WO2017209440A1

WO2017209440A1 - Method for recovery of high-grade scheelite concentrate and facility for recovery of scheelite concentrate

Info

Publication number: WO2017209440A1
Application number: PCT/KR2017/005446
Authority: WO
Inventors: 전호석; 김병곤; 김수강
Original assignee: 한국지질자원연구원
Priority date: 2016-06-02
Filing date: 2017-05-25
Publication date: 2017-12-07
Also published as: KR101710593B1; CN107922993A; CN107922993B

Abstract

Provided are a method for recovery of a high-grade scheelite concentrate and a facility for recovery of a scheelite concentrate. Specifically, provided is a method for recovery of a high-grade scheelite concentrate, the method comprising the steps of: mixing particulate products of scheelite ore with water to form an ore solution; subjecting the ore solution to froth flotation to obtain a rougher scheelite concentrate; and subjecting the rougher scheelite concentrate to froth flotation to obtain a selective scheelite concentrate, wherein the step for obtaining a rougher scheelite concentrate comprises a step for sequentially adding a pH adjuster and an inhibitor to the ore solution, and wherein the pH adjuster is Na₂CO₃ and the amount of the pH adjuster added is equal to or more than 2 kg/t and equal to or less than 3.5 kg/t; and the inhibitor is Na₂SiO₃ and the amount of the inhibitor added is equal to or more than 3.5 kg/t and equal to or less than 4.5 kg/t or less.

Description

Recovery method of high quality sinter concentrate and recovery facilities

The present invention relates to a method for recovering high-quality scheelite concentrates and a recovery facility for scheelite concentrates.

There are about twenty known minerals on earth, but the economically valuable developments are scheelite and wolframite. Among them, scheelite is known as the most economical mineral, and has a specific gravity of about 6.0, and if only the separation of the group in the assembler can be obtained high quality and recovery rate by the specific gravity screening method. But stony is generally produced at the junction between granite tungsten-containing minerals and carbonate sedimentary rocks, which are found in Skarne deposits and are formed by alternating action, most of which are produced as particulates. In addition, it is well known that even if the calcite is produced as a coarse granule, the brittleness is large and the generation of fine particles occurs during the crushing and grinding process. Therefore, for the beneficiation of scheelite, it is essential to develop floating screening technology that is effective for treating fine particles.

In the scheelite flotation, apatite, including scheelite, fluorite, calcite is to have similar solubility, in interaction with the fatty acid catcher claim separate the mineral because Ca ² ⁺ ions to the same action, without using the inhibitor nearly impossible.

However, Ca ² ⁺ inhibitor is used to inhibit a mineral containing the ions because it also suppresses the auditorium, in recent years, but it is made many studies in order to selectively inhibit the minerals containing Ca ² ⁺ ion, still greater There is difficulty.

SUMMARY OF THE INVENTION The problem to be solved by the present invention is to provide a method for recovering a high-quality and high recovery rate of sintered concentrate and a high-quality sintered recovery facility.

One embodiment of the present invention, the step of forming a mineral liquid by mixing the fine product of the feldspar ore with water; Flocculating the mineral liquid to obtain scheelite shipbuilding concentrate; And floating sorting the sintered shipbuilding concentrate to obtain the sintered mineral concentrate,

The step of obtaining the feldspar shipbuilding concentrate includes the step of sequentially adding a pH regulator and inhibitor to the mineral liquid, the pH regulator is Na ₂ CO ₃ , the addition amount of the pH regulator is more than 2 kg / t 3.5 kg / t Hereinafter, the inhibitor is Na ₂ SiO ₃ , and the addition amount of the inhibitor provides a recovery method of high-quality scheelite concentrate is 3.5 kg / t or more and 4.5 kg / t or less.

One embodiment of the present invention, a mineral liquid forming apparatus for forming a mineral liquid by mixing the fine products of the feldspar ore with water; A ship floating sorting device for sorting the mineral liquid to obtain a scheelite shipbuilding concentrate; And a sorting floatation sorting device for sorting the feldspar shipbuilding concentrate to obtain a slate concentrate concentrate,

The ship floating sorting device is a pH adjusting unit for adjusting the addition amount of Na ₂ CO ₃ pH adjuster to 2 kg / t or more to 3.5 kg / t or less, and the addition amount of the inhibitor Na ₂ SiO ₃ 3.5 kg / t or more 4.5 kg Inhibitor control unit for controlling to / t or less is provided in order to provide a recovery facility for slagite concentrate to sequentially add a pH regulator and inhibitor to the mineral liquid.

The recovery method of high-grade scheelite concentrate according to one embodiment of the present invention can effectively suppress Ca-based gangue minerals, and improve the recovery rate of high-quality scheelite.

According to another exemplary embodiment of the present invention, the method for recovering high-grade sinterite concentrate can be effectively suppressed and removed from silicate minerals, thereby obtaining high-quality sinterite concentrate.

In addition, the method for recovering high-grade sintered ore concentrate according to another embodiment of the present invention can obtain a high-quality sinterite concentrate with a high recovery rate, thereby increasing the added value of the mined ore and improving the development economic efficiency.

1 shows a method of recovering high-quality scheelite concentrate according to one embodiment of the invention.

Figure 2 shows a method of recovering high-quality scheelite concentrate according to another embodiment of the present invention.

Figure 3 shows a refined embodiment of the scheelite concentrate according to the particle size of the particulate product of 1 (grade of WO ₃₎ and recovery (recovery of WO _3).

Figure 4 shows the Example 2 and Comparative Example quality of scheelite concentrates according to the type of pH adjusting agent 1 (grade of WO ₃₎ and recovery (recovery of WO _3).

Figure 5 shows a third embodiment and a comparative example 2 of the quality of the scheelite concentrate according to the addition amount of the pH adjusting agent (grade of WO ₃₎ and recovery (recovery of WO _3).

Figure 6 shows a fourth embodiment and the comparative quality of the scheelite concentrate according to the added amount of the inhibitor of Example ₃ (grade of WO 3) and recovery (recovery of WO _3).

Figure 7 shows a fifth embodiment and the quality of the scheelite concentrate according to the order of addition of the reagent of Comparative Example 4 (grade of WO ₃₎ and recovery (recovery of WO _3).

Figure 8 shows a sixth embodiment according to the quality of the scheelite concentrate the reaction time after addition of the pH adjusting agent and the inhibitor (grade of WO ₃₎ and recovery (recovery of WO _3).

9 illustrates a seventh embodiment of a catcher refined scheelite concentrates according to the type of (grade of WO ₃₎ and recovery (recovery of WO _3).

Figure 10 shows a refined embodiment of the scheelite concentrate according to claim catcher amount of Example 8 (grade of WO ₃₎ and recovery (recovery of WO _3).

Figure 11 shows a ninth embodiment catcher after the addition of the quality of the scheelite concentrate according to the reaction time (grade of WO ₃₎ and recovery (recovery of WO _3).

Figure 12 shows a refined embodiment of the scheelite concentrate according to the type of foaming agent of Example 10 (grade of WO ₃₎ and recovery (recovery of WO _3).

Figure 13 shows the exemplary quality of scheelite concentrates according to the addition amount of the foaming agent of Example 10 (grade of WO ₃₎ and recovery (recovery of WO _3).

Figure 14 illustrates an exemplary quality of scheelite concentrate in accordance with the pulp density of Example 11 (grade of WO ₃₎ and recovery (recovery of WO _3).

15 is an XRD analysis of tailing, middleling and sackstone concentrates obtained according to Example 12. FIG.

In the present specification, when a part "contains" a certain component, this means that the component may further include other components, except for the case where there is no contrary description.

Hereinafter, this specification is demonstrated in detail.

Obtaining the scheelite shipbuilding concentrate includes the step of sequentially adding a pH regulator and inhibitor to the mineral liquid,

The pH adjusting agent is Na ₂ CO ₃ , The amount of the pH adjusting agent is more than 2 kg / t 3.5 kg / t,

The inhibitor is Na ₂ SiO ₃ , and the addition amount of the inhibitor provides a recovery method of high-quality scheelite concentrate is 3.5 kg / t or more and 4.5 kg / t or less.

Kg / t or g / t herein means the weight of the additive relative to the weight of the particulate product (solid material).

1 and 2 illustrate a method for recovering high-quality scheelite concentrates according to one embodiment of the invention. In detail, FIG. 1 illustrates a process of recovering sinter concentrate from three types of scouring shipbuilding concentrates, which are obtained by mixing the fine products of the feldspar ore with water, which is a suspension obtained through shipbuilding flotation. . However, the present invention is not limited to the process of FIG. 1, and additional steps may be further included or some steps may be excluded.

1 and 2, the middledling (middling) refers to a product in which scheelite and gangue are mixed together, and tailing (tailing) refers to a product that is not suspended during flotation and remains in the mineral liquid. For example, when the concentrate is selected to enhance the economic quality of the ship's concentrate, the remaining product in the mineral solution is generated, which loses a small amount of gangue minerals as well as some slate minerals. This product is called middleling. And, in theory, the product suspended during the sorting of the scheelite should be slate minerals, whereas the product that remains unfloated and remains in the mineral liquid should be gangue minerals, but in reality some small amounts of scheelite mineral particles may be lost in the tailings product.

According to an exemplary embodiment of the present invention, the method may further include mixing the suspended solid obtained by performing scavenging flotation between the step of obtaining the sintered shipbuilding concentrate and the step of obtaining the sintered rock concentrate. . The precipitate obtained through the blue wire flotation may be tailing.

According to an exemplary embodiment of the present invention, the pH adjusting agent is Na ₂ CO ₃ . By the pH adjusting agent, the pH of the mineral liquid may be adjusted to 9.5 to 10.5. Furthermore, when the pH adjuster is used as Na ₂ CO ₃ , it exhibits a better selection efficiency than other basic pH adjusters NaOH, CaO or Na ₂ S, there is an advantage that the quality and recovery rate of the recovered scheelite concentrate. Further, the addition amount of Na ₂ CO ₃ as the pH adjuster is 2 kg / t or more and 3.5 kg / t or less, specifically 2.5 kg / t or more and 3.5 kg / t or less, or 2.8 kg / t or more and 3.2 kg / t or less Specifically, in the case of 3 kg / t, the optimum screening efficiency can be exhibited. If the addition amount of the pH adjusting agent is less than 2 kg / t, the recovery rate of salt concentrate may not be high. In addition, when the addition amount of the pH adjusting agent is more than 3.5 kg / t, the quality of the salt concentrate can be sharply lowered. Therefore, Na ₂ CO ₃ may act as an important parameter in slate suspension as well as the role of pH regulator.

According to an exemplary embodiment of the present invention, the inhibitor is Na ₂ SiO ₃ . The inhibitor effectively inhibits silicate-based and Ca-based gangue minerals, and helps to efficiently select scheelite. Furthermore, when the addition amount of the inhibitor Na ₂ SiO ₃ is 3.5 kg / t or more and 4.5 kg / t or less, specifically 3.8 kg / t or more and 4.2 kg / t or less, more specifically 4 kg / t, the optimum screening efficiency Can exert.

When the addition amount of the inhibitor is less than 3.5 kg / t, it can be lowered the grade of salt concentrate without a noticeable increase in recovery because the silicate minerals, which are gangue minerals are not sufficiently inhibited.

In addition, as the addition amount of the inhibitor increases, the silicate mineral is more hydrophilized to suppress their floating, which increases the grade, but when the addition amount of the inhibitor is more than 4.5 kg / t, particles and some that are not separated from each other Scheelite can also be suppressed together, resulting in a sharp drop in the recovery of scheelite concentrate without a marked increase in dignity.

According to one embodiment of the present invention, the order of adding the pH regulator and the inhibitor is to add the inhibitor after the pH regulator is added. Specifically, when the inhibitor is added differently from the above addition order, the addition of the pH adjusting agent may cause a sharp decrease in the recovery rate of the sackstone concentrate and a sharp drop in the quality of the sackstone concentrate.

This case is first added to the pulp an inhibitor of Na ₂ SiO ₃ than pH adjusting agent, the addition of Na ₂ SiO ₃ is caused in the pulp HSiO ₃ ^- in excess of the ion generating effect, HSiO ₃ ^- ions are first on the surface of the mineral It can work so strongly that minerals can't be affected by the pH regulator added later.

When performed in the order of addition of the pH adjusting agent and the inhibitor, the Na ₂ SiO ₃ can maintain a strong inhibitory effect not only to silicate gangue minerals but also Ca ion-containing minerals, even if the pH adjusting agent Na ₂ CO ₃ is added. In the case of when Na ₂ CO ₃ is added, since the hydrophobic surface property by the catcher is maintained without the inhibitory effect of Na ₂ SiO ₃ , the recovery rate of scheelite concentrate can be greatly increased.

According to one embodiment of the present invention, the reaction time of adding the inhibitor after adding the pH adjusting agent may be 3 minutes or more and 7 minutes or less after the addition of the inhibitor. Specifically, the reaction time of adding the inhibitor after adding the pH adjusting agent may be 4 minutes or more and 6 minutes or less after the addition of the inhibitor. Specifically, the reaction time of adding the inhibitor after adding the pH adjusting agent may be 5 minutes after the addition of the inhibitor. If the reaction time is shorter than 3 minutes can be lower the grade of low gangue minerals, the lower the grade, and if the reaction time is longer than 7 minutes may not be effective because the recovery rate is reduced without a noticeable increase in grade. Furthermore, when the reaction time is within 5 minutes, Na ₂ CO ₃ and Na ₂ SiO ₃ Reagents may be the most efficient time for suppressing gangue minerals and recovering tungsten.

According to an exemplary embodiment of the present invention, before the step of obtaining the sintered shipbuilding concentrate, the step of flocculating the mineral liquid to remove molybdenum, and the step of flocculating the mineral liquid from which molybdenum is removed further comprising the step of removing sulfides Can be.

FIG. 2 illustrates a case of performing the sorting for removing molybdenum and sulfides prior to the sorting of the suspended solids in the method of recovering the high-grade sintered concentrate of FIG. 1. Specifically, after forming the mineral liquid, after performing the floating screening for the removal of molybdenum (Mo), after the floating screening for the removal of sulfides, the selection line for the concentration of shipbuilding floating and sintered stone concentrate for sintered shipbuilding concentrate The steps of floating screening are shown. However, the present invention is not limited to the process of FIG. 2, and additional steps may be further included or some steps may be excluded.

According to one embodiment of the present specification, removing the molybdenum and removing the sulfide may be performed sequentially. If, unlike the above sequence, after performing the flotation screen to remove the sulfide, and performs the flotation screen to remove molybdenum, the quality and recovery rate of the scheelite can be greatly reduced. Specifically, in the case of molybdenum, it is more effective to recover before the removal of sulfide due to the high natural abundance. In addition, if the sulfide is recovered prior to molybdenum, a considerable amount of tungsten can be removed together with the sulfide, which may cause a decrease in the recovery rate of tungsten.

According to one embodiment of the present invention, the step of obtaining the feldspar shipbuilding concentrate may further include adding a catcher and a foaming agent after adding the inhibitor.

According to an exemplary embodiment of the present invention, the order of adding reagents in the step of obtaining the feldspar shipbuilding concentrate may be to sequentially add a pH regulator, an inhibitor, a catcher, and a foaming agent.

According to an exemplary embodiment of the present invention, the catcher may be a fishery catcher. Specifically, the catcher may be oleic acid, AERO 726 of CYTEC, FS-2 of CLARIANT or sodium oleate. More specifically, the catcher may be oleic acid. When oleic acid is used as a catcher, it exhibits better screening efficiency than CYTEC's AERO 726, CLARIANT's FS-2 or sodium oleate, and has the advantage of high quality and recovery of recovered slate concentrate.

Furthermore, the addition amount of the catcher may exhibit an optimal screening efficiency when the amount of the catcher is 200 g / t or more and 300 g / t or less, specifically 230 g / t or more and 270 g / t or less, and more specifically 250 g / t.

When the amount of the catcher is less than 200 g / t, the selectivity to the desired mineral is low and the sinterite is gradually collected with Ca-containing minerals and Fe oxide minerals, so that the suspended solids of the sinterite is not sufficient. Problems with low recovery rates may occur. Furthermore, when the amount of the catcher is less than 200 g / t, the reason why the concentration of the sinter concentrate is low is that the sinter collected by the catcher forms a weak floc, and gangue minerals present between them are trapped in the concentrate. Because it can be recovered.

In addition, when the addition amount of the catcher is more than 300 g / t, only the quality of the feldspar concentrate can be slightly reduced without a clear increase in recovery, there may be a problem that only the amount of reagent used increases without a noticeable difference in screening efficiency. .

According to an exemplary embodiment of the present invention, the reaction time of the catcher may be 30 seconds or more and 2 minutes or less after the addition of the catcher. Specifically, the reaction time of the catcher may be 50 seconds or more and 80 seconds or less, more specifically 1 minute after the addition of the catcher. When the reaction time of the catcher is within the above range, the optimum screening efficiency can be exhibited. When the reaction time of the catcher exceeds 2 minutes after the addition of the catcher, a slight increase in the recovery rate of the feldspar concentrate may occur, but the quality may decrease rapidly. This is because oleic acid, a fatty acid-based catcher, has low selectivity for the desired mineral, and the longer the reaction time, the more calcite minerals such as Ca-containing minerals and Fe oxide minerals are recovered.

According to an exemplary embodiment of the present invention, the foaming agent may be a neutral foaming agent. When using a neutral foaming agent, there is an advantage that can effectively perform the pH control of the mineral liquid.

Specifically, the foaming agent may be Lankropol-8300, Fine Oil, AF 65 (Aerofroth 65) or MIBC (Methyl isobutyl carbinol) from Akzonoble. More specifically, the foaming agent may be Lankropol-8300 manufactured by Akzonoble. When Lankropol-8300 is used as a foaming agent, it may exhibit better screening efficiency than fine oil, AF 65 (Aerofroth 65) or MIBC (Methyl isobutyl carbinol).

According to the exemplary embodiment of the present invention, the amount of the foaming agent may be 30 g / t or more and 75 g / t or less. Specifically, the amount of the foaming agent may be 40 g / t or more and 60 g / t or less, more specifically 50 g / t. When the addition amount of the said foaming agent is 30 g / t or more and 75 g / t or less, optimal sorting efficiency can be exhibited. When the amount of the foaming agent is less than 30 g / t, the interfacial tension of the mineral liquid is not sufficiently lowered, so that a lot of coarse bubbles are generated, and the quality and recovery rate of the concentrate may be lowered. In addition, when the addition amount of the foaming agent exceeds 75 g / t, only the consumption of the foaming agent is increased without a clear increase in the screening efficiency can be increased only the treatment cost.

According to an exemplary embodiment of the present invention, the reaction time of the foaming agent may be 30 seconds or more and 90 seconds or less after the addition of the foaming agent. Specifically, the reaction time of the foaming agent may be 50 seconds or more and 70 seconds or less, more specifically 1 minute after the addition of the foaming agent.

According to an exemplary embodiment of the present invention, the particle size of the particulate product of the feldspar ore may be -170 mesh to -260 mesh. Specifically, the particle size of the particulate product of the feldspar ore may be -180 mesh to -220 mesh, more specifically -200 mesh. When the particle size of the particulate product of the feldspar ore is within the above range, an optimal sorting efficiency can be exhibited.

In the present specification, the particles of the particulate product may be particles used for flotation through a mesh. Furthermore, the particle size unit (-mesh) of the particulate product herein may refer to the size of the particles passing through the mesh. For example, when the particle size is -170 mesh, it may mean the size of the particles passing through the 170 mesh. Therefore, "-" in the mesh unit does not mean a general negative value, which is generally used in the art.

When the particle size of the granular product of the feldspar ore exceeds -260 mesh, that is, when the particle size is smaller than 260 mesh, a large amount of fine particles are generated and the selectivity is lowered so that a large amount of gangue minerals move to the foam layer. The problem of deterioration of concentrate may occur. In other words, if the particles of the particulate product are too small, the degree of separation is improved, but the hydrophilic gangue minerals are trapped in the water layer between the bubble and the bubble layer and are likely to move to the foam layer. This is because it is moved to the concentrate by the vacuum flow generated after the rising bubbles.

In addition, when the particle size of the particulate product of the feldspar ore is less than -170 mesh, that is, when the particle size is thicker than 170 mesh, the sinterite concentrate is relatively thick and part of it is not suspended and is treated with light or heavy light, so that the recovery rate of the feldspar concentrate is treated. This low problem can occur.

According to one embodiment of the present invention, the stirring speed at the time of sintered shipbuilding concentrate may be 1,300 rpm or more and 1,800 rpm or less. Specifically, the stirring speed during the sintered shipbuilding concentrate may be 1,500 rpm or more and 1,700 rpm or less. When the stirring speed is in the above range can be effectively carried out shipbuilding concentrate. If the stirring speed is slower than 1,300 rpm, the recovery rate may be reduced, and if the stirring speed is faster than 1,800 rpm, the mixing of gangue minerals in shipbuilding concentrate may increase.

According to one embodiment of the present specification, the particulate product may be formed by crushing and pulverizing feldspar ore. The crushing and crushing method may be crushed scheelite ore using a jaw crusher, a roll crusher or a rod mill.

According to an exemplary embodiment of the present invention, the concentration of the mineral liquid may be 25% solids or more and 40% solids or less. Specifically, the concentration of the mineral liquid may be 33% solids or more and 37% solids or less, more specifically 35% solids.

% Solids means the concentration of the solid phase in the mineral liquid. Specifically, the% solids may be the content of the particulate product in the mineral liquid, and more specifically, may refer to the weight ratio of the particulate product to the weight of the mineral liquid.

When the concentration of the mineral liquid is within the above range, it is possible to exhibit the optimum sorting efficiency.

When the concentration of the mineral liquid is more than 40% solids, there may be a problem that the quality of the sinter concentrate is lowered without a significant increase in recovery rate. This is because the lack of free space between the gangue mineral and the stalactite particles, the selectivity of the catcher is lowered to capture not only the slate, but also the gangue mineral.

An exemplary embodiment of the present invention provides a recovery device for the following slate concentrate that can implement the recovery method of the high-quality scheelite concentrate.

One embodiment of the present invention, a mineral liquid forming apparatus for forming a mineral liquid by mixing the fine products of the feldspar ore with water;

A ship floating sorting device for sorting the mineral liquid to obtain a scheelite shipbuilding concentrate; And

Floating sorting the feldspar shipbuilding concentrates, and includes a sorting floating screening device to obtain a slate concentrate concentrates,

The photoliquid forming apparatus is a device that implements the above-described forming of the photoliquid.

The ship floating sorting device is a device that implements the step of obtaining the above-described scheelite shipbuilding concentrate.

The above-mentioned floatation sorting device is a device for implementing the above-described slate concentrate concentrate.

According to an exemplary embodiment of the present invention, between the mineral liquid forming apparatus and the shipbuilding flotation device, a molybdenum flotation screening device for removing molybdenum by flotation of the mineral liquid, and the mineral liquid from which molybdenum is removed Sulfide flotation device to remove may be provided sequentially.

The molybdenum flotation screening device is a device for implementing the step of removing the molybdenum by flotation of the above-described mineral liquid.

The sulfide flotation screening apparatus is a device for implementing the step of removing the sulfides by flotation of the above-described mineral liquid.

The mineral liquid forming apparatus, the shipbuilding floating sorting device, the sorting floating sorting device, the molybdenum floating sorting device and the sulfide floating sorting device can be applied to the float sorting device in the art.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present invention to those skilled in the art.

[시료 및 실험 방법][Sample and Experiment Method]

As a sample for performing the following example, a tungsten sample collected from the Sangdong mine located in Sangdong, Yeongwol-gun, Gangwon-do was used. As a result of analyzing the components of the tungsten sample using ICP and XRF, the results shown in Table 1 were obtained.

화학 조성(%)Chemical composition (%)
WO₃ WO ₃	SiO₂ SiO ₂	Al₂O₃ Al ₂ O ₃	Fe₂O₃ Fe ₂ O ₃	CaOCaO	MgOMgO	K₂OK ₂ O	Na₂ONa ₂ O	TiO₂ TiO ₂	MnOMnO	P₂O₅ P ₂ O ₅	IglossIgloss
0.750.75	52.5652.56	9.939.93	17.1717.17	12.2912.29	2.562.56	0.820.82	0.110.11	0.730.73	0.870.87	0.730.73	1.481.48

The raw ore of the tungsten sample thus obtained was prepared using a jaw crusher, a roll crusher, and a rod mill to a particle size of a desired fine product after crushing and crushing. Float screening experiments were carried out using a laboratory Denver sub-A flotation screener and flotation screening to remove molybdenum and sulfides prior to shipbuilding screening. Then, reagents were added in the order of pH adjuster (Na ₂ CO ₃ ) -inhibitor (Na ₂ SiO ₃ ) -occasion agent (Oleic acid) -foaming agent (Lankropol-8300), where the concentration of the mineral solution was 35% solids and the particle size was -200. The mesh and the stirring speed were 1,500 rpm. In the case of selected flotation, the stirring speed was lowered to 1,200 rpm, and the experiment was performed without the addition of a pH regulator, inhibitor, catcher, and foaming agent. Furthermore, the oleic acid, which is a catcher, began to solidify from 14 or less, and thus, all experiments were conducted while maintaining the temperature of the mineral liquid at 25 ° C or higher.

[실시예 1] - 미립 산물의 입자 크기Example 1 Particle Size of Particle Product

In order to observe the effect of the particle size of the particulate product on the sputum suspension screening, particles from -100 mesh to -325 mesh were prepared, and then pH regulators (Na ₂ CO) at a mineral solution concentration of 35% solids and a stirring speed of 1,500 rpm, respectively. ₃ ) The experiment was performed by adding reagents in the order of 3 kg / t, 4 kg / t of inhibitor (Na ₂ SiO ₃ ), 250 g / t of oleic acid and 50 g / t of foaming agent (Lankropol-8300). . After the addition of the reagent, the reaction time was added to the pH adjuster and inhibitor in order, 5 minutes, each one minutes after the addition of the catcher and the foaming agent was given.

According to Figure 3, it can be seen that the recovery of sinter concentrate is greatly increased up to -200 mesh particles, but decreases as the particles become smaller from this point. In the case of -200 mesh particles, it is thought that the recovery rate was increased because the sintered stone which was not suspended in the coarse particles was effectively suspended.

Therefore, in consideration of the quality and recovery of scheelite concentrate, the particle size of the particulate product showed excellent efficiency when the particle size was -170 to -260 mesh, and the best efficiency when the -200 mesh. When the particle size of the particulate product was -200 mesh, the sintered concentrate was 67.6% WO ₃ and the recovery was 88.16%.

[실시예 2] - pH 조절제의 종류Example 2 Types of pH Control Agents

The experiment was conducted in the same manner as in Example 1, except that the particle size of the particulate product was -200 mesh.

[비교예 1] - pH 조절제의 종류Comparative Example 1 Types of pH Control Agent

In order to evaluate the performance of Na ₂ CO ₃ pH adjuster according to the present invention, the effects of on the sorting by selecting the representative basic pH regulators NaOH, CaO and Na ₂ S was compared. Experimental conditions were conducted in the same manner as in Example 2, except that the pH adjusting agent was NaOH, CaO or Na ₂ S.

According to FIG. 4, the most effective pH control agent was Na ₂ CO ₃ according to Example 2, and the grade and recovery rate of the sintered concentrate were 67.6% WO ₃ and 88.16%, respectively. Furthermore, in the case of NaOH and Na ₂ S according to Comparative Example 1, it was found that the grade and recovery rate of sintered concentrate were low. In addition, in the case of CaO according to Comparative Example 1, the grade and recovery of the sintered concentrate were 1.21% WO ₃ and 12.62%, respectively, which did not show a clear screening efficiency.

[실시예 3] - pH 조절제의 첨가량Example 3-Added amount of pH adjusting agent

The experiment was conducted in the same manner as in Example 2, except that the addition amount of Na ₂ CO ₃ , which is a pH regulator, was adjusted to 2 kg / t to 3 kg / t.

[Comparative Example 2] -Added amount of pH adjusting agent

The experiment was conducted in the same manner as in Example 3 except that the addition amount of Na ₂ CO ₃ , which is a pH regulator, was adjusted to 1 kg / t or 4 kg /.

According to Figure 5, it can be seen that the recovery of salt concentrate also increases as Na ₂ CO ₃ increases, the quality is similar trend up to 3 kg / t, it can be seen that sharply falls when the addition amount is increased. Specifically, when the addition amount of Na ₂ CO ₃ according to Comparative Example 2 is 1 kg / t, the recovery rate of sinter concentrate is low to 60% level, and when the addition amount of Na ₂ CO ₃ is 4 kg / t, the grade of salt concentrate It can be seen that falls too much.

Therefore, considering the grade and recovery rate of sinterite concentrate, it showed the best efficiency when the addition amount of pH adjuster was 3 kg / t, and it was judged that the optimum addition amount range of pH regulator was 2 kg / t to 3.5 kg / t. do. The grade and recovery of sintered concentrate at 3 kg / t of pH adjuster were 67.6% WO ₃ and 88.16%, respectively.

[실시예 4] - 억제제의 첨가량Example 4 Addition of Inhibitor

The experiment was conducted in the same manner as in Example 1 except that the particle size of the particulate product was -200 mesh and the amount of the inhibitor Na ₂ SiO ₃ added was 4 kg / t.

[비교예 3] - 억제제의 첨가량Comparative Example 3-Amount of Inhibitor Added

The experiment was conducted in the same manner as in Example 4, except that the addition amount of the inhibitor, Na ₂ SiO ₃ , was set to 1 kg / t to 3 kg / t and 5 kg / t.

According to FIG. 6, it can be seen that as the amount of the inhibitor is increased, the quality of the feldspar concentrate increases and the recovery rate decreases. Specifically, when the addition amount of Na ₂ SiO ₃ according to Comparative Example 3 is 1 kg / t to 3 kg / t, it can be seen that the grade of the feldspar concentrate is lower than 50% WO ₃ , the addition amount of Na ₂ SiO ₃ At 5 kg / t, it can be seen that the recovery rate of sinter concentrate sharply dropped. Furthermore, when the addition amount of Na ₂ SiO ₃ according to Example 4 is 4 kg / t, it can be seen that the critical point of the quality and recovery rate of sinterite concentrate.

Therefore, considering the grade and recovery of sinterite concentrate, it showed the best efficiency when the amount of inhibitor added was 4 kg / t, and the range of the optimum amount of inhibitor was 3.5 kg / t to 4.5 kg / t. .

[실시예 5] - 시약의 첨가 순서Example 5 Addition Procedure of Reagents

The experiment was conducted in the same manner as in Example 1, except that the particle size of the particulate product was -200 mesh. Specifically, the reagent addition order at this time was in the order of the pH regulator-inhibitor-aquatic agent-foaming agent.

[비교예 4] - 시약의 첨가 순서Comparative Example 4-Procedure for Adding Reagents

The experiment was conducted in the same manner as in Example 5, except that the addition order of the reagents was performed in the order of the inhibitor-pH regulator- catcher-foaming agent.

Figure 7 shows a fifth embodiment and the quality of the scheelite concentrate according to the order of addition of the reagent of Comparative Example 4 (grade of WO ₃₎ and recovery (recovery of WO _3). Specifically, (A) in FIG. 7 shows the scheelite concentrate and grade and recovery rate according to Example 5, and (B) shows the scheelite concentrate and grade and recovery rate according to Comparative Example 4. FIG.

According to FIG. 7, the grade of the sintered concentrate according to Example 5 was 67.6% WO ₃ , the recovery rate was 88.16%, and the grade of the sintered concentrate according to Comparative Example 4 was 1.21% WO ₃ , the recovery rate was 0.17%.

Therefore, it can be seen that the addition of the inhibitor after the addition of the pH adjuster as in Example 5 shows an excellent effect compared to the case of Comparative Example 4 in which the pH adjustment agent is added after the addition of the inhibitor.

[실시예 6] - pH 조절제 및 억제제 첨가 후의 반응 시간Example 6-Reaction time after addition of pH adjuster and inhibitor

Experiment was carried out in the same manner as in Example 1 except that the particle size of the particulate product was -200 mesh, and the pH adjusting agent and the inhibitor were sequentially added and the reaction time thereof was changed from 1 minute to 7 minutes.

According to Figure 8, if the reaction time after the addition of the pH regulator and inhibitor is shorter than 3 minutes, the inhibitory effect of the gangue minerals are lowered, the grade is lowered, if longer than 7 minutes it can be seen that the recovery rate is reduced without a noticeable dignity.

Therefore, considering the grade and recovery rate of sinterite concentrate, it showed the best efficiency when the reaction time after addition of pH adjuster and inhibitor was 5 minutes, and the range of reaction time after addition of optimum pH adjuster and inhibitor was 3 minutes to 7 minutes. It seems to be. When the reaction time after addition of the pH adjusting agent and the inhibitor was 5 minutes, the grade and recovery of the feldspar concentrate were 67.6% WO ₃ and 88.6%, respectively.

[실시예 7] - 포수제 종류Example 7 Type of Catcher

To determine the grade of WO ₃ and recovery of WO ₃ according to the type of catcher, choose oxalic acid, ER-2 726 from CYTEC, FS-2 from CLARIANT or sodium oleate. This study examined the effects on floating screening.

Specifically, the experiment was conducted in the same manner as in Example 1, except that the catcher was oleic acid, AERO 726, FS-2 or sodium oleate, and the particle size of the particulate product was -200 mesh.

According to FIG. 9, the most efficient screening agent was oleic acid, and the grade and recovery rate of sinter concentrate were the highest at 67.6% WO ₃ and 88.16%, respectively. Furthermore, in the case of sodium oleate, the grade of sinter concentrate was 65.74% WO ₃ and the recovery rate was 68.47%, showing good results. In the case of AERO 726 and Fs-2, AERO 726 has a relatively good grade and recovery rate of 62.58% WO ₃ and 75.05%, respectively, while FS-2 has 34.82% grade and recovery rate, respectively. The recovery rate was good at% WO ₃ and 73.55%, but the quality was lower than that of other catchers.

[실시예 8] - 포수제 첨가량Example 8-Addition amount of catcher

In order to investigate the effect of the addition amount of the catcher on the slate sorting, Example 1 was changed except that the amount of the catcher was changed from 100 g / t to 300 g / t, and the particle size of the particulate product was -200 mesh. The experiment was performed in the same manner.

According to Figure 10, it can be seen that as the addition amount of the catcher increases the highest efficiency when the quality and recovery of the sintered concentrate is 250 g / t, the increase in addition is no more apparent recovery and quality increase Able to know.

Therefore, considering the grade and recovery rate of sinterite concentrate, it showed the best efficiency when the addition amount of the catcher was 250 g / t, and the optimum amount of the addition of the catcher was determined to be 200 g / t to 300 g / t. do. When the addition amount of the catcher was 250 g / t, the grade and recovery of the sinter concentrate were 67.6% WO ₃ and 88.16%, respectively.

[실시예 9] - 포수제 첨가 후 반응 시간 Example 9-Reaction time after addition of catcher

In order to examine the effect of reaction time on the slate suspension after addition of the catcher, the reaction time was changed from 30 seconds to 5 minutes after the addition of the catcher, except that the particle size of the particulate product was -200 mesh. The experiment was conducted in the same manner as in Example 1.

According to FIG. 11, as the reaction time of the catcher was increased, the recovery rate of the feldspar concentrate increased but the quality decreased. Specifically, it can be seen that as the reaction time of the catcher starts, the rate of increase in the recovery rate of the sinter concentrate is slowed, and the quality tends to decrease.

Therefore, considering the grade and recovery rate of sinterite concentrate, it showed the best efficiency when the reaction time of the catcher was 1 minute, and the reaction time range of the optimum catcher was judged to be 30 seconds or more and 2 minutes or less. When the reaction time of the catcher was 1 minute, the grade and recovery of the sinter concentrate were 67.6% WO ₃ and 88.16%, respectively.

[실시예 10] - 기포제의 종류 및 첨가량[Example 10]-Type and amount of foaming agent

In order to examine the effect of the type of foaming agent on the sackstone suspension screening, the neutral foaming agent is Lankropol-8300 (Akzonoble), Pine oil, AF 65 (Aerofroth 65), or MIBC (Methyl isobutyl carbinol), The experiment was conducted in the same manner as in Example 1, except that the particle size of the particulate product was -200 mesh.

According to FIG. 12, Lankropol-8300 was found to be the most effective foaming agent in the grade and recovery rate of sintered concentrate was 67.6% WO ₃ and 88.16%, respectively. In addition, in the case of fine oil and MIBC, the grade and recovery rate of sintered concentrate were relatively low compared to Lankropol-8300, but showed a good screening efficiency. Furthermore, the AF 65 showed a good recovery rate of sintered concentrate, but showed a lower quality than other foaming agents. This is due to the strong surface activation function of AF 65, which has a catching ability, compared to other foams, and it is believed to be collected by collecting hydrite and hydrophilic minerals.

Further, the experiment was conducted in the same manner while adjusting the amount of the Lankropol-8300 foaming agent was adjusted from 25 g / t to 100 g / t.

According to FIG. 13, when the amount of the foaming agent is less than 30 g / t, the interfacial tension of the mineral liquid is not sufficiently lowered, so that a lot of coarse bubbles are generated, the quality and recovery rate are lowered, and when the amount of the foaming agent is greater than 75 g / t, a clear increase in the screening efficiency is achieved. You can see that it can not be confirmed.

Therefore, in consideration of the quality and recovery rate of sinterite concentrate, it showed the best efficiency when the addition amount of the foaming agent is 50 g / t, it is judged that the optimum amount of the foaming agent is more than 30 g / t 75g / t.

[실시예 11] - 광액 농도 Example 11 Mineral Solution Concentration

In order to determine the effect of mineral solution concentration on scheelite flotation, experiment was the same as in Example 1 except that the mineral solution concentration was changed from 15% solids to 45% solids, and the particle size of the particulate product was -200 mesh. Proceeded.

According to FIG. 14, as the concentration of mineral solution increases, the grade of sinter concentrate concentrates similarly, but when the concentration of mineral solution is higher than 35% solids, the grade tends to decrease. On the contrary, the recovery rate of sinter concentrate is gradually increased as the concentration of mineral solution increases. Specifically, the feldspar concentrate quality was the highest at 71.55% WO ₃ but the recovery was the lowest at 58.14% at 15% solids. In addition, at 25% solids and 35% solids concentrations of sinter concentrate concentrate similarly to 68.35% WO ₃ and 67.6% WO ₃ , respectively, but the recovery of sinter concentrate is 88.16% at 35% solids at 25% solids. Higher than 76.98% of the time.

Therefore, considering the grade and recovery of sintered concentrate, it showed the best efficiency when the concentration of the mineral liquid was 35% solids.

[실시예 12] - XRD 분석Example 12-XRD Analysis

Except that the particle size of the fine particles to -200 mesh, XRD analysis of the tailing, middle ring and scheelite concentrate obtained during the experiment as in Example 1 was carried out.

Specifically, A of FIG. 15 is a result of XRD analysis of tailing, and in the case of tailing, only peaks of silicate minerals appear, and quartz (Quartz) occupies the highest ratio. On the other hand, the peak of Scheelite did not appear, indicating that the screening efficiency was good. In addition, FIG. 15B is a result of XRD analysis of the middle ring. In the case of the middle ring, the peak of the sputum is shown to be insignificant, and the peak of many silicate gangue minerals still appears. Furthermore, FIG. 15C is the result of XRD literite of the final sinter concentrate, and quartz (quartz), chlornochlore, feldspar (Albite), and Hornblende, which are silicate gangue minerals that were present in the ore in the case of sinter concentrate As the peak of disappeared, it can be seen that the suppression and removal of silicate minerals was effective. Although a small amount, but the scheelite concentrate fluorite (Fluorite) was found to be that, if any, which the organic acid anion ionized by the oleic acid used zero catcher (C ₁₇ H ₃₃ COO ^-) is adsorbed on a metal ion (Ca ²⁺⁾ After insoluble metal salts are formed, the mineral surface is hydrophobic, which is believed to have been recovered with scheelite.

Claims

Mixing the fine product of scheelite ore with water to form a mineral liquid; Flocculating the mineral liquid to obtain scheelite shipbuilding concentrate; And floating sorting the sintered shipbuilding concentrate to obtain the sintered mineral concentrate,

Obtaining the scheelite shipbuilding concentrate includes the step of sequentially adding a pH regulator and inhibitor to the mineral liquid,

The pH adjusting agent is Na 2 CO 3 , The amount of the pH adjusting agent is more than 2 kg / t 3.5 kg / t,

The inhibitor is Na 2 SiO 3 , and the addition amount of the inhibitor is 3.5 kg / t or more 4.5 kg / t or less recovery method of high-quality scheelite concentrate.
The method according to claim 1,

The reaction time of the step of adding the inhibitor after adding the pH adjusting agent is a recovery method of high-quality scheelite concentrate that is 3 minutes or more and 7 minutes or less after the addition of the inhibitor.
The method according to claim 1,

Before the step of obtaining the feldspar shipbuilding concentrate, the step of sorting the mineral liquid to remove molybdenum, and the step of sorting the mineral liquid from which molybdenum has been removed further comprising the step of removing the sulfide concentrate.
The method according to claim 1,

The step of obtaining the feldspar shipbuilding concentrate further comprises the addition of a catcher and a foaming agent after the addition of the inhibitor.
The method according to claim 4,

The catcher is a hydroxyl type catcher, the addition amount of the catcher is 200 g / t or more 300 g / t or less recovery method of high-quality scheelite concentrate.
The method according to claim 4,

The reaction time of the catcher is a recovery method of high-quality scheelite concentrate that is 30 seconds or more and 2 minutes or less after the addition of the catcher.
The method according to claim 4,

Said foaming agent is a neutral foaming agent, The addition amount of the said foaming agent is 30g / t or more 75g / t or less.
The method according to claim 4,

The reaction time of the foaming agent is a recovery method of high-quality scheelite concentrate that is 30 seconds or more and 90 seconds or less after the addition of the foaming agent.
The method according to claim 1,

Particle size of the fine product of the feldspar ore is -170 mesh or more -260 mesh or less recovery method of high-quality scheelite concentrate.
The method according to claim 1,

The concentration of the mineral liquid is more than 25% solids 40% solids recovery method of high-quality scheelite concentrate.
A mineral liquid forming apparatus for mixing a fine product of scheelite ore with water to form a mineral liquid;

A ship floating sorting device for sorting the mineral liquid to obtain a scheelite shipbuilding concentrate; And

Floating sorting the feldspar shipbuilding concentrates, and includes a sorting floating screening device to obtain a slate concentrate concentrates,

The ship floating sorting device is a pH adjusting unit for adjusting the addition amount of Na 2 CO 3 pH adjuster to 2 kg / t or more to 3.5 kg / t or less, and the addition amount of the inhibitor Na 2 SiO 3 3.5 kg / t or more 4.5 kg Suppressor concentration recovery control device to adjust to / t or less is provided with a sequential concentration of the sulphite concentrate to sequentially add the pH regulator and the inhibitor to the mineral liquid.
The method according to claim 11,

Between the mineral liquid forming apparatus and the shipbuilding flotation device, a molybdenum flotation screening device for floating the mineral liquid to remove molybdenum and a sulfide flotation screening device for floating the mineral liquid from which molybdenum is removed to remove sulfides sequentially Equipment for the recovery of sack concentrate.