KR101973967B1 - An inorganic binder composition capable of improving initial strength and preventing initial frost resistance - Google Patents

Abstract

The present invention relates to an inorganic binder composition capable of enhancing initial strength and preventing initial freezing damage. More particularly, the present invention relates to an inorganic binder composition capable of enhancing initial strength and preventing initial freezing damage, which can be used with minimum curing conditions in hardening treatment of concrete and soft ground of an urgent construction or winter construction with low temperature by a function of curing promotion and freezing prevention due to incineration and combustion residues containing chlorine and a self-heating function of a petro coke combustion material. The composition comprises incineration and combustion residues having chlorine content of 0.5-30 wt%, a petro coke combustion material, and cement.

Description

[0001] The present invention relates to an inorganic binder composition capable of improving initial strength and preventing initial frost damage,

The present invention relates to an inorganic binder composition capable of improving initial strength and preventing initial frost damage. More specifically, the present invention relates to an inorganic binder composition capable of improving initial strength and preventing initial frost damage. More specifically, the present invention relates to an inorganic binder composition capable of accelerating curing and freezing prevention by chlorine- The present invention relates to an inorganic binder composition capable of improving initial strength and preventing initial frost damage, which can be used with minimum curing conditions in concrete construction and soft ground consolidation construction in a winter or low-temperature construction.

Since it is difficult to expect concrete strengths and durability of concrete structures constructed in long areas such as Korea during the winter season, it is inevitable to apply the method by the construction method of cold-side concrete.

According to the Ministry of Land, Transport and Maritime Affairs, the average daily temperature is below 4 ° C, and the local government and land and housing corporation are taking measures to stop water construction when the temperature is below 0 ° C. In the case of local organizations, it is 31 ~ 160 days. In the case of land and housing corporation, it is 20 ~ 120 days. In order to prevent the frost damage of concrete, it is required to satisfy the required performance such as strength and durability, and it is necessary to faithfully perform waterproof reaction during hardening and workability in an uncured state.

Especially important in concrete is to maintain proper hydration temperature conditions so that cement can hydrate sufficiently early. The hydration of the cement is delayed or stopped at low temperature and the required performance is not obtained.

Also, when the concrete is subjected to the initial frost damage, it is cracked due to expansion of the volume due to freezing of water, so that it is difficult to permanently express the strength. Therefore, construction work is not being carried out properly during the winter, and if the construction can be carried out regardless of the low temperature even during the winter season, the Remicon and the specialist of the foundation can compensate for the huge loss caused by the winter It is also very effective in terms of the employment increase effect.

Although most of the Korean concrete standards used in Korea are based on foreign norms, they are slightly different according to the domestic institutes and specifications, so it is necessary to prepare correct and uniform standards and apply them in the field. It is necessary to establish measures that can be facilitated and activated.

In the case of foreign countries, the development of effective Korean concrete is being actively pursued by the use of cold weathering, but development in Korea has been very limited, and it is only supplied to Remicon in the developed countries through the importation of antifreeze.

As the admixture which can lower the freezing temperature of concrete, most commonly used materials are calcium chloride, sodium chloride, potassium chloride, sodium acetate, sodium acetate, calcium acetate, calcium acetate, urea, bleaching powder, ethyl alcohol and ethylene alcohol .

In addition, inorganic substances such as chloride, carbonate, and nitrate, and triethanolamine, calcium nitrate, etc. are used as a substance promoting hydration reaction of cement. However, chlorides such as calcium chloride and sodium chloride are not only higher in price than one kind of ordinary cement (75,000 won / ton), but also have a high risk of corrosion of reinforcing bars in reinforced concrete structures.

In addition, since the price of the anti-seize admixture is very high at 50 ~ 200,000 KRW / ton, the Korean concrete is not widely used in Korea.

However, in the case of chloride-based antifreeze, it is possible to use more than 0.3% of chloride relative to the weight of cement in the field such as unused concrete products that are not used like rebar, mortar for mortar and soft ground fire. Can be.

In addition, there is a method that is used by heating water and aggregate as a general method to prevent the early frost damage of concrete. However, in reality, most concrete mixer factories are not equipped with facilities capable of producing concrete and water by heating water and aggregate. to be.

In addition, there is a method to prevent initial strength development and prevention of frost damage by using quick-setting cement. However, since the price of quick-setting cement is 4 ~ 20 times higher than that of one kind of ordinary cement, Have.

On the other hand, Patent Documents 0001 to 0005 and the like have been proposed in connection with a concrete composition capable of exhibiting initial strength and preventing corrosion.

[0001] The present invention relates to a concrete compounding composition and a concrete blending method for enhancing strength and anti-dying property, which comprises 15.5 to 21.5% by weight of sodium chloride, 11.5 to 17.5% by weight of ammonium chloride, 32.5 to 51% by weight of calcium chloride, A reinforcing concrete composition comprising 1.5 to 7.5% by weight of magnesium, 11.5 to 17.5% by weight of soda ash, 4.5 to 10.5% by weight of a surfactant and 4.5 to 10.5% by weight of propylene glycol, Lt; / RTI >

As Patent Document 0002 is about the construction methods of the cement composition, Korea and China concrete compositions and structures using the same, including this, including the self-heating slag, comprising a _{C 3 A (3CaO · Al 2} O 3) as the main mineral, Al ₂ O ₃ A composition containing self-heating slag, cement and gypsum generated in a refining process of a steelmaking process containing not less than 20% by weight.

[0002] The present invention relates to a cold weather accelerator composition for exothermic concrete, which is capable of exhibiting an early strength and is added for imparting a flammability, and is characterized in that it comprises a calcium chloride Admixture; (PF), potassium acetate (PA), calcium formate (CF), potassium nitrate, tartaric acid, and lithium carbonate, which are added to control the setting time and the heating time of the concrete. A second admixture comprising; And a compounding water used for mixing the first admixture and the second admixing agent.

Patent Document 0004 discloses an ultra rapid hardening cement composition comprising 40 to 60% by weight of powders obtained by crushing an Alwin clinker containing 60 to 85% of calcium sulfoaluminate, 15 to 30% by weight of a gypsum powder mixed with anhydrous gypsum and half- %, Usually 20 to 40 wt% of Portland cement, and 1 to 4 wt% of slaked lime.

Patent Document No. 0005 relates to a high durability ultra high speed light mixing cement composition comprising 29.3 to 43.1% by weight of a crude steel cement having 90 to 95% by weight of a clinker and 5.0 to 10.0% by weight of anisotrope, By weight, calcium sulfate sulphoaluminate (3CaO.3Al ₂ O ₃ .CaSO ₄ ) 32.5 to 33.5% by weight, C ₁₂ A ₇ 2.0 to 9.5% by weight, anhydrous gypsum 19.0 to 21.0% by weight, A high durability ultrahigh speed light mixing cement composition using silane and siloxane based silicone constituted by 0.5 to 0.7% by weight, a fluidizing agent of 0.3 to 0.5% by weight, a curing accelerator of 0.1 to 0.5% by weight, Lt; / RTI >

KR 10-1456041 B1 (2014.10.23) KR 10-1561003 B1 (2015.10.08) KR 10-1729216 B1 (2017.04.17) KR 10-0880930 B1 (2009.01.21) KR 10-1418238 B1 (2014.07.04)

In order to solve such conventional problems, the present invention is to solve the above-mentioned problems of the prior art, and to provide a cement mortar composition for a cement mortar composition, which comprises cement hardening promoting and freezing prevention function by chlorine-containing incineration and combustion residues, And to provide an inorganic binder composition capable of improving initial strength and preventing initial frost damage at a minimum curing condition at the time of construction of a soft ground reinforcement treatment.

According to an aspect of the present invention,

The present invention provides an inorganic binder composition capable of improving initial strength and preventing initial frost damage, which comprises combustion and incineration residues having a chlorine content of 0.5 to 30% by weight, petroleum cokes, and cement.

Particularly, 5 to 10,000 parts by weight of petroleum cokes and 5 to 10,000 parts by weight of cement are contained in 100 parts by weight of the incineration and combustion residue.

The petroleum coke combustion material is characterized by being a petroleum coke combustion material which generates hydration heat at 30 ° C or higher within 10 minutes when mixed with water at a ratio of 1: 1 by weight.

And 5 to 10,000 parts by weight of a circulating fluidized bed boiler coal ash which is a mixture of at least one of fly ash and bottom ash discharged from the circulating fluidized bed boiler with respect to 100 parts by weight of the incineration and combustion residue.

Wherein the circulating fluidized bed boiler coal ash is a circulating fluidized bed boiler coal ash capable of generating hydration heat at 30 ° C or higher within 10 minutes when mixed with water 1: 1.

And 0.5 to 200 parts by weight of a curing accelerator based on 100 parts by weight of the incineration and combustion residues.

And 10 to 10,000 parts by weight of a slag fine powder having a specific surface area of at least 3,500 cm ² / g with respect to 100 parts by weight of the incineration and combustion residues.

The inorganic binder composition capable of improving the initial strength and preventing the initial frost damage according to the present invention is characterized in that the inorganic binder composition capable of accelerating the hardening and freezing prevention by the incineration containing chlorine and the combustion residue and the hydrothermal heat of the petroleum coke combustion material can generate heat, It is effective to improve the initial strength and to prevent the initial frost damage, which is advantageous in that it can be used with minimum curing conditions in concrete and soft ground processing of construction.

Therefore, it can be said that it is very effective in terms of the employment increase effect, which can compensate for the huge loss due to the winter termination during the winter season.

Hereinafter, the inorganic binder composition capable of improving the initial strength and preventing initial frost damage according to the present invention will be described in detail.

The inorganic binder composition capable of improving the initial strength and preventing the initial frost damage according to the present invention comprises an incineration and combustion residue having a chlorine content of 0.5 to 30% by weight, petroleum cokes, and cement.

Generally, coal fly ash used in concrete does not contain chlorine components. However, the incineration and combustion residues of the present invention include waste vinyl, waste synthetic resin, waste wood, waste plaster, waste furniture and chlorine-containing sludge. It occurs during the process of solitary or simultaneous, and it has a freezing prevention function because it is a substance containing a large amount of chlorine by itself. In addition, the chlorine ion (Cl ^- ) contained in the incineration and combustion residues promotes the hydration reaction of cement, and can replace calcium chloride and sodium chloride commonly used in the field requiring initial strength in the winter season.

The incineration and combustion residue preferably has a chlorine content of 0.5 to 30 wt%. If the content of chlorine is less than 0.5 wt%, the effect of accelerating the cement hydration reaction is insufficient. If it exceeds 30 wt%, it reacts with the cement hydrate Ca (OH) ₂ to form CaO, CaCl ₂ .2H ₂ O, Mg ₂ (OH) ₃ Cl · 4H ₂ O may be generated, which may expand the volume after crystallization. Therefore, it is preferable to use a chlorine ion (Cl ^- ) content of 0.5 to 30% by weight by conducting quantitative analysis of the chlorine content before the stocking.

The petro coke oven material is discharged from a circulating fluidized-bed boiler where petroleum coke and limestone are mixed and desulfurized in the furnace. Limestone is injected into the combustion chamber and burned together with petro coke. The sulfur dioxide and limestone in the combustion gas react in the furnace to remove sulfur in the combustion gas and produce anhydrous gypsum. The limestone that has not reacted with sulfur is decarbonated, And then discharged. Therefore, it has a characteristic that it can generate heat when it reacts with water by the quicklime component of petro coke ovens. Therefore, it is not necessary to separately heat water and aggregate separately to prevent the early frost damage of winter concrete, Insulation curing is possible. In addition, the anhydrous gypsum component of petro coke oven can react with cement to produce ettringite and to perform cementing function.

It is preferable that the petroleum coke oven material is capable of generating hydration heat at 30 ° C or higher within 10 minutes when mixed with water at a ratio of 1: 1. If the exothermic temperature is less than 30 ° C, the effect of preventing the initial frost damage at low temperatures in winter is insufficient. Therefore, it is preferable to use a material capable of generating hydration heat at 30 占 폚 or higher within 10 minutes when mixing 1: 1 part by weight of water before the stock material. That is, Petro coke oven material capable of generating hydration heat at 30 ° C or more can heat the material itself due to hydration reaction under the freezing-and-cold conditions in the winter season, thereby preventing frost damage at the initial stage of coagulation curing and improving initial strength.

It is preferable that the petroleum coke oven material is mixed with 5 to 10,000 parts by weight with respect to 100 parts by weight of the incineration and combustion residue. When the amount is less than 5 parts by weight, the self-heating effect is not exhibited. When the amount is more than 10,000 parts by weight, heat is excessively generated, and expansion cracks may be generated.

The cement is preferably a mixture of any one or two or more of Portland cement, quasi-crude steel Portland cement, crude steel Portland cement, CSA (Calcium Sulfur Aluminate), C ₁₂ A ₇ , alumina cement and ultra fast cement. The cement is preferably mixed with 5 to 10,000 parts by weight based on 100 parts by weight of the incineration and combustion residues. If the amount is less than 5 parts by weight, the strength can not be exhibited. If the amount is more than 10,000 parts by weight, the strength is greatly increased but the chlorine content is decreased and the effect of preventing the freezing is greatly deteriorated.

Further, it is preferable that 5 to 10,000 parts by weight of the circulating fluidized bed boiler coal material capable of generating hydration heat at 30 ° C or higher within 10 minutes when 100 parts by weight of the incineration and combustion residues are mixed with water in a ratio of 1: 1.

The circulating fluidized bed boiler coal ash is a mixture of one or more of fly ash and bottom ash discharged from the circulating fluidized bed boiler. The circulating fluidized-bed boiler coal ash is generated in the process of desulfurizing the coal and limestone, which is combusted at a temperature of about 830 ° C., and thus can not cause a pozzolanic reaction like the coal ash discharged from a pulverized coal- It contains a large amount of CaSO ₄ component and can accelerate hydration of cement and hydration heat of self.

It is preferable that the circulating fluidized bed boiler coal ash is mixed with 5 to 10,000 parts by weight with respect to 100 parts by weight of the incineration and combustion residues. When the amount is less than 5 parts by weight, the self-heating effect is not exhibited. When the amount is more than 10,000 parts by weight, heat is excessively generated, and expansion cracks may be generated.

In addition, it is preferable that the incineration and combustion residues further comprise a curing accelerator. The curing accelerator is _{Calcium Formate (Ca (HCOO) 2} ), Li 2 CO 3, CaCl 2, CaSO 4, Na 2 SO 4, Na 2 CO 3, Al 2 (SO 4) which is selected from the group consisting of _3-one or It is preferable that the mixture is two or more. The curing accelerator accelerates the hydration of C ₃ S of the cement so that the initial strength is rapidly exerted, thereby helping to prevent the initial frost damage. The curing accelerator is preferably mixed with 0.5 to 200 parts by weight based on 100 parts by weight of the incineration and combustion residue. When the amount is less than 0.5 parts by weight, the effect of accelerating curing is not exhibited. When the amount is more than 200 parts by weight, the curing is too rapid and the workability is hardly secured.

It is also preferable that 10 to 10,000 parts by weight of the slag fine powder having a specific surface area of 3,500 cm ² / g or more is contained in 100 parts by weight of the incineration and combustion residue.

The slag fine powder may be at least one selected from the group consisting of a converter slag fine powder, an electric furnace slag fine powder, a blast furnace slag fine powder, an electric furnace reducing slag fine powder, a copper slag fine powder, a steelmaking process refining slag fine powder, a stainless steel refining slag fine powder, Fine powder, desulfurization slag fine powder, or a mixture of two or more thereof.

All of the above-mentioned slag fine powders are discharged as byproducts of steel making, steel making and non-ferrous metal manufacturing processes, and are pulverized into a fine powder having a specific surface area of 3,500 cm ² / g or more, so that micropore filling and potential hydration can be exhibited to further enhance strength and durability. The slag fine powder is preferably mixed with 10 to 10,000 parts by weight with respect to 100 parts by weight of the incineration and combustion residue. If the amount is less than 10 parts by weight, the strength and durability improving effect is not exhibited. If the amount is more than 10,000 parts by weight, the strength may be significantly lowered.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. The following examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention.

[Composition of Examples 1 to 3 and Comparative Example 1]

1 Cement and Chlorine-free Pulverized Coal Boiler Thermal power plant fly ash containing 5.1 wt% chlorine Waste wood ash, chlorine 21.5 wt% waste vinyl ash, waste coke oven material, circulating fluidized bed boiler fly ash, curing accelerator and specific surface area 4,250 cm ² / g of blast furnace slag were blended in the mixing ratios shown in Table 1 to obtain inorganic binder compositions of Comparative Examples 1 and 2 and Examples 1 to 4.

The pulverized coke oven material was mixed with water at a weight ratio of 1: 1, and after 60 seconds, the temperature was measured to be 92 ° C. The circulating fluidized bed boiler fly ash was mixed with water at a weight ratio of 1: 1, The measurement result is 46 ° C. CaCl ₂ was used as a curing accelerator.

Blending ratio (% by weight) Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 One kind cement 100 80 80 80 75 65 Pulverized coal boiler
Thermal power plant fly ash - 20 - - - - Waste wood ash - - 7 7 10 Waste vinyl waste - - - 7 - - Petroleum coke oven material - - 13 13 11 10 Circulating fluidized bed
Boiler fly ash - - - - 7 - Hardening accelerator - - - - - 2 Fine powder of blast furnace slag - - - - - 13

[Evaluation of compressive strength characteristics under low temperature environment]

As a basic test for evaluating whether the inorganic binder compositions of Comparative Examples 1 and 2 and Examples 1 to 4 can exhibit excellent strength in a low temperature environment, mortar was prepared in accordance with KS L ISO 679 (Cement Strength Test Method) After curing at -2 ℃, the compressive strength was evaluated according to age. The results are shown in Table 2 below.

For accurate experiments, all temperature conditions were compared with those of the same material by using a thermo-hygrostat, keeping the material and measurement container 24 hours before the test date. This test is the result of comparing and evaluating more than 3 times.

Evaluation test of compressive strength of mortar cured at -2 ℃
Compressive strength (MPa) 3 days 7 days 28th Comparative Example 1 5.6 14.8 31.2 Comparative Example 2 3.8 11.8 30.2 Example 1 10.4 21.3 35.7 Example 2 12.6 24.1 39.6 Example 3 9.7 22.7 34.1 Example 4 13.8 27.8 41.9

The uniaxial compressive strengths of Examples 1 to 4 are higher than those of Comparative Example 1, which is one kind of cement, and Comparative Example 2, which contains fly ash of a pulverized coal-fired boiler thermal power plant which does not contain any chlorine component appear.

It was confirmed that Example 2 using the incineration ash having a chlorine content about 4 times higher than the incineration ash used in Example 1 exhibited higher strength than Example 1. In Example 2, the initial strength was almost 1.2 times higher than that in Example 1 at 3 days, and the strength was about 11% higher at 28 days. Therefore, when the chlorine - containing incinerator is used, the initial strength development effect is manifested under the low temperature environment. The higher the chlorine content, the more remarkable the effect is.

Example 2 using chlorinated vinyl ash material, petro coke oven material and one kind of portland cement showed initial strength almost 2.2 times as compared with that of comparative example 1 using only one kind of cement, 14% higher strength was exhibited.

Example 3, which further included a circulating fluidized bed boiler fly ash in Example 1, showed a similar tendency to that of Example 1, and Example 4, in which the curing accelerator and the slag fine powder were further contained in Example 1, It was confirmed that not only the intensity of 2.5 times or more was exhibited in the ages, but the intensity was about 34% higher than that in the ages of 28 days. As described above, the inorganic binder of the present invention has an effect of promoting early cryopreservation and cement hydration reaction of incinerated and softened materials containing chlorine even at a low temperature of minus 2 ° C, and accelerating initial curing due to heat generation of petroleum coke burned material It was found that it is possible to secure the initial strength in the winter and to perform very effectively in preventing the early frost damage.

By using recycled resources that are not recycled, it is possible to expect cost reduction and environmental protection effect by reducing the amount of cement produced by mass consumption of natural resources and energy.

Claims (7)

5 to 10,000 parts by weight of petroleum cokes, 5 to 10,000 parts by weight of cement, and one of fly ash and bottom ash discharged from a circulating fluidized bed boiler, with respect to 100 parts by weight of incineration and combustion residues having a chlorine content of 0.5 to 30% Or 5 to 10,000 parts by weight of a circulating fluidized bed boiler coal as a mixture of two or more thereof,
The Petro coke oven material is a Petro coke oven material that hydration heat is generated at 30 ° C or higher within 10 minutes when mixed with water at a ratio of 1: 1,
Wherein the circulating fluidized bed boiler coal ash is a circulating fluidized bed boiler coal ash capable of generating hydration heat at 30 ° C or higher within 10 minutes when mixed with water at a ratio of 1:
The method according to claim 1,
Characterized in that 0.5 to 200 parts by weight of a curing accelerator is added to 100 parts by weight of the incineration and combustion residue, and an inorganic binder composition
The method according to claim 1,
And 10 to 10,000 parts by weight of a slag fine powder having a specific surface area of at least 3,500 cm ² / g with respect to 100 parts by weight of the incineration and combustion residues. The inorganic binder composition delete delete delete delete