WO2015152522A1 - Grinding aid for finely grinding minerals and grinding method using same - Google Patents

Abstract

The present invention relates to a grinding aid for finely grinding minerals and a grinding method using the same, the grinding aid comprising: a compound having a polyvalent hydroxyl group selected from glycerin or glycol; and a polyvalent hydroxyl group-containing aromatic compound generated by a reaction of an aromatic acid. The grinding aid of the present invention reduces residue and controls fineness, thereby improving grinding efficiency when used in a fine grinding process of minerals such as a cement material.

Description

Grinding aid for fine grinding of minerals and grinding method using same

The present invention relates to a crushing aid for pulverizing minerals such as cement raw materials and a crushing method using the crushing aid.

Generally, the manufacturing process of cement includes finely pulverizing (raw material milling) a cement raw material such as limestone, silica, clay, iron ore, clay mineral, slag or a mixture thereof, pulverizing raw materials at 1,450 ° C Firing the limestone component in the raw material to form a clinker by combining with silica, alumina, iron component or the like; and mixing the crushed clinker with the gypsum to obtain cement as a final product.

In the mineral pulverization process, when the raw material of cement is crushed without pulverizing aid, there is a problem that static electricity is generated and not finely pulverized. Therefore, there is a need for pulverizing preparation capable of finely pulverizing raw materials while suppressing the generation of static electricity.

Korean Patent Publication No. 1991-0001930 discloses a method of finely pulverizing a mineral using a terephthalic acid sludge produced as a byproduct in the production of terephthalic acid as a crushing accelerator. However, the terephthalic acid sludge has a solid phase at room temperature When the temperature is raised, it becomes a liquid phase, and mixing with water is very difficult, so that it is troublesome to use.

Korean Patent Laid-Open Publication No. 1984-0000447 discloses a cement grinding aid containing a mixture of phthalic anhydride, alkanolamine, glycols, alcohols and the like. At this time, a compound synthesized from a phthalic anhydride and a carboxy group used as a polishing aid and an alkanolamine synthesized from an anhydrous phthalic acid exhibits an effect in a mineral pulverization process, but the cost of the raw material itself is high and the economical efficiency is low.

Korean Patent Registration No. 0650175 discloses a pulverizing auxiliary for pulverization of minerals to improve pulverization characteristics and hydration characteristics of minerals by mixing glycol or amine with a high-performance water reducing agent for concrete, Korean Patent Registration No. 10-0222776 discloses a pulverizing auxiliary for ethylene Discloses a method of pulverizing a mineral by adding a waste antifreeze composition comprising glycol or propylene glycol, a corrosion inhibitor, an antirust agent and a stabilizer, and water to a cement raw material. However, the crushing aid has excellent performance in crusher crushing, but it has a problem that when used in mineral pulverization of pre-calcination mixed minerals, the residue is large, the particle size is large, and the price is high.

British Patent No. 386,385 discloses an alkyd resin containing phthalic anhydride and glycerin. However, the alkyd resin is added to improve the viscosity of a composition by mixing the cement with other materials to prepare a cement composition It is not used as a milling aid.

Therefore, in the initial process of pulverizing minerals as raw materials of cement, it is required to crush minerals into minute sizes to reduce residues and control the degree of pulverization, thereby improving the production efficiency and economical grinding aid.

[Prior Art Literature]

[Patent Literature]

(Patent Document 1) 1. Korean Patent Registration No. 10-0222776

(Patent Document 2) 2. Korean Patent Registration No. 10-0650175

(Patent Document 3) 3. Korean Patent Publication No. 1991-0001930

(Patent Document 4) 4. Korean Patent Publication No. 1984-0000477

(Patent Document 5) 5. Korean Patent Registration No. 10-0912033

(Patent Document 6) 6. Korean Patent Registration No. 10-0893585

(Patent Document 7) 7. Korean Patent Registration No. 10-0990758

(Patent Document 8) 8. Korean Patent Registration No. 10-1057366

(Patent Document 9) 9. British Patent No. 386,385

In order to solve the above-mentioned problems, the present invention is to solve the above-mentioned problems, and it is an object of the present invention to provide a method for improving the fine grinding efficiency of minerals by preventing the re-agglomeration of minerals by adsorption and electric repulsive action to minerals, The use of a hydroxyl group-containing aromatic compound as a crushing aid in the crushing of raw materials for cement to reduce residues and control the degree of powdering, and to provide a crushing aid and a crushing method using the same which are excellent in production efficiency and economical efficiency due to excellent quality of produced clinker and cement The purpose is to provide.

In order to achieve the above object, the present invention provides a pulverizing auxiliary for pulverization of minerals comprising a polyhydroxy group-containing aromatic compound produced by the reaction of a compound having a polyhydric hydroxy group selected from glycerin or glycols with an aromatic acid, to provide.

The aromatic acid is preferably benzene or naphthalene having a phthalic anhydride, phthalic acid, isophthalic acid, adipic acid, benzoic acid, or acetic acid substituent.

It is preferable that the glycerin is at least one selected from glycerin, diglycerin, triglycerin, polyglycerin, phosphoglycerin, diphosphoglycerin and triphosphoglycerin.

The glycols are preferably at least one selected from the group consisting of propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, monoethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.

The pulverizing assistant of the present invention may further contain one or more additives selected from the group consisting of glycerin, diglycerin, triglycerin, polyglycerin, phosphoglycerin, diphosphoglycerin, triphosphoglycerin, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, Diethylene glycol, triethylene glycol, and polyethylene glycol.

The pulverizing assistant of the present invention may further comprise a hydroxyl group-containing alkanolamine.

The grinding aid of the present invention may further comprise at least one selected from anhydrous phthalic acid, phthalic acid, and a carboxyl group-containing organic compound.

The crushing aid of the present invention can be used particularly for pulverizing minerals as raw materials for cement, and is preferably used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the cement raw material.

The present invention also provides a method for pulverizing a mineral characterized in that the pulverizing additive of any one of claims 1 to 8 is added to the mineral pulverizing step and pulverized.

The present invention also provides a method for producing a cement comprising a mineral pulverizing step and a clinker pulverizing step, wherein the pulverizing agent according to any one of claims 1 to 8 is added to the mineral pulverizing step or the clinker pulverizing step to 100 weight% 0.001 to 1 part by weight based on 100 parts by weight of the cement.

The pulverization aid of the present invention has both hydrophilic and hydrophobic groups in the molecule and is highly compatible with water, and adsorption to the mineral and electrical repulsion can prevent the re-aggregation of the minerals, thereby enhancing the milling efficiency of the mineral. Therefore, when used in the mineral pulverization or crusher crushing process of the cement raw material, it is possible to produce excellent cement because the residue is reduced and the pulverization efficiency is improved by controlling the powder degree, and the economical efficiency and efficiency are excellent.

Fig. 1 shows limestone, iron ore, fly ash, desulfurized gypsum and silica as cement raw materials.

FIG. 2 is a graph showing the results of measurement of a powder and a 88 μm residue with respect to time when pulverizing aid of the present invention was added.

FIG. 3 is a graph showing the results of measurement of powder and 44 μm residue according to time when pulverizing additive of the present invention is added.

FIG. 4 is a graph comparing the results of measuring the powder and the 88 μm residue of the conventional grinding aid according to the present invention. FIG.

FIG. 5 is a graph comparing the results of measuring the powder and 44 μm residue of the pulverizing aid of the present invention and the conventional pulverizing auxiliary over time.

6 is a graph showing a result of measurement of the discharge amount in the ball mill.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a grinding aid comprising a polyhydric hydroxy group-containing aromatic compound produced by the reaction of a compound having a polyhydric hydroxy group selected from glycerol or glycol with an aromatic acid. The "polyhydric hydroxy group-containing aromatic compound" of the present invention includes the final compound produced by the reaction of an aromatic acid with a compound having a polyhydric hydroxy group and all the isomers produced in the course of the reaction.

As the aromatic acid, benzene or naphthalene having a phthalic anhydride, phthalic acid, isophthalic acid, adipic acid, benzoic acid, or acetic acid substituent is preferably used, and it is more preferable to use phthalic anhydride.

The polyhydric hydroxy group-containing compound may be at least one selected from the group consisting of glycerin and glycols. It is also possible to add alcohols, alkanolamines or carboxylic acids thereto as needed. As the glycerin, glycerin, diglycerin, triglycerin, polyglycerin, phosphoglycerin, diphosphoglycerin (DPG), triphosphoglycerin (TPG) and the like are preferably used. Examples of the glycols include propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, monoethyleneglycol (MEG), diethylene glycol (DEG), triethylene glycol (TEG), polyethylene glycol . Examples of the amine alcohols include monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), monoisopropanolamine (MIPA), diisopropanolamine (DIPA) and triisopropanolamine (TIPA). As the compound having a polyhydric hydroxy group, glycerin having a large number of hydroxy groups can be used particularly preferably. Glycerin can be used as a by-product such as glycerin from very cheap biodiesel because it is much cheaper and has better performance than other raw materials.

The compound having an aromatic acid and a polyhydric hydroxy group is preferably reacted in a molar ratio of 1: 1 to 2, but is not limited thereto.

Representative examples of the polyhydric hydroxy group-containing aromatic compound of the present invention include compounds represented by the following formulas (1) to (6). In addition, intermediate compounds produced in the reaction process, other positions of the compound having a polyhydric hydroxy group, Bonding compounds and the like can all be included.

Formula 1

(2)

(3)

Formula 4

Formula 5

6

Since the polyhydroxy group-containing aromatic compound of the present invention contains both a hydrophilic group and a hydrophobic group in the molecule, it is highly compatible with water as compared with a general aromatic acid and adsorbs to minerals and electrostatic repulsion simultaneously, . Therefore, it is possible to reduce the residues and appropriately adjust the powdery degree when using as a pulverizing aid in the pulverization step of the mineral or the pulverization step of the clinker, so that the cement having excellent quality can be produced.

The pulverization aid of the present invention can be used by mixing a conventional pulverizing aid, and when they are used in combination, the pulverization efficiency can be further improved. Examples of the material that can contribute to grinding efficiency and strength include, but are not limited to, glycerin, diglycerin, triglycerin, polyglycerin, phosphoglycerin, diphosphoglycerin, triphosphoglycerin, propylene glycol, dipropylene glycol, It is preferable to use a propylene glycol, polypropylene glycol, monoethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, hydroxyl group-containing alkanolamine, phthalic anhydride, phthalic acid and a carboxyl group-containing organic compound.

Minerals suitable for application of the grinding aid of the present invention include, but are not limited to, limestone, zircon, iron ore, clay mineral, slag, fly ash, or mixtures thereof.

The pulverizing aid of the present invention can be applied particularly to pulverization of minerals which are raw materials for cement. At this time, it is preferable to use 0.001 to 1 part by weight of the pulverization auxiliary of the present invention for 100 parts by weight of the cement raw material to be the pulverization raw material.

When the pulverizing aid of the present invention is used, the pulverization efficiency 5-25%.

[Example]

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples illustrate the present invention, and the scope of the present invention is not limited by the following examples.

≪ Preparation Example 1 &

Anhydrous phthalic acid (1.00 mol, 148.12 g) and glycerin (1.00 mol, 92.09 g) were dissolved in methylene chloride (500 mL), and a reflux condenser was installed. After 1 hour, the reaction was terminated and the solvent was removed by rotary evaporation to obtain the final product containing the target compound, 2 - {(2,3-dihydroxypropoxy) carbonyl} benzoic acid.

The reaction is shown in Scheme 1 below. In addition to the target compound shown in the reaction formula, the final product may include a substance that binds to the intermediate hydroxy group in glycerin, a substance that forms a cyclic compound with phthalic acid, and the like.

[Reaction Scheme 1]

≪ Preparation Example 2 &

Anhydrous phthalic acid (1.00 mol, 148.12 g) and glycerin (2.00 mol, 184.18 g) were dissolved in methylene chloride (500 mL), and a reflux condenser was placed. After 2 hours, the reaction was terminated and the solvent was removed by rotary evaporation to obtain the final product containing bis (2,3-dihydroxypropyl) phthalate as the target compound.

The reaction is as shown in the following reaction formula 2. In addition to the target compound shown in the reaction formula, the final product includes a substance which binds to the intermediate hydroxy group of glycerin, a substance to which the intermediate hydroxy group and the first hydroxy group are bonded when the two moe are reacted, A material that binds to the intermediate hydroxide, and the like.

[Reaction Scheme 2]

≪ Preparation Example 3 &

Anhydrous phthalic acid (1.00 mol, 148.12 g) and ethylene glycol (1.00 mol, 62.07 g) were dissolved in methylene chloride (500 ml) and refluxed, followed by stirring at a temperature of 30 캜. After one hour, the reaction was terminated and the solvent was removed by rotary evaporation to give the final product containing the desired compound, 2 - {(2-hydroxyethoxy) carbonyl} benzoic acid.

The reaction is as shown in Reaction Scheme 3, and the reaction mechanism is as shown in Reaction Scheme 4 below. In addition to the target compound shown in the reaction formula, the final product may include an intermediate compound produced in the course of the reaction, a compound obtained by reacting 2 moles of ethylene glycol with phthalic anhydride, and the like.

[Reaction Scheme 3]

[Reaction Scheme 4]

≪ Preparation Example 4 &

Anhydrous phthalic acid (1.00 mol, 148.12 g) and ethylene glycol (2.00 mol, 124.14 g) were dissolved in methylene chloride (500 mL), and a reflux condenser was placed. After 2 hours, the reaction was terminated and the solvent was removed by rotary evaporation to give the final product containing the desired bis (2-hydroxyethyl) phthalate.

The reaction is as shown in Reaction Scheme 5, and the final product may include an intermediate compound produced in the reaction process, a compound obtained by reacting 1 mole of ethylene glycol with phthalic anhydride, etc., in addition to the target compound shown in the reaction formula.

[Reaction Scheme 5]

≪ Example 1 >

The raw materials having the composition shown in Table 1 below were crushed to a size of 5 mm or less as cement raw materials. Photographs of the raw materials are shown in FIG.

Table 1

Limestone	ironstone	Fly ash	Desulfurization plaster	burr
89.6%	4.2%	2.1%	0.4%	3.7%

A ball mill having a diameter of 500 mm and a width of 300 mm was filled with 148 kg of steel balls and then 10 kg of the cement raw material was charged. Using the final product obtained in Preparation Example 1 as a crushing aid, 0.015 part by weight was added to 100 parts by weight of the cement raw material, and the ball mill was pulverized by rotating at a rotation speed of 42 rpm.

≪ Example 2 >

The procedure of Example 1 was repeated except that 0.020 parts by weight of the pulverizing auxiliary was added to 100 parts by weight of the cement raw material.

≪ Example 3 >

The procedure of Example 1 was repeated except that 0.025 part by weight of the pulverizing auxiliary was added to 100 parts by weight of the cement raw material.

<Experimental Example 1>

In order to confirm the milling effect of the milling aids obtained from the final products in Examples 1 to 3 according to the milling time, the milling time was varied to 10 minutes, 20 minutes and 30 minutes. As a control, the same method was used without adding grinding aid.

Powder (Blaine, cm2 / g), 88 占 퐉 residue (%) and 44 占 퐉 residue (%) indicating the degree of grinding of the powder were measured for the powder obtained after the pulverization. The results are shown in Table 2 and Figs. 2 and 3.

Table 2

		Addition amount (parts by weight)	Degree of crushing
			88 占 퐉 residue (%)	88 탆 residue reduction ratio (%)	44 탆 Residue (%)	44 탆 Residual Reduction (%)	Powder (㎠ / g)	Powder also increased
10 minutes crushing	Control		0	23.1		49.1		2,860
	Example 1	0.015	17.2	5.9	43.1	6.0	2,998	138
	Example 2	0.020	16.6	6.5	41.4	7.7	3,015	155
	Example 3	0.025	14.2	8.9	39.5	9.6	3,111	251
20 minutes crushing	Control		0	10.6		39.0		3,969
	Example 1	0.015	3.7	6.9	24.2	14.8	4,522	553
	Example 2	0.020	2.1	8.5	22.2	17.0	4.703	734
	Example 3	0.025	2.0	8.6	19.5	19.5	4,823	854
30 minutes crushing	Control		0	7.0		30.9		5,222
	Example 1	0.015	1.5	5.5	18.0	12.9	5,807	585
	Example 2	0.020	0.6	6.4	15.6	15.3	6,055	833
	Example 3	0.025	0.5	6.5	14.0	16.9	6,101	879

<Experimental Example 2>

The grinding aid of the present invention was compared with the conventional grinding aid.

As a comparative example, 0.020 parts by weight of a pulverizer prepared by mixing diethylene glycol (DEG) and triethanolamine (TEA) in a ratio of 1: 1 was added to 100 parts by weight of the ground material. The results compared with Example 2 using the same amount of pulverizing aid are shown in Table 3 and in FIGS. 4 and 5.

Table 3

		Addition amount (parts by weight)	Degree of crushing
			88 占 퐉 residue (%)	88 탆 residue reduction ratio (%)	44 탆 Residue (%)	44 탆 Residual Reduction (%)	Powder (㎠ / g)	Powder also increased
10 minutes crushing	Control		0	23.1		49.1		2,860
	Example 2	0.020	16.6	6.5	41.4	7.7	3,015	155
	Comparative Example	0.020	18.3	4.8	43.2	5.9	3,524	664
20 minutes crushing	Control		0	10.6		39.0		3,969
	Example 2	0.020	2.1	8.5	22.2	17.0	4,703	734
	Comparative Example	0.020	3.3	7.3	28.1	10.9	4,830	861
30 minutes crushing	Control		0	7.0		30.9		5,222
	Example 2	0.020	0.6	6.4	15.6	15.3	6,055	833
	Comparative Example	0.020	1.2	5.8	22.4	8.5	6,105	883

As can be seen from Table 3, the pulverization assistant of the present invention had a smaller amount of 88 탆 residue and 44 탆 residue than that of the conventional pulverizing assistant, and the powderiness was suitably increased.

<Experimental Example 3>

The above Examples 1 to 3 and Comparative Example were pulverized for 30 minutes, and the discharge amount in the ball mill was measured. The results are shown in FIG.

As can be seen from the graph of FIG. 6, the discharge amount of the pulverizing auxiliary is higher than that of the case of not using the pulverizing auxiliary. Thus, it can be seen that the milling aid exhibits an excellent coating preventing effect on the milling media.

Claims (12)

1. A process for pulverizing a mineral containing a polyhydroxy group-containing aromatic compound produced by the reaction of a compound having a polyhydric hydroxy group selected from glycerol or glycol with an aromatic acid.
2. The method according to claim 1,

   Wherein the aromatic acid is at least one selected from benzene and naphthalene having phthalic anhydride, phthalic acid, isophthalic acid, adipic acid, benzoic acid, acetic acid substituent, and the like.
3. The method according to claim 1,

   Wherein the glycerin is at least one selected from the group consisting of glycerin, diglycerin, triglycerin, polyglycerin, phosphoglycerin, diphosphoglycerin and triphosphoglycerin.
4. The method of claim 3,

   Wherein the glycerin is obtained as a by-product of biodiesel.
5. 5. The method of claim 4,

   Wherein the aromatic acid is phthalic anhydride.
6. The method according to claim 1,

   Wherein the glycols are at least one selected from the group consisting of propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, monoethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.
7. The method according to claim 1,

   The pulverizing aid may be at least one selected from the group consisting of glycerin, diglycerin, triglycerin, polyglycerin, phosphoglycerin, diphosphoglycerin, triphosphoglycerin, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, monoethylene glycol, diethylene glycol , Triethylene glycol, and polyethylene glycol. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
8. The method according to claim 1,

   Wherein the milling aid further comprises at least one member selected from the group consisting of hydroxyl group-containing alkanolamine, phthalic anhydride, phthalic acid and a carboxyl group-containing organic compound.
9. 10. The method according to any one of claims 1 to 9,

   Wherein the mineral is a cement raw material.
10. 10. The method of claim 9,

    Wherein the crushing aid is used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the cement raw material.
11. A method for pulverizing a mineral according to any one of claims 1 to 8, wherein the pulverizing auxiliary is added to the mineral pulverizing step.
12. A method for producing a cement comprising a mineral fine grinding step and a clinker grinding step,

    The method for producing cement according to any one of claims 1 to 8, wherein 0.001 to 1 part by weight of the crushing aid is added to 100 parts by weight of the cement raw material and pulverized in the mineral pulverization step or the clinker crushing step.

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