open-nicol, (B) and (D) show the results observed under crossed nicol.
Polarization microscopy was used to identify the characteristics of the constituent minerals identified in the X-ray diffraction analysis of the ores and the interrelation between adjacent minerals.
In the open Nicole, the color and the color, the crystal form, and the cleavage of the mineral can be observed. In the quadrature nicol, the quenching or the interference color and the twin can be observed. Microscopic observations showed that quartz, muscovite and stonite were mainly observed. In the case of quartz, it was present as coarser and it was confirmed that it exhibited wavy extinction under quadrature Nicol.
In the case of the stone, the granularity is composed mostly of coarse granules, dark brown to black, and the color palette can be observed. In addition, it was possible to confirm the appearance accompanied with muscovite closely. In some cases, the crushed stone was observed inside the stone, and muscovite and quartz were partially filled or quartz veins were present. Since most of the stones are coarser, it is considered that the degree of group separation is comparatively good. It is considered that the group separation between the gangue minerals and the stones that are present or filled in the inside of the stone is easy .
2. Oresite floating sorting
First, in order to prepare the above-mentioned ore as a particle size suitable for float sorting, crushing was carried out using a jaw crusher, a cone crusher and a rod mill, and then the particle size was prepared with a sieve to a particle size of 150 mesh. In the float sorting experiment, a float sorting machine of Denver sub-A type was used. In a shipbuilding process, the mixture was adjusted to a liquid concentration of 20% solids and a particle size of 150 mesh and stirred at 1,500 rpm. Were added in that order. After the addition of the reagents, the condition time was 5 minutes for the inhibitor, 2 minutes for the catcher and 30 seconds for the foaming agent. Thereafter, 500 g / t of inhibitor was added to each of the shipyard concentrates obtained from the shipbuilding barge, and the pH of the optical fluid was maintained at 5, and the experiment was conducted to recover the high-quality tin concentrate through three rounds of screening.
< Experimental Example 1> Catcher effect
In order to observe the effect of catcher addition on the flotation of stones, we tested the catcher from 400g / t to 800g / t.
FIG. 4 is a graph showing influences on the flotation selection of stones according to the addition amount of the catching agent in the high-grade tin concentrate recovery method by the floating selection method according to the embodiment of the present invention.
(Na 2 SiF 6 ) 1,000 g / t-pH 5 (H 2 SO 4 ) - alkyl-hydroxamic acid (Na 2 SiF 6 ) at a concentration of 20% solids, particle size of -150 mesh, stirring speed of 1,500 rpm, ) -Bubbing agent (AF 65) in an amount of 20 g / t. In the case of the captive amine alkyl-hydroxamic acid, the solidification starts from below 15 ° C and decomposition starts from 75 ° C or higher. Therefore, in all experiments, the experiment was carried out while keeping the temperature of the liquid at 25 ° C.
As a result of the flotation test according to the amount of catcher added, the tin content decreased and the recovery rate tended to increase as the amount of catcher added increased. If the addition amount of the catcher is less than 600g / t, the recovery rate is decreased because some of the stone is retained in the liquid because the hydrophobicity and the collection force are not enough to collect enough stones. However, Therefore, it was confirmed that the dignity is high.
On the other hand, when the amount of the catcher is higher than 600 g / t, the surface of the stone is made strong hydrophobic to increase the collecting power, thereby increasing the recovery rate. However, Therefore, the declining tendency was shown.
Therefore, in this study, it was confirmed that the optimum addition amount of the catcher with a relatively high recovery rate of 600 g / t without decreasing the quality was obtained. The tin quality and recovery rate were 75.55% and 89.86%, respectively.
FIG. 5 is a graph comparing flotation results of stones using alkyl-hydroxamic acid trapping agent and flotation results of stones performed using a conventional oleic acid catching agent.
Referring to FIG. 5, in the case of oleic acid, the selectivity was low, and the final concentrate was obtained by subjecting to eight sequential processes, tin product and recovery rates of 55.32% and 77.24%, respectively. On the other hand, the final concentrate was recovered in the same manner as in Example 1, except that the selectivity was improved to 75.55% and 89.86%, respectively, by using the alkyl-hydroxoxane trapping agent. It was confirmed that it is a very effective catching agent for float sorting of stones than oleic acid catchers.
Therefore, when the alkyl-hydroxanic acid trapping agent is selected, the sorting process is simplified and the treatment cost is reduced, and the tin content and recovery rate of the final concentrate are improved by 20.23% p and 12.62% p, respectively, - hydroxamic acid was optimal.
< Experimental Example 2> inhibitor effect
In order to observe the effects of the inhibitor types on the stone sorting, 10 inhibitors were selected and flotation screening experiments were carried out.
6 is a graph showing the quality and recovering rate of tin recovered according to the flotation selection method according to the type of inhibitor.
Referring to FIG. 6, the quality and recoverability of sodium silicate (Na 2 SiO 3 ), which is known to be effective for dispersing and inhibiting silicate minerals, were 56.40% and 81.72%, respectively. However, sodium silicofluoride (Na 2 SiF 6 ), which is used as an inhibitor of silicate minerals with sodium silicate, has a significantly higher screening efficiency than other inhibitors used with 75.55% and 89.86% tin content and recovery, respectively In this experiment, sodium silico-fluoride was selected as an optimal inhibitor and the experiment was conducted to examine the addition amount of the inhibitor.
FIG. 7 is a graph showing the result of float selection of the stone according to the addition amount of the sodium silico-fluoride inhibitor in the high-grade tin concentrate recovery method by the floating selection method according to the embodiment of the present invention.
7, in order to observe the influence of the addition amount of sodium silico-fluoride selected as an inhibitor on the stone selection, the inhibitor was varied from 0 g / t to 1,000 g / t, The yield and the recovery rate increased with increasing the amount. However, when the addition amount was increased from 1000 g / t, the degree of decline was small, but the recovery rate was significantly decreased. If the amount of inhibitor added is less than 1,000 g / t, it can not effectively inhibit silicate gangue minerals present in the ore.
On the other hand, when the amount of the inhibitor added is more than 1,000 g / t, the recovery rate is reduced because some gypsum as well as gangue minerals are inhibited without further increase of the quality. Therefore, in this study, optimum condition was selected as the highest inhibitor additive amount of 1,000 g / t, which was 75.55% and 89.86%, respectively.
< Experimental Example 3> Catcher and inhibitor interrelationship
Sodium silicate and sodium silico - fluoride inhibitor were cross - reacted with oleic acid and alkyl - hydroxy siloxane inhibitor in order to observe the influence of the interrelation between catcher and inhibitor on sediment retention.
FIG. 8 is a graph showing the results of flotation of oleic acid and alkyl-hydroxamic acid as a trapping agent in the flotation screening method using cross sodium silicate and sodium silico-fluoride inhibitor.
Kind of collectors)
(Alkyl-hydroxamic acid)
(Alkyl-hydroxamic acid)
Table 2 shows the experimental results.
8 and Table 2, oleic acid and sodium silicate are used as (A), oleic acid and sodium silico-fluoride are used as (B), and (C) sodium salt and alkyl-hydroxamic acid are used , (D) used alkyl-hydroxamic acid and sodium silico-fluoride as catchers and inhibitors, respectively.
In the case of the alkyl - hydroxamic acid trapping agent, the selectivity was high and the sorption efficiency was higher than that of the oleic acid catcher when sodium silicate or sodium silico - fluoride was used as the inhibitor. However, when sodium silicate and sodium silico-fluoride inhibitor were compared in the alkyl-hydroxybutyrate, the sodium silico-fluoride was 19.15% p and 8.14% p higher than the sodium silicate inhibitor, Sodium fluoride was found to be a more effective inhibitor.
However, when oleic acid was used as a trapping agent, the screening efficiency was lower than that using sodium silicate fluoride inhibitor, and sodium silicate was a more effective inhibitor when oleic acid was used as a trapping agent.
The results show that sodium silicate and sodium silico-fluoride as silicate gangue mineral inhibitors all However, since the screening efficiency varies depending on the interaction between the inhibitor and the capturing agent, the selection of the inhibitor should be different according to the capturing agent, and when the alkyl-hydroxamic acid and the sodium silico-fluoride are used as the captive agent and the inhibitor, respectively Is optimal.
< Experimental Example 4> Mineral fluid pH effect
The effect of pH change on the stone floatation in the process of shipbuilding was confirmed.
FIG. 9 is a graph showing the effect of flotation according to the pH of a light liquid in a high-quality tin concentrate recovery method by a floating selection method according to an embodiment of the present invention.
Referring to FIG. 9, when the pH of the optical solution was changed from 3 to 11, as a result of the experiment of the pH change of the optical solution, when the pH was lower than the
Especially,
However, as the pH of the solution increased from 7 to 11, the gangue minerals activated during the shipbuilding process were not inhibited in the neutral and basic conditions of the selection process, so that the quality decreased drastically and the recovery rate increased slightly.
Therefore, it was confirmed that the optimum pH condition was maintained when the pH of the optical solution was kept at 5, and the quality and recoverability of tin were 75.55% and 89.86%, respectively.
< Experimental Example 5> Influence of the number of times in the selection process
In addition to the phenomenon that only the surface-hydrophobic minerals are attached to the bubbles and float, the entrainment of the hydrophilic mineral accompanied by the rising of the bubbles and the entrapment of the hydrophilic particles attached to the floating hydrophobic particles, , It is difficult to achieve the desired quality with only the shipbuilding line. Therefore, the optimum number of times of gangue minerals was confirmed in order to remove the gangue minerals through the selection process.
FIG. 10 is a graph showing the result of floating determination by varying the number of times of cleansing of a cleansing bar in the method of recovering high-quality tin by a floating sorting method according to an embodiment of the present invention.
10, in order to observe the influence of the number of selection lines on the stone selection, the number of lines was varied from 0 to 4. As the number of lines increases, the quality of the tins increases but the recovery rate decreases .
In the case of shipbuilding barges with zero barges, the large amount of gangue minerals other than stones floated nonselectively, and the recovery rate of the shipyard concentrates was as high as 98.13%, but the sorting efficiency was low at 10.50% Could know. On the other hand, in the case of three rounds of reclamation, the yield and recovery rate of tin were 75.55% and 89.86%, respectively. Compared with 0 rounds, the recovery rate decreased but the quality increased by 65.05% p.
However, if the number of times of selection is increased by 4, the recovery efficiency decreases due to the reduction of the collection power to the stones without a significant increase in the quality. Therefore, it is confirmed that the optimum number of times is three times the number of lines in the line selection process in this experiment.
< Experimental Example 6> Tin concentrate analysis
11 is a graph showing the results of X-ray diffraction analysis of tin concentrate by the high-grade tin concentrate recovery method by the floating selection method according to the embodiment of the present invention.
11, XRD results of tailings, middling 2 and final concentrate products recovered from the flotation of stones are shown in Fig. 11. In the tailings and
12 is an electron micrograph (SEM / EDS) photograph of the energy dispersion analysis of a tin concentrate product by a high-grade tin concentrate recovery method by a floating selection method according to an embodiment of the present invention.
Referring to FIG. 12, it was confirmed that a small amount of magnetite was present, although it was not confirmed in the XRD analysis, and a trace amount of iron (Fe) component was detected to overlap with the oxygen (O) component.
Accordingly, the high-quality tin concentrate recovery method according to the present invention provides a new floating selection method capable of calculating high-quality tin concentrate for domestic ore-derived ores.
It was confirmed that the optimum amount of inhibitor and the amount of addition of silicate minerals contained in Korean ore is high enough to inhibit the effect of silicate minerals. In consideration of mutual application of inhibitors, alkyl - hydroxamic acid with improved selectivity is selected as a catching agent, In addition, the number of times that the gangue minerals can be effectively controlled in addition to the stones was confirmed.
Although the specific embodiment of the high-grade tin concentrate recovery method according to the floating sorting method according to the present invention has been described so far, it is obvious that various modifications are possible within the scope of the present invention.
Therefore, the scope of the present invention should not be limited to the above-described embodiments, but should be determined by the scope of the appended claims and equivalents thereof.
It is to be understood that the foregoing embodiments are illustrative and not restrictive in all respects and that the scope of the present invention is indicated by the appended claims rather than the foregoing description, It is intended that all changes and modifications derived from the equivalent concept be included within the scope of the present invention.
Claims (16)
Crushing the crushed ore to less than 150 mesh to homogenize the particle size (second step);
Adding a reagent to the homogenized ore; adjusting the concentration of the liquid to be stirred; and obtaining a shipbuilding concentrate through a shipbuilding barge (third step); And
And recovering the tin concentrate by subjecting the shipbuilding concentrate to a cleaning process (Step 4)
In the third step,
The mixture is stirred for 3 to 5 minutes, a trapping agent is added, stirred for 1 to 2 minutes, foamed agent is added, stirred for 30 seconds,
The inhibitor may be,
Characterized in that it is sodium silicofluoride and is added at 500 to 1500 g / t. ≪ RTI ID = 0.0 > 11. < / RTI >
Wherein the pulverized ore is pulverized in the second step,
And when it is 150 mesh or more, it is repeatedly pulverized to homogenize the particle size. The method for recovering high-quality tin concentrate according to the floating sorting method.
The above-
A method for recovering high-quality tin concentrate by a floating sorting method, characterized in that it is made of cassiterite (SnO 2 ) and gangue minerals as tin light present in domestic deposits.
The gangue minerals,
Wherein the silicate minerals are silicate minerals containing one or more minerals selected from the group consisting of quartz, muscovite, muscovite, chlorite and amphibolite.
The crushing of the first stage
Wherein the ore is crushed using a crusher or a cone crusher to reduce the average particle size.
The pulverization of the second step
The method for recovering high-quality tin concentrate according to claim 1, wherein the ore having been crushed in the first step is pulverized to have an average particle size of less than 150 (mesh) using a rod mill.
In the third step
characterized in that sulfuric acid and sodium hydroxide are added as a pH regulator to maintain the pH of the light liquid between 4 and 7 during the shipbuilding line and the barge line process.
The light-
To 20% to 30% of the total amount of the concentrated tin concentrate.
The above-
Wherein the high-purity tin concentrate is recovered at a temperature of 1500 to 1800 rpm.
In the third step,
Wherein the temperature of the optical fluid is maintained at 15 to 75 ° C.
The catching agent may be,
Wherein the alkaline-hydroxamic acid is added in an amount of 500 to 700 g / t.
Wherein said inhibitor is sodium silicofluoride when said alky-lhydroxamic acid is used as said trapping agent. ≪ RTI ID = 0.0 > 11. < / RTI >
Wherein the fourth line of the regular line barriers comprises:
Wherein the tin concentrate is recovered from the distillation column by performing the filtration twice or four times to recover the tin concentrate.
A method for recovering high-quality tin concentrate according to the flotation selection method, characterized in that in the third step, the crude concentrate is obtained, the precipitated product is recovered, the tin concentrate is obtained in the fourth step and the precipitated product is recovered and treated .
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106622639A (en) * | 2016-12-23 | 2017-05-10 | 云南锡业股份有限公司卡房分公司 | Ore concentration technique for tin sulphide ore rough concentrate |
| CN108672105A (en) * | 2018-08-01 | 2018-10-19 | 中冶北方（大连）工程技术有限公司 | A kind of adjustable direct flotation system of energy-saving iron extract mine producation index |
| CN108672104A (en) * | 2018-08-01 | 2018-10-19 | 中冶北方（大连）工程技术有限公司 | A kind of adjustable reverse flotation system of iron concentrate grade |
| CN112237985A (en) * | 2020-10-09 | 2021-01-19 | 昆明理工大学 | Method for recovering cassiterite from tin-containing sulfide ore |
| KR102214170B1 (en) * | 2020-01-28 | 2021-02-09 | (주)광산기공 | Flotation system for extracting solid mineral material |
| KR102232912B1 (en) * | 2020-11-04 | 2021-03-26 | 한국지질자원연구원 | Beneficiation process of sericite |
| CN113908994A (en) * | 2021-09-27 | 2022-01-11 | 南华大学 | Flotation method of low-grade phosphate ore |
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2016
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| 최희경, 백상호, 김수강, 고상모, 전호석, 올레인산을 이용한 산성영역에서 주석광의 부유선별 특성연구, 한국자원공학회지, 52권 3호, pp.294-301* * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622639A (en) * | 2016-12-23 | 2017-05-10 | 云南锡业股份有限公司卡房分公司 | Ore concentration technique for tin sulphide ore rough concentrate |
| CN108672105A (en) * | 2018-08-01 | 2018-10-19 | 中冶北方（大连）工程技术有限公司 | A kind of adjustable direct flotation system of energy-saving iron extract mine producation index |
| CN108672104A (en) * | 2018-08-01 | 2018-10-19 | 中冶北方（大连）工程技术有限公司 | A kind of adjustable reverse flotation system of iron concentrate grade |
| CN108672104B (en) * | 2018-08-01 | 2020-09-18 | 中冶北方（大连）工程技术有限公司 | Reverse flotation system with adjustable iron ore concentrate grade |
| CN108672105B (en) * | 2018-08-01 | 2020-10-02 | 中冶北方（大连）工程技术有限公司 | Energy-saving iron concentrate product index adjustable direct flotation system |
| KR102214170B1 (en) * | 2020-01-28 | 2021-02-09 | (주)광산기공 | Flotation system for extracting solid mineral material |
| CN112237985A (en) * | 2020-10-09 | 2021-01-19 | 昆明理工大学 | Method for recovering cassiterite from tin-containing sulfide ore |
| CN112237985B (en) * | 2020-10-09 | 2021-08-24 | 昆明理工大学 | Method for recovering cassiterite from tin-containing sulfide ore |
| KR102232912B1 (en) * | 2020-11-04 | 2021-03-26 | 한국지질자원연구원 | Beneficiation process of sericite |
| CN113908994A (en) * | 2021-09-27 | 2022-01-11 | 南华大学 | Flotation method of low-grade phosphate ore |
| CN113908994B (en) * | 2021-09-27 | 2023-11-21 | 南华大学 | Flotation method of low-grade phosphorite |
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