KR100403111B1 - Solidification agent and manufacturing method thereof - Google Patents

Solidification agent and manufacturing method thereof Download PDF

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KR100403111B1
KR100403111B1 KR10-2001-0049238A KR20010049238A KR100403111B1 KR 100403111 B1 KR100403111 B1 KR 100403111B1 KR 20010049238 A KR20010049238 A KR 20010049238A KR 100403111 B1 KR100403111 B1 KR 100403111B1
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weight
parts
sodium silicate
solidifying agent
mixed
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KR10-2001-0049238A
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KR20030016451A (en
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류중근
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중앙방수기업주식회사
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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
    • C09K17/40Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic 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
    • 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00732Uses not provided for elsewhere in C04B2111/00 for soil stabilisation

Abstract

본 발명은 차수공법에서 지반을 안정처리하는 데 사용되는 고화제 및 그 제조방법에 관한 것으로서, 이는 다공성 세라믹이 혼합된 규산소다를 주성분으로 하여 연약지반, 해안습지, 항만, 폐기물 매립지 및 도로 조성등과 같이 유기물을 함유하거나 수분의 함유 비율이 높은 고화 대상토 또는 점토질이 많은 고화 대상토에 대하여 균열 발생없이 강도를 향상시킬 수 있으며, 또한 중금속 등 공해물질이 함유된 오염토를 고화처리할 수 있어 중금속 용출을 억제하고 차수효과를 얻어 자연환경을 보호할 수 있다.The present invention relates to a hardener and a method for producing the same, which are used for stabilizing the ground in a water-based method, which is composed of soft silica, mixed with porous ceramics, soft ground, coastal wetland, harbor, waste landfill and road composition. As such, it is possible to improve the strength of the solidified soil containing organic matter or a high content of moisture or the solidified soil having a lot of clay quality without cracking, and to contaminate contaminated soil containing pollutants such as heavy metals. It can protect the natural environment by inhibiting heavy metal leaching and obtaining the order effect.

Description

고성능 고화제 조성물 및 그 제조방법{Solidification agent and manufacturing method thereof}High performance solidifying agent composition and its manufacturing method {Solidification agent and manufacturing method

본 발명은 고성능 고화제 조성물 및 그 제조방법에 관한 것으로서, 더욱 상세하게는 다공성 세라믹이 혼합된 규산소다계를 주성분으로 하고 여기에 벤토나이트, 쿠마론 인덴 수지, 칼슘 설퍼 알루미네이트, 황산 나트륨, 황산 칼슘, 황산 알루미늄 및 나프탈렌 설퍼네이트 포름알데하이드 축합물을 첨가하여 유기물이나 고함수율로 인하여 고화가 어려운 연약지반, 해안습지, 항만 및 쓰레기 매립장의 지반을 강화시키거나 노상 강화 등에 사용되는 고성능 1성분계 다공성 세라믹이 혼합된 고화제 및 이를 제조하는 방법에 관한 것이다.The present invention relates to a high-performance solidifying agent composition and a method for producing the same, and more particularly, to a bentonite, coumarone indene resin, calcium sulfur aluminate, sodium sulfate, calcium sulfate , High performance one-component porous ceramics used for reinforcing grounds of soft ground, coastal wetlands, harbors and landfills that are difficult to solidify due to organic matter or high water content by adding aluminum sulfate and naphthalene sulfonate formaldehyde condensate. A mixed hardener and a method of preparing the same.

최근 국내외에서는 바다의 갯벌을 메우는 간척 사업, 일반 폐기물 매립장 건설, 인공섬의 축조, 신공항, 항만 및 도로 건설 등의 지반 강화나 차수벽의 건설 등을 위해 석회석이나 시멘트계 고화제를 사용하여 지반을 안정처리하여 기초 지반으로 활용하는 차수공법이 널리 이용되고 있다.Recently, at home and abroad, limestone or cement hardeners are used to stabilize the ground for reclamation projects to fill the tidal flats of the sea, construction of general waste landfills, construction of artificial islands, reinforcement of new airports, ports and roads, and construction of water barriers. As a result, the order method that is used as the foundation ground is widely used.

그러나, 이러한 연약지반 토양은 장기간의 퇴적이나 유기 폐기물에 의해 많은 유기 물질을 포함하고 있는 바, 이러한 유기물질이 토립자 표면에 흡착되어 있어 시멘트와 고화 대상토의 혼합 접촉을 방해한다. 또한, 고화대상 지반이 미립자로 구성되어 있어서 시멘트 수화물과 토립자간의 직접적인 반응을 저해하여 고화가 진행되기 어렵다. 그리고, 해안 등 고함수율의 토지는 시멘트에 대한 함수율이 너무 높아 종래에 사용하는 포틀랜트 시멘트, 조강 시멘트, 고로 시멘트 및 석회석 등을 사용할 경우 고화가 원활히 진행되지 못하여 만족할 만한 고결 강도를 얻지 못하였다.However, such soft ground soils contain many organic substances due to long-term deposition or organic waste, and these organic substances are adsorbed on the surface of the granules and thus prevent the mixed contact between cement and the solidified soil. In addition, since the ground to be solidified is composed of fine particles, it is difficult to solidify by inhibiting the direct reaction between the cement hydrate and the granules. In addition, the high water content of the coast, such as coastal water content is too high for cement, when using the conventionally used portland cement, crude steel cement, blast furnace cement and limestone, the solidification did not proceed smoothly did not obtain a satisfactory solidification strength.

이와같은 일반 시멘트나 석회석의 문제점을 보완하는 고화제들이 개발되었으나, 이 역시 일반 시멘트나 석회석을 주원료로 하여 다량 투입하기 때문에 경화가 느리고 고결시 열이 발생하여 체적 변화를 일으킴으로써 균열이 발생하는 하자가 있었다. 또한 일반 시멘트에 첨가하는 고화성분과 비율에 있어서 효율적인 유기물질 분해나 에트린가이트(etringite, 3CaO·Al2O5·3CaSO4·32H2O)가 생성되지 않아 퇴적토나 수분이 많은 지반 등에서는 고결이 잘 안되 경화도에 있어서도 기준에 못 미치는 문제점이 있었다.Although solidifying agents have been developed to compensate for the problems of general cement and limestone, this is also hard to be hardened due to the large amount of general cement or limestone as a main raw material, and cracks are generated by heat generation during solidification. There was. In addition, due to the solidification components and ratios added to general cement, efficient organic material decomposition and etrinite (etringite, 3CaO · Al 2 O 5 · 3CaSO 4 · 32H 2 O) are not produced. This did not work well, but there was a problem that does not meet the standard.

본 발명은 이러한 문제점을 해소하기 위한 것으로서, 연약지반, 해안습지, 항만, 폐기물 매립지 및 도로조성 등과 같이 유기물을 함유하거나 수분의 함유 비율이 높은 고화 대상토 또는 점토질이 많은 고화 대상토에 대하여 균열 발생없이강도를 향상시키고, 또한 중금속 등 공해 물질이 함유된 오염토를 고화처리하여 중금속 용출 억제 및 차수 효과를 얻어 자연환경도 보호할 수 있는 고성능 고화제를 제공하는 데 그 목적이 있다.The present invention is to solve this problem, and cracks occur for the solidified target soil having a high content of organic matter or a high clay content, such as soft ground, coastal wetland, harbor, landfill and road composition The purpose of the present invention is to provide a high-performance solidifying agent that can improve the strength, and also solidify contaminated soil containing pollutants such as heavy metals, thereby preventing heavy metal leaching and protecting the natural environment.

상기와 같은 목적을 달성하기 위한 본 발명의 고성능 고화제는 다공성 세라믹이 혼합된 규산소다 100중량부, 벤토나이트 40∼70중량부, 쿠마론 인덴 수지 30∼60중량부, 칼슘 설퍼 알루미네이트 20∼50중량부, 황산 나트륨 8∼15중량부, 황산 칼슘 10∼15중량부, 황산 알루미늄 12∼15중량부 및 나프탈렌 설퍼네이트 포름알데하이드 축합물 2∼5중량부로 이루어진 것임을 그 특징으로 한다.The high performance solidifying agent of the present invention for achieving the above object is 100 parts by weight of sodium silicate mixed with a porous ceramic, 40 to 70 parts by weight of bentonite, 30 to 60 parts by weight of coumarone indene resin, calcium sulfur aluminate 20 to 50 It is characterized by consisting of parts by weight, 8-15 parts by weight of sodium sulfate, 10-15 parts by weight of calcium sulfate, 12-15 parts by weight of aluminum sulfate, and 2-5 parts by weight of naphthalene sulfonate formaldehyde condensate.

이와같은 고성능 고화제를 제조하는 방법은 규산소다를 볼밀을 이용하여 분쇄한 후 체가름하여 40㎛ 이하의 크기만을 선별하여 다공성 세라믹과 1:1로 혼합하여 얻어진 다공성 세라믹이 혼합된 규산소다 100중량부를 파우더 혼합기에 넣고 벤토나이트 40∼70중량부, 칼슘 설퍼 알루미네이트 20∼50중량부, 황산 나트륨 8∼15중량부, 황산 칼슘 10∼15중량부, 황산 알루미늄 12∼15중량부, 나프탈렌 설퍼네이트 포름알데하이드 축합물 2∼5중량부를 첨가하여 2∼3시간 정도 교반시키는 제 1 단계; 및 쿠마론 인덴 수지를 볼밀을 이용하여 분쇄한 후 체가름하여 150∼250㎛ 크기의 입자만을 선별한 것 30∼60중량부를 상기 제 1단계의 교반물에 첨가하여 1∼2시간 정도 교반하는 제 2 단계를 포함한다.The method of preparing such a high performance solidifying agent is 100% by weight of sodium silicate mixed with porous ceramics obtained by pulverizing soda silicate using a ball mill and sifting to select only a size of 40 μm or less and mixing the porous ceramics 1: 1. To a powder mixer, bentonite 40 to 70 parts by weight, calcium sulfur aluminate 20 to 50 parts by weight, sodium sulfate 8 to 15 parts by weight, calcium sulfate 10 to 15 parts by weight, aluminum sulfate 12 to 15 parts by weight, naphthalene sulfonate form A first step of adding 2 to 5 parts by weight of an aldehyde condensate and stirring for about 2 to 3 hours; And pulverizing the coumarone indene resin using a ball mill and sieving to select only particles having a size of 150 to 250 μm. 30 to 60 parts by weight of the first step is added to the stirred material and stirred for about 1 to 2 hours. Includes two steps.

이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.

본 발명의 고성능 고화제는 40㎛ 이하 입자 크기의 규산소다와 다공성 세라믹을 1:1중량비로 혼합하여 얻어진 다공성 세라믹이 혼합된 규산소다를 주성분으로 함유한다.The high performance solidifying agent of the present invention contains, as a main component, sodium silicate mixed with porous silica obtained by mixing sodium silicate having a particle size of 40 μm or less and a porous ceramic in a 1: 1 weight ratio.

여기서, 규산소다(Na2O·nSiO2)는 무색 투명한 결정체로 토양의 음이온 물질과 결합하여 고화능력을 발휘시키고, 다공성 세라믹은 토양에 있는 수분을 흡수하여 고결화되므로 연약지반, 해안습지, 항만, 폐기물 매립지 및 도로 조성 등 유기물이 함유되거나 수분의 함유 비율이 높은 고화 대상토 또는 점토질이 많은 고화 대상토에 대하여 균열 발생없이 강도를 향상시키고, 또한 중금속 등 공해물질이 함유된 오염토를 고화처리하는 데 있어서 바람직하다.Here, sodium silicate (Na 2 O · nSiO 2 ) is a colorless transparent crystal that combines with anionic substances in the soil to show its solidification ability. For solidified target soils containing high organic matter or water content such as waste, landfills and roads, or solidified target soils with high clay quality without cracking, contaminated soil containing pollutants such as heavy metals It is preferable to.

이때, 규산소다의 입자크기가 40㎛ 보다 크면 토양의 음이온 물질들과의 결합력이 약해진다. 그리고, 다공성 세라믹과 규산소다의 혼합비율이 1:1이 아니고 어느 한쪽이 많거나 작게 되면, 즉 다공성 세라믹이 많으면 토양의 수분을 너무나 빠르게 흡수하여 규산소다와 토양의 음이온 물질이 결합하는데 방해하며, 또한 규산소다의 양이 많게 되면 상대적으로 다공성 세라믹의 함량이 적게되어 토양의 수분 흡수율이 낮아 강도가 저하되므로 다공성 세라믹과 규산소다의 혼합비율이 1:1인 것이 바람직하다.At this time, when the particle size of the sodium silicate is greater than 40㎛ bond strength with the anionic substances in the soil is weakened. And, if the mixing ratio of porous ceramics and sodium silicate is not 1: 1 and either side is large or small, that is, if there are many porous ceramics, the moisture of the soil is absorbed so quickly that it interferes with the bonding of sodium silicate and anionic substances in the soil, In addition, when the amount of sodium silicate is large, the content of the porous ceramic is relatively low, and the water absorption rate of the soil is low, so that the strength is lowered, so that the mixing ratio of the porous ceramic and sodium silicate is 1: 1.

이와같이 얻어진 다공성 세라믹이 혼합된 규산소다 100중량부를 파우더 혼합기에 넣고, 벤토나이트 40∼70중량부, 칼슘 설퍼 알루미네이트 20∼50중량부, 황산 나트륨 8∼15중량부, 황산 칼슘 10∼15중량부, 황산 알루미늄 12∼15중량부, 나프탈렌 설퍼네이트 포름알데하이드 축합물 2∼5중량부를 첨가하여 2∼3시간 동안 교반시킨다.100 parts by weight of sodium silicate mixed with the porous ceramics thus obtained was put into a powder mixer, and 40 to 70 parts by weight of bentonite, 20 to 50 parts by weight of calcium sulfur aluminate, 8 to 15 parts by weight of sodium sulfate, 10 to 15 parts by weight of calcium sulfate, 12 to 15 parts by weight of aluminum sulfate and 2 to 5 parts by weight of naphthalene sulfonate formaldehyde condensate are added and stirred for 2 to 3 hours.

벤토나이트는 큰 표면적을 이용하여 수분, 유해물질과 유기물 등을 흡착하는 능력을 가지는 것으로서, 그 함량이 다공성 세라믹이 혼합된 규산소다 100중량부에 대하여 40중량부 미만이면 흙과 혼합시에 반응속도가 떨어지며 초기 강도발현에 영향을 줄 수 있으며, 70중량부 초과면 반응속도는 빨라지나 급격한 반응으로 인한 수축현상으로 갈라짐 현상이 나타날 수 있고, 압축강도나 차수성이 떨어진다.Bentonite has the ability to adsorb moisture, harmful substances and organic substances by using a large surface area. When the content is less than 40 parts by weight based on 100 parts by weight of sodium silicate mixed with porous ceramics, the reaction rate is increased when mixed with soil. It may fall and affect the initial strength expression, and if it exceeds 70 parts by weight, the reaction rate is faster, but it may be cracked due to the shrinkage phenomenon due to the rapid reaction, and the compressive strength or the degree of inferiority.

그리고, 칼슘 설퍼 알루미네이트는 응집제 역할을 하며 입자와 입자간의 가교효과를 주는 주는 것으로서, 그 함량이 다공성 세라믹이 혼합된 규산소다 100중량부에 대하여 20중량부 미만이면 흙입자와 입사 사이에 응집력이 떨어져 수밀성 및 강도가 떨어지고, 50중량부 초과면 흙입자와 입자 사이에 응집력은 좋아지나 고화반응시 빠른 조강화 작용으로 인해 갈라짐 현상이 있을 수 있다.In addition, calcium sulfur aluminate acts as a coagulant and gives a crosslinking effect between particles. When the content is less than 20 parts by weight based on 100 parts by weight of sodium silicate mixed with porous ceramics, cohesion between soil particles and incidence is increased. Falling water-tightness and strength, and more than 50 parts by weight, the cohesion between the soil particles and particles is good, but there may be a cracking phenomenon due to the rapid strengthening action during the solidification reaction.

황산 나트륨, 황산 칼슘은 주로 석고라 부르며 급속한 고화가 특징이다. 또한 서서히 수산화칼슘과 무수황산 칼슘으로 고화되며 에트린가이트와 규산칼슘화 수화물 등의 수화생성물을 생출하는 작용으로 기여한다. 만일, 그 함량이 상기 범위에 위배되면 고화작용이 서서히 되어 초기강도 발현에 어려운 문제가 있다.Sodium sulfate and calcium sulfate are mainly called gypsum and are characterized by rapid solidification. In addition, it gradually solidifies with calcium hydroxide and anhydrous calcium sulfate, and contributes to the action of generating hydration products such as ethringite and calcium silicate hydrate. If the content is in violation of the above range, there is a problem in that the solidification action is gradually decreased in the initial strength.

그리고, 황산 알루미늄은 고화제 메카니즘 중 알칼리에 대한 자극제로 작용하여 고화후 알카리분의 산화촉진에도 작용하기 때문에 알칼리 용출의 방지에 사용된다. 그 함량이 다공성 세라믹이 혼합된 규산소다 100중량부에 대하여 12중량부 미만이면 고화 후 알칼리 용출이 나타날 수 있으며, 15중량부 초과면 고화시 초기조강효과가 빨리 나타나 갈라짐 현상이 나타날 수 있다.Aluminum sulfate is used to prevent alkali elution because it acts as a stimulant for alkali in the solidifying mechanism and also acts to promote oxidation of alkali powder after solidification. If the content is less than 12 parts by weight based on 100 parts by weight of sodium silicate mixed with porous ceramics, alkali elution may occur after the solidification. If the content is more than 15 parts by weight, the initial roughening effect may appear quickly, causing cracking.

나프탈렌 설퍼네이트 포름알데하이드 축합물은 변성 리그닌설폰산 유도체를 주성분으로 하여 염소이온을 함유하지 않고 얻어지는 것으로서, 이는 흙입자 사이에 고화제가 고루 분포될 수 있도록 해주는 계면활성제 역할을 한다. 이와같은 나프탈렌 설퍼네이트 포름알데하이드 축합물의 함량이 다공성 세라믹이 혼합된 규산소다 100중량부에 대하여 2중량부 미만이면 고화제가 고루 분포되지 않아 물성저하가 나타날 수 있고, 5중량부 초과면 혼화성은 좋아지나 고화후 수분이 침투시에 용출될 수 있는 단점이 있다.The naphthalene sulfonate formaldehyde condensate is obtained without a chlorine ion based on a modified lignin sulfonic acid derivative as a main component, which acts as a surfactant to distribute the solidifying agent evenly between the soil particles. If the content of such naphthalene sulfonate formaldehyde condensate is less than 2 parts by weight based on 100 parts by weight of sodium silicate mixed with porous ceramics, the solidifying agent may not be distributed evenly, and the physical property may be degraded. It is good, but there is a drawback that water can be eluted upon penetration after solidification.

한편, 쿠마론 인덴 수지는 토양의 응집력을 강화시켜 수밀성 확보를 용이하게 하는 바, 입자크기가 150㎛ 보다 작거나 250㎛ 보다 크면 토양 입자간의 응집력이 감소되어 수밀성 확보가 어려워 결과적으로 흡수비가 높아져 차수효과가 감소하므로 150∼250㎛ 크기의 입자를 사용하는 것이 바람직하다.On the other hand, the coumarone indene resin enhances the cohesiveness of the soil to facilitate water-tightness. When the particle size is smaller than 150 μm or larger than 250 μm, cohesion between soil particles is reduced, making it difficult to secure water-tightness, resulting in higher absorption ratio. Since the effect is reduced, it is preferable to use particles having a size of 150 to 250 mu m.

이를 위해서 쿠마론 인덴 수지를 볼밀을 이용하여 분쇄한 후 체가름하여 150∼250㎛ 크기의 입자만을 선별하여 이를 상기 제 1 단계의 교반물에 첨가하여 1∼2시간 정도 교반하면 본 발명의 고성능 고화제를 얻을 수 있다. 이때, 선별된 쿠마론 인덴 수지의 첨가량은 다공성 세라믹이 혼합된 규산소다 100중량부에 대하여 30∼60중량부인 것이 바람직한 바, 만일 그 함량이 30중량부 미만이면 흙과 흙 사이의 공극을 잘 막아주지 못해 수밀성의 저하 및 압축강도의 저하를 야기시키며, 60중량부 초과면 흙과 흙 사이 입자를 결합시키고 수밀성은 향상되나 온도차이에 의한 공극을 채우고 있는 수지의 수축으로 인해 갈라짐 현상이 나타날 수 있어 내구성에 문제가 있을 수 있다.To this end, the coumarin indene resin is pulverized using a ball mill and sieved to select only particles having a size of 150 to 250 μm, which are added to the stirred material of the first step and stirred for about 1 to 2 hours. You can get a topic. At this time, it is preferable that the added amount of the selected coumarone indene resin is 30 to 60 parts by weight based on 100 parts by weight of sodium silicate mixed with porous ceramics. If not more than 60 parts by weight, it causes a decrease in watertightness and a decrease in compressive strength, and if it exceeds 60 parts by weight, the particles are bonded to soil and the watertightness is improved, but cracking may occur due to shrinkage of the resin filling the pores due to temperature difference. There may be a problem with durability.

이와같이 제조한 고성능 고화제를 연약지반, 해안습지, 항만, 폐기물 매립지 및 도로조성 등과 같이 유기물을 함유하거나 수분의 함유 비율이 높은 고화 대상토 또는 점토질이 많은 고화 대상토에 사용하게 되면 균열 발생없이 강도를 향상시킬 수 있고, 또한 중금속 등 공해 물질이 함유된 오염토를 고화처리하여 중금속 용출 억제 및 차수효과를 얻어 자연환경도 보호할 수 있다.When the high performance solidifying agent is used in solidified soil containing high organic matter or high moisture content such as soft ground, coastal wetland, harbor, waste landfill and road composition, or solidified soil with high clay content In addition, the contaminated soil containing pollutants such as heavy metals can be solidified to prevent heavy metals from leaching and protect the natural environment.

이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

실시예 1Example 1

제 1단계First stage

규산소다를 볼밀(Ball mill HJ-100, 홍진정밀 제품)을 이용하여 분쇄한 후, 체가름하여 40㎛ 이하의 크기만을 선별하여 다공성 세라믹과 1:1로 혼합하여 다공성 세라믹이 혼합된 규산소다를 얻었다.Sodium silicate was pulverized using a ball mill (Ball mill HJ-100, Hongjin Precision Co., Ltd.), sieved, and then screened to a size of 40 μm or less, mixed with porous ceramics 1: 1 to mix sodium silicate mixed with porous ceramics. Got it.

얻어진 다공성 세라믹이 혼합된 규산소다 100중량부를 파우더 혼합기에 넣고 벤토나이트 50중량부, 칼슘 설퍼 알루미네이트 30중량부, 황산 나트륨 11중량부, 황산 칼슘 13중량부, 황산 알루미늄 13중량부, 나프탈렌 설퍼네이트 포름알데하이드 축합물 3중량부를 첨가하여 2∼3시간 정도 교반시켰다.100 parts by weight of sodium silicate mixed with the obtained porous ceramics was placed in a powder mixer, 50 parts by weight of bentonite, 30 parts by weight of calcium sulfur aluminate, 11 parts by weight of sodium sulfate, 13 parts by weight of calcium sulfate, 13 parts by weight of aluminum sulfate, naphthalene sulfonate form 3 parts by weight of the aldehyde condensate was added and stirred for about 2 to 3 hours.

제 2단계2nd step

쿠마론 인덴 수지를 볼밀을 이용하여 분쇄한 후 체가름하여 150㎛ 크기의 입자만을 선별한 것 30중량부를 상기 제 1단계에 첨가하여 1∼2시간 정도 교반하여고성능 고화제를 제조하였다.The coumarin indene resin was pulverized using a ball mill and sieved to select only particles having a size of 150 μm, and 30 parts by weight were added to the first step, and stirred for about 1 to 2 hours to prepare a high-performance solidifying agent.

실시예 2Example 2

상기 실시예 1과 동일한 방법으로 다공성 세라믹이 혼합된 규산소다계 고화제를 제조하되, 다만 벤토나이트를 60중량부 첨가하여 고성능 고화제를 제조하였다.In the same manner as in Example 1 to prepare a sodium silicate-based solidifying agent mixed with a porous ceramic, but by adding 60 parts by weight of bentonite to prepare a high-performance solidifying agent.

실시예 3Example 3

상기 실시예 1과 동일한 방법으로 다공성 세라믹이 혼합된 규산소다계 고화제를 제조하되, 다만 벤토나이트를 70중량부 첨가하여 고성능 고화제를 제조하였다.In the same manner as in Example 1 to prepare a sodium silicate-based solidifying agent mixed with a porous ceramic, but 70 parts by weight of bentonite was added to prepare a high-performance solidifying agent.

실시예 4Example 4

상기 실시예 1과 동일한 방법으로 다공성 세라믹이 혼합된 규산소다계 고화제를 제조하되, 다만 제 2단계의 쿠마론 인덴 수지의 양을 40중량부로 하여 고성능 고화제를 제조하였다.In the same manner as in Example 1 to prepare a sodium silicate-based solidifying agent mixed with a porous ceramic, but a high-performance solidifying agent was prepared by the amount of the coumarone indene resin of the second step to 40 parts by weight.

실시예 5Example 5

상기 실시예 1과 동일한 방법으로 다공성 세라믹이 혼합된 규산소다계 고화제를 제조하되, 다만 제 2단계의 쿠마론 인덴 수지의 양을 60중량부로 하여 고성능 고화제를 제조하였다.In the same manner as in Example 1 to prepare a sodium silicate-based solidifying agent mixed with a porous ceramic, but a high-performance solidifying agent was prepared by using the amount of the coumaron indene resin in the second step to 60 parts by weight.

비교예 1Comparative Example 1

상기 실시예 1과 동일한 방법으로 다공성 세라믹이 혼합된 규산소다계 고화제를 제조하되, 다만 벤토나이트를 100중량부 첨가하여 고화제를 제조하였다.In the same manner as in Example 1 to prepare a sodium silicate-based solidifying agent mixed with a porous ceramic, but by adding 100 parts by weight of bentonite to prepare a solidifying agent.

비교예 2Comparative Example 2

상기 실시예 1과 동일한 방법으로 다공성 세라믹이 혼합된 규산소다계 고화제를 제조하되, 다만 제 2단계의 쿠마론 인덴 수지의 함량을 100중량부로 하여 고화제를 제조하였다.In the same manner as in Example 1 to prepare a sodium silicate-based solidifying agent mixed with a porous ceramic, but a solidifying agent was prepared by using a content of the second stage coumarone indene resin to 100 parts by weight.

비교예 3Comparative Example 3

상기 실시예 1과 동일한 방법으로 다공성 세라믹이 혼합된 규산소다계 고화제를 제조하되, 다만 제 2단계의 쿠마론 인덴 수지의 입자크기를 500㎛인 것을 사용하여 고화제를 제조하였다.In the same manner as in Example 1, a sodium silicate-based solidifying agent mixed with a porous ceramic was prepared, except that a solidifying agent was prepared using a particle size of the second stage coumarone indene resin of 500 μm.

비교예 4Comparative Example 4

상기 실시예 1과 동일한 방법으로 다공성 세라믹이 혼합된 규산소다계 고화제를 제조하되, 다만 다공성 세라믹이 혼합된 규사소다를 70중량부만 첨가하여 고화제를 제조하였다.In the same manner as in Example 1 to prepare a sodium silicate-based solidifying agent mixed with a porous ceramic, but only 70 parts by weight of silica sand mixed with a porous ceramic was added to prepare a solidifying agent.

실험예Experimental Example

상기 실시예 및 비교예에 의해 얻어진 각각의 고화제와 기존 고화제를 함수비 55%의 점토 성분이 많은 시료토 1200㎥에 10kg 첨가하여 몰드를 만들어 KS F 1245(건축용 시멘트 방수제 시험방법)에 의거 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.10 kg of each of the hardeners and the existing solidifiers obtained by the above Examples and Comparative Examples were added to 1200 m 3 of the sample soil having a high water content of 55% clay to form a mold, and the physical properties according to KS F 1245 Was measured and the results are shown in Table 1 below.

여기서, 기존 고화제라 함은 석고 및 시멘트계로서 흙과 배합시 반드시 시멘트를 첨가, 혼합해야 하는 고화제이다.Here, the existing hardener is a hardener which must be added and mixed with cement when combined with soil as gypsum and cement.

실 시 예Example 비교예Comparative example 기존 고화제Existing hardener 1One 22 33 44 55 1One 22 33 44 압축강도(kgf/㎠)Compressive strength (kgf / ㎠) 7일7 days 25.325.3 25.925.9 25.125.1 24.924.9 24.724.7 20.420.4 24.524.5 23.623.6 19.519.5 19.319.3 14일14 days 38.738.7 38.138.1 40.540.5 40.940.9 41.941.9 32.032.0 35.735.7 33.733.7 28.628.6 29.829.8 28일28 days 50.150.1 50.850.8 51.551.5 51.351.3 52.752.7 41.741.7 49.649.6 45.345.3 39.839.8 42.542.5 투수비Pitching cost 0.630.63 0.620.62 0.550.55 0.590.59 0.530.53 0.680.68 0.650.65 0.710.71 0.640.64 0.830.83 흡수비Absorption ratio 1시간1 hours 0.550.55 0.500.50 0.480.48 0.520.52 0.540.54 0.590.59 0.570.57 0.600.60 0.610.61 0.840.84 5시간5 hours 0.650.65 0.630.63 0.600.60 0.610.61 0.580.58 0.710.71 0.690.69 0.720.72 0.700.70 0.890.89 24시간24 hours 0.740.74 0.700.70 0.690.69 0.720.72 0.710.71 0.870.87 0.820.82 0.810.81 0.830.83 0.950.95 비고Remarks 갈라짐 현상발생Cracking phenomenon

상기 표 1의 결과로부터, 본 발명에 따른 고화제는 점토성분이 많은 토양에 사용시 고결강도가 만족할만하며, 차수효과 또한 향상됨을 알 수 있다.From the results of Table 1, the solidifying agent according to the present invention can be seen that the high grain strength is satisfactory when used in the soil with a lot of clay components, the degree of ordering effect is also improved.

비교예 1과 같이 벤토나이트의 양이 과량이면 압축강도와 차수성이 떨어짐을 알 수 있으며, 쿠마론 인덴 수지가 과량으로 첨가될 경우(비교예 2)에는 압축강도에는 별다른 영향을 주지 않지만 투수비, 흡수비는 물성이 떨어지는 것을 알 수 있었다. 또한, 쿠마론 인덴 수지의 입자크기가 500㎛로 아주 미세하면 흡수비가 커져 차수성이 떨어짐을 알 수 있다. 그리고, 다공성 세라믹이 혼합된 규산소다의 양을 줄이면 전체적인 물성이 떨어지며, 특히 초기경화시간 및 초기강도에 문제가 있음을 알 수 있다.When the amount of bentonite is excessive, as in Comparative Example 1, the compressive strength and the water-order property are inferior, and when the coumarone indene resin is added in an excessive amount (Comparative Example 2), the compressive strength does not affect the permeability, but Absorption ratio was found to be inferior in physical properties. In addition, it can be seen that when the particle size of the coumarone indene resin is very fine (500 µm), the absorption ratio becomes large, resulting in poor orderability. In addition, if the amount of sodium silicate mixed with the porous ceramics is reduced, the overall physical properties decrease, and it can be seen that there is a problem in initial curing time and initial strength.

이상에서 상세히 설명한 바와 같이, 본 발명에 따라 다공성 세라믹이 혼합된 규산소다를 주성분으로 하는 고성능 1성분계 고화제는 연약지반, 해안습지, 항만, 폐기물 매립지 및 도로 조성등과 같이 유기물을 함유하거나 수분의 함유 비율이 높은 고화 대상토 또는 점토질이 많은 고화 대상토에 대하여 균열 발생없이 강도를 향상시킬 수 있으며, 또한 중금속 등 공해물질이 함유된 오염토를 고화처리할 수 있어 중금속 용출을 억제하고 차수효과를 얻어 자연환경을 보호할 수 있다.As described in detail above, the high performance one-component solidifying agent mainly composed of sodium silicate mixed with a porous ceramic according to the present invention may contain organic substances such as soft ground, coastal wetland, harbor, waste landfill and road composition, It can improve the strength of solidified soil with a high content ratio or solidified soil with a lot of clay quality without cracking, and it can solidify the contaminated soil containing pollutants such as heavy metals to suppress the leaching of heavy metals and improve the order effect. To protect the natural environment.

Claims (4)

다공성 세라믹이 혼합된 규산소다 100중량부, 벤토나이트 40∼70중량부, 쿠마론 인덴수지 30∼60중량부, 칼슘 설퍼 알루미네이트 20∼50중량부, 황산 나트륨 8∼15중량부, 황산 칼슘 10∼15중량부, 황산 알루미늄 12∼15중량부 및 나프탈렌 설퍼네이트 포름알데하이드 축합물 2∼5중량부로 이루어진 고성능 고화제 조성물.100 parts by weight of sodium silicate mixed with porous ceramics, 40 to 70 parts by weight of bentonite, 30 to 60 parts by weight of coumarone indene resin, 20 to 50 parts by weight of calcium sulfur aluminate, 8 to 15 parts by weight of sodium sulfate, and 10 to calcium sulfate A high performance solidifying agent composition comprising 15 parts by weight, 12-15 parts by weight of aluminum sulfate and 2-5 parts by weight of naphthalene sulfonate formaldehyde condensate. 제 1 항에 있어서, 다공성 세라믹이 혼합된 규산소다는 40㎛ 이하의 입자크기를 갖는 규산소다와 다공성 세라믹을 1:1중량비로 혼합하여 얻어진 것임을 특징으로 하는 고성능 고화제 조성물.The high performance solidifying agent composition according to claim 1, wherein the sodium silicate mixed with the porous ceramic is obtained by mixing the sodium silicate having a particle size of 40 µm or less and the porous ceramic in a 1: 1 weight ratio. 제 1 항에 있어서, 쿠마론 인덴 수지는 입자크기가 150∼250㎛인 것임을 특징으로 하는 고성능 고화제 조성물.The high performance solidifying agent composition according to claim 1, wherein the coumarone indene resin has a particle size of 150 to 250 µm. 규산소다를 볼밀을 이용하여 분쇄한 후 체가름하여 40㎛ 이하의 크기만을 선별하여 다공성 세라믹과 1:1로 혼합하여 얻어진 다공성 세라믹이 혼합된 규산소다 100중량부를 파우더 혼합기에 넣고 벤토나이트 40∼70중량부, 칼슘 설퍼 알루미네이트 20∼50중량부, 황산 나트륨 8∼15중량부, 황산 칼슘 10∼15중량부, 황산 알루미늄 12∼15중량부, 나프탈렌 설퍼네이트 포름알데하이드 축합물 2∼5중량부를 첨가하여 2∼3시간 정도 교반시키는 제 1단계; 및After grinding soda silicate using a ball mill, sifting and sifting only 40 µm or less in size, mixing 100 parts by weight of sodium silicate mixed with the porous ceramics in a powder mixer in a powder mixer, 40 to 70 weights of bentonite 20 to 50 parts by weight of calcium sulfur aluminate, 8 to 15 parts by weight of sodium sulfate, 10 to 15 parts by weight of calcium sulfate, 12 to 15 parts by weight of aluminum sulfate, and 2 to 5 parts by weight of naphthalene sulfonate formaldehyde condensate, A first step of stirring for about 2 to 3 hours; And 쿠마론 인덴 수지를 볼밀을 이용하여 분쇄한 후 체가름하여 150∼250㎛ 크기의 입자만을 선별한 것 30∼60중량부를 상기 제 1단계의 교반물에 첨가하여 1∼2시간 정도 교반하는 고성능 고화제의 제조방법.High-performance, high-performance high-moist mixture of coumarone indene resin using a ball mill, followed by sieving and screening only particles having a size of 150 to 250 μm and adding 30 to 60 parts by weight to the agitator of the first step. Preparation of Topicals.
KR10-2001-0049238A 2001-08-16 2001-08-16 Solidification agent and manufacturing method thereof KR100403111B1 (en)

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