JPH02187155A - Grinding aid for inorganic mineral - Google Patents

Abstract

PURPOSE:To enhance purity and yield of a product in the grinding and classifying stages by preparing a grinding aid for inorganic mineral wherein one or more kinds of aluminum alkoxide, titanium alkoxide and zirconium alkoxide are blended. CONSTITUTION:Grinding and classifying aids for inorganic mineral are prepared by blending one or more kinds of aluminum alkoxide, titanium alkoxide and zirconium alkoxide preferably aluminic ester, titanic acid ester or zirconic acid ester. These aluminic ester, titanic acid ester and zirconic acid ester are preferably shown in a formula (R shows 3-11 C alkyl group, M shows Al, Ti and Zr atom, (n) shows integer not less than 1, (i) shows 1 or 2).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an auxiliary agent used in the process of pulverizing and classifying inorganic raw materials such as clay and talc.

(Conventional technology) Generally, clay raw materials produced in the form of soil are agglomerated particles.

It is difficult to purify by a dry process because it tends to cause adhesion phenomena and the water content has a strong influence on these phenomena, so it is mostly produced industrially by a wet process (water belly process).

(Problems to be Solved by the Invention) However, the water belly method not only makes it difficult to secure water, but also requires a large area and huge drying equipment. Various attempts have been made to convert to the dry process, but success has only been achieved for very limited ores and applications. This is because, in the conventional dry refining method, the quality of fine grain products is inferior to that produced by the water abdominal method, and it is difficult to maintain the operating efficiency of the crushing and classifying equipment.

An object of the present invention is to provide a crushing and classification aid for inorganic minerals that solves the problems of the prior art.

(Means for Solving the Problems) The present inventors have discovered a grinding aid that does not have an adverse effect on the final product of inorganic minerals, and by applying this to the dry refining process, they have solved the conventional problems at once, and the We have completed a practical dry refining method.

It is a crushing and classification aid for inorganic minerals.

The grinding aid of the present invention can be applied to the crushing and classification processes of clay, waxite, talcum, lime, kaolin, etc., to obtain purified products using a dry process with purity and yield comparable to conventional wet processes. This enables revolutionary process improvements.

(Preferred Embodiments and Effects) The titanium alkoxide or the zirconia alkoxide is preferably an aluminate ester, a titanate ester or a zirconia acid ester, respectively. Aluminate ester, titanate ester or zirconia ester has the general formula %) [wherein R is an alkyl group having 1 to 18 carbon atoms, 9M is A,
i: Ti or Zr atom, n is an integer of 1 or more.

i is 1 or 2] Those shown are more preferable.

In the general formula, R is an alkyl group having 1 to 18 carbon atoms, and the 3 to 4 alkyl groups may be the same or different alkyl groups. Generally, the more carbon atoms an alkyl group has, the less likely it is that hydrolysis will occur. This hydrolysis is affected by the acidity of the surface of the raw ore, so if an auxiliary agent with a small number of carbon atoms, such as tetraethyl titanate, is applied to acidic ore, the auxiliary agent will be consumed before pulverization has sufficiently progressed. Reagglomeration may occur and the classification effect may be reduced. Therefore, it is desirable to add an appropriate amount of auxiliary agent, but there is no real benefit even if it is added in excess, and it is usually
．． About 1 to 2% (by weight) is used. Of course, it is possible to reduce the amount by using a hard-to-decompose auxiliary agent with a large number of carbon atoms, but the grinding auxiliary agent itself ultimately reacts with water to produce alcohol, which is adsorbed onto the surface of the inorganic mineral. Affect properties. In this case, the smaller the number of carbon atoms, the smaller the effect, and even if it does, it creates a hydrophilic surface with a smooth feel, has good dispersibility in aqueous systems, and is as good as water-based products, so it is actually preferable. Auxiliaries with alkyl groups having 8 or more carbon atoms provide moist, slightly lipophilic surface properties.

From the point of view of pulverizing effect alone, alkyl groups having 4 to 12 carbon atoms are particularly preferred; however, in practice, these points should also be taken into account when selecting an appropriate auxiliary agent from among alkyl groups having 1 to 1 g of carbon atoms. This is desirable.

Although M is an A, j, Ti, or Zr atom, the effect of this difference in atoms is not so great. i is defined by the valence of M, and when A is 1. For other atoms, it is 2. n is usually 1, and although a monomer is used, there is no significant difference in the effect even if a part or most of the dipolymer is mixed.

Specific examples of the grinding aid of the present invention include tetraisopropyl titanate, diethyl caprylaluminate, tripropyl aluminate, and tetrahexyl zirconate. Although organochlorotitanium compounds and organochloroalumine compounds were also found to be effective as crushing and classification aids, they are not suitable because they produce hydrogen chloride as a by-product.

The grinding aid of the present invention also exhibits an effect as a classification aid. When no auxiliary agent is added, the pulverized product often clogs the coarse particle removal holes of the classifier, and the 2-hour pulverized product is almost impossible to classify when actually purchased. On the other hand, when 0.5% of tetraisopropyl titanate is added, the pulverized material for 3 hours or more can be classified without any problem. Furthermore, analysis of the components of fine grains reveals that quartz properties are well separated in the case of additive addition, and clay properties are purified and concentrated to a greater extent than in the original mineral.

For example, in an example where raw ore with SiO/A 203 is 8.107 is crushed for 2 hours and classified as 0, if no additives are added, SiO/A
, e 20 a is 4.589, but when 0.5% of tetraisopropyl titanate is added, it is about 3.8.

Inorganic minerals that are crushed and classified using this auxiliary agent include waxite, talc, lime, kaolin, and feldspar.

Suitable for natural or synthetic inorganic minerals such as pottery stone, wollastonite, bentonite, sericite, zeolite, chlorite, magnesite, dolomite, mullite, gypsum, clay shale, bauxite, asbestos, cement clinker, etc. It can also be applied to other inorganic minerals.

The grinding aid of the present invention is generally added in its entirety at the beginning of the mineral grinding process, but it can also be added in two stages midway through, or added to the process after grinding with the main purpose of 1-class classification or surface treatment. .

Note that the grinding aid of the present invention can be synthesized by several methods. For example, it can be obtained by reacting alcohol with chloride.

The present invention can be used for pulverizing and classifying various inorganic raw materials, and the refined products can be used for rubber, synthetic resin photonics, ceramic raw materials, pharmaceuticals, cosmetics, a-medicines, detergents, paper manufacturing, paints, feedstuffs, and various other industrial products. It is industrially useful and can meet the requirements as a raw material.

Examples are shown below.

(Example) As a sample, waxite from Bonten Mine, Nagano Prefecture is used. The main components are pyrophyllite, quartz, and hematite.

Contains a small amount of Diasboa etc.

Grinding was done using a porcelain ball mill (7.3kg, 3kg of crushed material.

Porcelain ball 3kg (average radius 14.1am, 112
) The test was carried out under the conditions of rotation speeds of 58 r, p, m. 1 mm
After passing through a sieve, it was classified using a free-vortex centrifugal wind classifier. Tetraisopropyl titanate, tetrabutyl zirconate, and tributyl aluminate were used as auxiliary agents in an amount of 0.5% (weight) of the raw mineral.

Observing the state after 2 hours of grinding, in the example without additives, the entire amount adhered to the mill, and the specific surface area was 12000 cJ/sr.
Auxiliary agent addition example (t if tL b 10000~17
000cj/g. When the grinding was further extended to 5 hours, the specific surface area remained unchanged in the case of the additive-free example, but the specific surface area increased to 18,000 to 19,000 cJ/g in the case of the auxiliary agent of the present invention. Tetraisopropyl titanate 0.5%
Then, the effective time of the auxiliary agent is 8 hours, 1% is 12 hours, 2
% was 23 hours.

The yield of the purified product was 21% in the case of no addition and 38 to 43% in the case of addition in 3 hours. Further, in the case of the additive-free example, it was already impossible to classify the product after 2 hours of pulverization, but in the additive-free example, it could be classified without any trouble for more than 4 hours.

In this way, each of the grinding aids showed the effect of improving the efficiency of the nine-class grinding of raw ore.

Applicant: Katsukoyama Mining Co., Ltd. (1 other person) Agent: Patent attorney Tomomichi Kato (1 other person) Procedures issued by Hosei W. September 7, 1999 Kutoku 3'1 Office Commissioner Yoshi 1) Bunki Tono 1 Indication of Heisaku Patent Application No. 70890 of 1989 (filed on March 26, 1988) 2 Name of invention Grinding aid for inorganic minerals 3 Relationship with the case of arresting and correcting persons Special:! “Applicant name: Katsumitsuyama Mining Co., Ltd. (1 other person) 4
Agent Address: 4!1-12-8 Nishijin, Minato-ku, Tokyo 105
No. Nishi-Shinbashi Naka Building 51, 1999 June 7, 6 ↑Replenish the target of 111 positive.

1. Title of the invention: Grinding aid for inorganic minerals 2. Claims: (i) A grinding and classification aid for inorganic minerals containing one or more of aluminum alkoxide, titanium alkoxide, and zirconium alkoxide.

(2) The crushing and classification aid for inorganic minerals according to claim 1, wherein the aluminum alkoxide, titanium alkoxide, or zirconium alkoxide is an aluminate ester, a titanate ester, or a zirconate ester, respectively.

3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an auxiliary agent used in the process of pulverizing and classifying inorganic raw materials such as clay and talc.

(Conventional technology) Clay raw materials that are generally produced in the form of beads are agglomerated particles.

It is difficult to purify by a dry process because it tends to cause adhesion phenomena and the presence of water has a strong influence on these phenomena, so it is mostly produced industrially by a wet process (aqueous layer process).

(Problems to be Solved by the Invention) However, the aqueous layer method not only makes it difficult to secure water, but also requires a large area of land and huge drying equipment. Various attempts have been made to convert to the dry process, but success has only been achieved for very limited ores and applications. This is because, in the conventional dry refining method, the quality of fine grain products is inferior to that produced by the water abdominal method, and it is difficult to maintain the operating efficiency of the crushing and classifying equipment.

An object of the present invention is to provide a crushing and classification aid for inorganic minerals that solves the problems of the prior art.

(Means for Solving the Problems) The present inventors have discovered a grinding aid that does not adversely affect the final product of inorganic minerals, and by applying this to the dry refining process, they have solved the conventional problems at once. We have completed an industrially practical dry purification method.

Namely, one aspect of the present invention is aluminum alkoxide.

This is a crushing and classification aid for inorganic minerals containing one or more of titanium alkoxide and zirconium alkoxy.

The crushing aid of the present invention can be applied to the crushing and classification processes for clay, waxite, talc, limestone, kaolin, etc., and can be used to obtain purified products using a dry process with purity and yield comparable to conventional wet processes. This enables revolutionary process improvements.

(Preferred Embodiments and Effects) The grinding aid of the present invention contains one or more of aluminum alkoxide, titanium alkoxide, and zirconium alkoxide. Each of the aluminum alkoxide, titanium alkoxide, and zirconium alkoxide is an aluminate ester.

Preferably, it is a titanate ester or a zirconate ester. Aluminate ester, titanate ester or zirconate ester has the general formula % formula % [wherein R is an alkyl group having 3 to 18 carbon atoms 1M is A
, f:, Ti or Zr atom 2 n is an integer of 1 or more, i is 1 or 2] is more preferable.

In the general formula, R is an alkyl group having 3 to 18 carbon atoms, and the 3 to 4 alkyl groups may be the same or different alkyl groups.

Generally, the more carbon atoms an alkyl group has, the less likely it is that hydrolysis will occur. Because the hydrolysis rate of auxiliary agents with a small number of carbon atoms such as tetraisopropyl titanate is fast, the auxiliary agents may be decomposed and consumed before pulverization has sufficiently progressed, resulting in reagglomeration and a reduction in the classification effect. . R
It is desirable that the amount of the auxiliary agent having 3 or more carbon atoms is always appropriate to the total surface area of the pulverized material. Usually, about 0.1 to 2% (by weight) of the raw ore is used. When an auxiliary agent with a small carbon number is used, the pulverized product has a smooth feel and has good dispersibility in an aqueous system, and is as good as a water-based product, and is even more suitable. When an auxiliary agent having an alkyl group having 8 or more carbon atoms is used, the pulverized product has a moist and slightly lipophilic surface property and does not generate dust. From the point of view of pulverizing effect, alkyl groups having 4 to 12 carbon atoms are particularly preferable, but in practice, taking these points into account, suitable auxiliaries may be selected from among alkyl groups having 3 to 18 carbon atoms. It is desirable to select.

M is AJ, Ti, or 2 atoms, but the effect of this difference in atoms is not so large. i is defined by the valence of M, and is 1 for A1 and 2 for other atoms. .

n is usually 1, and a monomer is used, but there is no big difference in the effect even if a part or most of the monomer is mixed.

Specific examples of the grinding aid of the present invention include tetra-n-butyl titanate, diethyl caprylaluminate, and tetrahexyl zirconate. Although organochlortitanium compounds and organochloraluminum compounds were also found to be effective as 9-classification aids for grinding, they are not suitable because they produce hydrogen chloride as a by-product.

Similar to the action of the alkyl silicate in Patent Application No. 148,007 of 1972, the grinding aid of the present invention is also characterized by its remarkable effect as a dispersant in dry classification.

When no auxiliary agent is added, the pulverized material often clogs the coarse particle scraping holes of the classifier, and the pulverized material for a long period of time is virtually unclassifiable. On the other hand, when about 1% of tetra-n-butyl titanate is added, the pulverized material can be classified without agglomeration for about 3 hours or more, and as 9 hours pass during that period, the pulverization progresses.

Inorganic minerals that can be crushed and classified using this auxiliary agent include waxite, talcum, limestone, kaolin, feldspar, pottery stone, wollastonite, bentonite, and sericite.

It is suitable for natural or synthetic inorganic minerals such as zeolite, chlorite, magnesite, dolomite, mullite, gypsum, clay shale, bauxite, asbestos, alumina, etc., but can also be applied to other inorganic minerals.

The grinding aid of the present invention is generally added in its entirety at the beginning of the mineral grinding process, but it may also be added in two or more stages midway through the grinding process.
It can also be added to processes after pulverization for the main purpose of classification and surface treatment.

Note that the grinding aid of the present invention can be synthesized by several methods. For example, it can be obtained by reacting alcohol with chloride.

The present invention can be used to crush and classify various inorganic raw materials, and the refined products can be used as raw materials for rubber, synthetic resin brighteners, ceramic raw materials, pharmaceuticals, cosmetics, detergents, paper manufacturing, paints, and various other industrial products. It is an industrially useful product that can meet the requirements of

Examples are shown below.

(Example) Example 1 Rouseite from Katsumitsuyama, Hiroshima Prefecture is used as a sample. The main components are pyrophyllite and quartz, with small amounts of kaolinite and diaspores.

A starting sample was obtained by pre-pulverizing 60 g of 16 to 32 mesh waxite for 30 minutes (step 1), and 5 g of it was taken for one use. The pulverization was carried out using an agate planetary ball mill (500+oJ') manufactured by Fritsch Japan under the conditions of using 15 balls each having a diameter of 15 mm (the same applies hereinafter). To the remaining starting sample, 0.3 g of auxiliary agent was added and ground for 30 minutes (step 2), further ground for 30 minutes (step 3), and further ground for 15 minutes (step 4). In addition, after completing steps 2, 3, and 4, 5 samples each were prepared.
gram of each sample was collected.

Furthermore, after that, 0.2g of auxiliary agent (approximately 0.5% by weight based on the raw mineral) was added and crushed for 30 minutes in step 5), and 5g was taken as a sample and crushed for another 30 minutes in step 6).
, 5f was taken as a sample. Then, the mixture was further ground for 15 minutes (Step 7). When observed after the final 15 minute grinding step 7, some agglomeration was observed.

As an auxiliary agent, tetra n-butyl titanate (product name "Alcofine Tl-40" manufactured by Yoken Fine Chemicals) is used.
J) was used.

Comparative Example 1 Under the same conditions as in Example 1, but without adding any auxiliary agent,
Grinding was performed and samples were taken at the same elapsed time intervals as in Example 1. After the completion of the crushing step 6, the beginning of agglomeration was observed.

BET Specific Surface Area Measurement Results The BET specific surface areas of the samples obtained in Example 1 and Comparative Example 1 (samples after Step 4 and Step 6) were measured by the nitrogen adsorption method (BET method). The results are shown in Table 1.

Table 1 Particle Size Distribution Measurement Results The results of measuring the particle size distribution of each sample obtained in Example 1 and Comparative Example 1 were as shown in Figure 1.2. From FIG. 1, it can be seen that the content of particles of 1 μm or less increases with the grinding time when an auxiliary agent is added, but it does not increase much until 200 hours when no auxiliary agent is used. Furthermore, as shown in FIG. 2, the average particle diameter decreases with time when an auxiliary agent is added, but in the case without an auxiliary agent, the average particle size decreases only slightly even after 200 hours of treatment.

Observation of particles using an electron microscope After step 5 of Example 1 (after pulverization for a total of 135 minutes)
Figure 3 shows an enlarged photograph of the particles after step 6 (total 1
An enlarged photograph of the particles after pulverization for 65 minutes is shown in FIG.

Note that the magnification of each image is 10,000 times. 3rd to 4th
According to the figure, fine particles of 1 μm or less can be identified in isolation. This indicates that they can be easily separated from large particles or from each other and can be classified into two.

After step 5 of Comparative Example 2 (after pulverization for a total of 135 minutes)
Figure 5 shows an enlarged photograph of the particles after step 6 (total 1
An enlarged photograph of the particles (after pulverization for 65 minutes) is shown in FIG.

Note that the magnification of each image is 10,000 times. 5th to 6th
According to the figure, it can be seen that many fine particles are in an agglomerated state and it is difficult to classify them in one.

Example 2 Tetra n-butyl titanate Ti (0.
The fused alumina was ground using a vibrating mill using Bu)4. Details of the fused alumina as the starting powder and the conditions of the vibratory mill are shown below.

The starting powder is fused alumina (Showa Denko WA [100)
40μm or less 10% Average particle size 13.05μm 5096-721.75μ Low 90%” 34.89μm (Microtrack measurement) Vibration mill: Bot 2 (Volume ball 20 muφ Alumina 12kg
Starting powder 700g An auxiliary agent was added to 700g of the starting powder at a rate of 1 wt %, and the mixture was ground for 64 hours. Add 0.1w of auxiliary agent to this pulverized material.
It is further added at a ratio of t% and pulverized.

Milling was carried out until the total milling time from the starting powder was 180 hours. An auxiliary agent was further added to this pulverized product at a ratio of 0.2 vt %, and pulverization was performed until the total time of pulverization from the starting powder reached 320 hours.

The total grinding time is 40. G4.80. L[i
Table 2 shows the average particle diameters at o and 320 hours.

Comparative Example 2 Grinding was carried out in the same manner as in Example 2 except that no auxiliary agent was used.

The total grinding time is 40.84.80. The average particle size at 160 and 320 hours is shown in Table 2.

According to Table 2, it can be seen that the fused alumina could be pulverized satisfactorily and efficiently using the pulverizing aid.

Table 2

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the content of 1- or less at each processing time when a grinding aid was used (Example 1) and when it was not used (Comparative Example 1). FIG. 2 is a diagram showing the change in average particle diameter at each treatment time when a grinding aid was used (Example 1) and when it was not used (Comparative Example 1). FIGS. 3 and 4 are photographs showing the structure of particles obtained by grinding using an example of the grinding aid of the present invention. FIGS. 5 and 6 are photographs showing the structure of particles obtained by grinding without using a grinding aid. Applicant: Katsukoyama Mining Co., Ltd. (1 other person) Agent: Patent attorney Asa Kato Procedural amendment to Hokkaido No. 3 Japanese Map (voluntary) September 7, 1999

Claims (2)

[Claims] (1) A crushing and classification aid for inorganic minerals containing one or more of aluminum alkoxide, titanium alkoxide, and zirconia alkoxide. (2) The crushing and classification aid for inorganic minerals according to claim 1, wherein the aluminum alkoxide, titanium alkoxide, or zirconia alkoxide is an aluminate ester, a titanate ester, or a zirconia acid ester, respectively.