KR101357798B1 - Compositions for cement clinker grinding agents and cement clinker compositions comprising the same - Google Patents

Abstract

상기 식 중, X, Y 및 Z는 서로 독립적으로 비극성 작용기이고, W^-는 극성 작용기이다.There is provided a composition for cement clinker grinding aid comprising a grinding aid comprising a zwitterion structural compound represented by Formula 1 below:
≪ Formula 1 >

Wherein X, Y and Z are independently of each other a nonpolar functional group and W ⁻ is a polar functional group.

Description

Compositions for cement clinker grinding agents and cement clinker compositions comprising the same

The present invention relates to a composition for preparing cement clinker grinding, and more particularly, to a grinding aid including an amphoteric ionic structure compound to prevent static electricity generated from the surface of particles crushed during clinker grinding, thereby increasing the grinding efficiency of the clinker. The present invention relates to a composition for preparing cement clinker grinding and to a cement clinker composition using the same.

Cement is mainly made of clinker produced by mixing an appropriate amount of raw material from limestone and firing at 1400 ° C or higher. The produced clinker is cooled and mixed with an appropriate amount of gypsum or slag to be ground into a fine powder through a cement mill. At this time, a grinding aid is added to increase the grinding efficiency. In the category of energy consumption of 20 kWh / ton or less, the amount of clinker crushing increases linearly according to Rittinger's law, but at energy consumption above 20 kWh / ton, the grinding efficiency gradually decreases due to various factors. . Thus, an unproductive energy consumption will occur if an effective grinding system is not applied.

P: energy required for grinding

: 원료 양(feed rate to crusher)

: Feed rate to crusher

: 분쇄 전 평균 입자 크기

: Average particle size before grinding

: 분쇄 후 입자 크기

: Particle size after grinding

K _r : Rittinger's constant

Portland cement grinding equipment consumes energy to fine-tune the particle size of clinker, gypsum, and various other raw materials, which is a major factor in raising the production cost of the final product, especially in terms of resources. There is a big concern in terms of the cost of energy consumption through the use of depleted resources.

The principle for the grinding of anisotropic materials, such as clinkers, is that the grinding takes place from a relatively weak point where fine cracking points are present. The various external energies provided for the pulverization exert the highest forces on these weak spots, resulting in the destruction of the crystal structure of the compounds constituting the clinker, which leads to particle breakdown and micronization. Will be done. However, the breakdown of ionic bonds through mechanical processes results in the formation of highly active positive and negative charges on the surface of newly formed particles, and electrostatic attraction between particles. This results in the formation of agglomerates when the solid particles are milled, resulting in a direct and detrimental effect on the milling efficiency.

These agglomerates are formed by electrostatic interactions with van der Waals forces between individual particles, and the buffering action between agglomerates absorbs the pulverization energy due to the impact and friction generated within the grinding mechanism. A thin plate-like body is formed, which greatly reduces the grinding efficiency.

To date, numerous attempts have been made to reduce yields and methods of increasing yield in cement production.

For example, when TEA is used in an amount of 0.1 to 1% by weight, TEA promotes the hydration of C3A and delays the reaction of C3S during the hydration and curing of cement. However, when TEA is used in a high content, there is a problem that the strength at all ages is lowered.

In addition, U. S. Patent No. 6,641, 661 further includes at least one water reducing agent comprising a polyoxyalkylene polymer during grinding of cement; Sugar; Alkali or alkaline earth metal chlorides; And a method for improving the early strength of cement comprising introducing an amine into the cement, US Pat. No. 7,160,384 discloses diamines such as tetrahydroxyethylethylenediamine, and triethanolamine or tri as an aid for laying grinding efficiency. Cement treatment aids comprising alkanolamines such as isopropanolamine are disclosed. International Publication No. 2006/051574 discloses a method for improving compressive strength using raw glycerin. However, these methods leave room for improvement for more efficient grinding.

US Patent 6,641,661 US Patent No. 7,160,384 International Publication No. 2006/051574

One embodiment of the present invention provides a composition for cement clinker grinding aid that can prevent agglomeration during clinker grinding, including a grinding aid comprising a compound having an anionic functional group and a cationic functional group together.

Another embodiment of the present invention provides a cement clinker composition comprising the cement clinker grinding aid composition and a cement composition prepared using the cement clinker composition.

One aspect of the present invention provides a composition for cement clinker grinding aid comprising a grinding aid comprising a zwitterion structural compound represented by the following formula (1):

≪ Formula 1 >

Wherein X, Y and Z are independently of each other a nonpolar functional group and W ⁻ is a polar functional group.

The zwitterionic compound may be at least one selected from the group consisting of compounds represented by the following Chemical Formulas 2-9:

(2)

<Formula 3>

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

&Lt; Formula 9 >

Wherein a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer of 0 to 3, b1, b2, b3, b4, b5, b6, b7, b8, c1, c2, c3, c4, c5, c6, c7, c8, d2, d3, d4, d6, d7 and d8 are each independently an integer from 1 to 4.

The grinding aid may further comprise at least one of glycol and amine.

The glycol may include at least one selected from the group consisting of monoethylene glycol, diethylene glycol, propylene glycol, and polyethylene glycol.

The amine may include at least one selected from the group consisting of monoethanolamine, monoethanolamine, diethanolamine, triethanolamine, and triisopropanol amine.

The cement clinker grinding aid composition may further comprise 0.001 to 10,000 parts by weight of at least one or more of a hydration retarder or a hydration accelerator based on 100 parts by weight of the grinding aid.

The hydration retardant may include at least one or more selected from acetic acid, sodium gluconate, and fatty acids, and the hydration accelerator may include aluminum hydroxide.

Another aspect of the invention is a cement clinker; It provides a cement clinker composition comprising; and the composition for the cement clinker grinding aid described above.

Another aspect of the present invention provides a cement composition prepared using the cement clinker composition described above.

Cement clinker grinding aid composition according to an embodiment of the present invention, the anionic functional groups of the zwitterionic structure compound adsorbs on the cationic surface of the clinker and the cationic functional groups located on the other side induces repulsive force between the particles and the clinker The charge affinity with the constituent elements is improved to pulverize the fine powders formed during the pulverization and to prevent agglomeration between the fine powders. As a result, the time taken for clinker grinding is shortened, reducing energy consumption, improving the fluidity of the final cement produced and compressive strength at the age of 1, 3, 7, 28 days, and saving energy in the cement production process. The unit cost is reduced, and further, it can greatly affect the early strength and long-term strength improvement of the secondary product (cement, etc.) manufactured using the cement clinker grinding aid composition.

Hereinafter, it will be described in detail with respect to the composition for cement clinker grinding aid according to an embodiment of the present invention.

Cement clinker grinding aid composition according to an embodiment of the present invention comprises a grinding aid comprising a zwitterion structure compound represented by the following formula (1):

&Lt; Formula 1 >

In Formula 1, X, Y, and Z are each independently a nonpolar functional group, and W ⁻ is a polar functional group.

The grinding aid includes an amphoteric ionic structure compound represented by formula (1). The zwitterionic compound represented by the formula (1) contains cations and anions in the molecule, so that the surface of the particles is made into a heterogeneous state by adsorption on clinker particles. Specifically, since W ⁻ has a polarity, the zwitterionic compound compound molecules are adsorbed onto the surface of the polar particles while forming an affinity with the positively charged component of the clinker constituent elements, and nitrogen as the central atom is positively charged. Inducing repulsion between particles and X, Y and Z each more effectively assists in inducing repulsion between particles to prevent the formation of aggregates that can occur in clinker particles.

The zwitterionic compound may be at least one selected from the group consisting of compounds represented by the following Chemical Formulas 2-9:

(2)

<Formula 3>

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

&Lt; Formula 9 >

Wherein a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer of 0 to 3, b1, b2, b3, b4, b5, b6, b7, b8, c1, c2, c3, c4, c5, c6, c7, c8, d2, d3, d4, d6, d7 and d8 are each independently an integer from 1 to 4.

Compounds represented by Formulas 2 to 9, comprises a functional group having a functional group and the anionic with the cationic in the molecule at the same ^{time, -O -, -COO -, -OSO} 2 - , or -OHPO ₂ ^- anionic groups clinker constituent elements of The zwitterionic structural compound molecules are adsorbed onto the surface of the polar particles of the clinker while forming and adsorbing affinity with the positively charged component. Nitrogen, the central atom in the state where the molecule is adsorbed to the clinker, induces the repulsive force between the particles in the positively charged state, and the other nonpolar groups more effectively assist the inductive repulsive force between the particles. As a result, aggregate formation that may occur between the fine particles of the clinker can be effectively prevented.

The zwitterionic compound as described above has a polar functional group in the molecule, which can effectively destroy the large crystal structure of the clinker particles.

At the same time the charged clinker particle surface is neutralized by the zwitterionic compound and promotes the formation of new particles of fine size. The composition for cement clinker grinding aid comprising the amphoteric ion structural compound eventually improves the productivity of the cement and the uniformity of the distribution of the cement particles as well as the performance of the cement, and also the hydration reaction without affecting the mechanical properties of the cement and Pozzolanic reactions can be promoted.

The grinding aid may be formed of the amphoteric ionic structure compound represented by Formula 1 alone or one or more of the compounds represented by Formulas 2 to 8, but is not limited thereto. The grinding aid may further comprise at least one or more of glycol and amine.

Examples of the glycol include monoethylene glycol, diethylene glycol, propylene glycol, or polyethylene glycol. In addition, examples of the amine include monoethanolamine, monoethanolamine, diethanolamine, triethanolamine, or triisopropanolamine.

The cement clinker grinding aid composition may be composed only of the grinding aid including the compound represented by the formula (1), but in addition to the grinding aid, at least one or more of a hydration retarder and a hydration promoter may be used as needed. It is also possible.

At this time, the content of the added hydration retarder or hydration promoter is adjusted according to the content of the grinding aid. Specifically, the hydration retardant or the hydration accelerator may be used in an amount of 0.001 to 10,000 parts by weight based on 100 parts by weight of the grinding aid.

If the content of the hydration retarder or the hydration promoter is 10,000 parts by weight or more, the result will be reduced, which is undesirable.

Examples of the hydration retardant include acetic acid, sodium gluconate or fatty acids, and examples of the hydration accelerator include aluminum hydroxide.

In addition, if the additive is commonly used in the art is not limited and may be used by adding more. For example, water reducing agents such as lignin, naphthalene and melamine may be further added.

Cement clinker composition according to another embodiment of the present invention is a cement clinker; And the above-mentioned composition for cement clinker grinding aid. In this case, the content of the cement clinker grinding aid composition may be 0.001 to 1.0 parts by weight based on 100 parts by weight of the cement clinker. If the content is less than 0.001 parts by weight, the amount of the grinding aid contained in the composition for clinker grinding aid is insufficient, so that the concentration of the zwitterionic compound is low, which does not prevent aggregation between the pulverized particles. Degradation or excessive hydration delay or hydration promotion may occur.

Cement composition according to another embodiment of the present invention is prepared using the cement clinker composition.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these embodiments.

Example  One

A composition for cement clinker grinding aid was prepared using a grinding aid composed of the compound represented by Chemical Formula 1. After diluting 10 g of the composition for crushing preparation with 40 g of water, 2 g was collected, and charged into 2 kg of a clinker having a component shown in Table 1 below to perform pulverization.

Classification Component content and component composition ratio (parts by weight) Clinker SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO SO ₃ Na ₂ O K ₂ O L.O.I 19.8 5.8 2.5 64.4 1.8 2.6 0.096 0.5508 2.10 C3S C2S C3A C4AF 58.64 12.53 11.14 7.61

Example  2

Except for using the compound represented by the formula (2) instead of the compound represented by the formula (1) in Example 1, the grinding was carried out in the same manner as in Example 1.

Example  3

Except for using the compound represented by the formula (3) instead of the compound represented by the formula (1) in Example 1, the grinding was carried out in the same manner as in Example 1.

Example  4

Except for using the compound represented by the formula (4) instead of the compound represented by the formula (1) in Example 1, the grinding was carried out in the same manner as in Example 1.

Example  5

Except for using the compound represented by the formula (5) instead of the compound represented by the formula (1) in Example 1, the grinding was carried out in the same manner as in Example 1.

Example  6

Except for using the compound represented by the formula (6) instead of the compound represented by the formula (1) in Example 1, the grinding was carried out in the same manner as in Example 1.

Example  7

Except for using the compound represented by the formula (7) instead of the compound represented by the formula (1) in Example 1, the grinding was carried out in the same manner as in Example 1.

Example  8

Except for using the compound represented by the formula (8) instead of the compound represented by the formula (1) in Example 1, the grinding was carried out in the same manner as in Example 1.

Comparative Example  One

The grinding was performed in the same manner as in Example 1, except that the grinding aid was not used in Example 1.

Comparative Example  2

Except for using DEG (Diethylene glycol) instead of the compound represented by Formula 1 in Example 1, the grinding was carried out in the same manner as in Example 1.

Comparative Example  3

Except for using the compound represented by the formula (1) in Example 1 TEA (Triethanol amine), the grinding was carried out in the same manner as in Example 1.

Evaluation example

For Examples 1 to 8 and Comparative Examples 1 to 3, the powderiness of each grinding time was measured and the results of the grinding performance test are shown in Table 2. The mill used a drum mill with a rotational speed of 70 rpm and a drum size of 305 mm x 305 mm. In addition, the grinding performance test results (3300 ± 50 cm ² / g) leading to the same powder level was measured and the results of the grinding performance test are shown in Table 3. Powder and residue experiments were performed based on KS L 5112 and KS L 5106, respectively.

Using the cement thus obtained, the mortar compressive strength test was carried out, the strength of each age 18 hours, 3 days, 7 days, 28 days was measured and the results are shown in Table 3. The test specimen for strength test of concrete for measuring compressive strength was manufactured and cured according to KS L ISO 679. The specimens were measured for compressive strength every 18 hours, 3 days, 7 days, and 24 days using a 4 × 4 × 16 cm 3 mold.

division Compounds Used For Grinding Aids usage
(weight%) Powder level by grinding time (㎠ / g) 10 minutes 15 minutes 20 minutes 25 minutes 30 minutes 35 minutes Example 1 Formula 1 0.2 2197 2689 3161 3422 3544 3658 Example 2 (2) 0.2 2119 2681 3159 3347 3531 3638 Example 3 (3) 0.2 2216 2728 3247 3416 3668 3746 Example 4 Formula 4 0.2 2128 2690 3167 3369 3594 3711 Example 5 Formula 5 0.2 2219 2711 3246 3490 3638 3722 Example 6 6 0.2 2296 2737 3344 3485 3654 3748 Example 7 Formula 7 0.2 2260 2758 3354 3420 3728 3762 Example 8 8 0.2 2238 2746 3342 3498 3654 3732 Comparative Example 1 none - 1972 2438 2912 3192 3326 3488 Comparative Example 2 DEG 0.2 2016 2668 3131 3304 3471 3569 Comparative Example 3 TEA 0.2 2014 2551 3044 3252 3390 3517

division Compounds Used For Grinding Aids usage
(weight%) Grinding time
(minute) Final powder degree (㎠ / g) 44㎛ residue Example 1 Formula 1 0.2 27.0 3489 9.5% Example 2 (2) 0.2 26.5 3481 9.8% Example 3 (3) 0.2 25.5 3458 9.8% Example 4 Formula 4 0.2 27.0 3490 9.6% Example 5 Formula 5 0.2 24.5 3461 9.2% Example 6 6 0.2 24.5 3476 9.5% Example 7 Formula 7 0.2 25.0 3458 9.4% Example 8 8 0.2 25.5 3465 9.6% Comparative Example 1 none - 33.5 3458 15.8% Comparative Example 2 DEG 0.2 29.5 3468 11.4% Comparative Example 3 TEA 0.2 30.5 3451 11.0%

division Compressive strength (kgf / cm2) 18 hours 3 days 7 days 28th Example 1 126 328 426 532 Example 2 115 326 458 548 Example 3 125 324 434 534 Example 4 118 330 452 556 Example 5 121 331 448 548 Example 6 117 226 456 544 Example 7 120 229 451 533 Example 8 122 228 449 530 Comparative Example 1 86 306 406 498 Comparative Example 2 95 313 417 515 Comparative Example 3 118 326 413 440

Referring to Table 2, the case of Examples 1 to 8 was improved all the time-specific powder degree than the case of Comparative Examples 1 to 3. From this, it can be seen that when the composition for cement clinker grinding aid of the present invention is added, the powderiness of each hour is improved and the grinding efficiency is excellent.

Referring to Table 3, the total pulverization time reaching the same powder range (3450 ± 50 cm ² / g) was shorter than that of Comparative Examples 1 to 3 in the case of Examples 1 to 8, and the residual amount of 44 µm was reduced. . From this, it can be seen that the case where the composition for cement clinker grinding aid of the present invention is added is superior to the case where it is not.

Referring to Table 4, the case of Examples 1 to 8 was superior to both the early strength and long-term strength than the case of Comparative Examples 1 to 3. From this, the composition for cement clinker grinding aid of the present invention is to maximize the interaction between the ionized functional groups in the molecule by the adsorption and electrostatic repulsive force and to enable efficient grinding, the compressive strength of the cement mortar as a final step It can be seen to enhance.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various modifications and equivalent arrangements may be made therein without departing from the scope of the present invention . Accordingly, the true scope of the present invention should be determined by the technical scope of the appended claims.

Claims (10)

A composition for cement clinker grinding aid comprising a grinding aid comprising at least one amphoteric ion structural compound selected from the group consisting of compounds represented by formulas (2) to (9):
(2)

(3)

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

&Lt; Formula 9 >

Wherein,
a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer of 0 to 3,
b1, b2, b3, b4, b5, b6, b7, b8, c1, c2, c3, c4, c5, c6, c7, c8, d2, d3, d4, d6, d7 and d8 are each independently 1 to 4 Is an integer. delete The method of claim 1,
A composition for cement clinker grinding aid, wherein the grinding aid further comprises at least one of glycol and amine. The method of claim 3,
Cement clinker grinding aid composition comprising the glycol is at least one selected from the group consisting of monoethylene glycol (monoethylene glycol), diethylene glycol (diethylene glycol), propylene glycol (propylene glycol) and polyethylene glycol (polyethylene glycol) . The method of claim 3,
The amine is a monoethanolamine (monoethanolamine), diethanolamine (diethanolamine), triethanolamine (triethanolamine) and triisopropanolamine (triisopropanol amine) comprising at least one or more selected from the group consisting of crushing cement clinker composition. The method of claim 1,
A composition for cement clinker grinding aid, further comprising 0.001 to 10,000 parts by weight of at least one of a hydration retarder or a hydration accelerator, based on 100 parts by weight of the grinding aid. The method according to claim 6,
And a hydration retardant comprising at least one or more selected from acetic acid, sodium gluconate and a fatty acid, and the hydration accelerator comprises aluminum hydroxide. Cement clinker; And
The composition for cement clinker grinding aid according to any one of claims 1 and 3 to 7;
Cement clinker composition comprising a. 9. The method of claim 8,
A cement clinker composition having a content of the cement clinker grinding aid composition in an amount of 0.001 to 1.0 part by weight based on 100 parts by weight of the cement clinker. A cement composition prepared using the cement clinker composition according to claim 8.