KR102158524B1 - Eco-friendly solidifying composition for weak ground - Google Patents

Eco-friendly solidifying composition for weak ground Download PDF

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KR102158524B1
KR102158524B1 KR1020200045326A KR20200045326A KR102158524B1 KR 102158524 B1 KR102158524 B1 KR 102158524B1 KR 1020200045326 A KR1020200045326 A KR 1020200045326A KR 20200045326 A KR20200045326 A KR 20200045326A KR 102158524 B1 KR102158524 B1 KR 102158524B1
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blast furnace
slag
fine powder
slow cooling
eco
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Korean (ko)
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한상태
원미혜
전준영
장재환
황인혁
김영국
김정호
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고려에프에이(주)
고려기초소재 주식회사
고려산업(주)
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/02Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/10Cements, e.g. Portland cement
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04Waste materials; Refuse
    • C04B18/06Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/061Ashes from fluidised bed furnaces
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04Waste materials; Refuse
    • C04B18/06Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/067Slags
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04Waste materials; Refuse
    • C04B18/06Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08Flue dust, i.e. fly ash
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04Waste materials; Refuse
    • C04B18/06Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08Flue dust, i.e. fly ash
    • C04B18/084Flue dust, i.e. fly ash obtained from mixtures of pulverised coal and additives, added to influence the composition of the resulting flue dust
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04Waste materials; Refuse
    • C04B18/14Waste materials; Refuse from metallurgical processes
    • C04B18/141Slags
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04Waste materials; Refuse
    • C04B18/18Waste materials; Refuse organic
    • C04B18/20Waste materials; Refuse organic from macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02Treatment
    • C04B20/04Heat treatment
    • C04B20/06Expanding clay, perlite, vermiculite or like granular materials
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12Nitrogen containing compounds organic derivatives of hydrazine
    • C04B24/124Amides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Abstract

The present invention relates to an eco-friendly solidifying material composition for soft ground, comprising cement, blast furnace slag fine powder, anhydrous gypsum, desulfurized gypsum, IGCC slag, bypass dust, fly ashes, and circulating fluid bed ashes.

Description

연약지반용 친환경 고화재 조성물{Eco-friendly solidifying composition for weak ground}Eco-friendly solidifying composition for weak ground}

본 발명은 연약지반용 친환경 고화재 조성물에 관한 것이다.The present invention relates to an eco-friendly solidifying material composition for soft ground.

일반적으로 연약지반 개량공사에는 표층 및 심층의 자연상태 토사에 고화재를 투입 혼합하여 고화시킴으로써 연약한 지반을 개량하는 연약지반 고결공법이 많이 이용되고 있으며, 여기에 사용되는 고화재로는 보통 포틀랜드 시멘트나 슬래그시멘트 또는 이들 시멘트에 포졸란 물질을 추가 혼합한 시멘트계 고화재가 주로 사용되고 있다.In general, in soft ground improvement construction, a soft ground solidification method that improves the soft ground by solidifying by mixing and solidifying solidified material in the natural state of the surface and deep is widely used. The solidifying material used here is usually Portland cement or Slag cement or cement-based solidifying materials obtained by adding pozzolanic materials to these cements are mainly used.

통상 고화재는 시멘트 또는 고로수쇄슬래그, 플라이애시 등을 주원료로 사용하고 있다. 하지만, 상기 나열된 재료들은 토질 내에 존재하는 유기물질로 인해 수화물이 효과적으로 생성되지 않는 단점이 있다. 이러한 이유 때문에 소정의 강도발현에 장시간이 요구되고 연약지반보강에 비효율적이다.In general, cement or blast furnace crushing slag, fly ash, etc. are used as the main raw material for solidification. However, the materials listed above have a disadvantage in that hydrates are not effectively produced due to organic substances present in the soil. For this reason, a long time is required to develop a predetermined strength and is inefficient in reinforcing soft ground.

상기 문제점들을 최소화하기 위해 석고-석회계 재료를 적용한 조성물이 적용되어 있지만, 상대적으로 비싼 원료가격과 반응에 따른 알칼리화로 암모니아, 황화수소 등 발생 가스에 의한 부작용이 발생된다.In order to minimize the above problems, a composition using a gypsum-lime material is applied, but side effects due to gases such as ammonia and hydrogen sulfide are generated due to relatively expensive raw material prices and alkalinization according to the reaction.

한편, 기존 지반보강용 고화재의 주원료인 생석회와 시멘트는 석회석을 주원료로 하는 제품으로 1톤을 생산하기 위해 이산화탄소를 약 0.9톤 가량 배출하며, 이는 온실가스 증가로 나타나 최근의 환경정책에도 역행하는 결과를 낳고 있는 문제점이 있다.On the other hand, quicklime and cement, which are the main raw materials for solidifying materials for ground reinforcement, are products that use limestone as their main raw materials, and they emit about 0.9 tons of carbon dioxide to produce 1 ton. There is a problem that is producing results.

따라서, 토질의 종류, 지하수위, 주변환경 등 다양한 지반조건에 따라 친환경성 재료가 필요하며 친환경 재료를 이용한 설계, 시공품질을 만족시킬 수 있는 친환경성 재료의 개발이 필요하다.Therefore, eco-friendly materials are required according to various ground conditions such as the type of soil, groundwater level, and surrounding environment, and development of eco-friendly materials that can satisfy design and construction quality using eco-friendly materials is required.

대한민국 특허등록 제1444071호Republic of Korea Patent Registration No.1444071

본 발명은 앞에서 설명한 바와 같은 종래 기술의 문제점을 해결하기 위하여 발명된 것으로서, 시멘트 사용을 제어하여 친환경적이면서도 조강성, 작업성, 강도 등이 확보될 수 있는 고화재 조성물을 제공하고자 함이다.The present invention has been invented to solve the problems of the prior art as described above, and is intended to provide a solidifying material composition that is environmentally friendly and can secure crude stiffness, workability, strength, etc. by controlling the use of cement.

상기 목적을 달성하기 위한 본 발명의 연약지반용 친환경 고화재 조성물(이하 "본 발명의 조성물"이라함)은 시멘트, 고로슬래그 미분말, 무수석고, 탈황석고, IGCC 슬래그, 바이패스 더스트(BYPASS DUST), 플라이애시, 순환유동층애시를 포함하는 것을 특징으로 한다.The eco-friendly solidifying composition for soft ground of the present invention (hereinafter referred to as "composition of the present invention") to achieve the above object is cement, blast furnace slag powder, anhydrous gypsum, desulfurized gypsum, IGCC slag, bypass dust (BYPASS DUST) , Fly ash, characterized in that it comprises a circulating fluidized bed ash.

하나의 예로 망초가 더 포함되는 것을 특징으로 한다.As an example, it is characterized in that it further includes forget-me-not.

하나의 예로 상기 고로슬래그 미분말에는 고로 수쇄슬래그 미분말과 고로 서냉슬래그 미분말이 포함되는 것을 특징으로 한다. As an example, the blast furnace slag fine powder includes a blast furnace crushed slag fine powder and a blast furnace slow cooling slag fine powder.

하나의 예로 상기 고로 서냉슬래그 미분말은 그 표면에 이산화규소가 코팅된 것을 특징으로 한다.As an example, the blast furnace slow cooling slag fine powder is characterized in that the silicon dioxide is coated on its surface.

하나의 예로 세라마이드가 더 포함되는 것을 특징으로 한다.As an example, ceramide is further included.

상술한 본 발명의 조성물은 연약지반 개량시 지반 및 지하수 오염의 문제를 제어할 수 있어 친환경적인 장점이 있다.The composition of the present invention described above has an eco-friendly advantage because it can control the problem of ground and groundwater contamination when improving the soft ground.

또한 산업부산물을 다량으로 사용하여 경제성이 있음과 동시에 강도, 작업성, 내구성 등 물성이 우수한 장점이 있다.In addition, it has the advantage of being economical by using a large amount of industrial by-products and having excellent physical properties such as strength, workability, and durability.

이하, 실시 예를 통하여 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail through examples.

본 발명의 조성물은 시멘트, 고로슬래그 미분말, 무수석고, 탈황석고, IGCC 슬래그, 바이패스 더스트(BYPASS DUST), 플라이애시, 순환유동층애시를 포함하는 것을 특징으로 한다.The composition of the present invention is characterized by comprising cement, blast furnace slag powder, anhydrous gypsum, desulfurized gypsum, IGCC slag, BYPASS DUST, fly ash, and circulating fluidized bed ash.

또한 본 발명의 조성물에는 칼슘설포알루미네이트계 시멘트(CSA)가 더 첨가될 수 있는데, 칼슘설포알루미네이트계 시멘트(CSA)는 시멘트의 속경성, 팽창성, 무수축성이 요구되는 곳에 사용되는 시멘트인 바, 본 발명의 조성물에 고로슬래그 미분말이 첨가됨에 따라 동절기 등에 압축강도가 저하되는 경우가 있는데 이러한 문제를 해결하기 위해 칼슘설포알루미네이트계 시멘트(CSA)가 사용되어 온도영향을 덜 받도록 하기 위함이다.In addition, calcium sulfoaluminate-based cement (CSA) may be further added to the composition of the present invention, and calcium sulfoaluminate-based cement (CSA) is a cement used in places where fast setting, expansion, and non-shrinkability of cement are required. , As the fine blast furnace slag powder is added to the composition of the present invention, the compressive strength may decrease in winter, etc., but calcium sulfoaluminate-based cement (CSA) is used to solve this problem so that it is less affected by temperature.

상기 고로슬래그는 선철의 원료가 되는 철광석과 석회석 중 철 이외의 성분이 용해되어 밀도차에 의해 용선과 분리·부유된 부산물이다. 고로에서 배출되는 슬래그는 약 1,500℃ 내외의 고온의 용융상태에서 상온으로 냉각하는 방법에 따라 수쇄슬래그와 서냉슬래그로 구분된다.The blast furnace slag is a by-product separated and suspended from molten iron due to a difference in density by dissolving components other than iron among iron ore and limestone, which are raw materials for pig iron. The slag discharged from the blast furnace is classified into crushed slag and slow cooling slag according to the method of cooling to room temperature in a molten state at a high temperature of about 1,500℃.

상기 고로 수쇄슬래그는 배출된 고온·용융상태의 슬래그에 고압의 냉각수를 다량 방출하여 급랭시킨 슬래그이다, 냉각속도가 빠르기 때문에 결정질 조직이 형성되지 못하고 유리질이 90% 이상을 차지하는 비정질상을 형성한다. 상기 고로 수쇄슬래그는 화학조성이 일반 시멘트와 유사하고 시멘트의 수화반응에서 생성된 Ca(OH)2와 반응하여 잠재수경성을 나타내기 때문에 시멘트 및 콘크리트 혼화재료로 널리 사용되는 것이다. 즉 고로 수쇄슬래그의 첨가에 의해 잠재수경성이 발현되므로 압축강도면에서 유리한 장점이 있다.The blast furnace crushed slag is a slag that is rapidly cooled by discharging a large amount of high-pressure cooling water to the discharged high-temperature and molten slag.Since the cooling rate is fast, a crystalline structure cannot be formed, and an amorphous phase is formed that accounts for more than 90% of the glass. The blast furnace crushed slag is widely used as a cement and concrete admixture because its chemical composition is similar to that of ordinary cement and exhibits latent hydraulicity by reacting with Ca(OH) 2 generated in the hydration reaction of cement. That is, since latent hydraulicity is expressed by the addition of blast furnace crushed slag, it has an advantage in terms of compressive strength.

상기 고로 서냉슬래그는 고로에서 배출된 용융상태의 슬래그를 가압수의 공정을 거치지 않고 바로 야적장에 적재되어 결정질상태가 되는 고로슬래그이다. 결정질의 구조이므로 수경성이 없기 때문에 압축강도 발현성에 기여하지 못하며, 용도로는 성토용 골재, 도로용 매립재 등으로 매우 제한적으로 일부 사용되고 있다.The blast furnace slow cooling slag is a blast furnace slag in which the molten slag discharged from the blast furnace is loaded directly into a storage yard without going through a process of pressurized water to become a crystalline state. Since it has a crystalline structure, it does not contribute to the development of compressive strength because it does not have hydraulic properties, and it is partially used in a very limited manner as an aggregate for embankment and a landfill material for roads.

상기 고로 서냉슬래그의 경우 물과는 수화반응을 하지 않으나, 탄산화 양생하는 것에 의해 고로 서냉슬래그의 주요성분인 Melilite, α-Wollastonite가 반응을 하여 경화체의 치밀화가 유도된다. 즉 밀실한 경화체를 형성되도록 하는 것이다.In the case of the blast furnace slow cooling slag, it does not undergo a hydration reaction with water, but by carbonation curing, Melilite and α-Wollastonite, the main components of the blast furnace slow cooling slag, react, leading to densification of the hardened body. In other words, it is to form a tight hardened body.

이에 본 발명에서는 바람직하게 고로슬래그 미분말을 첨가하되, 고로 수쇄슬래그 미분말의 첨가에 의해 압축강도가 발현되도록 함과 동시에 고로 서냉슬래그 미분말이 첨가되도록 하여 중성화를 억제하고 작업성을 향상시키도록 하는 것이 타당하다.Therefore, in the present invention, preferably, the fine blast furnace slag powder is added, but it is reasonable to suppress the neutralization and improve the workability by allowing the compressive strength to be expressed by the addition of the fine blast furnace slag powder and at the same time adding the blast furnace slow cooling slag fine powder. Do.

한편 상기에서 언급한 바와 같이 본 발명의 조성물에는 고로 서냉슬래그가 첨가되어 작업성 및 내구성을 향상시키나, 고로 수쇄슬래그만 첨가하는 경우에 비해 다소 강도가 저하되는 문제가 있을 수 있다. 이에 본 발명에서는 개질 고로 서냉슬래그가 첨가되도록 하는데 개질 고로 서냉슬래그는 그 표면에 이산화규소가 코팅된 것이 적용되도록 하는 것이다.Meanwhile, as mentioned above, blast furnace slow cooling slag is added to the composition of the present invention to improve workability and durability, but there may be a problem in that the strength is somewhat lowered compared to the case where only blast furnace crushed slag is added. Accordingly, in the present invention, the modified blast furnace slow cooling slag is added, and the modified blast furnace slow cooling slag is coated with silicon dioxide on its surface.

상기에서 언급한 바와 같이 고로 서냉슬래그는 결정질의 구조이므로 수경성이 없기 때문에 압축강도 발현성에 기여하지 못하는 바, 이에 본 발명에서는 표면에 이산화규소가 코팅된 고로 서냉슬래그가 첨가되도록 하는 것이다.As mentioned above, since the blast furnace slow cooling slag has a crystalline structure, it does not contribute to the development of compressive strength because it does not have hydraulic properties.Therefore, in the present invention, the blast furnace slow cooling slag coated with silicon dioxide is added to the surface.

이와 같이 표면에 이산화규소가 코팅된 고로 서냉슬래그가 첨가되도록 함으로써 이산화규소(SiO₂)를 주성분으로 하는 포졸란(pozzolan)은 시멘트의 수화에 의해 생기는 수산화칼슘(Ca(OH)₂)과 반응하여 잠재수경성이 발현되도록 함으로써 고로 서냉슬래그의 첨가에도 불구하고 압축강도가 저하되는 것을 방지토록 하는 것이다.In this way, by adding silicon dioxide-coated blast furnace slow cooling slag to the surface, pozzolan, which is mainly composed of silicon dioxide (SiO₂), reacts with calcium hydroxide (Ca(OH)₂) generated by the hydration of cement, resulting in potential hydraulic hardening. This is to prevent the compressive strength from decreasing despite the addition of the blast furnace slow cooling slag.

표면에 이산화규소가 코팅된 고로 서냉슬래그는 고로에서 배출된 용융상태의 슬래그를 가압수의 공정을 거치지 않고 바로 야적장에 적재되도록 하되, 용융상태의 슬래그에 분쇄된 폐주물사 분말을 첨가하여 상호 혼합시키면서 자연냉각과정을 거치도록 함에 따라 표면에 이산화규소가 코팅된 고로 서냉슬래그가 제조되도록 하는 것이다. The blast furnace slow cooling slag coated with silicon dioxide on the surface allows the molten slag discharged from the blast furnace to be loaded directly into the storage yard without going through the process of pressurized water, but by adding pulverized waste foundry powder to the molten slag and mixing them together, it is natural. As the cooling process goes through, the blast furnace slow cooling slag coated with silicon dioxide on the surface is made.

상기 폐주물사는 주조(鑄造)후 남은 모래로써, 석영입자(규사; SiO₂성분이 포함된 석영 알갱이 모래)가 대부분으로 이러한 폐주물사를 분쇄하여 고로에서 배출된 용융상태 슬래그의 서냉과정에서 이를 첨가하여 혼합함으로써 고로 서냉슬래그의 표면에 이산화규소가 코팅이 되도록 하는 것이다.The waste foundry sand is the remaining sand after casting, and quartz particles (quartz sand; quartz grain sand containing SiO₂ component) are mostly pulverized and mixed by adding it during the slow cooling of the molten slag discharged from the blast furnace. Therefore, silicon dioxide is coated on the surface of the slow cooling slag.

상기 무수석고 및 탈황석고는 에트린자이트 생성 등으로 인하여 조직을 치밀화 시켜 조기강도 및 수축저감효과가 발현되도록 하는 것이다.The anhydrous gypsum and desulfurized gypsum are to densify the tissue due to the generation of ethrinzite, etc., so that the early strength and shrinkage reduction effect are expressed.

상기 바이패스 더스트(BYPASS DUST)는 시멘트 공정 산업부산물로서 소성공정의 순환물질 by-pass 설비에서 배출되는 부산물질로 시멘트 및 콘크리트의 응결 및 경화현상을 촉진시키는 염소이온 및 알칼리 이온이 함유되어 특히 동절기에 압축강도를 향상시키는 효과가 발현되도록 하는 것이다.The BYPASS DUST is a by-product of the cement process industry and is a by-product discharged from the by-pass facility, a circulating material in the firing process, and contains chloride ions and alkali ions that promote the condensation and hardening of cement and concrete. The effect of improving the compressive strength is to be expressed.

상기 순환유동층애시는 화력발전소의 순환유동층 연소방식의 보일러에서 발생되고 있으며, 순환유동층 보일러내에 탈황을 목적으로 석회석을 투입하면 로내의 온도에 의해 열분해가 일어나고 CaO 입자주변에 SO2 가스가 집중되면서 표면에서 황산화 반응이 일어나게 되며 CaSO4가 생성된다. 순환유동층애시의 특성으로는 CaO 및 SO3의 함유로 초기압축강도 증진효과 및 건조수축을 감소시키는 효과가 발현된다.The circulating fluidized bed ash is generated in a circulating fluidized bed combustion type boiler of a thermal power plant, and when limestone is introduced into the circulating fluidized bed boiler for desulfurization, pyrolysis occurs due to the temperature in the furnace, and SO 2 gas is concentrated around the CaO particles. Sulfation reaction takes place in and CaSO 4 is produced. As a characteristic of the circulating fluidized bed ash, the effect of improving initial compressive strength and reducing drying shrinkage is expressed by containing CaO and SO 3 .

상기 IGCC 슬래그는 석탄가스화기 복합발전소에서 철강슬래그의 수재슬래그 생산공정과 유사하게 물로 급랭하여 발생된다. IGCC 슬래그는 고로슬래그와 제조방식 및 화학성분이 유사하며, 색상은 석탄을 연소하여 전력을 발생하기 때문에 플라이애시와 유사한 진회색 형상을 지니고 있다.The IGCC slag is generated by rapid cooling with water in a coal gasifier combined cycle power plant, similar to the process of producing steel slag for water slag. IGCC slag is similar in manufacturing method and chemical composition to blast furnace slag, and has a dark gray shape similar to fly ash because it generates electric power by burning coal.

이러한 IGCC 슬래그가 첨가되는 이유는 플라이애시에 비해 IGCC 슬래그가 CaO 및 SO3를 다량 함유하고 있는 바, 플라이애시의 경우 초기강도가 낮은 문제가 있으며 이의 활성화를 위해 다량의 화학적 활성화제의 첨가가 필요한데 플라이애시의 이러한 점에 대한 대체제가 되는 것이며, 고로슬래그에 비해 Al2O3 등이 다량으로 함유되어 내구성(에트린자이트 생성) 등에서 고로슬래그를 보완하게 되는 것이다.The reason for the addition of such IGCC slag is that IGCC slag contains a large amount of CaO and SO 3 compared to fly ash. In the case of fly ash, there is a problem that the initial strength is low, and a large amount of chemical activator is required to activate it. It is a substitute for this point of fly ash, and it contains a large amount of Al 2 O 3 and the like compared to blast furnace slag, which complements the blast furnace slag in durability (generating ethrinite).

또한 본 발명의 조성물에는 상기 조성들 외에도 망초가 더 포함되도록 하는 예가 제시된다.In addition, the composition of the present invention is presented an example to further include forget-me-not in addition to the above compositions.

상기 망초(Na2SO4)는 나프탈렌 공정에서 발생되는 산업부산물로서 나프탈렌에 황산을 반응시켜 나프탈렌 설폰산염(Naphthalene Sulfonic acid)을 제조할 때 일부 슬러지로서 부산되며, 이러한 슬러지(망초)는 단위수량감소, 유동성 증진 등의 효과가 발현되도록 하는 것이다.The forget-me-not (Na 2 SO 4 ) is an industrial by-product generated in the naphthalene process, and when naphthalene sulfonic acid is produced by reacting sulfuric acid with naphthalene, it is partly produced as sludge, and such sludge (forget-me-not) is reduced in unit quantity. This is to allow effects such as improvement of fluidity to be expressed.

한편 본 발명에서는 산화칼슘(CaO) 및 삼산화황(SO3) 함량이 비교적 높은 재료를 사용하도록 하여 초기강도를 증진토록 하는데 초기강도의 증진에 따라 수축에 의한 균열문제가 야기될 수 있으며, 황산이온 등이 에트린자이트 생성과정 등에서 반응에 관여하지 않은 잔유물로서 페이스트에 존재할 수 있는데 이러한 황산이온 등의 존재는 황산화세균 등이 증식에 의해 열화를 야기 시킬 수 있는 문제가 있다.On the other hand, in the present invention, a material having a relatively high content of calcium oxide (CaO) and sulfur trioxide (SO 3 ) is used to increase the initial strength. As the initial strength increases, a crack problem due to shrinkage may be caused. The paste may exist as a residue that is not involved in the reaction in the process of ethrinzite production, etc., but the presence of such sulfate ions has a problem that may cause deterioration by proliferation of sulfated bacteria or the like.

이에 본 발명에서는 상기 조성외에도 사라마이드가 더 배합되도록 하는 예를 제시하고 있다.Accordingly, in the present invention, an example in which the salamide is further blended in addition to the above composition is presented.

상기 세라마이드는 보습에 의해 페이스트에서 모세관현상에 의해 수분이 증발하는 것을 방지함으로써 균열저항성을 향상시키도록 하는 것이다.The ceramide is to improve crack resistance by preventing evaporation of moisture from the paste due to capillary phenomenon by moisturizing.

또한 상기 세라마이드는 상기에서 언급한 바와 같이 황산이온의 존재 등에 의해 산화세균, 황산화세균이 증식하는 경우 페이스트의 열화를 야기시킬 수 있는 문제가 있는데 상기 세라마이드는 상기 산화세균, 황산화세균 등의 증식을 억제토록 하여 열화를 방지토록 함으로써 내구성을 우수하게 하는 것이다. In addition, as mentioned above, the ceramide has a problem that may cause deterioration of the paste when oxidizing bacteria and sulfated bacteria proliferate due to the presence of sulfate ions, and the ceramide is the proliferation of the oxidizing bacteria and sulfated bacteria. The durability is improved by preventing deterioration by suppressing it.

바람직하게 본 발명의 조성물은 시멘트 100중량부에 대해 고로슬래그 미분말 50 내지 150중량부, 플라이애시 10 내지 100중량부, 무수석고 1 내지 10중량부, 탈황석고 1 내지 10중량부, IGCC 슬래그 10 내지 100중량부, 바이패스 더스트(BYPASS DUST) 1 내지 10중량부, 순환유동층애시 10 내지 100중량부, 망초 1 내지 10중량부, 세라마이드 1 내지 5중량부를 배합하는 것이 타당하다. Preferably the composition of the present invention is based on 100 parts by weight of cement, 50 to 150 parts by weight of blast furnace slag powder, 10 to 100 parts by weight of fly ash, 1 to 10 parts by weight of anhydrite, 1 to 10 parts by weight of desulfurized gypsum, 10 to IGCC slag It is reasonable to mix 100 parts by weight, 1 to 10 parts by weight of BYPASS DUST, 10 to 100 parts by weight of circulating fluid bed ash, 1 to 10 parts by weight of forget-me-not, and 1 to 5 parts by weight of ceramide.

이하 실험예에 의해 본 발명의 실시예를 설명한다. Examples of the present invention will be described by the following experimental examples.

Figure 112020038724572-pat00001
Figure 112020038724572-pat00001

OPC: 1종 보통 포틀랜드 시멘트OPC: Type 1 Normal Portland Cement

SP: 고로슬래그 미분말(실시예 1 내지 3의 경우 고로 수쇄슬래그 미분말이 첨가된 시료이며, 실시예 3-1은 고로 수쇄슬래그 미분말과 고로 서냉슬래그 미분말이 중량비로 1:1로 혼합된 시료이며, 실시예 3-2는 고로 수쇄슬래그 미분말과 표면에 이산화규소가 코팅된 서냉슬래그 미분말이 중량비로 1:1로 혼합된 시료임)SP: blast furnace slag fine powder (in the case of Examples 1 to 3, blast furnace crushed slag fine powder is added, and Example 3-1 is a sample in which blast furnace crushed slag fine powder and blast furnace slow cooling slag fine powder are mixed at a weight ratio of 1:1, Example 3-2 is a sample in which the fine powder of blast furnace crushed slag and the fine powder of slow cooling slag coated with silicon dioxide on the surface are mixed at a weight ratio of 1:1)

FA: 플라이애시FA: fly ash

IGCC: IGCC 슬래그IGCC: IGCC slag

CFBC: 순환유동층애시CFBC: Circulating fluidized bed ash

GP-1: 천연무수석고GP-1: Natural anhydride gypsum

GP-2: 탈황석고GP-2: Desulfurized gypsum

BPD: 바이패스 더스트(by-pass bust)BPD: By-pass bust

NS: 나프탈렌 설폰산(Naphthalene Sulfonic acid) 슬러지(망초)NS: Naphthalene Sulfonic acid sludge (forget-me-not)

C: 세라마이드C: Ceramide

< 일축압축강도 시험(KS F 2343)><Uniaxial compressive strength test (KS F 2343)>

대상 점토로서 함수비 45.3%이며, 습윤 단위체적중량 1,762 ㎏/m3의 해상점토를 사용하였다. 본 발명의 비교예와 실시예에 의해 조합된 배합에 대해서 고화재 250 ㎏/m3, 물-결합재비 100%로 믹싱하여 실린더형 몰드 지름 50㎜ ㅧ 100㎜에 일축압축강도 시험용 공시체를 제작하였다.As the target clay, a water content of 45.3% and a wet unit volume weight of 1,762 kg/m 3 were used. For the combination of the comparative examples and examples of the present invention, a specimen for uniaxial compressive strength test was prepared in a cylindrical mold diameter of 50 mm ㅧ 100 mm by mixing with a solidifying material of 250 kg/m 3 and a water-binding material ratio of 100%. .

Figure 112020038724572-pat00002
Figure 112020038724572-pat00002

상기 표 2에서 보는 바와 같이 비교예와 실시예들을 대비시 플라이애시만을 첨가하는 경우보다 실시예들과 같이 순환유동층애시 및 IGCC 슬래그를 더 병용하여 첨가하는 경우가 조기강도 확보에 더욱 유리한 것을 알 수 있다.As shown in Table 2, it can be seen that the case of adding circulating fluidized bed ash and IGCC slag in combination as in the Examples is more advantageous in securing early strength than when only adding fly ash when comparing Comparative Examples and Examples. have.

실시예 2는 망초가 더 첨가된 시료로서 망초의 첨가로 단위수량 감소 및 유동성의 증가로 경화체를 치밀화시켜 실시예 1보다 압축강도에 유리한 결과가 도출됨을 알 수 있다.Example 2 is a sample to which forget-me-not was further added, and it can be seen that the addition of forget-me-not to reduce the unit quantity and increase the fluidity to densify the cured body, resulting in a result that is more advantageous in compressive strength than in Example 1.

실시예 3은 세라마이드가 더 첨가된 시료로서 세라마이드의 첨가에 의해 균열저항성을 향상시킴에 기해 압축강도에서 실시예 2보다 유리한 결과가 도출됨을 알 수 있다.Example 3 is a sample to which ceramide is further added, and since the addition of ceramide improves the crack resistance, it can be seen that the result is more advantageous than that of Example 2 in compressive strength.

실시예 3에 비해 실시예 3-1의 경우가 압축강도면에서 다소 불리한 효과가 발현되는 것을 알 수 있는데 이는 고로 서냉슬래그 미분말이 결정질로 되어있으므로 수화반응에 관여하지 못함에 의하여 압축강도가 감소되는 것으로 판단된다. 고로 수쇄슬래그 미분말 및 서냉슬래그 미분말을 병용(실시예 3-1)해서 사용할 경우가 고로 수쇄슬래그 미분말을 단독으로 사용한 경우(실시예 3)에 비하여 압축강도가 다소 감소됨을 알 수가 있다. 따라서 서냉슬래그는 결정질로서 수화반응에는 거의 관여하지 않는 것으로 판단된다.Compared to Example 3, it can be seen that the case of Example 3-1 exhibits a somewhat unfavorable effect in terms of compressive strength. This is because the blast furnace slow cooling slag powder is crystalline, so that the compressive strength is reduced by not participating in the hydration reaction. It is judged to be. It can be seen that when the blast furnace crushed slag fine powder and the slow-cooled slag fine powder are used in combination (Example 3-1), the compressive strength is somewhat reduced compared to the case of using the blast furnace crushed slag powder alone (Example 3). Therefore, it is judged that slow cooling slag is crystalline and hardly participates in the hydration reaction.

또한 고로 서냉슬래그를 적용함에 있어 표면에 이산화규소가 코팅된 고로 서냉슬래그(실시예 3-2)의 경우 실시예 3-1과 대비 압축강도 면에서 훨씬 유리한 효과가 발현되고 있는 것을 알 수 있다. 이는 고로 서냉슬래그 표면에 이산화규소에 의한 잠재수경성의 발현에 기인한 것으로 판단된다. 즉 고로 서냉슬래그의 첨가에 따른 압축강도 저하의 문제가 제어되면서도 유동성 등의 기능이 발현되도록 하는 것이다.In addition, in applying the blast furnace slow cooling slag, in the case of the blast furnace slow cooling slag (Example 3-2) coated with silicon dioxide on the surface, it can be seen that a much more advantageous effect is expressed in terms of compressive strength compared to Example 3-1. This is believed to be due to the expression of latent hydraulicity by silicon dioxide on the surface of the blast furnace slow cooling slag. In other words, while controlling the problem of lowering the compressive strength due to the addition of the blast furnace slow cooling slag, functions such as fluidity are expressed.

<투수계수 시험(KS F 2322: 변수위 투수 시험방법)><Permeability coefficient test (KS F 2322: Permeability test method on variable position)>

상기 시료들에 대해 재령 7일간 양생한 공시체의 투수계수 시험을 진행하였으며, 그 결과가 하기 표 3에 도시되고 있다.The samples were subjected to a permeability test of the specimens cured for 7 days of age, and the results are shown in Table 3 below.

Figure 112020038724572-pat00003
Figure 112020038724572-pat00003

실시예 1과 실시예 2를 대비시 실시예 2의 경우가 투수계수가 감소되는 것을 알 수 있는데, 이는 실시예 2의 경우 망초의 첨가로 단위수량 감소 및 유동성의 증가에 의해 경화체를 치밀화시킴에 기인한 것으로 판단된다. When comparing Example 1 and Example 2, it can be seen that in Example 2, the water permeability was decreased. This is because in Example 2, the hardened body was densified by reducing the unit amount and increasing the fluidity due to the addition of forget-me-not. It is believed to be caused by.

실시예 3의 경우가 실시예 2보다 투수계수가 감소되는 것을 알 수 있는데 이는 실시예 3에서 세라마이드가 더 첨가됨에 따라 균열저항성을 향상시킴에 기인한 것으로 판단된다.In the case of Example 3, it can be seen that the water permeability decreases compared to Example 2, which is considered to be due to the improvement of crack resistance as ceramide was further added in Example 3.

이상과 같이 본 발명은 비록 한정된 실시예와 도면에 의해 설명되었으나, 본 발명은 상기 실시예에 한정되지 않음은 물론이며, 본 발명이 속하는 분야에서 통상의 기술적 지식을 가진 자에 의해 상기 기재된 내용으로부터 다양한 수정 및 변형이 가능할 수 있음은 물론이다.As described above, although the present invention has been described by a limited embodiment and drawings, the present invention is not limited to the above embodiment, as well as from the above description by a person having ordinary technical knowledge in the field to which the present invention belongs. It goes without saying that various modifications and variations may be possible.

Claims (5)

시멘트, 고로슬래그 미분말, 무수석고, 탈황석고, IGCC 슬래그, 바이패스 더스트(BYPASS DUST), 플라이애시, 순환유동층애시를 포함하며,
상기 고로슬래그 미분말은 고로 수쇄슬래그 미분말과 고로 서냉슬래그 미분말이 포함되되, 상기 고로 서냉슬래그 미분말은 그 표면에 이산화규소가 코팅된 개질 고로 서냉슬래그인 것을 특징으로 하는 연약지반용 친환경 고화재 조성물.
Cement, blast furnace slag fine powder, anhydrous gypsum, desulfurized gypsum, IGCC slag, BYPASS DUST, fly ash, circulating fluidized bed ash,
The blast furnace slag fine powder includes blast furnace crushed slag fine powder and blast furnace slow cooling slag fine powder, the blast furnace slow cooling slag fine powder is an eco-friendly solidified composition for soft ground, characterized in that it is a modified blast furnace slow cooling slag coated with silicon dioxide on its surface.
제 1항에 있어서,
망초가 더 포함되는 것을 특징으로 하는 연약지반용 친환경 고화재 조성물.
The method of claim 1,
Eco-friendly solidifying composition for soft ground, characterized in that it further contains forget-me-not.
삭제delete 삭제delete 제 1항에 있어서,
세라마이드가 더 포함되는 것을 특징으로 하는 연약지반용 친환경 고화재 조성물.
The method of claim 1,
Eco-friendly solidifying composition for soft ground, characterized in that the ceramide is further included.
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KR102301242B1 (en) * 2020-12-02 2021-09-13 고려에프에이(주) Eco-friendly solidifying material composition for soft ground containing sodium bicarbonate
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