KR101459587B1

KR101459587B1 - Grinding aids for micro-crushing mineral and grinding method using it

Info

Publication number: KR101459587B1
Application number: KR1020140038459A
Authority: KR
Inventors: 유동우; 이승헌; 주연순
Original assignee: 유동우; 군산대학교건설소재알앤디협동조합; 주연순
Priority date: 2014-04-01
Filing date: 2014-04-01
Publication date: 2014-11-10
Also published as: WO2015152522A1

Abstract

The present invention relates to a grinding aid for micro-crushing mineral including an aromatic compound containing a polyhydric hydroxyl group which is generated through reaction between a compound having a polyhydric hydroxyl group selected from a glycerin group or glycol group, and an aromatic acid, and a grinding method using the same. A grinding aid according to the present invention can reduce residue when mineral such as a cement raw material is used in a micro-crushing process and can adjust fineness of powder, thereby improving crushing efficiency.

Description

[0001] The present invention relates to a grinding aids for micro-crushing of minerals and a grinding method using the 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.

1. Korean Patent Registration No. 10-0222776 2. Korean Patent Registration No. 10-0650175 3. Korean Patent Publication No. 1991-0001930 4. Korean Patent Publication No. 1984-0000477 5. Korean Patent Registration No. 10-0912033 6. Korean Patent Registration No. 10-0893585 7. Korean Patent Registration No. 10-0990758 8. Korean Patent Registration No. 10-1057366 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, 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 polyhydroxy group-containing aromatic ester compound produced by the reaction of a compound having a polyhydric hydroxy group selected from glycerin or glycol, with an aromatic acid. The "polyhydric hydroxy group-containing aromatic ester compound" of the present invention includes a final compound produced by an esterification 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 polyhydroxy group-containing ester aromatic compound of the present invention include compounds represented by the following general formulas (1) to (6). In addition, intermediate compounds produced in the course of the reaction, other positions of the compound having a polyhydric hydroxy group, And the like can be included.

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.

< Manufacturing 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]

< Manufacturing 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]

< Manufacturing 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]

< Manufacturing 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.

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.

Crushing auxiliary
Addition amount
(Parts by weight) Degree of crushing 88 탆 residue
(%) 88 탆 residue
Decrease (%) 44 탆 residue
(%) 44 탆 residue
Decrease (%) Powder (㎠ / g) Powder figure
increase
10 minutes
smash 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
smash
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
smash
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 milling aid prepared by mixing diethylene glycol (DEG) and triethanolamine (TEA) at 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.

Crushing auxiliary
Addition amount
(Parts by weight) Degree of crushing 88 탆 residue
(%) 88 탆 residue
Decrease (%) 44 탆 residue
(%) 44 탆 residue
Decrease (%) Powder (㎠ / g) Powder figure
increase 10 minutes
smash 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
smash 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
smash 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 is higher in the case of using the pulverizing auxiliary than in 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

A pulverizing auxiliary for pulverization of minerals comprising a polyhydric hydroxy group-containing aromatic ester compound produced by an esterification reaction of glycerin and phthalic anhydride as an active ingredient.

delete

The method according to claim 1,
Wherein the glycerin is obtained as a by-product of biodiesel.

The method according to claim 1 or 4,
Wherein the polyhydroxy group-containing aromatic ester compound is any one of compounds represented by the following formulas (1) to (6).
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

delete

The method according to claim 1 or 4,
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 > 11. < / RTI >

The method according to claim 1 or 4,
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.

The method according to claim 1 or 4,
Wherein the mineral is a cement raw material.

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.

The mineral pulverization method according to claim 1 or 4, wherein the pulverization auxiliary is added to the mineral pulverization step.

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 4, wherein 0.001 to 1 part by weight of the crushing aid is added to 100 parts by weight of the raw material for cement in the mineral pulverization process or the clinker crushing process.