JP2552128B2 - High-purity purification method for clay minerals - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method of purifying a clay raw material from a clay ore to a high purity and recovering a useful metal mineral.

(Prior Art) Clay raw ores containing clay minerals such as sericite, kaolin, and wax stones often contain sulfide minerals such as iron sulfide ore, arsenopyrite, sphalerite, and molybdenum sulfide. As a method of recovering clay minerals by removing these sulfide minerals, there are flotation methods such as multi-oil and foam methods, and oil extraction methods have been proposed.

(Problems to be solved by the invention) However, the sulfide mineral that can be removed by the flotation method is 10 μm
More than. Fine particles of sulfide less than this cannot be removed from the clay particles, so it was necessary to chemically remove the sulfide minerals.

The oil extraction method has been proposed as a method for separating fine metal minerals, but the adjustment of the conditions for separation is not clear, and it is still practical to separate ultrafine minerals in clay particles. It has not been converted.

It is an object of the present invention to provide a high-purity purification method for clay minerals that solves the problems of the conventional techniques.

(Means for Solving Problems) According to the present invention, in a method for recovering a clay mineral from a raw clay ore, a substance and a chelate compound that act as a reducing agent by using ultrafine sulfide minerals fixed to the clay mineral High-purity purification of clay minerals, characterized in that the clay minerals are pretreated with a substance capable of forming, and are subjected to multistage shaking flushing treatment with a hydrophobic medium and a hydrophilic medium to separate the clay minerals from the ultrafine sulfide minerals. The method achieves the above objectives.

Here, the flushing process is a process in which solid particles in a hydrophilic medium dispersion system are hydrophobized with a surfactant and transferred to a hydrophobic medium dispersion system.

(Preferred Embodiment) A method for highly purifying clay minerals according to the present invention is a method for purifying ultrafine sulfide minerals fixed to clay minerals by using a substance acting as a reducing agent and a substance capable of forming a chelate compound. It is characterized in that the mineral is pretreated so as to be released or easily released, and the clay mineral and the ultrafine sulfide mineral are separated by multistage shaking flushing treatment with a hydrophobic medium and a hydrophilic medium.

In order to separate ultrafine impurities adhering to the clay mineral from the clay mineral, a substance acting as a reducing agent and a substance capable of forming a chelate compound are used.

The substance that acts as a reducing agent may be any substance that can reduce an oxidation product such as a ferric compound such as ferric hydroxide that links a clay mineral and an ultrafine sulfide mineral. , It is preferable to use a reducing agent such as hydrosulfite.

As the substance having the ability to form a chelate compound, it is preferable to use a chelating agent such as polyaminocarboxylic acids such as EDTA and oxycarboxylic acids such as sodium citrate.

Separation of the separated ultrafine sulfide minerals and clay minerals is carried out by multistage shaking flushing treatment with a hydrophobic medium and a hydrophilic medium.

The hydrophobic medium used here is not particularly limited, and mineral oil containing kerosene as a main component can also be used.

The means for performing the multi-stage shaking flushing treatment with the hydrophobic medium and the hydrophilic medium uses an apparatus and conditions capable of efficiently incorporating ultrafine sulfide minerals into the hydrophobic medium,
For example, it is preferable to use the flushing device shown in FIG. 2 under predetermined conditions.

The flushing device shown in FIG. 2 is preferably used upright, and the clay suspension flowing in from the clay suspension inlet 22 in the upper part of the device is the aqueous phase from the refined clay suspension outlet 28 in the lower part of the device. As a hydrophobic medium inlet at the bottom of the device 27
The hydrophobic medium flowing in from is a countercurrent type in which it flows out as an oil phase from the sulfide mineral-containing hydrophobic medium suspension outlet 23 at the upper part of the apparatus.

Further, as shown in the drawing, the flushing device of FIG. 2 includes a six-plate turbine blade 29 alternately provided on a reciprocating drive shaft 25, a cylindrical blade 26 having perforations (through holes), and a baffle plate 24. Powerful shaking is performed in multiple stages,
The clay suspension flowing in from the upper part of the device is shaken toward the lower part of the device and the clay particles are gradually refined. By repeating this multi-step shaking, the sulfide mineral component is efficiently collected in the hydrophobic medium system.

Hereinafter, the high-purity purification method of the clay mineral of the present invention will be described based on the flow sheet of the method of the present invention of FIG. 1, but the present invention is not limited thereto.

In the classification process of the flow sheet, water glass,
The clay suspension dispersed with sodium polyphosphate or the like is cut to a predetermined particle size by a known continuous or batch classifier.

In the condition adjustment process, the solid concentration, pH,
Adjust the conditions necessary for separation such as redox potential and electrolyte concentration, and add a separation aid. The solid concentration differs depending on the clay, and is preferably about 10% for kaolin and several% for sericite.
The pH and redox potential are −1000 mV or less at a pH of 7 to 4.5 (platinum electrode-within the range where the sulfide mineral oxidation products adhering to the clay particle surface are dissolved and the sulfide mineral and clay particles are easily dispersed
Silver chloride electrodes) are preferred. If the pH is higher than this, the separation efficiency of sulfide minerals tends to decrease, and if it becomes lower, the agglomeration of clay becomes remarkable. The electrolyte concentration is preferably 1000 μs / cm or less. As a separation aid, an appropriate amount of a reducing agent such as hydrosulfite and a chelating agent such as sodium citrate are used for dissolution of the oxidation product and chelation of dissolved ions. Chelating agents also help disperse the clay on the acidic side. In addition, a very small amount of a surfactant is used as a separation aid to control the size of oil droplets and to make the surface of sulfide mineral particles hydrophobic. Mineral acids other than nitric acid, caustic soda, and water glass solutions are used to adjust the pH.

In the flushing process, the conditioned clay suspension and oil were sent to the countercurrent flushing device capable of multi-stage shaking shown in Fig. 2 by the metering pumps, respectively, to obtain the clay suspension and the oil suspension of sulfide minerals. To be separated. The oil is a mixture of mineral oil containing kerosene as a main component and methyl isobutyl ketone as an oil / water separation aid. The mixing amount is preferably from 10% by volume of methyl isobutyl ketone to 100 parts by volume of mineral oil. The mixing ratio of the clay suspension and the oil is preferably several% to 10% by volume of oil with respect to 100 parts by volume of the clay suspension. The separated clay suspension is concentrated by adding an acid or other coagulant, and is recovered using a known apparatus such as a pressure furnace, a pressure furnace or a spray dryer. The oil suspension is subjected to solid / liquid separation using a known apparatus such as a pressure furnace or a vacuum furnace, and useful sulfide minerals are recovered, and the oil is reused.

The flushing device mixes oil and clay suspension to incorporate sulfide mineral particles into oil droplets dispersed in a controlled size, and subsequently combine the oil droplets to combine oil suspension and clay suspension. It is preferable that the material is composed of a mechanism that efficiently separates the liquid, and that the material does not easily generate hydrogen.

There is a counterflow type flushing device newly developed to satisfy these conditions, which enables the multistage shaking treatment of Fig. 2, and the reciprocating rotation of its blade is sufficiently powerful to separate sulfide minerals from clay minerals. Shaking shock shall occur. More specifically, a vertical cylindrical body has an inlet for oil and clay suspension, an outlet for oil suspension and clay suspension, and a three-plate turbine that facilitates dispersion and coalescence of oil droplets. And Shimazaki Seisakusho Co., Ltd. has a rotary shaft with multi-stage mounting, a drive mechanism for reciprocating the rotary shaft at the top of the main body, and a liquid level adjustment mechanism for adjusting the height of the oil / water interface outside the main body. Each is installed. Further, baffle plates are installed between the blades to prevent uneven flow of each other.

 Next, the present invention will be described in more detail with reference to Examples.

(Example) Example 1 A sericite original ore from the Tagokura mine was thrown into water, water glass was added to a clay suspension of 60 mesh or less from which coarse tailings were removed using a mesh to disperse, and continuous high-speed centrifugation was performed. Clay suspension 500 cut into a specified particle size through a mold classifier
(Seric mica concentration 5 wt%) is used as a feed suspension. The feed suspension is conditioned by adding the chemicals shown in Table 1, and after 30 minutes, it is passed through a flushing device together with oil under the conditions shown in the same table. The flushing device operates at a reciprocating rotation cycle corresponding to an input speed of 450 rpm.

Table 1 Sodium citrate 50g Sodium oleate (0.5% solution) 20ml Erofloat 208 (0.5% solution) 20ml Hydrosulfite 50g Hydrochloric acid pH 5 amount After that, wash with water, press and dry sericite Got After passing through the flushing device once, the zinc component, which is the main impurity in clay, was removed from the feed suspension, and as a result of analysis, the amount of zinc remaining in sericite was 147 ppm.

Example 2 and Comparative Example Table 2 shows the concentrations of zinc, lead and arsenic remaining in the sericite obtained by purifying the sericite raw ore from the Tagokura Mine in the same manner as in Example 1 with high purity.

Table 2 also shows the results of the conventional flotation method as a comparative example.

(Effects of the Invention) Since the method of the present invention can remove ultrafine sulfide minerals as is clear from the examples, it is possible to purify clay minerals to a higher purity than in conventional flotation methods. You can

By the method of the present invention, a low-grade clay resource which remains unutilized because it was difficult in principle or economically by the conventional beneficiation method mainly on flotation, and valuable powdered ore contained therein, In addition, many clay and other non-metal minerals and valuable metal minerals that are currently discarded as tailings for flotation can be utilized. For example, not only the huge amount of clay in the tailing tailings of the Kuroko mine in Japan can be utilized as a resource, but also the coarse particles from which clay has been removed can be used as an anti-internal filler, which further solves the waste dam problem. It is also connected to.

The method of the present invention can also be applied to recovery of valuable minerals other than clay mineral-sulfide minerals and removal of impurities.

For example, in the case of sericite from the Tagokura mine, which can be separated by strict classification without inclusion of quartz particles, the sericite from which the sulphide mineral containing sphalerite as a main component is removed is used for conventional sericite. Besides, it can be applied to applications with new functions such as solid lubricants and lubricity coatings.

[Brief description of drawings]

FIG. 1 is a flow sheet showing one embodiment of the method of the present invention, FIG. 2 is a view showing a flushing device that can be used in the method of the present invention, and FIG. 3 is a view showing pores (through holes) of the flushing device. 4 is a plan view of the cylindrical blade having the perforations (through holes), FIG. 5 is a sectional view of the six-plate turbine blade of the flushing device, and FIG. 6 is the six-plate. FIG. 7 is a plan view of a turbine blade, and FIG. 7 is a view showing a part of a process flow of one embodiment of the method of the present invention. 21 ...... Reciprocating rotary drive part, 2 ...... Clay suspension inlet 23 ...... Hydrophobic medium suspension outlet containing sulfide mineral 24 ...... Baffle plate, 25 ...... Drive shaft 26 ...... Cylindrical blade 27 with porosity 27 ...... … Hydrophobic medium inlet 28 …… Refined clay suspension outlet 29 …… Six-plate turbine blades, 31,41 …… Through-hole 71 …… Kerosene tank 72 …… Methyl isobutyl ketone tank 73, 73 ′, 75, 75 ′, 79,82 …… Valve 74 …… Mixed oil and tank, 76,83 …… Pump 77 …… Sulfide mineral oil suspension and tank 78 …… Flushing device, 80 …… Level adjusting tank 81 …… Refined clay suspension Suspension and tank 84 …… Clay suspension and tank 85 …… Condition adjusting tank

Claims (1)

(57) [Claims] 1. A method for recovering a clay mineral from a raw clay ore, wherein the ultrafine sulfide mineral adhered to the clay mineral is treated with a substance acting as a reducing agent and a substance capable of forming a chelate compound. A high-purity method for purifying clay minerals, which comprises pre-treating the clay mineral and precipitating the clay mineral with a hydrophobic medium and a hydrophilic medium to separate the clay mineral from the ultrafine sulfide mineral.