KR100540826B1 - 소각재를 이용한 결정화 대리석 및 그 제조방법 - Google Patents

소각재를 이용한 결정화 대리석 및 그 제조방법 Download PDF

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KR100540826B1
KR100540826B1 KR1020030097134A KR20030097134A KR100540826B1 KR 100540826 B1 KR100540826 B1 KR 100540826B1 KR 1020030097134 A KR1020030097134 A KR 1020030097134A KR 20030097134 A KR20030097134 A KR 20030097134A KR 100540826 B1 KR100540826 B1 KR 100540826B1
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South Korea
Prior art keywords
marble
incineration
weight
crystallized
ash
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KR1020030097134A
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KR20050065962A (ko
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유영석
신현철
지재성
엄수자
김대연
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한국건설기술연구원
주식회사 효성
주식회사 에코썸
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Priority to KR1020030097134A priority Critical patent/KR100540826B1/ko
Priority to JP2004367403A priority patent/JP2005194178A/ja
Priority to US11/019,433 priority patent/US20050179159A1/en
Priority to CN2004100115389A priority patent/CN1648097B/zh
Publication of KR20050065962A publication Critical patent/KR20050065962A/ko
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    • C03—GLASS; MINERAL OR SLAG WOOL
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    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
    • C03C1/06—Opacifiers, e.g. fluorides or phosphates; Pigments to produce non-uniformly pigmented, e.g. speckled, marbled, or veined products
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    • C04B18/00—Use 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
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/54—Producing shaped prefabricated articles from the material specially adapted for producing articles from molten material, e.g. slag refractory ceramic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
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Abstract

본 발명은 소각재를 이용한 결정화 대리석 및 그 제조방법에 관한 것으로, 소각 비산재 50~80중량%, SiO2 20~50중량% 및, 발색과 청징, 강화용 첨가제 0.1~3중량%를 혼합하고 1300~1500℃에서 0.5~1.5시간 용융한 후 급냉 배출한 다음, 입도조절 후 내화틀내에 슬래그를 적재하고, 1000~1200℃에서 10분~1시간, 850~1050℃에서 0.5~2시간으로 열처리하여 얻어지는 것이다.
본 발명에 따르면, 쓰레기 소각 후 배출되는 특정폐기물인 비산 소각재를 유리화, 결정화 공정을 통하여 궁극적으로 고가의 처리비가 소요되는 특정폐기물을 1/10~1/30 정도로 부피를 감량하고, 고품질, 고부가가치성 건축자재인 마블계 대리석을 얻을 수 있다.
쓰레기, 소각재, 결정화, 대리석, 염기도

Description

소각재를 이용한 결정화 대리석 및 그 제조방법{CRYSTALLIZED MARBLE AND ITS MANUFACTURING METHOD BY USING BURNED ASH}
도1은 본 발명의 소각재를 이용한 결정화 대리석의 제조 공정도
도2는 본 발명의 소각재를 이용한 결정화 대리석 제조에 있어서의 온도 스케줄 그래프
도3은 본 발명의 소각재를 이용한 결정화 대리석의 사진
도4는 본 발명의 소각재를 이용한 결정화 대리석 제조에 있어서의 열처리 과정에서 생긴 석출상 사진
본 발명은 소각재를 이용한 결정화 대리석 및 그 제조방법에 관한 것으로, 소각 비산재 50~80중량%, SiO2 20~50중량% 및, 발색과 청징, 강화용 첨가제 0.1~3중량%를 혼합하고 1300~1500℃에서 0.5~1.5시간 용융한 후 급냉 배출한 다음, 입도조절 후 내화틀내에 슬래그를 적재하고, 1000~1200℃에서 10분~1시간, 850~1050℃에서 0.5~2시간으로 열처리하여 얻어지는 것이다.
본 발명에 따르면, 쓰레기 소각 후 배출되는 특정폐기물인 비산 소각재를 유리화, 결정화 공정을 통하여 궁극적으로 고가의 처리비가 소요되는 특정폐기물을 1/10~1/30 정도로 부피를 감량하고, 고품질, 고부가가치성 건축자재인 마블계 대리석을 얻을 수 있다.
경제가 발전하고 산업이 발달하면서 가정과 사회에서 각종 쓰레기가 발생하고 있다.
이와 같이 가정이나 산업 현장에서 발생하는 쓰레기는 일정한 곳에 분리 수거된 다음, 일부는 재활용 되고, 나머지는 매립되거나 혹은 소각되고 있다.
소각하는 경우, 생활 쓰레기 혹은 산업 쓰레기는 주변 여건에 따라 소규모 혹은 대규모의 소각장에서 일정한 단위로 소각하게 되는데, 일부는 단순 소각되지만 소각 보조제를 혼합하여 소각하는 경우도 많다.
이러한 소각 처리의 가장 큰 관심사는 소각으로 인한 대기의 오염 문제이지만, 소각 후 발생하는 소각재의 처리도 상당한 연구가 진행되고 있다.
일반적으로 소각재에는 CaO, Cl, SiO2 등 다양한 성분이 존재하는 것으로, 상기 소각재를 건축, 토목용 자재를 제조하는데 첨가제로서 활용하거나, 혹은 소각재를 그대로 건축, 토목용 자재의 주성분으로 적용하는 예가 시도되고 있다.
일부 국가에서는 바닥재를 분리, 선별 등의 전처리 공정으로 처리하는 반면, 비산재의 경우는 중금속 및 염소 성분을 다량으로 함유하므로, 그 유해성에 의해 필수 불가결하게 1300~1500℃에서 용융 처리한 후, 비구조용 골재 및 성토재료로서 활용하는 기술이 대두되고 있다.
또한, 소각재와 첨가제를 혼합한 후 1400~1500℃의 고온에서 용융한 후 900℃에서 2~3시간 1회 열처리하여 착색된 결정화 유리를 제조하는 경우도 있으나, 물리적 강도와 경도가 떨어짐은 물론, 표면 무늬 등의 발현이 힘들고 다양하지 못하여 상업적으로 취약한 기술로 들어 났다.
한편, 국내에서는 1200℃ 이상의 고온에서 10시간 이상 장시간 소성하여 여러 제품을 만드는 기술이 제시된 바 있고, 수세 등의 염소성분 세척과정과 분말 건조단계를 거쳐 1단계의 용융, 결정화 과정을 거치는 기술 등이 제시된 바 있다.
그러나, 전자의 경우, 재료의 물성면에서 재현성을 확보하기 힘든 경우이고, 후자의 경우는 실제 많은 량의 비산재를 물로 세척하는 공정의 실적용이 힘들 뿐만 아니라, 많은 량의 세척수의 오염물질의 재배출 및 처리문제와 건조과정 등의 고비용, 대량처리 문제, 그리고 내부전체 결정화가 어려운 문제 등이 있다고 할 수 있다.
따라서, 본 발명은 상기 종래의 문제점을 감안하여 이루어진 것으로, Cl 등과 중금속이 다량 함유되어 있는 비산 소각재를 원료로 하고, 비용이 많이 드는 수세, 건조 등의 전처리 공정 없이 소량의 첨가제와 SiO2 만으로 염기도를 조절하여 1차 용융, 2차 결정화의 단계를 거쳐 심미적인 색상과 무늬를 갖는 마블계 결정화 대리석을 제공하고자 한다.
본 발명은, 소각 비산재 50~80중량%, SiO2 20~50중량% 및, 발색과 청징, 강화용 첨가제 0.1~3중량%를 혼합하고 1300~1500℃에서 0.5~1.5시간 용융한 후 급냉 배출한 다음, 입도조절 후 내화틀내에 슬래그를 적재하고, 1000~1200℃에서 10분~1시간, 850~1050℃에서 0.5~2시간으로 열처리하여 얻어지는 것이 특징이다.
도1은 본 발명의 소각재를 이용한 결정화 대리석의 제조 공정도, 도2는 본 발명의 결정화 대리석 제조공정에 있어서의 온도 스케줄 그래프이다.
도면에서와 같이, 소각 비산재와 첨가제를 혼합하고 용융하여 수쇄형태로 배출한 다음, 입도조절하여 내화틀내에 슬래그를 넣고 열처리, 결정화하는 것이다.
여기서, 상기 SiO2의 함량이 20중량% 미만이면 염기도 조절이 어렵고, 반대로 50중량% 이상이면 제품의 성형이 어렵다.
또한, 상기 발색과 청징, 강화용 첨가제로서는, 발색제로서 TiO2, ZrO2, CaF2, ZnO, PbO, Cr2O3, MnO2, Co3O4, NiO, CuO, SeO2, Cd(NO3)2 를 사용하고, 강화제 및 융제로서 Na2O, B2O3, CaF2 를 사용하는 것이 바람직하다.
이하, 실시예를 통하여 본 발명을 좀더 상세히 설명한다.
실시예
먼저, 소각 비산재 60.0중량%, SiO2 39.8중량%와, 발색과 청징, 강화용 첨가 제 0.2중량%를 혼합한다.
이어서, 1400℃에서 1시간 용융한 후 수쇄형태로 급냉 배출한 다음, 스크린을 통한 입도조절 후 내화틀내에 슬래그를 평평하게 적재한다.
그 다음, 열처리로에서 1000~1200℃에서 50분, 850~1050℃에서 1.8시간으로 열처리하여, 소정의 결정화 대리석을 얻을 수 있었다.
이 때, 필요에 따라, 화이트그린(white green), 닥그린(dark green), 닥블루(dark blue), 레디쉬브라운(redish brown), 네이비(navy), 딤그레이(dimgray), 올리브그레이(olivegray), 닥카키(darkkhaki)색 등의 다양한 색상과 무늬의 제품을 얻을 수 있었다.
도3은 이렇게 얻어진 본 발명의 소각재를 이용한 결정화 대리석의 사진, 도4는 열처리 과정에서 생긴 석출상 사진을 각 나타낸다.
상기 실시예에서 얻어진 본 발명의 결정화 대리석과 기존제품, 일반 대리석, 세립화강암의 물성을 비교하여 하기 표1에 나타낸다.
실시예 마블라이트 (기존 제품) 대리석 세립화강암
비중 2.74 2.7 2.7 2.6
굽힘강도 460 510 170 150
압축강도 3900 3400 1.6 1.8
경도 6.5 6.5 4 5.5
흡수율 0.00 0.00 0.30 0.10
상기 표에서 확인할 수 있는바와 같이, 본 발명의 결정화 대리석은 기존의 마블라이트, 일반 대리석 혹은 세립화강암에 비해 손색이 없는 제품임을 알 수 있다.
상기와 같이, 본 발명에서는 수세, 건조 등의 전처리 공정이 없어 공정이 단순하고 비용이 절감되며, 입도조절에 의한 다양하고 외관이 미려한 마블무늬의 발현이 가능하고, TiO2, ZrO2, CaF2, ZnO, PbO, Cr2O3, MnO2, Co3O4, NiO, CuO, SeO2, Cd(NO3)2 등의 산화물을 미량 첨가하여 다양한 발색이 가능한 것이다.
따라서, 고가의 천연 대리석이나 화강석 등에 비해 부드러운 질감과 우수한 강도, 내후성을 가지는 고부가가치 제품으로서, 별도의 가공 공정없이 두께 10mm 이하의 박판, 경량화가 가능하여 실내,외벽, 상판, 마감재 등으로 활용될 수 있다.
이상 설명한 바와 같이, 본 발명에 따르면, Cl 등과 중금속이 다량 함유되어 있는 비산 소각재를 원료로 하고, 비용이 많이 드는 수세, 건조 등의 전처리 공정 없이 소량의 첨가제와 SiO2 만으로 염기도를 조절하여 1차 용융, 2차 결정화의 단계를 거쳐 심미적인 색상과 무늬를 갖는 마블계 결정화 대리석을 얻을 수 있어, 관련 분야에의 이용 및 응용이 기대된다 하겠다.

Claims (3)

  1. 소각 비산재 50~80중량%, SiO2 20~50중량% 및, 발색과 청징, 강화용 첨가제 0.1~3중량%를 혼합하고 1300~1500℃에서 0.5~1.5시간 용융한 후 급냉 배출한 다음, 입도조절 후 내화틀내에 슬래그를 적재하고, 1000~1200℃에서 10분~1시간, 850~1050℃에서 0.5~2시간으로 열처리하여 얻어지는 것을 특징으로 하는 소각재를 이용한 결정화 대리석의 제조방법
  2. 제1항에 있어서,
    상기 발색과 청징, 강화용 첨가제로서는, 발색제로서 TiO2, ZrO2, CaF2, ZnO, PbO, Cr2O3, MnO2, Co3O4, NiO, CuO, SeO2 , Cd(NO3)2 를 사용하고, 강화제 및 융제로서 Na2O, B2O3, CaF2 를 사용하는 것을 특징으로 하는 소각재를 이용한 결정화 대리석의 제조방법
  3. 제1항 또는 제2항의 제조방법으로 얻어진 결정화 대리석
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