KR102119471B1 - Inorganic binder composition capable of promoting heat generation and resistance to cold - Google Patents

Abstract

The present invention is an inorganic binder composition capable of facilitating heat and cold resistance, and more specifically, it promotes curing by incineration and combustion residues containing chlorine, and prevents freezing, and when it is mixed with water, it has a low temperature due to its self-heating function and winter construction. B. In the case of urgent construction of concrete and soft ground solidification treatment, it relates to an inorganic binder composition capable of promoting heat generation and cold resistance, which has the advantage of being equipped with minimum curing conditions.

Description

Inorganic binder composition capable of promoting heat generation and resistance to cold}

The present invention is an inorganic binder composition capable of facilitating heat and cold resistance, and more specifically, it promotes curing by incineration and combustion residues containing chlorine, and prevents freezing, and when it is mixed with water, it has a low temperature due to its self-heating function and winter construction. B. In the case of urgent construction of concrete and soft ground solidification treatment, it relates to an inorganic binder composition capable of promoting heat generation and cold resistance, which has the advantage of being equipped with minimum curing conditions.

Concrete structures constructed in regions with long winter periods, such as Korea, cannot be expected to have a predetermined strength and durability, so construction by the construction method of Korea-China concrete is inevitable. According to the specifications of the Ministry of Land, Infrastructure and Transport in Korea, Korea-China concrete is defined as a day with an average daily temperature of 4℃ or less, and local governments and land and housing corporations are required to stop water construction when the temperature is below 0℃. It is 31 to 160 days for local organizations and 20 to 120 days for land and housing construction, which causes enormous losses due to suspension of construction. In order to prevent the thawing of concrete, first, the required performance such as strength and durability must be satisfied, and the construction work in a hard state and the hydration reaction during curing must be faithfully performed. In particular, the most important thing for concrete should be the proper hydration temperature condition so that cement can have sufficient hydration reaction at the beginning. Hydration of the cement delays or stops the reaction at low temperatures, preventing the required performance. In addition, when the concrete suffers from the initial East Sea, cracking due to volume expansion occurs due to freezing of water, making it difficult to permanently develop strength. Due to this, construction work is not being carried out properly during the winter season, and if the construction can be done regardless of the low temperature during the winter season, it is possible to compensate for the massive loss caused by the winter construction interruption of the ready-mixed concrete and ground solidifying construction companies in winter. It is also very effective in terms of the employment increase effect.

Many of the Korea-China concrete standards currently used in Korea are made on the basis of foreign standards, but they are slightly different according to each domestic society or specification, so it is necessary to prepare accurate and unified standards and apply them in the field. It is necessary to establish a plan that can be easily and activated. In the case of foreign countries, the development of effective Korea-China concrete has been actively carried out by the use of cold protection, but development in Korea is very poor, and only developed countries are supplying to some ready-mixed concrete through the import of cold protection. As a admixture capable of lowering the freezing temperature of concrete, a lot of conventionally used substances are substances such as calcium chloride, sodium chloride, potassium chloride, sodium acetate, sodium nitrite, calcium acetate, calcium acetate, urea, bleaching powder, ethyl alcohol, and ethylene alcohol. . In addition, inorganic substances such as chloride, carbonate, and nitrate, triethanolamine, and calcium nitrate are used as materials for promoting the hydration of cement. However, chlorides such as calcium chloride and sodium chloride have a higher unit price than ordinary cement (75,000 won/ton), and the risk of corrosion of reinforcing bars in reinforced concrete structures is high, making it difficult to use more than 0.3% by weight compared to cement weight. Donghae prevention admixtures are very expensive, with prices ranging from 500,000 to 2 million won/ton, and thus, Korea-China concrete is not widely used in Korea. However, in case of chloride-based cold weather, in case of unreinforced concrete products that are not used with reinforcing bars, mortar for finishing, and soft ground solidifying materials, chloride of 0.3% or more compared to cement weight can be used, so it is very effective in initial copper sea. Can be

In addition, there is a method that is used by heating water and aggregate as a method commonly used to prevent the initial thawing of concrete, but in reality, most of the ready-mixed concrete plants are not equipped with facilities to produce ready-mixed concrete by heating water and aggregate. to be.

In addition, there is a method to prevent the occurrence of initial strength and prevention of frost damage by using fast-hardening cement, but the price of fast-hardening cement is about 4 to 20 times higher than that of normal cement, which is difficult to use except for emergency repair work. Have.

Looking at the prior patent literature,

The Republic of Korea Patent Registration No. 101456041 "strengthening the concrete composition and the concrete mixing method for preventing and preventing the East Sea" is sodium chloride 15.5% by weight to 21.5% by weight, ammonium chloride 11.5% by weight to 17.5% by weight, calcium chloride 32.5% by weight to 51% by weight, Magnesium chloride 1.5 wt% to 7.5 wt%, soda ash 11.5 wt% to 17.5 wt%, surfactant 4.5 wt% to 10.5 wt%, propylene glycol 4.5 wt% to 10.5 wt% contained in the concrete composition for enhancing strength and preventing thawing This is disclosed.

The Republic of Korea Patent Registration No. 101561003, "Cement composition including self-heating slag, the construction method of the Chinese-Chinese concrete composition including the same, and a structure using the same" includes C ₃ A (3CaOㅇAl ₂ O ₃ ) as the main mineral, and Al ₂ O Disclosed is a composition comprising self-heating slag, cement and gypsum generated in the refining process of a steelmaking process containing ₃ % by weight or more.

In the Republic of Korea Patent No. 101729216, "Cold-resistant accelerator composition for heat-generating concrete", a cold-resistant accelerator composition for heat-generating concrete capable of expressing early strength is added to impart anti-rotation properties, and includes calcium nitrate, calcium nitrite and lithium nitrite. 1 admixture; It is added to control the setting time and heating time of concrete, and any one or more selected from the group consisting of potassium formate (PF), potassium acetate (PA), calcium formate (CF), potassium nitrate, tartaric acid and lithium carbonate A second admixture comprising; And a blending water used for mixing the first admixture and the second admixture.

The Republic of Korea Patent Registration No. 100880930 "super-hard cement composition" is 40 to 60% by weight of a powder obtained by grinding an arwin-based clinker containing 60 to 85% calcium sulfoaluminate, and 15 to 30 gypsum powder mixed with anhydrous gypsum and hemihydrate gypsum. Superhard cement compositions comprising 20% to 40% by weight of ordinary Portland cement and 1 to 4% by weight of slaked lime are disclosed.

In the Republic of Korea Patent No. 101418238, "high-durability super-hard mixed cement composition", clinker 90 to 95% by weight, Isu gypsum 5.0 to 10.0% by weight, coarse-grained cement 29.3 to 43.1% by weight, siloxane silicone 0.5 to 1.0% by weight, calcium sulfoaluminate (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, slaked lime High durability ultra-fast cemented cement composition using silane and siloxane-based silicone composed of 2.0 to 4.0% by weight, 0.3 to 0.5% by weight of fluidizing agent, 0.1 to 0.5% by weight of curing accelerator, and 0.5 to 0.7% by weight of coagulation retarder This is disclosed.

Republic of Korea Patent Registration No. 101456041 Republic of Korea Registered Patent No. 101561003 Republic of Korea Registered Patent No. 101729216 Republic of Korea Registered Patent No. 100880930 Republic of Korea Registered Patent No. 101418238

The present invention has been devised to solve the above-mentioned problems, and an object of the present invention is an inorganic binder composition capable of promoting heat generation and cold resistance suitable for use in winter construction at low temperatures, by incineration and combustion residues containing chlorine components. It provides an inorganic binder that has the advantage of being able to use with minimum curing conditions in the construction of concrete and soft ground in winter construction or emergency construction where the temperature is low due to the function of promoting cement hardening and preventing freezing and self-heating when mixed with water. Is in

The present invention for achieving the above object,

For 100 parts by weight of incineration and combustion residues containing chlorine

5 to 10,000 parts by weight of a heat generating agent capable of generating hydration heat of 60°C or more within 10 minutes when mixing with 1:1 parts by weight of water,

5-10,000 parts by weight of coal ash in the desulfurization circulating circulation bed boiler in the furnace,

It provides an inorganic binder composition capable of promoting heat and cold, characterized in that it contains 5 to 10,000 parts by weight of fine blast furnace slag.

The incineration and combustion residues preferably have a chlorine content of 0.1 to 30% by weight.

In addition, the heating agent may use any one or a mixture of two or more selected from the group consisting of quicklime, light dolomite, petroleum coke, and aluminum dross. In particular, it is preferable to use a petroleum coke combustor as the heating agent, and the petroleum coke combustor preferably contains 50 to 100 parts by weight based on 100 parts by weight of the incineration and combustion residue.

The in-furnace desulfurization type circulating fluidized bed boiler coal ash can generate hydration heat of 30°C or more within 10 minutes when mixed with water by 1 part by weight, and any one or two or more of fly ash and bottom ash discharged from the desulfurization type circulating fluidized bed boiler in the furnace It is good to be a mixture.

In addition, with respect to 100 parts by weight of the incineration and combustion remnants, the curing accelerator further comprises 0.5 to 200 parts by weight,

The curing accelerator is Calcium Formate (Ca(HCOO) ₂ ), Li ₂ CO ₃ , CaCl ₂ , CaSO ₄ , K ₂ SO ₄ , MgSO ₄ , Na ₂ SO ₄ , Na ₂ CO ₃ , Al ₂ (SO ₄ ) ₃ It is preferred that any one or a mixture of two or more selected from the group consisting of.

And, with respect to 100 parts by weight of the incineration and combustion residues, it further comprises 5 to 5,000 parts by weight of cement to improve the initial strength,

The cement is usually Portland cement, semi-joint steel Portland cement, crude steel Portland cement, CSA (Calcium Sulfur Aluminate), C ₁₂ A ₇ , alumina cement, superhard cement, or any one or more mixture of two or more.

According to the present invention, at least in the case of winter or low-concrete concrete and soft ground solidification treatment due to the self-heating function when mixing with water and promoting freezing and preventing freezing by incineration and combustion residues containing chlorine components It has the advantage of being able to use and have curing conditions. It can improve the initial strength and prevent the initial dynamics. Therefore, it is possible to compensate for the huge loss caused by the suspension of winter construction in the winter season, and it is also very effective in terms of the employment increase effect.

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

The inorganic binder according to the present invention is a heat generating agent capable of generating hydration heat of 60° C. or more within 10 minutes when mixing with 1:1 parts by weight of water with respect to 100 parts by weight of incineration and combustion residues having a chlorine content of 0.1 to 30% by weight, 5 to 10,000 parts by weight It contains 5 to 10,000 parts by weight of pulverized blast furnace slag and 5 to 10,000 parts by weight of blast furnace slag, which can generate hydration heat at 30°C or more within 10 minutes when mixing with 1 part by weight of water and water.

In general, in the case of fly ash discharged to a boiler that burns only 100% of coal, it does not contain a chlorine component, but the incineration and combustion residues of the present invention are waste vinyl, waste synthetic resin, waste wood, waste sheet, waste furniture and chlorine. It is generated during the process of alone or mixing the sludge containing, and has a freeze prevention function because it is a substance that contains a large amount of chlorine itself. In addition, the chloride ion (Cl ^-) may be substituted for the calcium chloride is generally used in the field requiring an initial strength in winter it has the characteristics of promoting the hydration reaction of cement and sodium chloride and the like.

The incineration and combustion residues preferably have a chlorine content of 0.1 to 30% by weight. When the chlorine content is less than 0.1% by weight, the anti-freezing function and the effect of promoting the cement hydration reaction are insufficient, and when it exceeds 30% by weight, it reacts with the cement hydration product Ca(OH) ₂ to cause CaO, CaCl ₂ ㅇ2H ₂ O, Mg ₂ After the formation of crystals of (OH) ₃ Clㅇ 4H ₂ O, salt damage may occur that may expand the volume. Therefore, to be carried out before the chlorine content quantitation wearing material of chloride ion (Cl ^-) is preferably used in the amount 0.1 to 30% by weight.

The exothermic agent is for preventing the initial thawing at low temperature in winter by generating high temperature heat by hydration reaction with water, any one or more selected from the group consisting of quicklime, light dolomite, petroleum coke burning material, aluminum dross It is preferably a mixture.

Quicklime and light dolomite are commercially available products. Calcined limestone and dolomite are fired at high temperature and decarbonized. When mixed with water, CaO and MaO components hydration to generate heat at a high temperature of 80 to 120℃. have. In addition, Ca(OH) ₂ or Mg(OH) ₂ produced by reacting with water acts as an alkali stimulus to the fine powder of the blast furnace slag, so that it is possible to exert latent hydraulic properties.

Petro coke combustibles are discharged from a circulating fluidized bed boiler that mixes Petro coke and limestone to desulfurize the furnace. Limestone is injected into the combustion chamber to burn together with petroleum coke, and sulfur phosphate and limestone in the combustion gas react in the furnace to remove sulfur in the combustion gas and anhydrous gypsum, and limestone that has not reacted with sulfur is decarbonized and transferred to the raw lime component. Is discharged. Therefore, it has the feature that it can self-heat when reacted with water by the quick-lime component of the Petro Coke combustor, so it can prevent the initial thawing without the need to separately heat the water and aggregate to prevent the initial thawing of concrete in winter. Insulating curing is possible. In addition, the anhydrous gypsum component of the petroleum coke combustor can function to accelerate the curing reaction of the blast furnace slag fine powder while reacting with the fine blast furnace slag to produce ettringite. Aluminum dross is a by-product generated in the aluminum manufacturing process, and reacts with water to generate hydrogen gas and ammonia, so the reaction proceeds as an exothermic reaction. Due to the exothermic reaction, moisture distributed in the soil or sludge in a high water content state can be rapidly evaporated.

It is preferable to use a heat generating agent capable of generating hydration heat of 60°C or more within 10 minutes when mixing 1:1 parts by weight with water. When the heating temperature is less than 60°C, the effect of preventing the initial winter sea at a low temperature in winter is insufficient. Therefore, it is preferable to use one capable of generating hydration heat of 60°C or more within 10 minutes when mixing 1:1 parts by weight with water before receiving the raw materials. That is, when the heat of hydration of 60°C or higher is possible, the material itself heats up in a hydration reaction under the freezing temperature environment of winter, so it is possible to prevent the defrosting at the beginning of condensation hardening and to increase the initial strength.

The exothermic agent is preferably mixed with 5 to 10,000 parts by weight with respect to 100 parts by weight of the incineration and combustion remnants. If it is less than 5 parts by weight, the self-heating effect is not exerted. It can be generated and excessively absorbed moisture can significantly decrease the fluidity.

In addition, the desulfurization circulating fluidized bed boiler coal ash in the furnace is preferably a mixture of any one or two or more of fly ash and bottom ash. The circulating fluidized bed boiler coal ash is generated in a desulfurization process in the furnace that mixes coal and limestone. Since it is burned at a temperature of about 830°C and has no glassy components, it cannot cause a pozzolanic reaction like fly ash discharged from a pulverized coal boiler of a thermal power plant, but CaO And CaSO ₄ component is contained in a large amount of self hydration heat generation and blast furnace slag potential hydraulic exertion is possible. The circulating fluidized bed boiler coal ash is preferably mixed in an amount of 5 to 10,000 parts by weight with respect to 100 parts by weight of the incineration and combustion remnants having a chlorine content of 0.1 to 30% by weight. If it exceeds the weight part, excessive heat generation may cause expansion cracks, and excessive absorption of moisture may significantly degrade fluidity.

The blast furnace slag fine powder can be used as long as it is a pulverized product in the form of a fine powder having a specific surface area of 3,500 cm ² /g or more commonly distributed on the market.

In addition, it is preferable to further contain 0.5 to 200 parts by weight of a curing accelerator with respect to 100 parts by weight of the incineration and combustion residues.

The curing accelerator is any one selected from the group consisting of 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 ) ₃ It is preferably a mixture of two or more. The curing accelerator helps to prevent initial copper thawing by promoting the hydration of blast furnace slag fine powder and cement to C ₃ S and rapidly exhibiting initial strength. The curing accelerator is preferably mixed in an amount of 0.5 to 200 parts by weight with respect to 100 parts by weight of incineration and combustion remnants. If it is less than 0.5 parts by weight, the curing promoting effect is not exhibited. It is difficult to secure.

In addition, it is preferable to further contain 5 to 5,000 parts by weight of cement with respect to 100 parts by weight of the incineration and combustion residues to improve the initial strength. The cement is usually Portland cement, quasi-steel Portland cement, crude steel Portland cement, CSA (Calcium Sulfur Aluminate), C ₁₂ A ₇ , alumina cement, it is preferably a mixture of one or more of cemented carbide. In addition, the cement is preferably mixed with 5-10,000 parts by weight with respect to 100 parts by weight of incineration and combustion remnants. If it is less than 5 parts by weight, strength cannot be exhibited. The content is reduced, and the anti-freezing effect is greatly reduced.

Preferred examples and comparative examples of the present invention will be described below. In addition, the following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

[Compositions of Examples 1 to 5 and Comparative Example 1]

Inorganic binder compositions of Examples 1 to 5 and Comparative Example 1 were prepared by mixing in the mixing ratio shown in Table 1.

At this time, a waste wood chip incinerator having a chlorine content of 6.5% by weight was used as the incinerator, and the raw lime was mixed with water in a weight ratio of 1:1, and the heat generation temperature was 104°C after 60 seconds, and the petrol coke combustion material was petroleum coke and limestone. Petroleum coke combusted material discharged from a circulating fluidized bed boiler, which was mixed and desulfurized in a furnace, was used, and after mixing with water in a weight ratio of 1:1, the heating temperature was 90° C. after 60 seconds. And the coal ash used a circulating fluidized bed boiler bottom ash, and after mixing with water in a weight ratio of 1:1, the exothermic temperature was 46° C. after 60 seconds. For the blast furnace slag, blast furnace slag fine powder having a specific surface area of 4,250 cm 2 /g was used.

Mixing ratio (% by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 1 type cement - - 18 - - 100 Incineration ash 20 18 10 20 18 - Fever quicklime 15 10 10 - - - Petrocox Combustion Materials - - - 15 10 - Coal ash 15 20 10 15 20 - Blast furnace slag 50 50 50 50 50 - Hardener - 2 2 - 2 -

(Evaluation of compressive strength characteristics under low temperature environment)

As a basic test to see if the inorganic binder compositions of Examples 1 to 5 and Comparative Example 1 can express excellent strength in a low-temperature environment, 400 kg of one type of cement or inorganic binder composition and 320 kg of water are compulsory based on 1 m ³ of soluble clay. Mix thoroughly with a type mixer to prepare milk infusion material, mix homogeneously with 1 m ^{3 of} marine clay, prepare 9 specimens of φ10 cm×20 cm size, cure at -2°C using a thermo-hygrostat, and then age 3, 7, Intensity was measured 28 days. Thereafter, the results are shown in Table 2 below.

<Test for evaluation of compressive strength of mortar cured under -2℃>

Compressive strength (MPa) 3 days 7 days 28 days Example 1 0.34 0.75 1.23 Example 2 0.41 0.79 1.26 Example 3 0.58 0.87 1.74 Example 4 0.39 0.77 1.25 Example 5 0.45 0.80 1.28 Comparative Example 1 0.21 0.48 0.81

Compressive strengths of Examples 1 to 5 were all found to exhibit high strength compared to Comparative Example which is a type 1 cement. Example 1 using chlorine-containing waste wood chip incinerator, quicklime, circulating fluidized bed boiler coal ash, and blast furnace slag fine powder showed an initial strength close to 1.6 times at 3 days of age compared to Comparative Example 1 using only one type of cement, and even at 28 days of age About 50% higher intensity was expressed. Example 2, which further included a curing accelerator in Example 1, had an effect of enhancing strength by about 20% at 3 days of age, compared to Example 1, and the 7th and 28th days showed similar trends. In Example 1, Example 3, which further contained a curing accelerator and cement, was able to confirm that not only the strength of 2.5 times or more was expressed at 3 days of age, but also about 2 times or more strength at 28 days of age, compared to Comparative Example 1.

In particular, unlike Examples 1 and 2, in the case of Examples 4 and 5, which used petroleum coke as a heating agent, the exothermic temperature when reacting with water was lower than that of the quicklime of Examples 1 and 2, but higher at 3 days of age The initial strength was expressed, and it was confirmed that superior compressive strength was expressed even at the age of 28 days.

As described above, the inorganic binders of Examples 1 to 5 of the present invention prevent the initial freezing of ignition and combustion materials containing chlorine and promote hydration reaction, and heat generating agents such as quicklime and circulating fluidized bed boiler coals even at low temperature of 2℃ below zero It was found that due to the effect of promoting initial curing due to heat generation, it is possible to exert very effective performance in securing initial strength and preventing initial frost in winter construction.

In addition, it is possible to expect the effect of cost reduction and environmental protection by reducing the amount of cement produced by consuming large amounts of natural resources and energy by utilizing circulating resources that are insufficiently recycled.

Claims (8)

With respect to 100 parts by weight of incineration and combustion residues with a chlorine content of 0.1 to 30% by weight
5 to 10,000 parts by weight of a heat generating agent capable of generating hydration heat of 60°C or more within 10 minutes when mixing with 1:1 parts by weight of water,
When mixing with water at 1:1 parts by weight, hydration heat can be generated within 10 minutes or more, and desulfurization type circulation distribution bed boiler in the furnace, which is a mixture of any one or more of fly ash and bottom ash discharged from the desulfurization type circulation fluidized bed boiler in the furnace 5 to 10,000 parts by weight of coal ash,
An inorganic binder composition capable of promoting heat and cold, characterized in that it contains 5 to 10,000 parts by weight of fine blast furnace slag.
According to claim 1,
The heating agent is an inorganic binder composition capable of promoting heat and cold resistance, characterized in that it is any one or a mixture of two or more selected from the group consisting of quicklime, light dolomite, petroleum coke, and aluminum dross.
According to claim 1,
The heating agent is made of a petroleum coke combustion material, the petroleum coke combustion material is an inorganic binder composition capable of promoting heat and cold, characterized in that it comprises 50 to 100 parts by weight based on 100 parts by weight of the incineration and combustion residue.
According to claim 1,
With respect to 100 parts by weight of the incineration and combustion remnants, the curing accelerator further comprises 0.5 to 200 parts by weight,
The curing accelerator is Calcium Formate (Ca(HCOO) ₂ ), Li ₂ CO ₃ , CaCl ₂ , CaSO ₄ , K ₂ SO ₄ , MgSO ₄ , _{Na 2 SO 4, Na 2 CO} 3, Al 2 (SO 4) heating to one or characterized in that a mixture of two or more selected from the group consisting of ₃ cold and facilitate the possible inorganic binder composition.
According to claim 1,
With respect to 100 parts by weight of the incineration and combustion residue, 5 to 5,000 parts by weight of cement is further included to improve initial strength,
The cement is a common Portland cement, semi-joint steel Portland cement, crude steel Portland cement, CSA (Calcium Sulfur Aluminate), C ₁₂ A ₇ , alumina cement, superhard cement, or a mixture of one or more of two or more, characterized in that the exotherm and cold resistance promotion This possible inorganic binder composition. delete delete delete