KR100332368B1 - Method of the preparation of multi-functional and porous ceramics - Google Patents

Method of the preparation of multi-functional and porous ceramics Download PDF

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KR100332368B1
KR100332368B1 KR1019980046843A KR19980046843A KR100332368B1 KR 100332368 B1 KR100332368 B1 KR 100332368B1 KR 1019980046843 A KR1019980046843 A KR 1019980046843A KR 19980046843 A KR19980046843 A KR 19980046843A KR 100332368 B1 KR100332368 B1 KR 100332368B1
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weight
gypsum
porous ceramics
stirring
cement
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Korean (ko)
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KR19990014365A (en
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롱 최
이승규
이임창
이동호
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쌍용양회공업(주)
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/02—Selection of the hardening environment
    • C04B40/024—Steam hardening, e.g. in an autoclave
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/36—Inorganic materials not provided for in groups C04B14/022 and C04B14/04 - C04B14/34
    • C04B14/361—Soil, e.g. laterite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/06—Oxides, Hydroxides
    • C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
    • C04B22/064—Oxides, Hydroxides of the alkali or alkaline-earth metals of the alkaline-earth metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/10—Clay

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatment Of Sludge (AREA)
  • Fertilizers (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

PURPOSE: A multifunctional porous ceramics and its preparation method are provided, to improve the moisture controlling property, the deodorization, the phosphorus removing property, the radioactive waste solidification efficiency, and the microorganism cultivation effect. CONSTITUTION: The method comprises the steps of mixing 40-80 wt% of clay sand, coal ash, biotite or slag, 10-30 wt% of cement, 10-40 wt% of quicklime and 2-10 wt% of gypsum to make the molar ratio of CaO/SiO2 be 0.45-2.3; adding 45-65 wt% of water based on the weight of the total solid component and stirring the mixture; adding 0.05-0.5 wt% of aluminum paste or powder as a foaming agent to the mixture and stirring the mixture to prepare a slurry; completely curing the slurry at a temperature of 120 deg.C; controlling the obtained green body to the granule or block form and curing it under the saturated vapor pressure of 10-20 atm for 3-10 hours; and pulverizing the cured one.

Description

다기능성 다공성 세라믹스의 제조방법{METHOD OF THE PREPARATION OF MULTI-FUNCTIONAL AND POROUS CERAMICS}Manufacturing method of multifunctional porous ceramics {METHOD OF THE PREPARATION OF MULTI-FUNCTIONAL AND POROUS CERAMICS}

본 발명은 다기능성 다공성 세라믹스의 제조방법에 관한 것으로, 구체적으로는 규산질 원료로서 마사토, 석탄회, 흑운모 또는 슬래그와 같은 산업부산물을 사용하여 수분조절, 악취제거, 인제거(녹조방지/억제), 비료화 증진, 방사성폐기물 고형화 및 종균/미생물 배양 효과가 우수한 다기능성 다공성 세라믹스를 경제적으로 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a multifunctional porous ceramics, specifically, by using industrial by-products such as masato, coal ash, biotite or slag as siliceous raw material, moisture control, odor removal, phosphorus removal (anti-rust / inhibition), fertilizer The present invention relates to a method for economically manufacturing multifunctional porous ceramics having excellent promotion, radioactive waste solidification, and spawn / microbial culture effects.

일반적으로 축산 분뇨처리를 위해 톱밥이 사용되는데, 그 사용방법에는 2가지가 있다. 즉, 분뇨저장소에 저장된 분뇨에 톱밥을 80:20 내지 60:40의 중량비로 혼합하여 고온발효시켜 비료화하는 방법과, 축사 바닥에 톱밥을 수분조절제로서 깔아 주어 축산 폐수가 흡수되게 하여 악취 감소 및 폐수 누출을 방지하는 방법이 있으며, 현재 가장 많이 이용되고 있다. 그러나, 톱밥은 주로 수지와 셀룰로오즈 성분으로 구성되어 있기 때문에 분해가 어려워 부숙기간이 6개월 정도 소요되며, 비료화 과정에서 완전한 호기성 조건이 아니기 때문에 악취가 심하고, 안정적인 공급이 어렵고 원목 처리시 화학약품이 혼입되는 등 문제점을 갖는다.In general, sawdust is used for livestock manure treatment, there are two ways to use it. That is, a method of fertilizing the sawdust in a manure stored in the manure storage in a weight ratio of 80:20 to 60:40 and fermentation by hot fermentation, and spreading the sawdust as a moisture control agent in the bottom of the barn to absorb livestock waste water to reduce odor and waste water There are ways to prevent leaks and are currently the most used. However, since sawdust is mainly composed of resin and cellulose components, it is difficult to decompose and it takes about 6 months to be lodged. Since it is not a complete aerobic condition during fertilization, it has a bad smell, difficult to supply stable, and chemicals are mixed when processing wood. Etc. have problems.

이를 개선하기 위해, 대한민국 특허공보 제 4435 호 및 제 4282 호에서는 규산칼슘 다공질체를 이용한 기술을 개시하고 있으며, 일본 특허공개공보 소 60-180972 호에서는 겔공극을 증가시킨 다공질체를 제조하여 축산 폐수의 처리와 이의 비료화를 도모하였다. 상기 기술들에 의해 채택되고 일반적으로 사용되는 다공질체(경량기포 콘크리트) 제조법에 의하면, 석회질 원료(예: 시멘트 또는 생석회)와 규산질 원료(예: 석영, 모래)의 혼합물에 기포제로서 알루미늄 페이스트 또는 분말을 첨가하여 대기압하에서 수소 가스에 의해 생성되는 1.5mm 이하의 기공을 함유하는 그린체를 제조한 후, 10 내지 12 기압의 수증기압하에서 상기 그린체를 8 내지 12시간 양생하여 가공성, 내화성 및 단열성 등이 우수한 다공질체를 제조한다.In order to improve this, Korean Patent Publication Nos. 4435 and 4282 disclose a technique using a calcium silicate porous material, and Japanese Patent Publication No. 60-180972 discloses a porous material having increased gel voids for livestock wastewater. The treatment and fertilization thereof were planned. According to the porous body (light foamed concrete) manufacturing method adopted by the above techniques and generally used, aluminum paste or powder as a foaming agent in a mixture of lime raw material (e.g. cement or quicklime) and siliceous raw material (e.g. quartz, sand) To prepare a green body containing pores of 1.5 mm or less produced by hydrogen gas under atmospheric pressure, and then cured the green body under water vapor pressure of 10 to 12 atm for 8 to 12 hours to improve workability, fire resistance and heat insulation. Excellent porous body is produced.

그러나, 이들 다공질체는 톱밥보다는 좋은 흡수능을 가지나, 폐기공에 의한 제한적인 흡수능 및 대공극(macro pore)에 의해 비료화가 진행되면서 발생하는 CH4및 NH3를 효과적으로 제어하기가 어렵고, 제조원가가 높아 공급이 제한적일 수 밖에 없으며, 기본 사용 목적이 건축자재이므로 수분조절제 및 기타 여러 가지 환경적인 용도로 사용하기에는 적절하지 못하다.However, these porous bodies have better absorption ability than sawdust, but it is difficult to effectively control CH 4 and NH 3 generated by fertilization due to limited absorption capacity and macropore by waste pores and high manufacturing cost. The supply is limited and the basic use is for building materials, which is not suitable for use in moisture control and many other environmental uses.

이에 본 발명자들은 예의 연구한 결과, 규산질 원료로서 마사토, 석탄회, 흑운모 또는 슬래그와 같은 산업부산물을 사용하고 고온고압 증기 양생시간을 조절함으로써 다기능성 다공성 세라믹스를 경제적으로 제조할 수 있음을 발견하고 본 발명을 완성하게 되었다.Accordingly, the present inventors have diligently researched and found that multifunctional porous ceramics can be economically produced by using industrial by-products such as masato, coal ash, biotite or slag as a siliceous raw material, and controlling high temperature and high pressure steam curing time. To complete.

본 발명의 목적은 산업부산물을 사용하여 경제적으로 제조가능하면서도 수분조절제, 악취제거제, 인제거제(녹조방지/억제제), 비료화 증진제, 방사성폐기물 고형화제 및 종균/미생물 담체로서의 효과가 우수한 다기능성 다공성 세라믹스의 제조방법을 제공하는 것이다.An object of the present invention is to produce economically using industrial by-products, but also has excellent effects as moisture control agents, odor removers, phosphorus removers (anti-greening / inhibiting agents), fertilizer enhancers, radioactive waste solidifying agents, and spawn / microbial carriers. It is to provide a manufacturing method.

상기 목적을 달성하기 위하여 본 발명에서는 마사토, 석탄회, 흑운모 또는 슬래그 40 내지 80 중량%, 시멘트 10 내지 30 중량%, 생석회 10 내지 40 중량% 및 석고 2 내지 10 중량%를 혼합한 후, 전체고형분의 45 내지 65 중량%의 물을 첨가하여 1차 교반하고, 여기에 발포제로서 알루미늄 페이스트 또는 분말을 0.05 내지 0.5 중량% 첨가하고 2차 교반하여 제조된 슬러리를 상온 내지 120℃에서 전치양생한 후, 생성된 그린체(Green Body)를 그래뉼 또는 블록 형태로 조절하여 10 내지 20 기압의 포화수증기압하에서 3 내지 10시간동안 양생한 후 분쇄하는 것을 포함하는, 다기능성 다공성 세라믹스의 제조방법을 제공한다.In order to achieve the above object, in the present invention, after mixing 40 to 80% by weight of masato, coal ash, biotite or slag, 10 to 30% by weight of cement, 10 to 40% by weight of quicklime and 2 to 10% by weight of gypsum, 45 to 65% by weight of water is added thereto, followed by primary stirring, and 0.05 to 0.5% by weight of aluminum paste or powder is added thereto as a blowing agent, and the slurry prepared by secondary stirring is precured at room temperature to 120 ° C., and then produced. It provides a method for producing a multi-functional porous ceramics comprising the green body (Granule or block) to form a granule or block to cure for 3 to 10 hours under saturated steam of 10 to 20 atm and then pulverized.

이하 본 발명에 대하여 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명에 따르면, 광산에서 암석 채취시 걷어내버리는 마사토, 흑운모, 또는 산업폐기물인 석탄회, 슬래그 등을 규산질 원료로서 사용함으로써 다공성 세라믹스를 경제적으로 제조할 수 있으며, 사용량은 40 내지 80 중량%로서 40 중량% 미만으로 투입하면 전치양생시간과 오토클레이브 양생시간이 증가하며, 80 중량%를초과하여 투입하면 경화가 늦어지는 등 제조원가의 상승을 가져온다.According to the present invention, porous ceramics can be economically manufactured by using masato, biotite, or industrial waste coal ash, slag, etc., which are removed from the rock in a mine as a siliceous raw material, and the use amount is 40 to 80 wt%, 40 wt%. If the amount is less than%, the pretreatment time and the autoclave curing time increase, and if it exceeds 80% by weight, the curing cost is increased, resulting in an increase in manufacturing cost.

또한, 시멘트는 10 내지 30 중량%의 양으로 투입되는데, 10 중량% 미만으로 투입하면 다공체의 강도가 저하되며, 30 중량%를 초과하면 오토클레이브 처리시 파열할 가능성이 있고 발포과정에서 경화체의 침하가 일어나 다공체 제조의 수율이 떨어진다.In addition, the cement is added in an amount of 10 to 30% by weight, but if it is added in an amount less than 10% by weight, the strength of the porous body is lowered. Arises and the yield of porous body manufacture falls.

본 발명에서 사용하는 생석회는 시판되는 것이거나 CaO 함량이 30 내지 50 중량%인 석회석을 1000 내지 1100℃ 및 회전속도 1.0rpm의 로타리 킬른(rotary kiln)을 통과시켜 제조할 수 있다. 세라믹스 다공체 제조용 생석회를 제조하는 경우에는 세라믹스 제조시 사용하는 주/부원료의 종류 또는 원료의 배합비에 따라 최적의 조성을 갖는 석회석을 선별하여 생석회를 제조하여야 한다. 이 생석회는 10 내지 40 중량%의 양으로 사용되며, 그 사용량이 10 중량% 미만이거나 40 중량%를 초과하면 경화속도와 발포시간에 좋지 않은 영향을 준다.The quicklime used in the present invention may be commercially available or prepared by passing a limestone having a CaO content of 30 to 50% by weight through a rotary kiln of 1000 to 1100 ° C and a rotational speed of 1.0 rpm. When preparing quicklime for the manufacture of porous ceramics, quicklime should be prepared by selecting limestone having an optimal composition according to the kind of main / subsidiary raw materials used in the manufacture of ceramics or the mixing ratio of raw materials. This quicklime is used in an amount of 10 to 40% by weight, and if the amount used is less than 10% by weight or more than 40% by weight, the curing rate and the foaming time are adversely affected.

또한, 2 내지 10 중량%의 양으로 투입되는 석고로는 화력발전소 탈황공정 중에 발생되는 부산 석고(이하, 탈황 석고라 지칭함) 또는 티탄 정제공정 중 발생되는 부산 석고(이하, 티탄 석고라 지칭함)를 사용하여 제조비용을 절감할 수 있으며, 2 중량% 미만으로 투입하거나 10 중량%를 초과하여 투입하면 경화시간과 생석회의 반응속도에 좋지 않은 영향을 준다.In addition, gypsum added in an amount of 2 to 10% by weight may include Busan gypsum (hereinafter referred to as desulfurization gypsum) generated during a thermal power plant desulfurization process or Busan gypsum (hereinafter referred to as titanium gypsum) generated during a titanium refining process. It is possible to reduce the manufacturing cost by using, if the addition of less than 2% by weight or more than 10% by weight has an adverse effect on the curing time and the reaction rate of quicklime.

본 발명에 따르면, 필요에 따라 규산질 원료 또는 석회질 원료의 대체재료로서 상/하수도 슬러지, 유리연마 슬러지 또는 시멘트 공장의 바이-패스 분진(by-pass dust)을 사용할 수 있으며, 전체고형분의 10 내지 40 중량%로 투입할 수 있다. 또한, 상기 세라믹스 제조시 사용되는 원료물질들을 혼합함에 있어서 CaO/SiO2의 몰비가 0.45 내지 2.30이 되도록 투입하는 것이 바람직하다.According to the present invention, water / sewage sludge, glass polishing sludge, or by-pass dust of a cement plant may be used as an alternative material of siliceous raw material or lime raw material if necessary, and 10 to 40% of the total solid content may be used. It can be added in weight percent. In addition, in mixing the raw materials used in the manufacture of the ceramics, it is preferable to add a CaO / SiO 2 molar ratio of 0.45 to 2.30.

본 발명에 따르면, 상기 혼합물에 물을 첨가하고 1차 교반한 후 알루미늄 페이스트 또는 분말을 발포제로서 첨가할 수 있으며, 발포제로는 이외에도 알칼리 분위기에서 수소를 발생시키는 금속을 선택적으로 첨가할 수 있고, 발포제의 사용량은 0.05 내지 0.5 중량% 범위이다. 이어, 이 혼합물을 2차 교반하여 제조된 슬러리를 전치양생 및 양생하는데, 고온고압하에서 증기양생하는 경우 양생시간에 따라 결정 형태 및 광물 조성이 달라지며, 이러한 변화에 따라 다공성 세라믹스의 특성이 변하게 된다. 본 발명에서는 상온 내지 120℃ 범위의 온도에서 전치양생을 수행하고, 생성된 그린체를 그래뉼 또는 블록 형태로 만든 다음 목적하는 세라믹스 최종 용도에 따라 10 내지 20 기압의 포화수증기압하에서 3 내지 10시간동안 양생한 후, 용도에 적합하게 90㎛ 내지 10mm의 범위내의 크기로 분쇄하여 세라믹스 다공체를 제조할 수 있다.According to the present invention, water may be added to the mixture, followed by primary stirring, and then aluminum paste or powder may be added as a blowing agent. In addition to the blowing agent, a metal that generates hydrogen in an alkaline atmosphere may be selectively added. The amount of is used ranges from 0.05 to 0.5% by weight. Subsequently, the mixture prepared by the second stirring of the mixture is pre-cured and cured. In the case of steam curing under high temperature and high pressure, the crystal form and the mineral composition vary according to the curing time, and the characteristics of the porous ceramics change according to the change. . In the present invention, pretreatment is carried out at a temperature ranging from room temperature to 120 ° C., and the resulting green body is formed into granules or blocks, and then cured for 3 to 10 hours under saturated steam pressure of 10 to 20 atm depending on the desired ceramic end use. After that, the ceramic porous body can be prepared by pulverizing to a size within the range of 90 μm to 10 mm to suit the purpose.

본 발명의 제조방법에 따라 제조된 세라믹스는 규칙적인 배열을 형성하는 개기공으로서 0.01 내지 0.8㎛ 범위의 입자간 공극(interparticle pore), 6㎛ 내지 0.1mm 범위의 과립 공극(intercluster pore) 및 0.3 내지 3mm 범위의 대공극(macro pore)을 가져, 내부의 개기공까지 가스의 확산이 가능하므로 여러 가지 악취원을 효과적으로 흡착할 수 있고, 개기공의 높은 비표면적에 의해 뛰어난 흡수 및 보수 능력을 유지할 수 있다. 또한, 균일한 미세기공에 의한 수분조절능의 향상으로 비료화 기간을 단축할 수 있고, 거대기공에 의해 통기성을 확보할 수 있어 호기성 조건을 형성함으로써 미생물인 박테리아, 곰팡이 및 방선균류 등의 담체로서의 역할 또한 원활하게 수행할 수 있다.The ceramics prepared according to the manufacturing method of the present invention are open pores forming a regular array as interparticle pores in the range of 0.01 to 0.8 μm, granule pores in the range of 6 μm to 0.1 mm and 0.3 to It has a macro pore in the 3mm range, which allows gas to diffuse into the open pores so that various odor sources can be effectively adsorbed, and the high specific surface area of the open pores maintains excellent absorption and repair capability. have. In addition, it is possible to shorten fertilizer period by improving moisture control ability by uniform micropores, and to ensure breathability by macropores, and to form aerobic conditions, thereby serving as a carrier of microorganisms such as bacteria, fungi and actinomycetes. It can also be run smoothly.

따라서, 본 발명의 세라믹스는 수분조절제, 악취제거제, 인제거제(녹조방지/억제제), 비료화 증진제, 방사성폐기물 고형화제 또는 종균/미생물 담체 등으로 유용하게 사용될 수 있다.Therefore, the ceramics of the present invention can be usefully used as a moisture control agent, odor remover, phosphorus remover (anti-rust / inhibitor), fertilizer enhancer, radioactive waste solidifying agent or spawn / microbial carrier.

이하, 본 발명을 하기 실시예에 의거하여 좀더 상세하게 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위가 이들만으로 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

하기 실시예 및 비교예에서 제조된 다공성 세라믹스의 성능을 평가하기 위해 사용된 측정법은 다음과 같다.Measurement methods used to evaluate the performance of the porous ceramics prepared in the following Examples and Comparative Examples are as follows.

1) 가용성 규산의 양(규산질 비료 품질)1) amount of soluble silicic acid (silicate fertilizer quality)

시료 50g을 100㎖ 플라스크에 취하고, 여기에 1N-NaOAc 완충용액(pH 4.0)을 50㎖ 가한 다음 60℃의 수조에서 90분간 진탕한 후 냉수로 5분간 급냉시키고 와트만(Whatman) 여지(No. 6)로 여과하였다. 여액중 10㎖를 비이커에 취해 온도를 30 내지 35℃로 유지하면서 0.6N HCl 5㎖ 및 10% 몰리브덴산암모늄 5㎖를 순차적으로 가하였다. 3분 후 17% 황산나트륨 10㎖를 가하고 30℃에서 20분간 발색시켜 원자 흡광분석기를 이용하여 파장 700nm에서 발광정도를 측정하였다.50 g of the sample was taken in a 100 ml flask, and 50 ml of 1N-NaOAc buffer solution (pH 4.0) was added thereto, followed by shaking for 90 minutes in a 60 ° C water bath, followed by quenching with cold water for 5 minutes, and Whatman. 6). 10 ml of the filtrate was taken in a beaker and 5 ml of 0.6N HCl and 5 ml of 10% ammonium molybdate were added sequentially while maintaining the temperature at 30 to 35 ° C. After 3 minutes, 10 ml of 17% sodium sulfate was added, followed by color development at 30 ° C. for 20 minutes, and the degree of luminescence was measured at 700 nm using an atomic absorption spectrometer.

2) 흡수성(수분조절 효과)2) Absorbency (moisture control effect)

밀폐용기내에 KNO3과포화 수용액을 제조한 후 90% 상대습도를 일정하게 유지시켰다. 시료 50g을 취해 110℃에서 24시간동안 건조시켜 칭량한 후, KNO3포화 수용액 표면으로부터 3cm 떨어지도록 장치하고 24시간 경과 후에 변화된 중량과 건조중량을 비교하여 흡수성을 결정하였다.90% relative humidity was kept constant after preparing a supersaturated aqueous KNO 3 solution in an airtight container. 50 g of the sample was taken, dried at 110 ° C. for 24 hours, weighed, and placed 3 cm away from the surface of saturated aqueous KNO 3 solution, and the absorbency was determined by comparing the changed weight with the dry weight after 24 hours.

3) 탈취 효과3) deodorizing effect

삼각플라스크 용기내에 시료를 넣고 트리메틸아민을 첨가한 후 트리메틸아민의 함유량의 변화를 기체 크로마토그래피를 이용하여 측정하였다. 처음에 첨가한 트리메틸아민의 양을 1/10로 감소시키는 시료의 첨가량의 역수를 탈취 효과로 산출하였다.After the sample was placed in the Erlenmeyer flask, trimethylamine was added, and the change in the trimethylamine content was measured using gas chromatography. The reciprocal of the addition amount of the sample which initially reduces the amount of trimethylamine added to 1/10 was calculated as the deodorizing effect.

4) 비료화 효과4) fertilizer effect

제조된 시료의 비료화 효과를 실험하기 위하여 축산 분뇨 및 음식물 쓰레기의 비료화 실험을 하였다. 축분은 아산에 위치한 슬러리 돈사에서 채취하였고, 음식물 쓰레기는 31평 규모의 한식당에서 공급하였으며, 축분과 시료는 80:20의 중량비로, 음식물 쓰레기와 시료는 1:1.5의 중량비로 혼합하였다. 정체식 퇴비 단공법(Aeration system)을 사용하여 30일동안 상기 혼합물로 비료화 실험을 수행하고 온도, 수분함량, pH 및 C/N비 등을 측정하였다. 이때 C/N비는 미생물의 에너지원인 탄소와 세포형성에 필요로 되는 질소의 중량비를 의미하며, 비료로서 바람직한 C/N비는 20 내지 30이다.In order to test the fertilization effect of the prepared samples, fertilization experiments were conducted for livestock manure and food waste. The livestock was collected from Slurry Donsa located in Asan. Food waste was supplied from a Korean restaurant with a size of 31 pyeong, and the livestock and the sample were mixed at a weight ratio of 80:20 and the food waste and the sample at a weight ratio of 1: 1.5. Fertilization experiments were carried out with the mixture for 30 days using a static compost Aeration system and the temperature, water content, pH and C / N ratio were measured. In this case, the C / N ratio means a weight ratio of carbon, which is an energy source of microorganisms, and nitrogen required for cell formation, and a preferable C / N ratio is 20 to 30 as a fertilizer.

5) 인제거(녹조 방지) 효과5) Phosphorus removal (greening prevention) effect

스크레파 방식의 축산에서 축산 폐수를 채취하여 인의 농도를 측정하였더니 230ppm이었다. 이 축산 폐수와 시료를 90:10의 부피비로 혼합하여 24시간동안 폭기한 후 여액을 채취하여 여액중에 남아있는 인의 농도를 측정하였다.The livestock wastewater was collected from screpa-type livestock and the concentration of phosphorus was 230 ppm. The livestock wastewater and the sample were mixed at a volume ratio of 90:10, aerated for 24 hours, and then the filtrate was collected to measure the concentration of phosphorus remaining in the filtrate.

6) 버섯종균 배양 효과6) Mushroom spawn culture effect

20cm의 플라스틱 종균배양통을 이용하여 종균배양용 담체인 시료를 18cm 채우고, 병원균의 침입을 방지하기 위해 나머지 2cm를 솜과 같은 여과제로 채웠다. 이어, 담체가 채워진 종균배양통의 상부에 버섯종균을 식재하고, 8일 후 종균배양 깊이를 측정하였다.Using a 20 cm plastic spawn container, 18 cm of the sample for the spawn culture carrier was filled, and the remaining 2 cm was filled with a filter such as cotton to prevent invasion of pathogens. Subsequently, mushroom seedlings were planted on the top of the carrier-filled seedling culture container, and the seeding culture depth was measured after 8 days.

실시예 1Example 1

마사토 50 중량%(구성성분: 하기 표 1 참조), 시멘트 20 중량%, 생석회 25 중량% 및 석고 5 중량%를 건식 혼합한 후 전체고형분의 60 중량%에 해당하는 물을 첨가하여 슬러리 상태로 1차 교반하였다. 교반이 끝난 슬러리에 발포제로서 알루미늄 페이스트를 0.1 중량% 첨가한 후 2차 교반하였다. 제조된 슬리리를 60℃에서 전치양생하여 그린체를 생성하고, 이 그린체를 180℃ 및 11기압의 포화수증기압하에서 8시간동안 양생처리한 후 약 3mm로 분쇄하여 다공성 세라믹스를 제조하였다. 제조된 세라믹스의 효과 실험 결과를 하기 표 2 내지 4에 나타내었다.50% by weight of masato (components: see Table 1 below), 20% by weight of cement, 25% by weight of quicklime and 5% by weight of gypsum were mixed in a slurry state by adding water corresponding to 60% by weight of the total solids. Stirring a little. 0.1 wt% of aluminum paste was added to the slurry after stirring as a blowing agent, followed by secondary stirring. The prepared slimies were precured at 60 ° C. to produce a green body, and the green body was cured for 8 hours at 180 ° C. and 11 atm of saturated steam pressure, and then ground to about 3 mm to prepare porous ceramics. Results of the effect experiment of the ceramics are shown in Tables 2 to 4 below.

실시예 2Example 2

석탄회 60 중량%(구성성분: 하기 표 1 참조), 시멘트 15 중량%, 생석회 20 중량% 및 석고 5 중량%를 사용하여 상기 실시예 1과 동일한 방법으로 다공성 세라믹스를 제조하였다. 제조된 세라믹스의 효과 실험 결과를 하기 표 2 내지 4에 나타내었다.Porous ceramics were prepared in the same manner as in Example 1 using 60 wt% of coal ash (components: see Table 1 below), 15 wt% of cement, 20 wt% of quicklime, and 5 wt% of gypsum. Results of the effect experiment of the ceramics are shown in Tables 2 to 4 below.

실시예 3Example 3

흑운모 50 중량%(구성성분: 하기 표 1 참조), 시멘트 20 중량%, 생석회 25 중량% 및 티탄 석고 5 중량%(구성성분: 하기 표 1 참조)를 사용하여 상기 실시예 1과 동일한 방법으로 다공성 세라믹스를 제조하였다. 제조된 세라믹스의 효과 실험 결과를 하기 표 2 내지 6에 나타내었다.Porous in the same manner as in Example 1 using 50 wt% biotite (components: see Table 1 below), 20 wt% cement, 25 wt% quicklime and 5 wt% titanium gypsum (components: see Table 1 below) Ceramics were prepared. The results of the effect experiments of the prepared ceramics are shown in Tables 2 to 6 below.

실시예 4Example 4

슬래그 65 중량%(구성성분: 하기 표 1 참조), 시멘트 10 중량%, 생석회 20 중량% 및 티탄 석고 5 중량%를 사용하여 상기 실시예 1과 동일한 방법으로 다공성 세라믹스를 제조하였다. 제조된 세라믹스의 효과 실험 결과를 하기 표 2 내지 6에 나타내었다.Porous ceramics were prepared in the same manner as in Example 1 using 65 wt% slag (components: see Table 1 below), 10 wt% cement, 20 wt% quicklime, and 5 wt% titanium gypsum. The results of the effect experiments of the prepared ceramics are shown in Tables 2 to 6 below.

실시예 5Example 5

흑운모 35 중량%, 시멘트 14 중량%, 생석회 17.5 중량% 및 티탄 석고 3.5 중량%(구성성분: 하기 표 1 참조)를 사용하고, 추가로 상수도 슬러지 30 중량%(구성성분: 하기 표 1 참조)를 첨가하여 상기 실시예 1과 동일한 방법으로 다공성 세라믹스를 제조하였다. 제조된 세라믹스의 효과 실험 결과를 하기 표 2 내지 6에 나타내었다.35 wt% biotite, 14 wt% cement, 17.5 wt% quicklime and 3.5 wt% titanium gypsum (components: see Table 1 below), and 30 wt% tap water sludge (components: see table 1 below) To add a porous ceramics was prepared in the same manner as in Example 1. The results of the effect experiments of the prepared ceramics are shown in Tables 2 to 6 below.

실시예 6Example 6

상수도 슬러지 대신에 유리연마 슬러지(구성성분: 하기 표 1 참조)를 사용한 것을 제외하고는 상기 실시예 5와 동일한 조성을 가지고 상기 실시예 1과 동일한 방법으로 다공성 세라믹스를 제조하였다. 제조된 세라믹스의 효과 실험 결과를 하기 표 2 내지 6에 나타내었다.Porous ceramics were prepared in the same manner as in Example 1, except that glass polishing sludge (components: see Table 1 below) was used instead of tap water. The results of the effect experiments of the prepared ceramics are shown in Tables 2 to 6 below.

실시예 7Example 7

상기 실시예 1에서 제조된 그린체를 180℃ 및 11기압의 포화수증기압하에서 3시간동안 양생처리한 후 약 3mm로 분쇄하여 다공성 세라믹스를 제조하였다. 제조된 세라믹스의 효과 실험 결과를 하기 표 2 내지 7에 나타내었다.The green body prepared in Example 1 was cured for 3 hours under saturated steam at 180 ° C. and 11 atm, and then ground to about 3 mm to prepare porous ceramics. The results of the effect experiments of the prepared ceramics are shown in Tables 2 to 7 below.

(단위: 중량%)(Unit: weight%) 구분division SiO2 SiO 2 Al2O3 Al 2 O 3 Fe2O3 Fe 2 O 3 CaOCaO MgOMgO Na2ONa 2 O K2OK 2 O SO3 SO 3 소각시 손실량Loss in Incineration 마사토Masato 77.477.4 13.1813.18 1.231.23 0.480.48 0.090.09 5.245.24 -- -- -- 석탄회Coal ash 59.259.2 2727 4.44.4 4.54.5 1.11.1 0.540.54 1.11.1 0.10.1 0.10.1 흑운모Biotite 71.771.7 13.113.1 4.364.36 1.381.38 0.440.44 2.022.02 5.475.47 -- 0.70.7 슬래그Slag 34.034.0 15.415.4 1.11.1 42.042.0 6.96.9 0.190.19 0.540.54 -- -0.5-0.5 유리연마 슬러지Glass Grinding Sludge 57.957.9 12.212.2 9.99.9 1.41.4 1.31.3 3.143.14 2.262.26 -- 7.47.4 상수도 슬러지Running water sludge 34.834.8 31.131.1 5.185.18 1.11.1 0.90.9 0.760.76 1.911.91 -- -- 하수도 슬러지Sewage sludge 52.552.5 23.423.4 8.018.01 3.653.65 2.052.05 1.051.05 3.613.61 0.10.1 탈황 석고Desulfurization Plaster 0.90.9 0.30.3 0.10.1 31.831.8 0.50.5 0.090.09 0.020.02 43.643.6 22.6922.69 티탄 석고Titanium plaster 2.72.7 1.31.3 15.615.6 24.224.2 2.22.2 0.040.04 0.030.03 31.231.2 22.322.3

비교예 1Comparative Example 1

규석 60.4 중량%, 시멘트 20 중량%, 생석회 14.6 중량% 및 석고 5 중량%에 전체고형분의 60 중량%에 해당하는 물을 가하여 습식 혼합한 후, 발포제로서 알루미늄 분말을 0.1 중량% 첨가하고 180℃, 11기압하에서 12시간동안 오토클레이브하였다. 제조된 일반 경량기포 콘크리트를 약 3mm로 분쇄하여 실시한 실험 결과를 하기 표 2 내지 4에 나타내었다.60.4% by weight of silica, 20% by weight of cement, 14.6% by weight of quicklime and 5% by weight of gypsum were added by wet mixing to 60% by weight of total solids, 0.1% by weight of aluminum powder was added as a blowing agent, and 180 ° C. Autoclave for 12 hours under 11 atmospheres. The results of experiments performed by pulverizing the prepared lightweight lightweight concrete to about 3 mm are shown in Tables 2 to 4 below.

비교예 2Comparative Example 2

통상적으로 수분흡수제 또는 종균배양용 배지로 사용되는 톱밥을 약 5mm로 분쇄하여 실시한 실험 결과를 하기 표 2 내지 4 및 표 6에 나타내었다.Experimental results of grinding the sawdust usually used as a water absorbent or spawn culture medium to about 5mm are shown in Tables 2 to 4 and Table 6 below.

비교예 3Comparative Example 3

상기 실시예 1에서 제조된 그린체를 일반적인 다공체의 제조방법인 180℃ 및 11기압의 포화수증기압하에서 12시간동안 양생처리한 후 약 3mm로 분쇄하여 다공성 세라믹스를 제조하였다. 제조된 세라믹스의 효과 실험 결과를 하기 표 7에 나타내었다.The green body prepared in Example 1 was cured for 12 hours at 180 ° C. and 11 atm of saturated steam pressure, which is a method for preparing a porous body, and then ground to about 3 mm to prepare porous ceramics. The results of the effect experiments of the prepared ceramics are shown in Table 7 below.

비교예 4Comparative Example 4

통상적으로 녹조방지제, 즉 인제거제로 사용되는 황토를 사용하여 실시한 실험 결과를 하기 표 5에 나타내었다.Experimental results using ocher, which is typically used as an algae inhibitor, ie, a phosphorus remover, are shown in Table 5 below.

세라믹스의 특성 변화Characteristics of Ceramics 구 분division 비중importance 흡수성(%)Absorbency (%) 탈취 효과Deodorant effect 압축강도Compressive strength 실시예 1Example 1 0.400.40 14.114.1 0.430.43 4646 실시예 2Example 2 0.420.42 14.214.2 0.40.4 4747 실시예 3Example 3 0.480.48 18.418.4 0.920.92 5151 실시예 4Example 4 0.440.44 16.716.7 0.740.74 4949 실시예 5Example 5 0.500.50 17.817.8 0.620.62 4545 실시예 6Example 6 0.470.47 16.416.4 0.700.70 4747 비교예 1Comparative Example 1 0.400.40 14.114.1 0.430.43 4646 비교예 2Comparative Example 2 0.200.20 7.27.2 0.020.02 --

비료화 효과 실험에서의 온도 변화(단위:℃)Temperature change in the fertilizer effect experiment (unit: ℃) 구 분division 1 일1 day 3 일3 days 6 일6 days 9 일9 days 15 일15th 20 일20 days 25 일25 days 30 일30 days 축산 분뇨Livestock manure 실시예 1Example 1 73.373.3 71.371.3 64.064.0 36.836.8 22.022.0 2121 2020 2020 실시예 2Example 2 72.572.5 69.569.5 53.053.0 39.839.8 21.021.0 2020 2020 2020 실시예 3Example 3 72.272.2 72.072.0 64.364.3 37.237.2 33.133.1 27.327.3 24.324.3 2121 실시예 4Example 4 71.371.3 71.071.0 63.163.1 35.935.9 32.832.8 27.727.7 25.125.1 2222 실시예 5Example 5 72.072.0 71.971.9 62.362.3 34.934.9 33.533.5 26.926.9 25.225.2 22.822.8 실시예 6Example 6 71.971.9 71.771.7 64.064.0 36.736.7 33.033.0 27.027.0 24.724.7 21.921.9 실시예 7Example 7 72.072.0 70.870.8 64.764.7 35.435.4 33.133.1 27.327.3 24.324.3 21.021.0 비교예 1Comparative Example 1 67.867.8 65.365.3 6060 31.231.2 21.021.0 1919 1919 1818 비교예 2Comparative Example 2 73.873.8 59.359.3 5858 32.532.5 17.317.3 1717 1717 1616 음식물 쓰레기Food waste 실시예 1Example 1 66.366.3 62.162.1 55.155.1 35.735.7 30.130.1 28.228.2 25.325.3 22.722.7 실시예 2Example 2 63.163.1 59.359.3 56.256.2 40.140.1 35.235.2 29.329.3 24.824.8 21.321.3 비교예 1Comparative Example 1 65.365.3 6060 54.254.2 39.239.2 32.732.7 25.225.2 22.722.7 20.420.4 비교예 2Comparative Example 2 60.360.3 59.859.8 53.853.8 37.237.2 32.132.1 30.630.6 25.325.3 21.921.9

비료화 효과 실험에서의 수분 함량, pH 및 C/N비의 변화Changes in Water Content, pH and C / N Ratio in Fertilizer Effect Experiments 구 분division 수분 함량(%)Moisture content (%) pHpH C/N비C / N ratio 개시Start 20일20 days 30일30 days 개시Start 20일20 days 30일30 days 개시Start 20일20 days 30일30 days 축산 분뇨Livestock manure 실시예 1Example 1 56.756.7 31.231.2 19.819.8 8.758.75 8.878.87 8.738.73 18.918.9 17.8717.87 17.317.3 실시예 2Example 2 57.457.4 29.329.3 20.120.1 8.738.73 8.978.97 8.998.99 17.717.7 16.516.5 20.820.8 실시예 3Example 3 55.755.7 32.132.1 19.219.2 8.538.53 8.318.31 8.308.30 20.620.6 20.420.4 20.020.0 실시예 4Example 4 55.055.0 33.233.2 18.918.9 8.128.12 8.118.11 8.118.11 21.421.4 20.020.0 20.120.1 실시예 5Example 5 55.955.9 31.031.0 18.918.9 8.218.21 8.208.20 8.118.11 21.121.1 2121 20.920.9 실시예 6Example 6 54.854.8 32.332.3 18.718.7 8.198.19 8.128.12 8.108.10 22.622.6 22.022.0 21.921.9 실시예 7Example 7 53.953.9 33.733.7 17.417.4 8.628.62 8.518.51 8.218.21 22.922.9 22.722.7 21.921.9 비교예 1Comparative Example 1 58.958.9 29.729.7 20.920.9 8.838.83 9.009.00 9.039.03 18.618.6 17.417.4 20.420.4 비교예 2Comparative Example 2 66.266.2 44.444.4 23.823.8 8.168.16 9.349.34 9.089.08 22.722.7 26.926.9 31.531.5 음식물 쓰레기Food waste 실시예 1Example 1 55.155.1 29.229.2 20.120.1 8.28.2 8.548.54 8.218.21 18.418.4 17.317.3 19.819.8 실시예 2Example 2 56.856.8 30.130.1 21.221.2 8.58.5 8.728.72 8.738.73 19.219.2 18.618.6 21.221.2 비교예 1Comparative Example 1 55.455.4 28.828.8 19.619.6 8.728.72 8.928.92 9.029.02 18.918.9 18.218.2 19.919.9 비교예 2Comparative Example 2 62.262.2 46.846.8 25.125.1 8.18.1 9.029.02 8.028.02 23.823.8 25.725.7 30.630.6

인제거 효과Phosphorus Removal Effect 구 분division 초기농도(ppm)Initial concentration (ppm) 여액의 농도(ppm)Concentration of the filtrate (ppm) 인 제거율(%)Phosphorus Removal Rate (%) 실시예 3Example 3 230230 41.1741.17 82.182.1 실시예 4Example 4 230230 46.2346.23 79.979.9 실시예 5Example 5 230230 35.4235.42 84.684.6 실시예 6Example 6 230230 33.5833.58 85.485.4 실시예 7Example 7 230230 43.9343.93 80.980.9 비교예 4Comparative Example 4 230230 63.7163.71 72.372.3

버섯종균 배양 효과Mushroom spawning effect 구 분division 8일 후의 성장 깊이Growth Depth After 8 Days 성장율(성장깊이/18cm)Growth Rate (Growth Depth / 18cm) 실시예 3Example 3 12.312.3 68 %68% 실시예 4Example 4 11.911.9 66 %66% 실시예 5Example 5 13.013.0 72 %72% 실시예 6Example 6 12.812.8 71.1 %71.1% 실시예 7Example 7 10.310.3 57.2 %57.2% 비교예 2Comparative Example 2 3.783.78 21 %21%

양생시간 변화에 따른 세라믹스의 특성 변화Characteristics of Ceramics with Varying Curing Time 구 분division 비중importance 압축강도Compressive strength 반응 생성물Reaction product 가용성 규산Soluble silicic acid 실시예 7Example 7 0.520.52 46kg/cm2 46 kg / cm 2 토버모라이트, 미반응 SiO2, 세리사이트(K2O·3Al2O3·6SiO2·2H2O)Tobermorite, unreacted SiO 2 , sericite (K 2 O · 3Al 2 O 3 · 6SiO 2 · 2H 2 O) 19∼22 %19-22% 비교예 3Comparative Example 3 0.50.5 48kg/cm2 48 kg / cm 2 토버모라이트, 미반응 SiO2, 세리사이트Tobermorite, unreacted SiO 2 , sericite 9∼11 %9-11%

본 발명에 따라 제조된 다공성 세라믹스는, 산업부산물인 마사토, 석탄회, 흑운모 또는 슬래그를 사용하여 경제적으로 제조가능하면서도 톱밥이나 다른 경량다공질체에 비해 수분조절, 악취제거, 인제거(녹조방지/억제), 방사성폐기물 고형화 및 종균/미생물 배양 효과가 우수하고, 비료화 기간의 단축 및 비료화 효과의 증진을 가져올 수 있다.Porous ceramics prepared in accordance with the present invention can be economically manufactured using industrial by-products masato, coal ash, biotite or slag, but moisture control, odor removal, phosphorus removal (anti-greening / suppression) compared to sawdust or other lightweight porous materials In addition, the radioactive waste solidification and the spawn / microbial culture effect are excellent, and the fertilization period can be shortened and the fertilization effect can be enhanced.

Claims (5)

마사토, 석탄회, 흑운모 또는 슬래그 40 내지 80 중량%, 시멘트 10 내지 30 중량%, 생석회 10 내지 40 중량% 및 석고 2 내지 10 중량%를 CaO/SiO2몰비가 0.45 내지 2.3 범위가 되도록 혼합한 후, 전체고형분의 45 내지 65 중량%의 물을 첨가하여 1차 교반하고, 여기에 발포제로서 알루미늄 페이스트 또는 분말을 0.05 내지 0.5 중량% 첨가하고 2차 교반하여 제조된 슬러리를 상온 내지 120℃에서 전치양생한 후, 생성된 그린체(Green Body)를 그래뉼 또는 블록 형태로 조절하여 10 내지 20 기압의 포화수증기압하에서 3 내지 10시간동안 양생한 후 분쇄하는 것을 포함하는, 다기능성 다공성 세라믹스의 제조방법.40 to 80% by weight of masato, coal ash, biotite or slag, 10 to 30% by weight cement, 10 to 40% by weight quicklime and 2 to 10% by weight gypsum are mixed so that the CaO / SiO 2 molar ratio is in the range of 0.45 to 2.3, 45 to 65% by weight of the total solids of water is added to the first stirring, and the slurry prepared by adding 0.05 to 0.5% by weight of aluminum paste or powder as a blowing agent and stirring the second time at room temperature to 120 ℃ pre-cured Thereafter, by adjusting the resulting green body in the form of granules or blocks, curing and pulverizing for 3 to 10 hours under a saturated steam pressure of 10 to 20 atm, and then pulverizing. 제 1 항에 있어서,The method of claim 1, 고형분 원료의 10 내지 40 중량%가 상/하수도 슬러지, 유리연마 슬러지 또는 시멘트 공장의 바이-패스 분진(by-pass dust)으로 대체된 것을 특징으로 하는 방법.10 to 40% by weight of the solid raw material is replaced by water / sewage sludge, glass polishing sludge or by-pass dust of cement plant. 제 1 항에 있어서,The method of claim 1, 석고가 탈황 석고 또는 티탄 석고인 것을 특징으로 하는 방법.The gypsum is desulfurized gypsum or titanium gypsum. 상기 제 1 항에 따른 방법에 의해 제조된 다공성 세라믹스.Porous ceramics produced by the method according to claim 1. 제 4 항에 있어서,The method of claim 4, wherein 수분조절제, 악취제거제, 인제거제(녹조방지/억제제), 비료화 증진제, 방사성폐기물 고형화제 또는 종균/미생물 담체로 사용되는 것을 특징으로 하는 다공성 세라믹스.Porous ceramics, characterized in that it is used as a moisture control agent, odor remover, phosphorus remover (anti-rust / inhibitor), fertilizer enhancer, radioactive waste solidifying agent or spawn / microbial carrier.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ299909B6 (en) * 2007-01-02 2008-12-29 Ústav struktury a mechaniky hornin AV CR, v. v. i. Solidification and stabilization method of radioactive waste
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KR20160111642A (en) * 2015-03-17 2016-09-27 주식회사 자연 A cargo box equipped with the guard rail of the cargo truck

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KR100358888B1 (en) * 1999-11-29 2002-11-01 최식영 The multi-pore ceramic using the slag of the by-products from iron-steel-industry and waste casting sand dust and method of making the same
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KR100820055B1 (en) * 2007-07-27 2008-04-08 디에스케이엔지니어링(주) The water absorption silicic acid matter numerous hole body production techniques for which natural mineral matter was used
KR100887663B1 (en) * 2007-10-05 2009-03-11 디에스케이엔지니어링(주) The bio mineral numerous hole body production techniques for which remnant food and drink waste water was used
WO2013022197A2 (en) * 2011-08-09 2013-02-14 Sur Seung Surk Mortar or concrete composition using coal ash, and usage thereof
KR101367591B1 (en) * 2013-04-25 2014-02-27 (주)엔바이로솔루션 Fabrication method of blistered ceramic

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60180972A (en) * 1984-02-29 1985-09-14 小野田エー・エル・シー株式会社 Manufacture of calcium silicate porous body
JPH04170375A (en) * 1990-10-30 1992-06-18 Kanebo Ltd Ceramics porous body
KR950003217A (en) * 1993-07-27 1995-02-16 강박광 Porous ceramic material using waste and its manufacturing method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60180972A (en) * 1984-02-29 1985-09-14 小野田エー・エル・シー株式会社 Manufacture of calcium silicate porous body
JPH04170375A (en) * 1990-10-30 1992-06-18 Kanebo Ltd Ceramics porous body
KR950003217A (en) * 1993-07-27 1995-02-16 강박광 Porous ceramic material using waste and its manufacturing method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ299909B6 (en) * 2007-01-02 2008-12-29 Ústav struktury a mechaniky hornin AV CR, v. v. i. Solidification and stabilization method of radioactive waste
KR101126097B1 (en) 2009-10-14 2012-03-29 (주)알디케이 Bio-concrete ball and method for fabricating the same
KR20160111642A (en) * 2015-03-17 2016-09-27 주식회사 자연 A cargo box equipped with the guard rail of the cargo truck

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