KR102261971B1 - Ready-mixed concrete eco admixture for reducing specific air pollutants - Google Patents
Ready-mixed concrete eco admixture for reducing specific air pollutants Download PDFInfo
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Abstract
Description
콘크리트의 고성능화, 고강도화, 고내구성 등 콘크리트 기술이 비약적으로 발전하면서, 다양한 혼화제가 이용되고 있다. 혼화제는 시멘트, 물, 골재 이외의 재료로서 물리 화학적 작용에 의해 경화 전후의 콘크리트 및 경화 중의 콘크리트 성질을 개선하거나 경제성 향상 등의 목적으로 사용되는 재료이다. 상기와 같은 혼화제는 적절히 사용하면, 효과를 극대화시킬 수 있지만, 잘못 사용하면 오히려 콘크리트에 해악을 끼지는 성질을 가지고 있어, 혼화제의 선정 및 사용에 있어서는 각각의 품질이나 효과를 충분히 파악한 후 적절히 현장 혹은 제품의 환경을 고려하여 사용해야만 한다.As concrete technologies such as high performance, high strength, and high durability of concrete develop rapidly, various admixtures are being used. Admixtures are materials other than cement, water, and aggregate, which are used for the purpose of improving the properties of concrete before and after hardening and concrete during hardening by physical and chemical action, or improving economic efficiency. The above-mentioned admixtures can maximize the effect when properly used, but if used incorrectly, they have the property of harming concrete. It must be used in consideration of the environment of the product.
본 발명은 콘크리트(레미콘) ECO 혼화제 조성물에 관한 것으로, 구체적으로 콘크리트 레미콘의 유동성과 작업성, 강도증대 등 품질을 향상시키며, 레미콘 제조시 수화반응 등에 의해 생성, 배출되는 유해물질을 착염화시켜, 대기중으로 방출을 저감시키고 시멘트를 고형화시키는 역활을 하는 레미콘용 ECO 혼화제 제조에 관한 것이다.The present invention relates to a concrete (ready-mixed concrete) ECO admixture composition, which specifically improves the quality such as fluidity, workability, and strength increase of concrete ready-mixed concrete, and complexes the harmful substances generated and discharged by hydration reaction during production of ready-mixed concrete, It relates to the manufacture of an ECO admixture for ready-mixed concrete, which reduces emissions to the atmosphere and serves to solidify cement.
과거에는 시멘트 제조시 석회석이나 규사 등 천연광물 등을 사용하여 제조하였으나, 근래에는 천연광물의 고갈과 산업부산물의 재활용 목적으로, 각종 슬래그, 하수슬러지, 폐주물사 등 각종 폐기물들을 시멘트 원료로 사용하고 있다. 이에따라, 시멘트·콘크리트에서 암모니아(NH3)나 시안화수소(HCN)등과 같은 유해물질이 허용치 이상으로 배출되고 있는 실정이다. 그러나, 지금까지 통상적으로 사용하는 콘크리트 혼화제들은 콘크리트의 성질, 워커빌리티, 블리딩, 응결시간, 압축강도, 길이변화, 중성화, 동결융해작용 및 화학물질의 침식 등에 대한 내구성, 수화열 억제 등의 개선을 목적으로 사용되며, 특수한 혼화제로 콘크리트 중의 철근 부식을 억제하는 방청제, 콘크리트에 점성과 유동성을 부여하여 수중에서의 재료분리 저항성을 높이는 수중콘크리트용 혼화제 등이 주류를 이루고 있어, 유동성이나 작업성, 강도 증진 등의 효능은 발휘하였으나, 유해물질 저감 기능은 발휘하지 못함은 물론 오히려 증대시키는 문제점이 있다.In the past, natural minerals such as limestone and silica sand were used to manufacture cement, but in recent years, various wastes such as various slags, sewage sludge, and waste casting sand are used as cement raw materials for the purpose of depletion of natural minerals and recycling of industrial by-products. As a result, harmful substances such as ammonia (NH3) and hydrogen cyanide (HCN) are being discharged from cement and concrete beyond the allowable level. However, concrete admixtures commonly used so far have been used for the purpose of improving the properties of concrete, workability, bleeding, setting time, compressive strength, length change, neutralization, freeze-thaw action, and durability against chemical erosion, suppression of heat of hydration, etc. Used as a special admixture, rust preventives that suppress corrosion of reinforcing bars in concrete, admixtures for underwater concrete that increase resistance to material separation in water by imparting viscosity and fluidity to concrete, etc. Although the efficacy of the toxic substance was exhibited, there is a problem in that it does not exhibit the function of reducing harmful substances and rather increases it.
이에 따라, 상기 유해성분들을 저감시키기 위한 친환경적인 콘크리트 혼화제의 개발이 절실히 요구되고 있고, 이들 문제점을 해결하고자 선행기술들이 개발되었다.Accordingly, the development of an eco-friendly concrete admixture for reducing the harmful components is urgently required, and prior technologies have been developed to solve these problems.
일예로, 국내등록특허 제1406926호에서는 도데실벤젠설폰산철염과 나프탈렌포름알데히드설폰산철염을 사용하여, 유해한 6가크롬을 3가크롬으로 환원시키며, 철이온은 시멘트에 함유된 암모니아와 염을 형성하여 암모니아 방출을 저감시키는 기술이 개시되어 있다. 또한, 국내 등록특허 제1152361호에는 온천수에 다량 함유되어 있는 (CO3)2-, (HCO3), (SO4)2- 등의 음이온과 시멘트에 함유되어 있는 암모니아나 6가 크롬을 반응시켜 암모니아의 발생을 저감시키며, 또한, Fe 철염과 6가 크롬을 반응시켜 화학식 1과 같이 3가 크롬으로 환원시키는 기술이 개시되어 있다. 또한, 국내등록특허공보 제1613906호에는 암모니아를 저감시키고, 콘크리트의 감수성, 유동성 및 분산성을 증대시켜 작업성을 향상시키는 복합기능의 혼화제가 개시되어 있으며, 국내등록특허 10-0879140에는 방향족 산화물을 포함하는 폐기물에 산성 또는 염기성 용액을 가하여 중화 처리한 콘크리트 혼화제가 개시되어 있다. 국내공개특허 제2013-76596호에는 암모니아수를 이용하여 이산화탄소, 황화수소 및 시안화수소를 동시에 제거하는 방법의 발명이 개시되어 있으며, 국내 등록특허 제10-2144327호에는 천이 금속 또는 란탄 금속 촉매을 이용하여 암모니아 전구체의 존재하에 반응시켜 연도가스 내의 HCN을 제거하는 방법의 발명이 개시되어 있다. 그러나, 기존 콘크리트 혼화제 기능을 수행하면서 유해물질을 저감시키는 기능을 동시에 발휘할 수 있는 복합기능의 혼화제 개발에 어려움이 있었다. 이에 본 발명자는 다년간의 연구와 실험 등을 통하여 암모니아(NH3)나 시안화수소(HCN)의 생성을 저감하는 혼화제를 개발하게 되었다. For example, in Korean Patent No. 1406926, dodecylbenzenesulfonate iron salt and naphthaleneformaldehydesulfonate iron salt are used to reduce harmful hexavalent chromium to trivalent chromium, and iron ions reduce ammonia and salts contained in cement. Techniques for reducing ammonia emissions by forming are disclosed. Also, According to Korean Patent Registration No. 1152361, the generation of ammonia is reduced by reacting anions such as (CO3)2-, (HCO3), (SO4)2-, etc. contained in hot spring water with ammonia or hexavalent chromium contained in cement. Also, a technique for reducing Fe iron salt and hexavalent chromium to trivalent chromium as shown in Formula 1 is disclosed. In addition, Korean Patent Publication No. 1613906 discloses an admixture with a complex function that improves workability by reducing ammonia and increasing the sensitivity, fluidity and dispersibility of concrete. Disclosed is a concrete admixture in which an acidic or basic solution is added to the containing waste to be neutralized. Korean Patent Publication No. 2013-76596 discloses an invention of a method for simultaneously removing carbon dioxide, hydrogen sulfide and hydrogen cyanide using ammonia water, and Korean Patent No. 10-2144327 discloses an ammonia precursor using a transition metal or lanthanum metal catalyst. Disclosed is a method for removing HCN in flue gas by reacting in the presence of However, there was a difficulty in developing an admixture with a complex function that can simultaneously exhibit the function of reducing harmful substances while performing the function of the existing concrete admixture. Accordingly, the present inventors have developed an admixture for reducing the production of ammonia (NH3) or hydrogen cyanide (HCN) through many years of research and experiments.
본 발명의 목적은 기존 콘크리트 혼화제의 기능을 보완 및 개선시켜 레미콘 제조시 생성 배출되는 특정 대기유해물질들을 저감시키는데 있다. An object of the present invention is to reduce specific air pollutants generated and discharged during the production of ready-mixed concrete by supplementing and improving the function of the existing concrete admixture.
본 발명의 또 다른 목적은 유해물질의 재생성을 방지하는 기능을 갖는 혼화제를 개발하는데 있다.Another object of the present invention is to develop an admixture having a function of preventing the regeneration of harmful substances.
본 발명의 또 다른 목적은 본 발명 ECO혼화제를 사용하여 친환경 콘크리트 레미콘을 개발하는데 있다.Another object of the present invention is to develop an eco-friendly concrete ready-mixed concrete using the ECO admixture of the present invention.
상기의 목적을 달성하기 위하여 본 발명에서는 폴리카르본산계 감수제, AE제, 질산금속염, 황산금속염, 킬레이트계분산제 등을 사용하여 레미콘 제조시 생성·배출되는 특정 대기유해물질 저감용 ECO 혼화제를 개발하였고, 그 조성 성분 조성비율은 다음과 같다.In order to achieve the above object, in the present invention, polycarboxylic acid water reducing agent, AE agent, metal nitrate salt, metal sulfate, chelate-based dispersant, etc. are used to reduce specific atmospheric pollutants generated and emitted during the manufacture of ready-mixed concrete ECO Admixture was developed. , its composition component composition ratio is as follows.
① 폴리카르본산계감수제 10 ~ 60 중량부① 10 to 60 parts by weight of polycarboxylic acid water-reducing agent
② 공기연행제(AE제) 2 ~ 5 중량부② Air entraining agent (AE agent) 2 ~ 5 parts by weight
③ 질산금속염 1 ~ 15 중량부③ 1 ~ 15 parts by weight of metal nitrate salt
④ 황산금속염 1 ~ 10 중량부④ 1 to 10 parts by weight of metal sulfate
⑤ 컬레이트계분산제 0.5 ~ 5 중량부⑤ 0.5 to 5 parts by weight of cholate-based dispersant
⑥ 희석수 80 ~ 200 중량부⑥ Dilution water 80 ~ 200 parts by weight
또한, 본 발명은 시멘트 100중량부에 잔골재 240~360 중량부, 굵은골재 300~390 중량부, 물 40~70 중량부, ECO 혼화제 0.5~5 중량부를 배합하여 친환경 레미콘을 제조함을 목적으로 한다. In addition, the present invention aims to produce eco-friendly ready-mixed concrete by mixing 240 to 360 parts by weight of fine aggregate, 300 to 390 parts by weight of coarse aggregate, 40 to 70 parts by weight of water, and 0.5 to 5 parts by weight of ECO admixture to 100 parts by weight of cement. .
본 발명의 ECO 혼화제는 콘크리트 레미콘의 유동성과 작업성 향상 강도 증대 등의 기능을 발휘하여, 레미콘 제조시 생성 배출되는 암모니아(NH3)를 착염화하여 암모니아 방출을 저감시키고 , 부반응으로 생성 배출되는 특정대기유해물질인 시안화수소(HCN)를 난용성염으로 착염화시켜, 유해물질로 인한 대기 오염을 감소 시키고, 또한, 유독성 6가 크롬을 무해한 3가 크롬으로 환원시켜 작업 환경을 개선시키는 복합기능의 ECO 혼화제이다.The ECO admixture of the present invention exhibits functions such as improving the flowability and workability of concrete ready-mixed concrete, increasing strength, and reducing ammonia emission by complexing ammonia (NH 3 ) generated and discharged during the production of ready-mixed concrete, and is produced and discharged as a side reaction. Composite function ECO that reduces air pollution caused by harmful substances by complexing hydrogen cyanide (HCN), a pollutant in the atmosphere, with a sparingly soluble salt, and also reduces toxic hexavalent chromium to harmless trivalent chromium to improve the working environment. It is an admixture.
도1 및 도2는 본 발명에 따른 ECO 혼화제에 대한 시험 성적서이다.1 and 2 are test reports for the ECO admixture according to the present invention.
유해가스의 발생에 따른 환경문제는 생태계를 파괴하며, 인체에 치명적인 영향을 미치는 등, 더 이상 방치할 수 없는 현실이다.Environmental problems caused by the generation of harmful gases are a reality that can no longer be neglected, such as destroying the ecosystem and having a fatal effect on the human body.
대기오염물질로 황사, 미세먼지, 매연, 각종 유독가스 등이 거론되고 있고, 최근, 레미콘 제조시설에서 특정 대기유해물질인 시안화수소(HCN)와 포르말린(HCHO), 암모니아(NH3) 및 크롬 등이 배출 및 검출되어 지방자치단체에서는 해당 시설에서의 레미콘 생산을 중단시키는 행정 처분의 사건이 발생하는 등 문제점이 제기되고 있다. 그 이유는 그동안 레미콘 사업장은 분진 문제만 관리하였고, 대기 유해물질에 대해서는 거의 무관심하게 방치하여 관리(처리)되지 않고 있는 실정이었다.Yellow dust, fine dust, soot, and various toxic gases are being discussed as air pollutants. Recently, certain air pollutants such as hydrogen cyanide (HCN), formalin (HCHO), ammonia (NH 3 ) and chromium in ready-mixed concrete manufacturing facilities. Due to this emission and detection, problems are being raised such as an administrative disposition to stop the production of ready-mixed concrete in the relevant facility in the local government. The reason is that the ready-mixed concrete plant has only managed the dust problem, and it has not been managed (treated) by neglecting the air pollutants.
레미콘 사업장들의 상당수가 전국 각 지역에 고루 분포되어 있어, 여기에서 배출되는 유해물질들이 인체에 영향을 미칠 것으로 예상된다. A significant number of ready-mixed concrete business sites are evenly distributed throughout the country, so it is expected that harmful substances emitted from them will affect the human body.
상기와 같은 문제점을 해결하기 위하여 레미콘 제조시설에서 대기 중으로 배출 또는 방출되는 특정 대기유해물질의 처리방법과 해결책을 강구하고자 본 연구 발명을 실행하였다. In order to solve the above problems, this research invention was carried out to find a treatment method and solution for specific atmospheric pollutants discharged or released into the atmosphere in a ready-mixed concrete manufacturing facility.
검토결과 레미콘 제조시설인 시멘트 혼합기(cement mixer)에서 대기 중으로 배출되는 대기오염물질 중, 분진(미세먼지) 등은 각 제조시설에 집진기가 설치되어 있어 배출 허용치 이하이나, 암모니아(NH3)와 시안화수소(HCN)는 배출허용치를 넘어서는 문제점이 발생하였다. As a result of the review, among the air pollutants emitted into the atmosphere from the cement mixer, a ready-mixed concrete manufacturing facility, dust (fine dust) is below the emission limit because a dust collector is installed in each manufacturing facility, but ammonia (NH 3 ) and cyanide Hydrogen (HCN) had a problem exceeding the allowable emission level.
특히, 대기환경보전법에 특정대기유해물질로 규정된 시안화수소(HCN)의 경우, 레미콘 제조시설이 있는 지역에서는 배출농도가 0.1 - 0.4ppm으로 일반지역의 배출농도 기준인 0.05ppm 보다 월등히 높아 레미콘 제조시설의 폐쇄가 우려되는 등 심각한 사회 현실문제로 대두하였다.In particular, in the case of hydrogen cyanide (HCN), which is prescribed as a specific air hazardous substance in the Air Environment Conservation Act, the emission concentration is 0.1 - 0.4ppm in the area where the ready-mixed concrete manufacturing facility is located, which is much higher than the 0.05ppm emission concentration standard of the general area. It has emerged as a serious social reality problem, such as concerns about the closure of the facility.
일반적으로, 시안화물(CN)은 우레탄 스티로폼 연소가스나 담배연기 등에서 발생하는 것으로 알려져 있고, 레미콘 제조 시에는 암모니아가 발생한다는 사실은 알려져 있었지만, 시안화수소(HCN)가 발생한다는 사실은 지금까지 알려진 바가 없었다. In general, cyanide (CN) is known to be generated from urethane styrofoam combustion gas or cigarette smoke, and it was known that ammonia is generated during the manufacture of ready-mixed concrete, but the fact that hydrogen cyanide (HCN) is generated is not known until now. there was no
그러나, 레미콘 생산시설의 대기에 대하여 반복적으로 측정한 결과 시안화수소(HCN)가 검출됨이 확인되었고 생성·배출 원인을 추적한 결과, 레미콘 원료들의 혼합시 수화반응 등 화학적 반응에 의해 암모니아(NH3)와 시안화수소(HCN)가 발생할 수 있다는 사실을 발견하게 되었다. However, as a result of repeatedly measuring the atmosphere of the ready-mixed concrete production facility, it was confirmed that hydrogen cyanide (HCN) was detected, and as a result of tracing the cause of generation and discharge, ammonia (NH 3 ) and hydrogen cyanide (HCN).
<레미콘 제조시 암모니아(NH3) 발생 메카니즘><Mechanism of ammonia (NH3) generation during production of ready-mixed concrete>
레미콘(콘크리트) 제조시 사용하는 시멘트, 골조, 슬러그, 애쉬 등에 함유되어 있는 질산화물(NOx)이 수화반응 시 알카리에 가수분해되어, 암모늄이온이 발생되고 수분증발로 pH가 높아져, 고알카리에 의해 암모늄 이온이 분해되어 [표 1]과 같이 NH3를 발생시킨다.Nitric oxide (NOx) contained in cement, frame, slug, ash, etc. used in the production of ready-mixed concrete (concrete) is hydrolyzed to alkali during hydration reaction to generate ammonium ions and increase in pH due to water evaporation. Ions are decomposed to generate NH 3 as shown in [Table 1].
<레미콘 제조시 시안화수소(HCN) 발생 메커니즘><Mechanism of hydrogen cyanide (HCN) generation during production of ready-mixed concrete>
시안화수소(HCN)는 아래의 세가지 방법으로 합성 제조된다.Hydrogen cyanide (HCN) is synthesized by the following three methods.
① CH4 + NH3 →(산화) HCN + 3H2 ↑① CH 4 + NH 3 → (oxidation) HCN + 3H 2 ↑
② 2CH4 + 2NH3 + 3O2 → 2HCN + 6H2O② 2CH 4 + 2NH 3 + 3O 2 → 2HCN + 6H 2 O
③ H + + NaCN → HCN + Na+ ③ H + + NaCN → HCN + Na +
이와 같이 시안화수소(HCN) 발생원인 물질은 탄화수소(CH4)와 암모니아(NH3)이며, 시안화수소(HCN) 발생량은 함유 질소량에 비례하는 것으로 나타났다.As such, the hydrogen cyanide (HCN) generation source is hydrocarbon (CH 4 ) and ammonia (NH 3 ), and the amount of hydrogen cyanide (HCN) generation was found to be proportional to the nitrogen content.
그리고, 상기의 시안화수소(HCN) 발생원인 물질 중 암모니아의 발생 메카니즘은 표1과 같고, 한국 콘크리트 학회에서 발행된 자료에 의하면, 레미콘 생산시 배출되는 대기오염물질인 CO2, SO2, NOx, VOC, CH4, CO 등으로 이중, 탄화수소인 CH4는 ㎥당 3,32g이 생성 배출 되는 것으로 나타났다. And, the mechanism of ammonia generation among the hydrogen cyanide (HCN) generation source materials is shown in Table 1, and according to the data published by the Korean Society of Concrete, CO 2 , SO 2 , NOx, air pollutants emitted during the production of ready-mixed concrete,
상기 이론을 근거로, 레미콘 제조시 배출되는 탄화수소인 CH4가 레미콘 제조시 수화반응으로 생성 배출되는 암모니아(NH3)와 반응하여 시안화수소(HCN)가 생성 발생되는 것으로 확인하였다. Based on the above theory, it was confirmed that CH 4, which is a hydrocarbon discharged during the production of ready-mixed concrete, reacts with ammonia (NH 3 ) generated and discharged through a hydration reaction during production of ready-mixed concrete to generate hydrogen cyanide (HCN).
이에 따라 시안화수소(HCN)의 발생을 저감시키려면 원인물질인 암모니아 (NH3)와 탄화수소(CH4)의 생성을 억제시키는 것이 필요하나, 탄화수소는 무해한 물질이므로 탄화수소의 발생 억제 보다는 암모아의 생성을 억제하는 것이 바람직하다. 특히, 석회석을 소성하는 과정에서 주 원료인 유연탄을 사용하지 않고, 각종 쓰레기 등 페기물을 태워 석회를 소성하는 과정에서 암모니아(NH3)가 발생하므로 본 발명에서는 인체에 유해한 유독물질인 암모니아(NH3)의 발생을 저감 또는 억제시키는 방법을 사용하였다.Accordingly, in order to reduce the generation of hydrogen cyanide (HCN), it is necessary to suppress the production of ammonia (NH 3 ) and hydrocarbon (CH 4 ), which are the causative substances, but since hydrocarbons are harmless substances, the generation of ammonia rather than suppression of hydrocarbon generation It is preferable to suppress In particular, without the use of the main raw material coal in the process of calcination of limestone, because the ammonia (NH 3) generated in the course of various kinds of waste such as to burn waste burning the lime in the present invention, the harmful toxic substances in the human body ammonia (NH 3 ) was used to reduce or suppress the occurrence of
<암모니아(NH3) 저감><Ammonia (NH 3 ) Reduction>
황산 금속염과 암모니아를 착염화시켜 시멘트(콘크리트)에 고화시킨다. Metal sulfate and ammonia are complexed and solidified in cement (concrete).
NH3 + H20 → NH4OHNH 3 + H 2 0 → NH 4 OH
MnS04 + 2NH4OH → Mn(OH)2 + (NH4)2S04 MnS0 4 + 2NH 4 OH → Mn(OH) 2 + (NH 4 ) 2 S0 4
ZnS04 + 2NH4OH → Zn(OH)2 + (NH4)2S04 ZnS0 4 + 2NH 4 OH → Zn(OH) 2 + (NH 4 ) 2 S0 4
FeSO4 + 2NH4OH → Fe(OH)2 + (NH4)2S04 FeSO 4 + 2NH 4 OH → Fe(OH) 2 + (NH 4 ) 2 S0 4
Fe(SO4)3 + 6NH4OH → 2Fe(OH)3 + 3(NH4)2S04 Fe(SO 4 ) 3 + 6NH 4 OH → 2Fe(OH) 3 + 3(NH 4 ) 2 S0 4
즉, 음이온인 황산염(sulfate)과 암모니아가 반응하여 아래와 같이 착염을 생성한다. That is, an anion, sulfate, and ammonia react to form a complex salt as shown below.
2NH4OH + S04 → (NH4)2S04 2NH 4 OH + S0 4 → (NH 4 ) 2 S0 4
<시안화수소(HCN) 저감><Hydrogen cyanide (HCN) reduction>
시안화수소(HCN)를 저감시키기 위한 본 발명의 에코 혼화제는 다음과 같은 조성성분 및 조성비율로 이루어져 있다. The eco admixture of the present invention for reducing hydrogen cyanide (HCN) consists of the following components and composition ratios.
① 폴리카르본산계감수제 20 - 50 중량부① Polycarboxylic acid water reducing agent 20 - 50 parts by weight
② 공기연행제(AE제) 2 - 5 중량부 ② Air entraining agent (AE agent) 2 - 5 parts by weight
③ 질산금속염 1 - 10 중량부③ Metal nitrate salt 1 - 10 parts by weight
④ 황산금속염 1 - 10 중량부④ Metal sulfate 1 - 10 parts by weight
⑤ 컬레이트계분산제 0.1 - 1 중량부⑤ cholate dispersant 0.1 - 1 part by weight
⑥ 희석수 100 중량부⑥ 100 parts by weight of diluted water
상기의 질산 금속염인 Ca(N03)2, Fe(N03)2, Zn(N03)2 등은 시멘트에 친화적인 물질로 콘크리트 조기 강도 발현을 증대시키며, 특히 질산아연(Zn(NO3)2)은 시안화수소(HCN)와 반응하여 불용성인 시안화아연(Zn(CN)2)를 생성한다. 또한, 황산 금속염은 MnS04, ZnS04, FeSO4 또는 Fe(SO4)3 를 사용할 수 있으며, 이들 중 단독 또는 복수의 황산 금속염을 사용할 수 있으며, 컬레이트계 분산제로 글루콘산철(Fe-gluconate)을 사용한다. Ca(N0 3 ) 2 , Fe(N0 3 ) 2 , Zn(N0 3 ) 2 which is the above metal nitrate salt Etc. is a cement-friendly material and increases the early strength development of concrete. In particular, zinc nitrate (Zn(NO 3 ) 2 ) reacts with hydrogen cyanide (HCN) to produce insoluble zinc cyanide (Zn(CN) 2 ). . In addition, as the metal sulfate salt, MnS0 4 , ZnS0 4 , FeSO 4 or Fe(SO 4 ) 3 may be used. Among them, single or a plurality of metal sulfate salts may be used, and as a cholate-based dispersant, iron gluconate (Fe-gluconate) may be used. ) is used.
ZnS04 + 2HCN → Zn(CN)2 + H2S04 ZnS0 4 + 2HCN → Zn(CN) 2 + H 2 S0 4
Zn(NO3)2 + 2HCN → Zn(CN)2 + 2HN03 Zn(NO 3 ) 2 + 2HCN → Zn(CN) 2 + 2HN0 3
본 발명의 레미콘 혼화제는 암모니아와 시안화 수소를 저감시킬 뿐 아니라 컬레이트계분산제에 의해 분산력과 유동성을 증대시켜 콘크리트의 품질과 시공성을 개선시킨다. 또한, 공기연행제(Air Entranining agent)는 콘크리트에 미세한 구형의 공기포를 균일하게 연행시켜 굳지않은 상태에서는 미세한 기포의 볼 베어링 효과로 콘크리트의 워커빌리티를 증진시키고 굳은 후에는 동결융해에 대한 저항성을 증가시키며, 질산금속염 및 황산금속염을 첨가함으로써 시안화수소를 불용성인 시안화아연(Zn(CN)2)을 생성시켜 시안화 수소를 저감시키고 또한, 콘크리트의 강도를 강도를 증진시키는 기능을 가지고 있다. 본 발명에 따른 콘크리트 혼화제의 제조하기 위한 실시예 및 시험예를 통하여 본 발명을 보다 구체적으로 설명하지만 아래 기재에 의해 본 발명이 한정되는 것은 아니다.The ready-mixed concrete admixture of the present invention not only reduces ammonia and hydrogen cyanide, but also improves the quality and workability of concrete by increasing the dispersing power and fluidity by the cholate-based dispersant. In addition, the air entraining agent uniformly entrains fine spherical air bubbles in the concrete to enhance the workability of the concrete with the ball bearing effect of fine bubbles in the unconsolidated state, and increase the resistance to freezing and thawing after hardening. By adding metal nitrate and metal sulfate salts, hydrogen cyanide is produced insoluble zinc cyanide (Zn(CN) 2 ), thereby reducing hydrogen cyanide, and increasing the strength of concrete. The present invention will be described in more detail through Examples and Test Examples for manufacturing the concrete admixture according to the present invention, but the present invention is not limited by the description below.
<실시예 1><Example 1>
① 폴리카르본산계감수제 50 중량부① 50 parts by weight of polycarboxylic acid water reducing agent
② 공기연행제(AE제) 5 중량부 ② 5 parts by weight of air entraining agent (AE agent)
③ 질산금속염 10 중량부③ 10 parts by weight of metal nitrate salt
④ 황산금속염 10 중량부④ 10 parts by weight of metal sulfate
⑤ 컬레이트계분산제 1 중량부⑤ 1 part by weight of cholate-based dispersant
⑥ 희석수 100 중량부⑥ 100 parts by weight of diluted water
를 투입하고 균일하게 혼합하여 본 발명의 에코 혼화제를 제조하였다.was added and uniformly mixed to prepare the eco admixture of the present invention.
<실시예 2><Example 2>
① 폴리카르본산계감수제 20 중량부① 20 parts by weight of polycarboxylic acid water-reducing agent
② 공기연행제(AE제) 2 중량부 ② Air entraining agent (made by AE) 2 parts by weight
③ 질산금속염 1 중량부③ 1 part by weight of metal nitrate salt
④ 황산금속염 1 중량부④ 1 part by weight of metal sulfate
⑤ 컬레이트계분산제 0.1 중량부⑤ 0.1 parts by weight of cholate-based dispersant
⑥ 희석수 100 중량부⑥ 100 parts by weight of diluted water
를 투입하고 실시예 1과 같이 균일하게 혼합하여 에코 혼화제를 제조하였다.was added and uniformly mixed as in Example 1 to prepare an eco admixture.
<비교예 1><Comparative Example 1>
말레인산 에스테르 : 100중량부Maleic acid ester: 100 parts by weight
폴리글루코스 : 25중량부Polyglucose: 25 parts by weight
공기연행제 : 10중량부Air entraining agent: 10 parts by weight
리그닌염 : 30중량부Lignin salt: 30 parts by weight
질산칼슘 : 30중량부Calcium nitrate: 30 parts by weight
트리에탄올 아민 : 10중량부Triethanolamine: 10 parts by weight
희석수 : 150 중량부Dilution water: 150 parts by weight
를 투입하고 혼합하여 소취형 혼화제를 제조하였다was added and mixed to prepare a deodorizing type admixture
<시험예 1><Test Example 1>
상기 실시예 1 혼화제의 시료(P) 및 실시예 2 혼화제의 시료(1)와 비교예의 혼화제의 시료(2)를 이용하여 레미콘을 제조하였고, 상기의 혼화제들을 제조된 레미콘의 시안화 수소와 암모니아 저감율에 대한 시험을 한국화학 융합시험원에 의뢰하여 시험하였고, 그 결과는 [표 2] 및 [표 3]에 나타내었다.Ready-mixed concrete was prepared using the sample (P) of the admixture of Example 1 and the sample (1) of the admixture of Example 2 and the sample (2) of the admixture of Comparative Example, and hydrogen cyanide and ammonia reduction rate of the ready-mixed concrete prepared by using the admixtures The test was commissioned by the Korea Chemical Convergence Testing Institute, and the results are shown in [Table 2] and [Table 3].
상기 [표 2] 및 [표 3]에서 알 수 있듯이 본 발명의 실시예 1 및 실시예 2에 따른 에코 레미콘 혼화제는 유해 물질인 암모니아 및 시안화수소의 저감효능이 기존의 혼화제를 사용한 레미콘에 비하여 뛰어난 것으로 확인되었으며, 상기 [표 3]에 의하면 암모니아의 탈취율 역시도 기본의 혼화제에 비하여 본 발명의 혼화제가 탈취율이 띄어난 것으로 확인되었다. As can be seen from [Table 2] and [Table 3], the eco-ready concrete admixture according to Examples 1 and 2 of the present invention has a lower efficacy of ammonia and hydrogen cyanide, which are harmful substances, superior to that of the ready-mixed concrete using the existing admixture. It was confirmed that, according to [Table 3], the deodorization rate of ammonia was also confirmed to be superior to that of the admixture of the present invention compared to the basic admixture.
Claims (5)
공기연행제(AE제) 2 - 5 중량부
질산금속염 1 - 10 중량부
황산금속염 1 - 10 중량부
Fe-gluconate 분산제 0.1 - 1 중량부
희석수 100 중량부
을 함유하는 것을 특징으로 하는 특정대기유해물질 저감용 혼화제.Polycarboxylic acid water reducing agent 20 - 50 parts by weight
Air entraining agent (AE agent) 2 - 5 parts by weight
1 - 10 parts by weight of metal nitrate salt
1 - 10 parts by weight of metal sulfate
Fe-gluconate dispersant 0.1 - 1 part by weight
100 parts by weight of diluted water
Admixture for reducing specific air pollutants, characterized in that it contains
질산 금속염은 Ca(N03)2, Fe(N03)2, 또는 Zn(N03)2 중 어느 하나, 또는 2 이상인 것을 특징으로 하는 특정대기유해물질 저감용 혼화제.According to claim 1,
Metal nitrate salt is Ca(N0 3 ) 2 , Fe(N0 3 ) 2 , or Zn(N0 3 ) 2 An admixture for reducing specific air pollutants, characterized in that it is any one, or 2 or more.
상기의 황산 금속염은 MnS04, ZnS04, FeSO4, Fe(SO4)3 중 어느 하나 또는 2 이상을 사용하는 것을 특징으로 하는 특정대기유해물질 저감용 혼화제.
According to claim 1,
The metal sulfate salt is MnS0 4 , ZnS0 4 , FeSO 4 , Fe(SO 4 ) 3 Admixture for reducing specific air pollutants, characterized in that any one or two or more are used.
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