KR20190081081A - Composition of grinding aids for micro-crushing mineral comprising diamine compound and aluminate compound, and micro-crushing method of mineral using it - Google Patents

Abstract

The present invention relates to a composition of a mineral fine-grinding aid comprising: a reaction mixture of a diamine compound and phthalic anhydride; and a water soluble aluminate compound in an aqueous solution state with 20-45% of the solid content generated by reacting aluminium hydroxide and alkali hydroxides, to a mineral fine-grinding method using the same and to a concrete product prepared by using mineral ground by using the same. The composition of a mineral fine-grinding aid of the present invention increases grinding efficiency, inhibits quick setting of concrete which can occur due to residual aluminate when concrete is placed after grinding and maintains flowability, thereby improving workability.

Description

[0001] The present invention relates to a grinding aid composition for grinding a mineral, which comprises a diamine compound and an aluminate compound, and a method for grinding a mineral using the same, and a micro-crushing method of mineral using it}

The present invention relates to a crushing aid composition for fine crushing of minerals and a method for finely pulverizing minerals using the same. More particularly, the present invention relates to a crushing aid composition for crushing minerals, And a method for pulverizing a mineral using the same. BACKGROUND ART

In the pulverizing step of the mineral, it is preferable that the mineral is finely pulverized to make the particles into fine powder to increase the specific surface area. When pulverizing particles into fine powder, limestone becomes easier to sinter when it is made into clinker, and cement clinker improves the physical properties of concrete such as hydration reactivity and compressive strength. Further, in the case of coal, when pulverized with a fine powder, the residual amount of unburned carbon is small and combustion power is high when burned.

In the process of pulverizing minerals such as limestone, cement, slag, and coal, a ball mill is generally used. Ball is a sort of metallic beads that crushes minerals. At this time, suppressing the generation of static electricity between the ground particles and between the ball and ground particles prevents the re-agglomerating of the ground particles and the degradation of the ground performance due to the adherence of the ground particles to the ball, thereby finely grinding the starting material Grinding aids are used to improve grinding 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 it is 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.

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. Rapid settling is a material used to accelerate the setting of cement for the purpose of increasing initial strength.

When such an aluminate compound is used as a milling aid, the aluminate-based compound remaining after the milling causes a sudden phenomenon, which reduces the workability at the stage of pouring the concrete, which limits its use.

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 relates to a water-soluble inorganic compound, an aluminate-based compound, which has been used only as a chemical admixture for concrete, by applying the aluminate-based compound to a crushing aid for crushing of cement clinker, thereby preventing the crushing It is another object of the present invention to provide a crushing auxiliary composition for mineral pulverization that can simultaneously increase the crushing efficiency at the time of crushing and improve the workability at the time of pouring concrete by using the diamine compound.

In order to accomplish the above object, the present invention provides a process for producing a mineral containing a water-soluble aluminate compound in an aqueous solution state having a solid content of 20 to 45% produced by reacting a reaction mixture of a diamine compound and phthalic anhydride and an aluminum hydroxide with an alkali hydroxide A pulverizing auxiliary composition for fine pulverization is provided.

In the above composition, the reaction mixture of the diamine compound and phthalic anhydride is preferably used in an amount of 40 to 60 parts by weight based on 100 parts by weight of the water-soluble aluminate compound.

In the composition, the reaction mixture of the diamine compound and the phthalic anhydride and the water-soluble aluminate compound are preferably mixed at a weight ratio of 1 to 2: 1 based on the weight of the solid content.

In the above composition, the reaction mixture of the diamine compound and phthalic anhydride is preferably a reaction mixture produced by reacting 1 mole of a diamine compound and 1 to 2 moles of phthalic anhydride.

In the above composition, the diamine compound is preferably at least one selected from the group consisting of ethylenediamine, N - (2-hydroxyethyl) ethylenediamine and N, N' -bis (2-hydroxyethyl) ethylenediamine.

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

In the composition, the water-soluble aluminate compound is preferably 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.

In the composition, the water-soluble aluminate compound preferably 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 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 this composition, the amines may be selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N, N -bis (2-hydroxypropyl) ethanolamine, N, N -bis -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, characterized in that 0.001 to 3 parts by weight of the pulverizing auxiliary composition for fine pulverization of minerals 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 produced from the pulverized minerals by using the pulverizing auxiliary composition for fine pulverization of minerals.

When the aluminate compound is used as a pulverizing aid by using a reaction mixture of a diamine compound and phthalic anhydride, the pulverizing and preparing composition for fine pulverization for mineral pulverization of the present invention aluminate remains after mineral pulverization, especially after concrete pulverization of cement clinker It is possible to prevent the occurrence of a sudden phenomenon of concrete that may occur and to maintain the fluidity, thereby improving the workability. In addition, since the minerals can be finely pulverized effectively using the aluminate-based compound as the crushing aid without the side effect of the sharpening phenomenon, the sintering action becomes easy when the limestone is made into the clinker, and the cement clinker is excellent in the hydration reactivity, The physical properties are improved, and when the coal is burned, the residual amount of unburnt carbon is small and the thermal power is increased.

The pulverizing and grinding aid composition for mineral pulverization of the present invention comprises a water-soluble aluminate compound in an aqueous solution state having a solid content of 20 to 45% produced by reacting a reaction mixture of a diamine compound and phthalic anhydride with aluminum hydroxide and an alkaline hydroxide .

The water-soluble aluminate-based compound plays a role in enhancing the pulverization efficiency of the mineral pulverization.

The water-soluble aluminate-based compound is an aqueous solution having a solid content of 20 to 45% by weight produced by reacting aluminum hydroxide [Al (OH) ₃ ] with an alkaline hydroxide. An aqueous solution having a solids content of 30 to 45% by weight is preferred, and an aqueous solution having a solids content of 40% by weight is particularly preferred.

The alkaline hydroxide is preferably sodium hydroxide (NaOH) or potassium hydroxide (KOH).

Accordingly, the water-soluble aluminate 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.

Aluminate-based look at the sodium aluminate (NaAlO ₂₎ Examples of the compound, sodium aluminate reacts with water generated aluminum hydroxide (Al (OH) ₃₎ and sodium hydroxide (NaOH), and aluminum hydroxide are the cement particles Hydration (Ca (OH) ₂ ), which is produced in the course of the reaction. It is known that sodium hydroxide accelerates the hydration reaction of cement by raising the pH to rapidly produce calcium silicate hydrate, which is involved in the rapid reaction, and aluminum hydroxide is chemically reacted with calcium hydroxide to sharpen the cement. This reaction formula is shown in the following chemical formula 1.

[Chemical Formula 1]

_{2Al (OH) 3 + Ca (} OH) 2 → 3CaO · Al 2 O 3 · 6H 2 O

The reaction mixture of the diamine compound and the phthalic anhydride plays a role of maintaining the fluidity by solving the problem that the fluidity is lowered due to the rusting when the aluminate is used.

The reaction mixture of the diamine compound and the phthalic anhydride is preferably a reaction mixture of 1 mole of diamine and 1 to 2 moles of phthalic anhydride, more preferably a reaction mixture of 1 mole of diamine and 2 moles of phthalic anhydride.

Wherein the diamine compound is ethylenediamine (Ethylenediamine), N - (2-hydroxyethyl) ethylenediamine {N - (2-Hydroxyethyl) ethylenediamine} and N, N '- bis (2-hydroxyethyl) ethylenediamine {N, N'- bis (2-hydroxyethyl) ethylenediamine}, and the like.

For example, in the case of sodium aluminate as the aluminate compound, the reaction mixture of the diamine compound and the anhydrous phthalic acid as described above is prepared by neutralizing sodium hydroxide produced by the reaction of sodium aluminate with water, And the non-covalent electron pair of oxygen interacts (coordinates) with the aluminum ion to inhibit the reaction of the above formula (1), thereby preventing the occurrence of spins.

The reaction mixture of the diamine compound and the phthalic anhydride is preferably used in an amount of 40 to 60 parts by weight per 100 parts by weight of the water-soluble aluminate compound, more preferably 50 parts by weight per 100 parts by weight of the water-soluble aluminate compound Do.

The reaction mixture of the diamine compound and the phthalic anhydride and the water-soluble aluminate compound are preferably mixed in a weight ratio of 1: 1 to 2: 1 based on the weight of the solid content.

The pulverizing auxiliary composition for fine pulverization of mineral according to the present invention may further comprise an organic compound.

The organic compound is preferably at least one selected from GMP {2 - [(2,3-dihydroxypropoxy) carbonyl] benzoic acid}, sodium gluconate (SG), 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 can be selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N, N -bis (2-hydroxypropyl) ethanolamine, N, N -bis (2-hydroxyethyl) And N -methyl diethanolamine.

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 an aqueous solution state.

In the case of further containing an organic compound, by using a water-soluble inorganic compound and an organic compound in combination, the grinding efficiency and workability can be further improved.

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.

It is preferable to use limestone, coal, slag, fly ash, clinker, silica sand and montmorillonite-based minerals as 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.

The present invention also provides a concrete product produced from the pulverized mineral using the pulverizing auxiliary composition for fine 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.

The concrete product of the present invention is produced from fine pulverized minerals using the crushing aid of the present invention. When the limestone is made into a clinker, the sintering action is facilitated. In the cement clinker, the physical properties of concrete such as hydration reactivity and compressive strength are improved , Coal has a small residual amount of unburnt carbon when burned and has a high firepower, and it is possible to prevent sudden phenomenon due to the included diamine compound, in particular, a sudden phenomenon that may occur at the time of concrete pouring, .

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 >

Preparation of reaction mixture of ethylenediamine and phthalic anhydride

60.2 g (1.0 mole) of ethylenediamine and 296.2 g (2.0 mole) of phthalic anhydride were placed in a 500 ml round-bottomed flask and the temperature of the reaction was maintained at 105 ° C for 1 hour, then elevated to 135 ° C for 3 hours, And when the temperature reached 70 DEG C, 152.7 g of water was added to prepare a 70% aqueous solution.

The reaction scheme of the above reaction is as follows.

≪ Example 2 >

N - Preparation of Reaction Mixture of (2-hydroxyethyl) ethylenediamine and Phthalic Anhydride

104.2 g (1.0 mol) of N - (2-hydroxyethyl) ethylenediamine and 296.2 g (2.0 mol) of phthalic anhydride were placed in a 500 mL round bottom flask and the reaction temperature was maintained at 105 캜 for 1 hour, After heating for 3 hours, heating was stopped. When the temperature reached 70 ° C, 171.6 g of water was added to prepare a 70% aqueous solution.

The reaction scheme of the above reaction is as follows.

≪ Example 3 >

N, N ' - Bis (2-hydroxyethyl) ethylenediamine and  Preparation of reaction mixture of phthalic anhydride

148.2 g (1.0 mol) of N, N ' -bis (2-hydroxyethyl) ethylenediamine and 296.2 g (2.0 mol) of phthalic anhydride were placed in a 500 mL round bottom flask and the reaction temperature was maintained at 105 DEG C for 1 hour. The mixture was maintained at 135 캜 for 3 hours and then heated. When the temperature reached 70 캜, 190.5 g of water was added to prepare a 70% aqueous solution.

The reaction scheme of the above reaction is as follows.

<Example 4>

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).

&Lt; Example 5 >

Preparation of sodium aluminate

Water was added to the 42% aqueous solution of sodium aluminate (NaAlu) prepared in Example 4 to dilute it to obtain a 30% aqueous solution of sodium aluminate (NaAlu).

< Example  6>

Preparation of a pulverizing auxiliary composition

The compound prepared in Example 1 and the aqueous solution of sodium aluminate (NaAlu) prepared in Example 5 were mixed at a weight ratio of 1: 1 with respect to solid content to prepare a pulverizing auxiliary composition having a solid content of 42%.

< Example  7>

Preparation of a pulverizing auxiliary composition

The compound prepared in Example 2 and the aqueous solution of sodium aluminate (NaAlu) prepared in Example 5 were mixed at a weight ratio of 1: 1 with respect to solid content to prepare a pulverizing auxiliary composition having a solid content of 42%.

< Example  8>

Preparation of a pulverizing auxiliary composition

The compound prepared in Example 3 and the aqueous solution of sodium aluminate (NaAlu) prepared in Example 5 were mixed at a weight ratio of 1: 1 with respect to the solid content to prepare a pulverizing auxiliary aqueous solution having a solid content of 42%.

< 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, the pulverizing auxiliary compositions prepared in Examples 6 to 8 were used. As a comparative example, DEG (Diethylene glycol) and TIPA (Triisopropanolamine), which are conventionally used pulverizing additives, were used.

As the minerals to be ground, clinker was used, and the crushing aid compositions of Examples 6 to 8 and the comparative examples were ground using DEG and TIPA as crushing aids. The grinding 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 52 3,410 18.0 DEG 99 0.020 49 3,496 18.4 Example 6 42 0.020 51 3,437 18.0 Example 7 42 0.025 51 3,459 18.2 Example 8 42 0.020 52 3,444 18.0 The amount used is based on 100 parts by weight of the mineral to be ground (cement clinker).

As shown in the results of Table 1, the grinding aid composition of the present invention had a solid content of 42% by weight, which was much better than that of the comparative examples. Further, it can be confirmed that even when the synthesis mixture of the diamine compound and the phthalic anhydride is added, the grinding efficiency is not reduced.

<Experimental Example 2>

The workability of the crushing aid composition for fine grinding of the present invention was tested as follows.

The pulverizing auxiliary compositions prepared in Examples 6 to 8 were used as the pulverizing auxiliary of the present invention. In order to compare the workability, the sodium aluminate aqueous solution prepared in Example 5 was used alone. The slump test was carried out on each of the pulverizing additives and the results are shown in Table 2 below.

Crushing auxiliary Slump (mm) Air volume (%) Early After 1 hour Early After 1 hour Example 5 150 135 5.3 4.9 Example 6 200 185 5.8 5.4 Example 7 195 180 5.6 5.4 Example 8 200 180 5.5 4.9 25-24-180, W / C = 48.5%, s / a = 39.6%, W 165, C 340, Sand 731, Coarse aggregate 1117, 2.04

As shown in the results of Table 2, the grinding aid of Example 5 using aluminate (NaAlu) alone had a relatively low initial slump value and an after-hour change value due to the drop in fluidity due to the swelling, while the diamine compound and anhydrous The grinding aid of Examples 6 to 8, in which the reaction mixture of phthalic acid was added, maintained fluidity, and the initial slump value and the value after one hour were relatively large.

Claims (16)

A water-soluble aluminate compound in the form of an aqueous solution having a solid content of 20 to 45%, which is produced by reacting a diamine compound with phthalic anhydride, and reacting aluminum hydroxide with an alkaline hydroxide. The method according to claim 1,
Wherein the reaction mixture of the diamine compound and the phthalic anhydride is used in an amount of 40 to 60 parts by weight based on 100 parts by weight of the water-soluble aluminate compound. The method according to claim 1,
Wherein the reaction mixture of the diamine compound and the phthalic anhydride and the water-soluble aluminate compound are mixed in a weight ratio of 1 to 2: 1 based on the weight of solid content. The method according to claim 1,
Wherein the reaction mixture of the diamine compound and the phthalic anhydride is a reaction mixture produced by reacting 1 mole of the diamine compound and 1 to 2 moles of phthalic anhydride. The method according to claim 1,
Wherein the diamine compound is at least one selected from the group consisting of ethylenediamine, N - (2-hydroxyethyl) ethylenediamine and N, N' -bis (2-hydroxyethyl) ethylenediamine. A pulverizing auxiliary composition. 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. 10. The method of claim 9,
Wherein the glycerin family comprises glycerin, diglycerin, triglycerin, polyglycerin, phosphoglycerin, diphosphoglycerin and triphosphoglycerin. 10. The method of claim 9,
Wherein the glycols include propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, monoethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol. 10. The method of claim 9,
The amines can be selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N, N -bis (2-hydroxypropyl) ethanolamine, N, N -bis (2-hydroxyethyl) And N -methyldiethanolamine. &Lt; RTI ID = 0.0 &gt; 8. &lt; / RTI &gt; 10. The method of claim 9,
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 13, wherein 0.001 to 3 parts by weight of the pulverizing auxiliary composition for fine pulverization for mineral pulverization is added to 100 parts by weight of the pulverized material. 15. The method of claim 14,
Wherein the mineral is limestone, coal, slag, coal fly ash, clinker, silica sand, or montmorillonite mineral. 14. A concrete product produced from a pulverized mineral using the pulverizing auxiliary composition for pulverization of a mineral according to any one of claims 1 to 13.