KR101276084B1 - White cement composition and process for preparation thereof - Google Patents

Abstract

In the present invention, after mixing 100 kg of cement, 50 to 70 kg of slag, 10 to 15 kg of gypsum, 10 to 15 kg of slaked lime, 1 to 3 kg of alkaline stimulant, 1 to 3 kg of white pigment and 1 to 20 kg of back cement , 1 The present invention relates to a back cement composition and a method for producing energy reduction and CO 2 reduction, which are prepared by pulverizing and preparing a secondary ball mill after tea premixing, and pulverizing and preparing a specific surface area of 2,500 to 5,500 cm 2 / g depending on the type.

Description

WCITE CEMENT COMPOSITION AND PROCESS FOR PREPARATION THEREOF

The present invention relates to an environmentally friendly and economical back cement composition and a method for producing the slag, which are energy-saving and CO 2 reduced.

Recently, in the cement industry, various mixtures of slag and fly ash have been developed in order to reduce CO 2 and satisfy various performance requirements of customers. However, commercially available back cements have had many limitations in developing alternative materials. However, in the case of quicklime which is the main component of slag, the color of the raw stone itself is aggregate having whiteness, and it can be seen that a product having high whiteness is produced when grinding a high purity product during the slag production process.

Therefore, it can be said that the core of the present technology is to develop a back cement by adding a mixed material for increasing strength to such a high white slag (specific surface area of 4,000 to 6,000 cm 2 / g).

In addition, back cement (specific surface area around 3,500㎠ / g) is currently used in non-structural parts such as design effects or tile adhesives and tile joints, rather than applied to major structural materials in the market unlike ordinary ordinary Portland cement. . Therefore, it is possible to secure high economical efficiency compared to the back cement in the existing market when applying the activity standard rather than comparing the strength condition of the back cement and the equivalent strength like slag cement or fly ash cement.

The related technology is also a technology that can greatly reduce the CO2 generation portion generated in a large amount of normal cement production process, as verified in many papers.

At present, there are many patents for cement, but there are no reports of development of back cement through slag with high whiteness. In the existing Republic of Korea Patent No. 10-0138403 related to cement "manufactured mixed cement using reduced slag (2007)" is a method of manufacturing cement using reduced slag, after addition of fly ash and ordinary portland cement, alkaline chloride calcium chloride and or sulfate activator The furnace is related to a process for producing mixed cement, which comprises mixing a binder prepared by adding gypsum with ordinary portland cement, but the related method is related to the concept of mixing a certain amount of each material. Verification of the physical and chemical effects of the composition is unclear, and it is difficult to find a differentiation because it is similar to a general mixed cement production method by a simple technique of replacing a certain reducing slag with the basic physical properties of existing ordinary Portland.

Republic of Korea Patent No. 10-0002531 and "method of manufacturing high strength hydraulic back cement (1985)" is based on blast furnace slag 1-80 parts of back cement or 5-80 parts of back cement clinker and pulverized with other mixture materials and After the removal of Fe2O3 by using alumina ball, it is characterized by the fine powder mixing by using an alumina ball, but the scope of technology is enormous and there is no clear presentation about the progress of each technology or the quality characteristics of each material used. to be. It can be seen that many parts lack access to core performance and required performance of back cement.

In the case of the conventional general back cement is produced by the same operation method as the general cement production process is to solve the problem that the required energy consumption and CO 2 reduction cost is expensive to produce the problem to be solved by the present invention. .

The present invention to solve the above problems 100kg cement, 50 ~ 70 kg slag, 10 ~ 15 kg gypsum, 10 ~ 15 kg slaked lime, 1 ~ 3 kg alkaline stimulant, 1 ~ 3 kg white pigment, 1 ~ 20 back cement It is a problem solving means of the present invention to provide a high-powder back cement composition and a method of manufacturing the same by mixing the kg , passing the first premixing process, and then grinding with a second ball mill.

The present invention has been developed a new product that can replace the existing domestic annual consumption of 250,000 tons, about 50 billion market, it is applied to the existing market such as color exposed concrete, tile adhesive, artificial stone grind, and when producing conventional back cement Required energy consumption and CO2 reduction technology is shown in Table 1 below,

 List of energy consumption and CO2 emission amount when manufacturing 1 ton of white cement Category / Type White cement Invention back cement Energy and CO2
Reduction rate (%) Coal 110 kg 67 kg 39 power 110 kWh 92 kWh 16.5 CO2 generation amount Approximately 870 kg Approximately 478 kg 45

Assuming that the reduction rate is 250,000 tons of back cement, the energy and CO2 reduction effects shown in Table 2 below are eco-friendly and economical.

Reduction of Energy and CO2 Emissions Assuming 250,000 Tons of Back Cement Market Category / Type White cement Invention back cement Energy and CO2
Reduction rate (%) Coal 27,500 tons 16,750 tons 39 power 27,500,000 kWh 23,000,000 kWh 16.5 CO2 generation amount About 217,500 tons 119,500 kg 45

Figure 1 Compressive strength comparison result chart for each product of the present invention
Figure 2 powder and whiteness comparison test chart for each product of the present invention
Figure 3 Analysis of the conventional back cement chemical composition
(Using the X-Ray Diffractometer (XRD)
Figure 4 Analysis diagram of the back cement chemical composition of the present invention (Example 2)
(Using the X-Ray Diffractometer (XRD)
5 analysis diagram of the back cement chemical composition of the present invention (Example 3)
(Using the X-Ray Diffractometer (XRD)

The present invention is to develop a white cement through the combination of powder with whiteness, cement 100kg, slag 50 ~ 70 kg, gypsum 10 ~ 15 kg, slaked lime 10 ~ 15 kg, alkali stimulant 1 ~ 3 kg, white pigment 1 ~ It relates to an energy reduction and CO2 reduction back cement composition and a method of manufacturing the composition 3 kg, 1 to 20 kg of cement.

The manufacturing method of the present invention is a manufacturing method capable of activating the chemical action of the composition through pre-mixing the mixed composition, milling, preparation process,

Per 100 kg of cement, 52 kg of slag, 12 kg of gypsum, 12 kg of lime, 20 kg of back cement, 2 kg of 99.99% calcium hydroxide, 2 kg of zinc oxide, and then 2 kg of triisopropanol amine acetate, a functional grinding aid based on amine acetate, is added. After the first premixing, the powder was ground in a second ball mill, and a brain (specific surface area) 2,500 to 5,500 cm 2 / g was ground to prepare a back cement composition.

Brain is a unit for testing the powder level of Portland cement, which appears as a specific surface area, using a brain air permeation device, expressed in cm ² / g.

 (Related standard: KS L 5106)

Slag and back cement mixing ratio is 50:15 (50:25) ~ 70: 15 when slag cement and other technologies are applied in ordinary concrete technology, compared to the product technology using 50:50 ratio of slag and ordinary portland cement. The strength expression performance was enhanced through alkali stimulants while minimizing the amount of back cement to (70:25).

Slag used in the present invention used a product having a specific surface area of 4,000 ~ 6,000 ㎠ / g, gypsum product of a specific surface area of 2,800 ㎠ / g ~ 4,200 ㎠ / g, slaked lime of 4,000 ㎠ / g ~ 5,000 ㎠ / g Products and back cements have a specific surface area of around 3,500 cm2 / g. Alkali stimulants include 99.0% of calcium hydroxide, potassium hydroxide, sodium hydroxide or sodium silicate, and calcium sulfate and sulfate Aluminum or the like was mixed or one of the compounds selected was used.

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As a white pigment, a commercially available product containing components such as zinc oxide, titanium oxide, and white lead was used.

In the above raw materials, when there is a change in the quality of each raw material, it is possible to adjust the formulation so that the quality can be stabilized by changing the amount of usage to stabilize the quality through mutual complementary.

Looking at the function (role) of each component,

 Slag: Main raw material to replace back cement as basic binder

 Gypsum: the role of mineral stimulant to stimulate slag

 Slaked lime: Role of controlling high chemical reactions such as slag and gypsum

 Back cement: Slag stimulator and quality stabilizer

 Alkali Stimulant: Stimulates fusion of slag, gypsum, and white cement

 White Pigment: Functions as a functional material for whiteness of white cement.

The reason for limiting the compositional component ratio of each of the compositional components of the present invention was developed by optimizing the range of the technology that can be produced to reflect the production conditions and economic feasibility of the product for the future use within the relevant range.

Hereinafter, the present invention will be described in detail with reference to the following Examples.

Example 1

Per 100 kg of cement, 52 kg of slag, 12 kg of plaster, 12 kg of slaked lime, 20 kg of white cement, 2 kg of 99.99% calcium hydroxide, 2 kg of zinc oxide, 2 kg of triisopropanol amine acetate was added, followed by primary premixing and pulverization with a second ball mill. , Brain (specific surface area) was ground to 4,500 cm 2 / g to prepare a cement composition.

Brain is based on the size of the particles resulting from the grinding and preparation of cement. The finer the particles, the faster the chemical reaction is.

It can be seen that the prepared back cement composition has the following physical properties.

division
Compressive strength (MPa) Chromaticity analysis importance
brain
(Cm 2 / g) 3 days 7 days 28 days L (hunter type) KS standard 13.0 20.0 29.0 89.0 or more - More than 3,000 General back cement 25.1 38.2 50.2 90.5 3.15 3,500 Example 1 29.9 43.9 55.5 88.2 3.12 4,566

Example 2

Per 100 kg of cement, 55 kg of slag, 12 kg of plaster, 15 kg of hydrated lime, 15 kg of back cement, 2 kg of 99.99% calcium hydroxide, 1 kg of zinc oxide, and then premixed with a second ball mill, brain (specific surface area) 4,400 ㎠ The cement composition was prepared by trituration at / g .

Example 3

Per 100 kg of cement, 60 kg of slag, 12 kg of gypsum, 15 kg of slaked lime, 10 kg of back cement, 2 kg of 99.99% calcium hydroxide, 1 kg of zinc oxide, after the first premixing, the second ball mill brain (specific surface area) is 5,300 cm 2 / g Grinding to prepare a back cement composition.

It can be seen that the prepared back cement composition has the following physical properties.

division
Compressive strength (MPa) Chromaticity analysis importance
brain
(Cm 2 / g) 3 days 7 days 28 days L (hunter type) KS standard 13.0 20.0 29.0 89.0 or more - More than 3,000 General back cement 25.1 38.2 50.2 90.5 3.15 3,500 Example 2 22.8 34.6 49.2 83.2 2.92 4,483 Example 3 21.7 29.4 34.9 84.5 2.95 5,385

Example 4

Per 100 kg of cement, 65 kg of slag, 12 kg of gypsum, 15 kg of slaked lime, 4 kg of back cement, 2 kg of 99.99% calcium hydroxide and 2 kg of zinc oxide were mixed and premixed to prepare a back cement composition having a brain (specific surface area) of 2,800 cm 2 / g .

Example 5

Per 100 kg of cement, 70 kg of slag, 12 kg of gypsum, 14 kg of slaked lime, 2 kg of 99.99% calcium hydroxide, and 1 kg of zinc oxide were mixed and premixed to prepare a back cement composition having a brain (specific surface area) of 2,800 cm 2 / g .

It can be seen that the prepared back cement composition has the following physical properties.

division
Compressive strength (MPa) Chromaticity analysis importance brain
(Cm 2 / g) 3 days 7 days 28 days L (hunter type) KS standard 13.0 20.0 29.0 89.0 or more - More than 3,000 General back cement 25.1 38.2 50.2 90.5 3.15 3,500 Example 4 12.5 18.9 24.3 83.1 2.83 2,835 Example 5 5.2 10.2 15.3 82.5 2.75 2,826

Experimental Example

In the present invention, the experimental value was used as the result of the small amount process test shown in FIG. 1 as the differentiation technology for the manufacturing technology together with the differentiation of raw materials, and during mass production, a large amount through a slag factory or a remittal (dry cement mortar) factory Production is possible. This is a proven part of the feasibility part through general cement production.

In addition, in the present invention, the chemical reaction of the back cement was increased by pulverizing / preparing the mixed product for more advanced product development.

This can be said to be a technology that can produce a composition dedicated to the back cement, which requires a different raw materials through the grinding process. In mass production of the relevant technology, it can be produced through the large crushing / preparation process of slag plant or cement plant.

Finally, in order to increase the completeness of the present invention, the triisopropanol amine acetate, which is a functional grinding aid of the amine acetate component, was added in the grinding / preparation process to maximize the chemical action of the cement, thereby attempting a technical approach for final quality stabilization. In the case of the grinding aid, it was found to play a role in improving the dispersibility and homogeneity, which is a performance required for cement products.

As a result of examining the quality characteristics for each product developed through the present invention is shown as shown in FIG.

Compared with the general back cement, Example 1 and Example 2 showed similar or slightly higher quality characteristics, and Example 3 showed similar quality characteristics as the KS standard.

Next, in the experiments on the compressive strength and the whiteness part, the compressive strength was found to be somewhat higher than that of the general back cement in Examples 1 to 3, and Examples 4 and 5 were slightly lower than the KS standard.

The whiteness was slightly lower than the general white cement and KS standard, but the general white cement also showed 3 ~ 5% of white pigment in the process of manufacturing color white concrete. The whiteness part of the can be reduced by the technical approach.

Meaning of L, a, b in colorimeter division Chromaticity Optical justification L Black (0) White (100) Lighthess a Green (-) Red (+) Hue
Chroma b Bule (-) Yellow (+)

In the case of the back cement was based on the powder state, in the present invention, the technical differentiation was increased by measuring the whiteness of the mortar product for evaluation of the final technology.

The present invention is a part that can be seen that there is a difference between the composition and the general back cement, but in the case of the general back cement and the composition material, quality control is applied to the market use method through the application of the same range.

Back cement composition composition ratio (wt%) of the present invention division Slag gypsum Lime lime White cement irritant Pigment Sum Grinding aid Example 1 52 12 12 20 2 2 100% Total X 0.02 Example 2 55 12 15 15 2 One 100% Example 3 60 12 15 10 2 One 100% Example 4 65 12 15 4 2 2 100% Example 5 70 12 14 - 2 One 100%

Comparative analysis of the main components of the back cement and the developed main back cement of the present invention is shown in Table 8 below, the related characteristics are shown in Figures 3 to 5. As shown in the table, in the case of the back cement developed in the present invention, the present state of the composition is different from that of the general cement, and the present state of the composition of the main component part of the general cement is also different.

Table of General Back Cement and Back Cement Chemical Composition of the Present Invention division General back cement Example 1 Example 2

chief ingredient
C ₃ S 51.37 16.12 9.12 C ₂ S 28.52 15.53 16.02 C ₃ A 1.56 2.24 0.56 C ₄ AF 1.64 3.74 3.10 quicklime Lime 0.37 0.42 0.00 magnesium Periclase 0.31 0.25 0.11 Gypsum plaster Gypsum 4.67 0.06 1.62 Half gypsum Bassanite bezou 0.15 2.06 5.61 Anhydrous gypsum Anhydrite 0.71 14.49 10.17 Limestone Calcite 8.85 19.28 12.50 Etc 1.85 41.93 41.19 Sum 100% 100% 100%

This invention can be said to be an example of a fusion technology that satisfies the quality of the final product through the proper use of multifunctional raw materials in the quality evaluation through the main component of the general cement.

In the case of the back cement according to the present invention, three manufacturing methods were applied to five products according to the technical classification, and thus, the possibility of inventing the back cement was studied. As a result, in the case of the manufacturing method, in Example 1, the compressive strength characteristics were improved by 91% or more compared to the KS standard, and were found to be more than 10% higher than the general product.

In the case of the manufacturing method of Example 2 and Example 3, the compressive strength characteristics were improved by 20 to 69% or more compared to the KS standard, and the result was about -2 to -30% lower than the general product.

In the manufacturing method of Examples 4 and 5, the compressive strength characteristics were -16 to -47% lower than the KS standard, and -51 to -69% lower than the general product.

In the case of the back cement of the present invention shows the quality characteristics and composition differences according to the manufacturing technology. Therefore, it is confirmed that there is enough application part of general back cement, and if the activity side is examined like blast furnace slag cement or fly ash cement, it can be seen that there is a method that can be applied as a new back cement.

Claims (3)

In the back cement composition,
100 kg of cement, 50 to 70 kg of slag, 10 to 15 kg of gypsum, 10 to 15 kg of slaked lime, 1 to 3 kg of alkaline stimulant, 1 to 3 kg of white pigment, 1 to 20 kg of white cement , and a specific surface area of 2,500 to 5,500 Cm 2 / g, wherein the alkaline stimulant is any one or more compounds selected from calcium hydroxide, potassium hydroxide, sodium hydroxide, sodium silicate, calcium sulfate and aluminum sulfate. In the method for producing a back cement composition,
100 kg of cement, 50 to 70 kg of slag, 10 to 15 kg of gypsum, 10 to 15 kg of slaked lime, 1 to 3 kg of alkaline stimulant, 1 to 3 kg of white pigment, 1 to 20 of cement A method of producing a back cement composition, comprising mixing kg , and then grinding and preparing with a secondary ball mill after primary premixing, and grinding and preparing with a specific surface area of 2,500 to 5,500 cm 2 / g , depending on the type. In the method for producing a back cement composition,
After mixing 100 kg of cement, 50 to 70 kg of slag, 10 to 15 kg of gypsum, 10 to 15 kg of slaked lime, 1 to 3 kg of alkaline stimulant, 1 to 3 kg of white pigment, and 1 to 20 kg of white cement , triisopropanol amine acetate was added. After the addition of 2kg, after the first premixing, it was ground by a second ball mill, and prepared by grinding a specific surface area of 2,500 ~ 5,500 cm 2 / g ,
The alkaline stimulant is prepared by using any one compound selected from calcium hydroxide, potassium hydroxide, sodium hydroxide, sodium silicate, calcium sulfate and aluminum sulfate or two or more compounds .

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