KR20180058170A - Composition of grinding aids for micro-crushing mineral and micro-crushing method of mineral using it - Google Patents

Abstract

The present invention relates to a composition for grinding aids for micro-crushing minerals including a water-soluble aluminate compound; and to a micro-crushing method of minerals using the same. The composition for grinding aids for micro-crushing minerals not only has high crushing efficiency but also is stable in heat based on inorganic materials, and is about 1/2 cheaper than conventional organic-based grinding aids such as DEG, TIPA, and the like. The composition is very economical by having similar grinding efficiency even when less than half the amount is used based on the solid content.

Description

TECHNICAL FIELD The present invention relates to a grinding aid composition for fine grinding of minerals and a method for grinding minerals using the same,

More particularly, the present invention relates to a grinding aid composition for mineral pulverization which can increase the grinding efficiency of minerals by using an aluminate compound as a water-soluble inorganic compound.

In the process of pulverizing minerals such as limestone, cement, slag, coal and the like, a crushing aid is used to finely grind raw materials while suppressing the generation of static electricity and to improve crushing productivity.

In this regard, Korean Patent Publication No. 1991-0001930 discloses a method for pulverizing minerals using a terephthalic acid sludge produced as a by-product in the preparation of terephthalic acid as a crushing accelerator. However, terephthalic acid sludge has excellent performance in clinker milling, but it is expensive when used in mineral pulverization of pre-fired mixed minerals.

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.

DEG (Diethylene glycol, diethylene glycol) and TIPA (triisopropanol amine, triisopropanolamine), which are most commonly used as pulverizing additives, are excellent in terms of performance, but because they are organic substances, There is a problem that it can be deformed when the frictional heat is increased, so there is a burden to control the frictional heat so that the frictional heat does not rise above a certain level at the time of grinding, and there is a problem that the cost is also increased and the production cost is increased.

Conventionally, water-soluble inorganic compounds have been used only as a chemical admixture for concrete and the like. In particular, aluminate compounds have been used as quick-setting admixtures for concrete admixtures. Quick-setting is a compound (substance) used to accelerate the setting of cement for the purpose of increasing initial strength.

Korean Patent Registration No. 10-0222776 Korean Patent Registration No. 10-0650175 Korean Patent Publication No. 1991-0001930 Korean Patent Publication No. 1984-0000477 Korean Patent Registration No. 10-0912033 Korean Patent Registration No. 10-0893585 Korean Patent Registration No. 10-0990758 Korean Patent Registration No. 10-1057366 British Patent No. 386,385

The present invention is applicable to grinding aids for pulverization of minerals such as limestone, coal, slag, fly ash, clinker, silica sand, and montmorillonite-based minerals, which are water-soluble inorganic compounds that have been used only as concrete admixtures for concrete, The present invention provides a grinding aid composition for fine grinding of minerals which is low in cost and relatively low in use amount compared with a grinding aid based on an organic material and is excellent in terms of grinding efficiency and productivity, .

It is another object of the present invention to provide a pulverizing auxiliary composition for fine pulverization which can further improve pulverization efficiency by using a water-soluble inorganic compound and an organic compound in combination.

In order to achieve the above object, in the present invention,

There is provided a pulverizing auxiliary composition for fine pulverization for mineral pulverization comprising a water-soluble aluminate compound in an aqueous solution state produced by reacting aluminum hydroxide with an alkaline hydroxide and having a solid content of 20 to 45% as an active ingredient.

In the above composition, the alkaline hydroxide is preferably sodium hydroxide or potassium hydroxide.

In the composition, the water-soluble aluminate compound is preferably sodium aluminate obtained by reacting 20 parts by weight of aluminum hydroxide and 10 to 22 parts by weight of sodium hydroxide in 58 to 70 parts by weight of water.

In the composition, the water-soluble aluminate compound is preferably potassium aluminate obtained by reacting 20 parts by weight of aluminum hydroxide and 14 to 31 parts by weight of potassium hydroxide in 49 to 66 parts by weight of water.

The composition may further comprise at least one organic compound selected from GMP (2 - [(2,3-dihydroxypropoxy) carbonyl] benzoic acid, sodium gluconate, glycerin, glycols and amines.

In the composition, it is preferable that the glycerin includes glycerin, diglycerin, triglycerin, polyglycerin, phosphoglycerin, diphosphoglycerin and triphosphoglycerin.

In the composition, it is preferable that the glycols include propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, monoethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol.

In the above composition, the amines include monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N, N-bis (2-hydroxypropyl) -2-propanol and N-methyldiethanolamine.

In the above composition, the organic compound is preferably used in an amount of 20 to 80 parts by weight based on 50 parts by weight of the water-soluble aluminate compound.

Further, the present invention provides a method for pulverizing a mineral, wherein 0.001 to 3 parts by weight of the pulverizing auxiliary composition for fine pulverization for mining is added to 100 parts by weight of the pulverized material.

In the above method, the mineral is preferably limestone, coal, slag, fly ash, clinker, silica or montmorillonite-based mineral.

The present invention also provides a concrete product ground and produced by using the above-described crushing auxiliary composition for mineral pulverization.

The grinding aid composition for fine grinding the mineral using the aluminate compound of the present invention has a high grinding efficiency when applied to a pulverizing effect with a small use amount and a pulverizing effect when applied to a milling process of limestone, coal, slag, fly ash, clinker, silica, montmorillonite- The productivity of crushing can be increased. Further, the pulverizing and grinding aid composition for mineral pulverization according to the present invention is heat-stable based on an inorganic substance and is about 1/2 cheaper than an organic material-based grinding aid such as DEG and TIPA conventionally used, Which is less than about 1/2, and has a similar crushing efficiency, which is very economical. Further, by using the aluminate compound according to the present invention in combination with an organic compound, the milling efficiency of the mineral can be further improved.

The pulverizing and grinding aid composition for mineral pulverization according to the present invention is an active ingredient for improving the pulverization efficiency, which is produced by reacting aluminum hydroxide [Al (OH) ₃ ] with an alkaline hydroxide, and has a solid content of 20 to 45% Soluble aluminate-based compounds.

The water-soluble aluminate-based compound is preferably an aqueous solution having a solids content of 30 to 45%, more preferably a 40% aqueous solution.

The alkaline hydroxide is preferably sodium hydroxide (NaOH) or potassium hydroxide (KOH). Accordingly, the water-soluble aluminate-based compound is preferably sodium aluminate or potassium aluminate. The sodium aluminate is particularly preferably sodium aluminate obtained by reacting 20 parts by weight of aluminum hydroxide and 10 to 22 parts by weight of sodium hydroxide in 58 to 70 parts by weight of water. The potassium aluminate is particularly preferably potassium aluminate obtained by reacting 20 parts by weight of aluminum hydroxide and 14 to 31 parts by weight of potassium hydroxide in 49 to 66 parts by weight of water.

The pulverizing auxiliary composition for fine pulverization of the present invention may contain an organic compound in addition to the water-soluble aluminate-based compound. At this time, the organic compound is preferably at least one selected from GMP (2 - [(2,3-dihydroxypropoxy) carbonyl] benzoic acid, SG (sodium gluconate), glycerin, glycols and amines.

GMP is a compound produced by the reaction of phthalic anhydride with glycerin.

The glycerin family includes glycerin, diglycerin, triglycerin, polyglycerin, phosphoglycerin, diphosphoglycerin and triphosphoglycerin.

The glycols include propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, monoethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol.

The amines include monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N, N-bis (2-hydroxypropyl) ethanolamine, N, And N-methyldiethanolamine.

The organic compound is preferably used in a proportion of 20 to 80 parts by weight based on 50 parts by weight of the water-soluble aluminate compound in the aqueous solution state.

The crushing aid composition for mineral pulverization of the present invention is used as a crushing aid in the pulverization process of minerals.

In the mineral pulverization method of the present invention, 0.001 to 3 parts by weight of the pulverizing auxiliary composition for fine pulverization of mineral is added to 100 parts by weight of the mineral to pulverize the mineral. More preferably 0.01 to 0.03 parts by weight based on 100 parts by weight of the mineral.

The crushing aid composition for fine grinding of the present invention is preferably used for limestone, coal, slag, fly ash, clinker, silica sand and Montmorillonite-based minerals.

The slag includes blast furnace slag, steel making slag, converter slag and electric furnace slag. The fly ash includes fly ash and bottom ash. Such sandstorms include natural sand dunes such as coastal sand dune, sand dune sand, and synthetic sand dune. The montmorillonite-based mineral includes Na-bentonite and Ca-bentonite.

Further, the present invention provides a concrete product ground and produced by using the crushing aid composition for mineral pulverization of the present invention. The concrete product includes a brick, a block, a tile, a sewer pipe, a boundary stone, a concrete file, a prestressed concrete pile, a concrete panel, a concrete pipe, a manhole, a foam concrete, a concrete structure and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. The following examples illustrate the invention and are not to be construed as limiting the scope of the invention.

< Example  1>

Sodium aluminate  Produce

20 g of aluminum hydroxide and 22 g of sodium hydroxide were added to 58 g of water and mixed and heated to 80 to 100 캜 with stirring to conduct the reaction. When the reaction solution became almost transparent, the reaction was terminated to obtain a 42% aqueous solution of sodium aluminate (NaAlu).

< Example  2>

Preparation of sodium aluminate

Water was added to a 42% aqueous solution of sodium aluminate (NaAlu) prepared in Example 1 to dilute it to obtain a 30% aqueous solution.

< Example  3>

Of potassium aluminate  Produce

20 g of aluminum hydroxide and 31 g of potassium hydroxide were mixed in 49 g of water and heated to 80 to 100 캜 while stirring to conduct the reaction. When the reaction solution became almost transparent, the reaction was terminated to obtain a 51% aqueous solution of potassium aluminate (KAlu). Subsequently, water was added and diluted to obtain a 40% aqueous solution.

< Example  4>

Preparation of potassium aluminate

Water was added to the 51% aqueous solution of potassium aluminate (KAlu) prepared in Example 3 to dilute it to obtain a 30% aqueous solution.

< Experimental Example  1>

The milling efficiency of the milling auxiliary composition for fine grinding of the present invention was tested as follows.

As the pulverizing auxiliary of the present invention, aqueous solutions of sodium aluminate (NaAlu) and potassium aluminate (KAlu) obtained in Examples 1 to 4 were used.

As a comparative example, DEG and TIPA, which are conventionally used milling additives, were used.

Sodium aluminate and aluminum potassium of the present invention and DEG and TIPA as comparative examples were used as a crushing aid, and the minerals to be crushed were crushed using a clinker. Crushing conditions and results are shown in Table 1 below.

Crushing auxiliary Solid content (%) Amount used (parts by weight) Grinding time (min) Powder (Blain) Emissions (kg) TIPA 99 0.020 51 3,380 18.0 DEG 99 0.020 49 3,446 18.4 NaAlu (Example 1) 42 0.020 46 3,418 18.0 NaAlu (Example 1) 42 0.025 45 3,427 18.2 NaAlu (Example 2) 30 0.020 50 3,408 18.0 KAlu (Example 3) 40 0.020 46 3,431 18.2 KAlu (Example 3) 40 0.025 44 3,447 18.1 KAlu (Example 4) 30 0.020 49 3,410 18.1 The amount used is based on 100 parts by weight of the minerals to be ground.

As shown in the results of Table 1 above, the overall grinding time and pulverization efficiency of the aluminate compound of the present invention is similar to that of DEG and TIPA. However, when comparing the amount of the solid used as a reference, it can be seen that the grinding aid of the present invention has a much smaller amount of solid content of 30 to 42% than DEG and TIPA having a solid content of 99%.

When the amount of the aluminate compound used is increased by 0.005 parts by weight, the grinding time is about 3 minutes faster than that of DEG, and the grinding efficiency is also increased.

< Experimental Example  2>

The milling efficiency of the milling auxiliary composition for fine grinding of the present invention was tested as follows.

DEG, GMP and SG, which are used as typical grinding aids for comparison, were used.

As the pulverizing aid of the present invention, a mixture (NaAlu / SG) in which sodium aluminate (NaAlu) and GMP were mixed in a weight ratio of 1: 1 of Example 1 and SG alumina (NaAlu) : 1 (NaAlu / SG) was used.

The grinding aids of the present invention, NaAlu / GMP and NaAlu / SG, and DEG, GMP and SG as grinding aids for comparison were used as grinding aids. The minerals to be grinded were pulverized using a clinker. The grinding conditions and results are shown in Table 2 below.

Crushing auxiliary ratio(%) Amount used (parts by weight) Grinding time (min) Powder (Blain) Emissions (kg) DEG 100 0.020 49 3,446 18.4 GMP 100 0.020 53 3,079 17.3 SG 100 0.020 54 2,985 16.9 NaAlu / GMP 50/50 0.020 50 3,308 17.9 NaAlu / SG 50/50 0.020 50 3,289 18.0 The amount used is based on 100 parts by weight of the minerals to be ground.

As shown in the above Table 2, when GMP and SG were used alone, grinding time was 4 minutes and 5 minutes longer than DEG, respectively, and grinding efficiency was lower than that of DEG. On the other hand, it can be seen that the NaAlu / GMP and NaAlu / SG of the present invention shorten the milling time by 3 minutes and 4 minutes, respectively, and the milling efficiency is significantly improved.

< Experimental Example  3>

In order to confirm the effect of the crushing aid composition for mineral pulverization of the present invention on the amine compound, an amine compound, which is a typical crushing aid, was tested.

N, N-bis (2-hydroxypropyl) ethanolamine, "A1" as the milling aid for comparison, DEG, N-methyl diethanolamine (hereinafter referred to as 'A3') and N-methyl diethanolamine (hereinafter referred to as 'N-methyl diethanolamine' ] Were used.

As the pulverizing aid of the present invention, an aqueous solution of sodium aluminate (NaAlu) prepared in Example 1 and A1, A2 and A3 were mixed at a weight ratio of 1: 1, respectively.

A mixture (NaAlu / Al) of sodium aluminate as a pulverizing aid of the present invention (NaAlu / A1), a mixture (NaAlu / A2) of sodium aluminate and a mixture of sodium aluminate and A3 (NaAlu / A3) DEG, A1, A2 and A3 were used as the milling aid, and the minerals to be milled were pulverized using a clinker. The grinding conditions and results are shown in Table 3 below.

Crushing auxiliary ratio(%) Amount used (parts by weight) Grinding time (min) Powder (Blain) Emissions (kg) DEG 100 0.020 42 3,432 18.4 A1 100 0.020 41 3,547 18.9 A2 100 0.020 40 3,508 18.4 A3 100 0.020 40 3,592 18.9 NaAlu / A1 50/50 0.020 39 3,412 18.4 NaAlu / A2 50/50 0.020 40 3,425 18.4 NaAlu / A3 50/50 0.020 38 3,429 18.4 The amount used is based on 100 parts by weight of the minerals to be ground.

As shown in the results of Table 3 above, A1, A2, and A3 alone exhibited excellent grinding efficiency compared to DEG, but they were mixed with sodium aluminate (NaAlu) to replace 50% Respectively.

The sodium aluminate used in the present invention is economical because the raw material cost or the production cost is much lower than that of the amine compound, and the milling time is shortened, so that the productivity is improved.

Claims (13)

Wherein the water-soluble aluminate-based compound is produced by reacting aluminum hydroxide with an alkaline hydroxide and having a solid content of 20 to 45% as an active ingredient. The method according to claim 1,
Wherein the alkaline hydroxide is sodium hydroxide or potassium hydroxide. The method according to claim 1,
Wherein the water-soluble aluminate compound is composed mainly of sodium aluminate obtained by reacting 20 parts by weight of aluminum hydroxide and 10 to 22 parts by weight of sodium hydroxide in 58 to 70 parts by weight of water. The method according to claim 1,
Wherein the water-soluble aluminate-based compound comprises potassium aluminate as a main component, which is obtained by reacting 20 parts by weight of aluminum hydroxide and 14 to 31 parts by weight of potassium hydroxide in 49 to 66 parts by weight of water. The method according to claim 1,
Wherein the composition further comprises at least one organic compound selected from GMP (2 - [(2,3-dihydroxypropoxy) carbonyl] benzoic acid, sodium gluconate, glycerin, glycols and amines A fine grinding aid composition for pulverization. 6. The method of claim 5,
Wherein the GMP is a compound produced by reacting phthalic anhydride with glycerin. 6. The method of claim 5,
Wherein the glycerin family comprises glycerin, diglycerin, triglycerin, polyglycerin, phosphoglycerin, diphosphoglycerin and triphosphoglycerin. 6. The method of claim 5,
Wherein the glycols include propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, monoethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol. 6. The method of claim 5,
The amines include monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N, N-bis (2-hydroxypropyl) ethanolamine, N, And N-methyldiethanolamine. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 6. The method of claim 5,
Wherein the organic compound is used in an amount of 20 to 80 parts by weight based on 50 parts by weight of the water-soluble aluminate compound. A method for pulverizing a mineral according to any one of claims 1 to 10, wherein 0.001 to 3 parts by weight of the pulverizing auxiliary composition for pulverization for mineral pulverization is added to 100 parts by weight of the pulverized material. 12. The method of claim 11,
Wherein the mineral is limestone, coal, slag, coal fly ash, clinker, silica sand, or montmorillonite mineral. A concrete product ground and produced by using the crushing aid composition for mineral pulverization according to any one of claims 1 to 10.