KR20230059587A - A composite of eco-friendly cement additive for solidification of heavy metal ions - Google Patents
A composite of eco-friendly cement additive for solidification of heavy metal ions Download PDFInfo
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- 239000004568 cement Substances 0.000 title claims abstract description 46
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 43
- 150000002500 ions Chemical class 0.000 title claims abstract description 32
- 239000000654 additive Substances 0.000 title claims abstract description 27
- 230000000996 additive effect Effects 0.000 title claims abstract description 27
- 238000007711 solidification Methods 0.000 title abstract description 7
- 230000008023 solidification Effects 0.000 title abstract description 7
- 239000002131 composite material Substances 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 34
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000002893 slag Substances 0.000 claims abstract description 12
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 10
- 239000010455 vermiculite Substances 0.000 claims abstract description 10
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 10
- 239000005909 Kieselgur Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052925 anhydrite Inorganic materials 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 26
- 239000000292 calcium oxide Substances 0.000 description 25
- 239000002956 ash Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000010881 fly ash Substances 0.000 description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000005341 cation exchange Methods 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000012190 activator Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- -1 and at this time Inorganic materials 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009841 combustion method Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003100 immobilizing effect Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000010882 bottom ash Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910001653 ettringite Inorganic materials 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 208000004998 Abdominal Pain Diseases 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 201000007455 central nervous system cancer Diseases 0.000 description 1
- 208000015114 central nervous system disease Diseases 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions 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
- C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust cements
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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
- 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
- C04B14/08—Diatomaceous earth
-
- 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
- C04B14/20—Mica; Vermiculite
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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
- 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
- C04B14/20—Mica; Vermiculite
- C04B14/204—Mica; Vermiculite expanded
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- 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
- C04B14/30—Oxides other than silica
-
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- 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
- C04B14/30—Oxides other than silica
- C04B14/308—Iron oxide
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- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
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- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
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- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
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- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/143—Calcium-sulfate
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions 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
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
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- C04B2111/00017—Aspects relating to the protection of the environment
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Abstract
Description
본 발명은 일반 시멘트 중의 친환경 중금속 이온 고정용 시멘트 첨가제 조성물에 관한 것이다.The present invention relates to a cement additive composition for fixing environment-friendly heavy metal ions in general cement.
시멘트가 건축물에 사용되면서 사용량이 폭발적으로 증가하였으나, 시멘트의 유해성은 현재까지도 논란을 야기하고 있다. 특히, 웰빙에 관심이 많은 현대인에게 시멘트의 유해성은 심각한 문제로 인식되고 있다. As cement was used in buildings, its usage increased explosively, but the harmfulness of cement still causes controversy. In particular, the harmfulness of cement is recognized as a serious problem by modern people who are interested in well-being.
구체적으로 시멘트로 제조된 콘크리트 건물은 통기성이 나쁘고 독성인 자극성 취기를 방출함으로써 실내 공기의 질을 저하시키는 문제를 야기한다. 또한, 겨울철에는 결로현상에 의한 곰팡이 증식을 야기하므로, 호흡기 및 피부에 좋지 않은 영향을 끼친다. 따라서 실내에서 보내는 시간이 많은 현대인에게 이러한 시멘트의 유해성은 매우 심각한 문제가 아닐 수 없다. Specifically, concrete buildings made of cement have poor air permeability and emit toxic irritating odors, thereby causing a problem of deteriorating indoor air quality. In addition, since it causes mold growth due to dew condensation in winter, it has a bad effect on the respiratory system and skin. Therefore, the harmfulness of cement is a very serious problem for modern people who spend a lot of time indoors.
특히, 2021년 6월부터 8월까지 3개월간 (사)한국환경사회정책연구소가 국내산 5개사와 외국산 6개사의 시멘트 제품에 대한 중금속 용출시험을 실시한 결과 국내산에서 수은과 6가 크롬 등이 각각 지정폐기물 유해물질함유기준인 0.005mg/L과 1.5mg/L를 초과하여 용출된 것으로 확인되었다. 이는 시멘트 생산 시 다량 다종의 산업폐기물을 부원료 및 보조연료로 사용하고 있어 직간접적으로 나타난 결과로 판단된다. 상기 수은은 중추신경장애 및 암을 유발하고, 6가 크롬은 피부암 및 구토, 복통, 설사를 유발시키는 것으로 알려져 있다. 따라서, 이러한 시멘트 유해성 시험결과는 매우 심각한 것으로 판단된다. In particular, for three months from June to August 2021, the Korea Environment and Social Policy Research Institute conducted a heavy metal elution test on cement products from 5 domestic and 6 foreign companies, and as a result, mercury and hexavalent chromium were designated as It was confirmed that it was eluted in excess of 0.005mg/L and 1.5mg/L, which are waste hazardous substance content standards. This is judged to be a direct or indirect result of using a large amount of various types of industrial waste as auxiliary raw materials and auxiliary fuel in cement production. It is known that mercury causes central nervous system disorders and cancer, and hexavalent chromium causes skin cancer, vomiting, abdominal pain, and diarrhea. Therefore, these cement hazard test results are judged to be very serious.
한편, 이러한 시멘트를 사용하여 건축 및 토목용 콘크리트를 생산하여 사용할 경우, 2차 오염이 야기될 수 있다. 즉, 일반 시멘트의 경우 중성화 과정에서 중금속이 용출되는데, 이러한 용출 중금속은 토양생물 및 식물들에게 흡수되고, 다시 인간에게 되돌아오게 되므로, 심각한 악순환을 야기할 수 있다.On the other hand, when such cement is used to produce and use concrete for construction and civil engineering, secondary contamination may occur. That is, in the case of general cement, heavy metals are eluted during the neutralization process, and these leached heavy metals are absorbed by soil organisms and plants and returned to humans, which can cause a serious vicious cycle.
이와 같은 시멘트의 독성으로 인한 문제를 방지하기 위하여, 1종 포틀랜드 시멘트를 사용하지 않고 기타 고가의 재료를 혼합하여 사용하는 방법이 제안되고 있으나, 이러한 방법은 공사비용을 턱없이 높이므로, 현실성이 낮은 실정이다. In order to prevent such a problem caused by the toxicity of cement, a method of mixing and using other expensive materials without using type 1 Portland cement has been proposed, but this method raises the construction cost unreasonably, so it is not realistic. The situation is.
본 발명은 종래기술의 상기와 같은 문제를 해결하기 위하여 안출된 것으로서,The present invention was made to solve the above problems of the prior art,
시멘트에 함유된 6가 크롬 및 중금속을 고정 및 안정화시킴으로써, 이러한 유해 성분 용출에 의한 2차 오염을 효과적으로 방지할 수 있는 시멘트 첨가제 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a cement additive composition capable of effectively preventing secondary contamination caused by the elution of harmful components by fixing and stabilizing hexavalent chromium and heavy metals contained in cement.
또한, 유동층상 보일러에서 발생하는 애시, 무수석고 분말 및 양이온 교환능이 있는 다공성 광물을 사용함으로써, 친환경적으로 6가 크롬 및 중금속을 고정 및 안정화시킬 수 있는 시멘트 첨가제 조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a cement additive composition capable of fixing and stabilizing hexavalent chromium and heavy metals in an environmentally friendly manner by using ash generated in a fluidized bed boiler, anhydrite powder, and porous minerals having cation exchange ability.
또한, 폐자원인 유동층상 보일러에서 발생하는 애시를 사용함으로써, 자원 재활용 효과를 제공하되, 알칼리 활성화제를 전혀 사용하지 않음으로써, 경제성 및 친환경성이 강화된 시멘트 첨가제 조성물을 제공하는 것을 목적으로 한다.In addition, by using ash generated in a fluidized bed boiler, which is a waste resource, to provide a resource recycling effect, but to provide a cement additive composition with enhanced economic feasibility and eco-friendliness by not using an alkali activator at all. .
또한, 시멘트의 수화속도를 향상시켜 작업성을 향상시키며, 양이온 교환 성능을 갖는 수화반응체를 형성하여 시멘트의 내화학성을 향상시키며, 염분 침투나 중성화에 대한 저항성을 향상시킬 수 있는 시멘트 첨가제 조성물을 제공하는 것을 목적으로 한다.In addition, a cement additive composition capable of improving workability by improving the hydration rate of cement, improving chemical resistance of cement by forming a hydration reactant having cation exchange performance, and improving resistance to salt penetration or neutralization intended to provide
상기와 같은 문제점을 해결하기 위하여, 본 발명은 In order to solve the above problems, the present invention
(1) 유동층상 보일러 애시 50 내지 85 중량%; (1) 50 to 85% by weight of fluidized bed boiler ash;
(2) 무수석고 분말 1 내지 15 중량%; (2) 1 to 15% by weight of anhydrite powder;
(3) 고로슬래그 5 내지 20 중량%; (3) 5 to 20% by weight of blast furnace slag;
(4) 다공성 팽창질석 미분 및 팽창 규조토 미분으로 이루어진 군으로부터 선택되는 1종 이상 5 내지 10 중량%; 및(4) 5 to 10% by weight of one or more selected from the group consisting of porous expanded vermiculite powder and expanded diatomaceous earth powder; and
(5) 산화철 분말 1 내지 5 중량%;를 포함하는 친환경 중금속 이온 고정용 시멘트 첨가제 조성물을 제공한다.(5) 1 to 5% by weight of iron oxide powder; provides an environmentally friendly cement additive composition for fixing heavy metal ions.
본 발명의 중금속 이온 고정용 시멘트 첨가제 조성물은 시멘트에 함유된 6가 크롬 및 중금속을 효과적으로 고정 및 안정화시킴으로써, 이러한 유해 성분 용출에 의한 2차 오염을 효과적으로 방지하는 효과를 제공한다. The cement additive composition for fixing heavy metal ions of the present invention effectively fixes and stabilizes hexavalent chromium and heavy metals contained in cement, thereby effectively preventing secondary contamination caused by the elution of harmful components.
또한, 유동층상 보일러에서 발생하는 애시, 무수석고 분말 및 양이온 교환능이 있는 다공성 광물을 사용함으로써, 친환경적으로 6가 크롬 및 중금속을 고정 및 안정화시키는 효과를 제공한다.In addition, by using ash generated in a fluidized bed boiler, anhydrite powder, and porous minerals having cation exchange ability, an effect of fixing and stabilizing hexavalent chromium and heavy metals in an environmentally friendly manner is provided.
또한, 폐자원인 유동층상 보일러에서 발생하는 애시를 사용함으로써, 자원 재활용 효과를 제공하되, 알칼리 활성화제를 전혀 사용하지 않음으로써, 우수한 경제성 및 친환경성을 제공한다.In addition, by using ash generated in a fluidized bed boiler, which is a waste resource, a resource recycling effect is provided, but excellent economic feasibility and eco-friendliness are provided by not using an alkali activator at all.
또한, 시멘트의 수화속도를 향상시켜 작업성을 높이며, 양이온 교환 성능의 수화반응체를 형성하여 시멘트의 내화학성을 향상시키며, 염분 침투나 중성화에 대한 저항성을 향상시키는 효과를 제공한다.In addition, it improves the workability by improving the hydration rate of cement, improves the chemical resistance of cement by forming a hydration reactant with cation exchange performance, and provides the effect of improving resistance to salt permeation or neutralization.
도 1은 시험예 1의 시험을 모식적으로 나타낸 도면이다.1 is a diagram schematically showing the test of Test Example 1.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.Unless otherwise defined, technical terms and scientific terms used in the present invention have meanings commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention is unnecessary in the following description. Descriptions of known functions and configurations that may be obscure are omitted.
본 발명의 친환경 중금속 이온 고정용 시멘트 첨가제 조성물은 (1) 유동층상 보일러 애시 50 내지 85 중량%; (2) 무수석고 분말 1 내지 15 중량%; (3) 고로슬래그 5 내지 20 중량%; (4) 다공성 팽창질석 미분 및 팽창 규조토 미분으로 이루어진 군으로부터 선택되는 1종 이상 5 내지 10 중량%; 및 (5) 산화철 분말 1 내지 5 중량%;를 포함하는 것을 특징으로 한다.The eco-friendly cement additive composition for fixing heavy metal ions of the present invention includes (1) 50 to 85% by weight of fluidized bed boiler ash; (2) 1 to 15% by weight of anhydrite powder; (3) 5 to 20% by weight of blast furnace slag; (4) 5 to 10% by weight of one or more selected from the group consisting of porous expanded vermiculite powder and expanded diatomaceous earth powder; and (5) 1 to 5% by weight of iron oxide powder.
상기 유동층상 보일러 애시는 유동층상 보일러 바텀애시 및 플라이애시 중에서 선택되는 1종 이상일 수 있다. The fluidized bed boiler ash may be at least one selected from fluidized bed boiler bottom ash and fly ash.
특히, 상기 바텀애시 및 플라이애시 중에서도 free-CaO의 함량이 5 내지 45 중량%인 것이 바람직하게 사용된다. 상술한 free-CaO는 일반적인 화학조성 상 나타나는 CaO의 함량이 아니라, 별도로 분리되어 CaO 상태로 존재하는 산화칼슘(CaO)을 의미한다. 일반적으로 광물의 화학조성에서는 CaSO4 같이 CaO가 다른 성분과 화합물 상태로 결합되어 있는 것도 모두 CaO 성분으로 인식하고 있다. 그러나 본원 발명에서의 free-CaO는 CaSO4 같이 CaO와 다른 성분이 화합물 상태로 결합되어 있지 않은 CaO를 의미한다. In particular, among the bottom ash and fly ash, one having a free-CaO content of 5 to 45% by weight is preferably used. The above-mentioned free-CaO does not mean the content of CaO appearing in the general chemical composition, but refers to calcium oxide (CaO) that is separated and exists in the CaO state. In general, in the chemical composition of minerals, CaO is recognized as a CaO component, such as CaSO 4 , in which CaO is combined with other components in a compound state. However, free-CaO in the present invention means CaO in which CaO and other components are not combined in a compound state, such as CaSO 4 .
상기 free-CaO는 본 발명의 구성에서 매우 중요한 특징의 하나로서, free-CaO 상태의 산화물이 존재하여야 시멘트에 포함된 알루미나 분말과 함께 중금속 이온을 흡착하여 칼슘-알루미늄-중금속으로 구성되는 고화체를 형성할 수 있다. The free-CaO is one of the very important characteristics in the configuration of the present invention. When free-CaO oxide is present, heavy metal ions are adsorbed together with the alumina powder included in the cement to form a solidified body composed of calcium-aluminum-heavy metal. can do.
또한, 본 발명에서는 free-CaO 함량이 높아야 물과의 혼합에 의해 수화(slake) 반응이 진행되며, 이때 알루미나가 수화 반응된 free-CaO와 반응하여 칼슘알루미네이트 화합물이 생성되고, 생성되는 칼슘 알루미네이트 화합물에 의하여 중금속이온이 공중합체로서 고화되어 중금속 이온용출을 방지할 수 있는 것이다. In addition, in the present invention, when the free-CaO content is high, a slake reaction proceeds by mixing with water, and at this time, alumina reacts with the hydrated free-CaO to produce a calcium aluminate compound, and the resulting calcium aluminate Heavy metal ions are solidified as a copolymer by the nate compound, thereby preventing the elution of heavy metal ions.
상기 유동층상 보일러 애시에 있어서, free-CaO의 함량이 5 중량% 미만일 경우, 알루미나 성분과의 반응에 의하여 생성되는 칼슘 알루미네이트 생성량이 적어 중금속 이온 고정화가 약해지며, free-CaO의 함량이 45 중량%를 초과하면, 칼슘 알루미네이트 생성량이 많아지므로 중금속 이온의 고정화에는 유리하지만 빠른 경화속도로 인하여 작업성이 저하되는 단점이 발생할 수 있다. 상기 free-CaO의 함량은 7 내지 30 중량%인 것이 더욱 바람직하게 사용될 수 있다. In the fluidized bed boiler ash, when the content of free-CaO is less than 5% by weight, the amount of calcium aluminate produced by the reaction with the alumina component is small, and the fixation of heavy metal ions is weakened, and the content of free-CaO is 45% by weight When % is exceeded, since the amount of calcium aluminate produced increases, it is advantageous for immobilizing heavy metal ions, but a disadvantage in that workability may deteriorate due to a fast curing speed may occur. The content of free-CaO may be more preferably used in the range of 7 to 30% by weight.
일반적으로 미분탄 보일러 플라이애시에는 CaO가 0.5 내지 3 중량%로 함유되며, 이는 화학적 조성에 의한 CaO로서 free-CaO와는 다른 화학적 결합물 상태로 존재한다. 이러한 성분 상의 차이는 보일러 연소방식에 기인한다. 즉, 유동층상 보일러의 연소방식에 따라 발생하는 플라이애시는 미분탄 보일러 연소방식과는 다른 소성형태를 나타내며, 이에 따라 미분탄 보일러 연소에 의한 플라이애시와 다른 화학적 조성을 갖는다. 특히 유동층상 보일러 플라이애시에 함유되는 CaO는 미분탄 보일러 연소시에 발생하는 플라이애시에 함유되어 있는 Ca 화합물과는 다르게 free-CaO의 상태로 존재한다. In general, pulverized coal boiler fly ash contains 0.5 to 3% by weight of CaO, which is CaO by chemical composition and exists in a chemical bond state different from free-CaO. The difference in these components is due to the boiler combustion method. That is, the fly ash generated according to the combustion method of the fluidized bed boiler exhibits a different firing form from the pulverized coal boiler combustion method, and thus has a different chemical composition from the fly ash generated by the pulverized coal boiler combustion. In particular, CaO contained in the fluidized bed boiler fly ash exists in a free-CaO state, unlike Ca compounds contained in the fly ash generated during combustion of a pulverized coal boiler.
한편, 유동층상 보일러에서 발생하는 플라이애시라고 하더라도 사용하는 연료의 특성 및 종류에 따라 CaO의 함량이나 상태가 다르게 나타난다. 왜냐하면, 사용하는 석탄의 발열량에 따라 free-CaO의 함유량이 달라지기 때문이다. On the other hand, even in fly ash generated in a fluidized bed boiler, the content or state of CaO appears differently depending on the characteristics and types of fuel used. This is because the content of free-CaO varies depending on the calorific value of the coal used.
그러므로, 본 발명에서는 유동층상 보일러 발생 애시 중에서도 free-CaO 함량이 5 내지 45 중량%인 것을 사용하는 것을 특징으로 한다.Therefore, in the present invention, among the ash generated by the fluidized bed boiler, it is characterized in that the free-CaO content is 5 to 45% by weight.
참고로, 미분탄 보일러 석탄회와 유동층상 보일러 석탄회의 성분 및 물성은 다음과 같이 비교될 수 있다. For reference, the components and physical properties of pulverized coal boiler fly ash and fluidized bed boiler fly ash can be compared as follows.
본 발명에 있어서, 상기 유동층상 보일러 애시는 미리 수화시킨 것이 사용된다. 상기 수화는 물과의 혼합시에 이루어질 수 있다. 이와 같이, 미리 수화된 유동층상 보일러 애시는 수화되지 않은 유동층상 보일러 애시와 달리 칼슘 알루미네이트 화합물을 생성하는 기능을 제공한다. In the present invention, the fluidized bed boiler ash is pre-hydrated. The hydration may be achieved upon mixing with water. In this way, the previously hydrated fluidized bed boiler ash provides a function of generating a calcium aluminate compound, unlike unhydrated fluidized bed boiler ash.
본 발명의 친환경 중금속 이온 고정용 시멘트 첨가제 조성물은 유동층상 보일러 애시를 사용하되 알칼리 활성화제를 전혀 사용하지 않고 무수석고 분말 및 양이온 교환능이 있는 이온 교환 다공성 재료를 사용하여 유동층상 보일러 애시를 경화시킴으로써 경제성 및 친환경성을 획기적으로 개선시키는 효과를 제공한다.The eco-friendly cement additive composition for fixing heavy metal ions of the present invention uses a fluidized bed boiler ash, but does not use an alkali activator at all, and uses anhydrite powder and an ion exchange porous material having cation exchange ability to harden the fluidized bed boiler ash, thereby providing economic feasibility. And it provides an effect of dramatically improving eco-friendliness.
상기 친환경 중금속 이온 고정용 시멘트 첨가제 조성물에 있어서, 상기 무수석고 분말은 1 내지 15 중량%로 포함되며, 바람직하게는 5 내지 10 중량%로 포함될 수 있다. 상기 무수석고 분말이 1 중량% 미만으로 포함되는 경우, 에트링자이트 생성량이 적어 중금속 이온의 고정화 효과가 저하되며, 15 중량%를 초과하는 경우에는 에트링자이트 생성량이 많아서 팽창에 의한 균열을 야기할 수 있으므로 바람직하지 않다. In the environmentally friendly cement additive composition for fixing heavy metal ions, the anhydrite powder may be included in an amount of 1 to 15% by weight, preferably 5 to 10% by weight. When the anhydrite powder is included in less than 1% by weight, the amount of ettringite produced is low, and the effect of immobilizing heavy metal ions is reduced. This is undesirable because it can cause
상기 무수석고 분말은 CaSO4의 함량이 30 중량% 이상인 것이 바람직하게 사용될 수 있다. 상기 CaSO4의 함량이 30 중량% 미만인 무수석고 분말이 사용될 경우, 중금속 이온 고정화 효과가 있는 에트링자이트의 생성량이 적어 중금속 이온 고정화 효과가 떨어지는 점에서 바람직하지 않다.The anhydrite powder may preferably have a CaSO 4 content of 30% by weight or more. When the CaSO 4 content of less than 30% by weight of anhydrite powder is used, it is not preferable in that the effect of fixing heavy metal ions is poor because the amount of ettringite having a heavy metal ion fixation effect is small.
상기 친환경 중금속 이온 고정용 시멘트 첨가제 조성물에 있어서, 상기 고로슬래그로는 특히, 급냉 고로 수쇄슬래그가 바람직하게 사용될 수 있다.In the environmentally friendly cement additive composition for fixing heavy metal ions, as the blast furnace slag, in particular, quenched blast furnace granulated slag may be preferably used.
상기 급냉 고로 수쇄슬래그를 사용하는 경우에는 우수한 경화 후 장기 압축강도 향상 효과를 얻을 수 있으므로 바람직하다.In the case of using granulated slag as the quenching furnace, it is preferable because an excellent effect of improving long-term compressive strength after hardening can be obtained.
상기 고로슬래그는 유동층상 보일러 애시의 고형화를 위하여 사용되며, 5 내지 20 중량%로 포함되며, 더욱 바람직하게는 7 내지 18 중량%로 포함될 수 있다. 상기 고로슬래그가 5 중량% 미만으로 포함되면 충분한 고형화 반응이 진행되지 못하여 고형화 압축강도가 미약한 단점이 발생하며, 20 중량%를 초과하면 필요 이상으로 고형화 압축강도가 발현되어 경제적이지 못하다. The blast furnace slag is used for solidification of fluidized bed boiler ash, and may be included in an amount of 5 to 20% by weight, more preferably 7 to 18% by weight. When the blast furnace slag is included in less than 5% by weight, sufficient solidification reaction does not proceed, resulting in weak solidification compressive strength, and when it exceeds 20% by weight, solidification compressive strength is expressed more than necessary, which is not economical.
상기 친환경 중금속 이온 고정용 시멘트 첨가제 조성물에 있어서, 상기 다공성 팽창질석 미분 및 팽창 규조토 미분으로 이루어진 군으로부터 선택되는 1종 이상은 다공성 재료로서 양이온 교환 성능을 가지며, 중금속을 흡착하는 기능을 수행한다. 또한, 산성수의 중화 및 중금속 이온의 고정화 반응을 촉진시키는 역할을 수행한다.In the eco-friendly cement additive composition for fixing heavy metal ions, at least one selected from the group consisting of porous expanded vermiculite powder and expanded diatomaceous earth powder has cation exchange performance as a porous material and performs a function of adsorbing heavy metals. In addition, it serves to promote the neutralization of acidic water and the immobilization of heavy metal ions.
상기 팽창질석은 질석을 800 내지 1,100℃에서 가열 및 가압하여 제조할 수 있다. 즉, 가열에 의해 층 사이에 존재하는 수분이 수증기로 변하며, 가압에 의해 6~30배 박리 팽창하여 다공성 결정체인 팽창질석이 형성된다. The expanded vermiculite may be prepared by heating and pressing vermiculite at 800 to 1,100 ° C. That is, the moisture present between the layers is changed into water vapor by heating, and expanded vermiculite, which is a porous crystal, is formed by peeling and expanding by 6 to 30 times by pressing.
상기 팽창 규조토 미분은 일반 규조토를 500 내지 800℃에서 가열하는 방법으로 제조될 수 있다.The expanded diatomaceous earth fine powder may be prepared by heating general diatomaceous earth at 500 to 800 ° C.
상기 다공성 팽창질석 미분 및 팽창 규조토 미분으로 이루어진 군으로부터 선택되는 1종 이상은 5 내지 10 중량%로 포함되며, 상기 성분이 5 중량% 미만으로 포함되면, 산성수의 중화 및 중금속 이온의 고정화 효과가 낮아 본 발명의 목적을 달성할 수 없으며, 10 중량%를 초과하여 포함되는 경우에는 경제적으로 바람직하지 못하다.At least one selected from the group consisting of porous expanded vermiculite powder and expanded diatomaceous earth powder is included in 5 to 10% by weight, and when the component is included in less than 5% by weight, the effect of neutralizing acidic water and immobilizing heavy metal ions is increased. It is not possible to achieve the object of the present invention because it is low, and it is economically undesirable when it is included in an amount exceeding 10% by weight.
상기 미분은 평균 입도가 10㎛ 내지 100㎛인 분말을 의미한다.The fine powder means a powder having an average particle size of 10 μm to 100 μm.
상기 친환경 중금속 이온 고정용 시멘트 첨가제 조성물에 있어서, 상기 산화철 분말은 1 내지 5 중량%로 포함되며, 바람직하게는 2 내지 4 중량%로 포함될 수 있다. 상기 산화철 분말은 중금속 이온을 고화시키는 기능을 수행한다.In the environmentally friendly cement additive composition for fixing heavy metal ions, the iron oxide powder may be included in an amount of 1 to 5% by weight, preferably 2 to 4% by weight. The iron oxide powder serves to solidify heavy metal ions.
상기 산화철 분말은 Fe2O3의 함량이 60 중량% 이상인 것이 바람직하게 사용될 수 있다. 상기 Fe2O3의 함량이 60 중량% 미만일 경우, 중금속 이온 고정화 및 경화특성이 지연될 수 있으므로, 바람직하지 않다. Fe2O3의 함량은 65 내지 80인 것이 더욱 바람직할 수 있다. The iron oxide powder may preferably have an Fe 2 O 3 content of 60% by weight or more. When the content of Fe 2 O 3 is less than 60% by weight, heavy metal ion fixation and curing characteristics may be delayed, which is not preferable. The content of Fe 2 O 3 may be more preferably 65 to 80.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시 예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다. Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples may be appropriately modified or changed by those skilled in the art within the scope of the present invention.
실시예 1~5: 친환경 중금속 이온 고정용 시멘트 첨가제 조성물 제조Examples 1 to 5: Preparation of environmentally friendly cement additive composition for fixing heavy metal ions
하기 표 1과 같은 성분들을 혼합하고, 상기 혼합물 100 중량부에 대하여 물 50 중량부를 혼합하여 분체 혼합물을 제조하였다. A powder mixture was prepared by mixing the components shown in Table 1 below and mixing 50 parts by weight of water with respect to 100 parts by weight of the mixture.
시험예 1: 본 발명 조성물의 물성평가Test Example 1: Evaluation of physical properties of the composition of the present invention
1) 중금속 이온 고정화 특성 측정1) Measurement of heavy metal ion immobilization characteristics
상기 실시예에서 제조된 첨가제 조성물의 성능을 평가하기 위하여, 도 1에 도시된 바와 같이, 윗부분이 오픈되고, 중간에 물빠짐 패널(31)이 고정된 직경 30cm의 원통형 컬럼(30)을 준비하였다. In order to evaluate the performance of the additive composition prepared in the above example, as shown in FIG. 1, a
상기 실시예 1 내지 5의 각 실시예 첨가제 조성물들 10 중량%를 시멘트 90 중량%와 분체로 혼합하여 슬러리를 제조한 후, 상기 물빠짐 패널(31) 위에 20 cm 높이로 채웠다(10). 10% by weight of the additive compositions of Examples 1 to 5 were mixed with 90% by weight of cement as a powder to prepare a slurry, and then the
다음으로, 컬럼의 위쪽에서 50 L의 이온 정제수(20)를 부어 아래로 통과시켰다. 상기 통과된 여과수(21)를 모아 중금속 함유량을 측정하였다. 상기 이온 정제수(20)로는 실험실에서 제조한 증류수를 이온교환수지로 한번 더 정제한 것을 사용하였다. Column에 유입되는 증류수의 속도는 20cc/sec로 하였다.Next, 50 L of ion-purified water (20) was poured from the top of the column and passed down. The filtered
비교예로는 본 발명의 첨가제 조성물을 혼합하지 않은 시멘트 슬러리를 사용하였다. As a comparative example, a cement slurry not mixed with the additive composition of the present invention was used.
상기 실시예 및 비교예의 Column에서 여과된 여과수를 유도결합 플라즈마 질량 분석법(ICP-MS)으로 분석하고 그 결과를 하기 표 2에 나타내었다. The filtered water filtered from the column of the above examples and comparative examples was analyzed by inductively coupled plasma mass spectrometry (ICP-MS), and the results are shown in Table 2 below.
상기 표 2로부터 확인되는 바와 같이, 본 발명의 실시예의 첨가제 조성물을 사용하는 경우, 여과수에서 일반 시멘트에 포함된 중금속인 Cu, Pb, As, Cd, Hg 및 Cr+6 이온이 전혀 검출되지 않았다. As confirmed from Table 2, when using the additive composition of Example of the present invention, Cu, Pb, As, Cd, Hg, and Cr +6 ions, which are heavy metals included in general cement, were not detected at all in the filtered water.
반면, 본 발명의 첨가제 조성물을 사용하지 않은 비교예에서는 다양한 중금속이 검출되었으며, 특히, 인체에 해로운 납, 카드뮴, 6가 크롬 등이 검출되었으며, 6가 크롬의 경우 상당량이 용출된 것으로 확인되었다. On the other hand, in Comparative Examples in which the additive composition of the present invention was not used, various heavy metals were detected, and in particular, lead, cadmium, and hexavalent chromium harmful to the human body were detected.
본 발명의 사상은 설명된 실시예에 국한되어 정해져서는 안 되며, 후술하는 특허청구범위뿐만 아니라 이 특허청구범위와 균등하거나 등가적 변형이 있는 모든 것들은 본 발명 사상의 범주에 속한다고 할 것이다.The spirit of the present invention should not be limited to the described embodiments and should not be determined, and all things equivalent or equivalent to the claims as well as the claims described later fall within the scope of the present invention.
Claims (5)
(2) 무수석고 분말 1 내지 15 중량%;
(3) 고로슬래그 5 내지 20 중량%;
(4) 다공성 팽창질석 미분 및 팽창 규조토 미분으로 이루어진 군으로부터 선택되는 1종 이상 5 내지 10 중량%; 및
(5) 산화철 분말 1 내지 5 중량%;를 포함하는 친환경 중금속 이온 고정용 시멘트 첨가제 조성물.(1) 50 to 85% by weight of fluidized bed boiler ash;
(2) 1 to 15% by weight of anhydrite powder;
(3) 5 to 20% by weight of blast furnace slag;
(4) 5 to 10% by weight of one or more selected from the group consisting of porous expanded vermiculite powder and expanded diatomaceous earth powder; and
(5) 1 to 5% by weight of iron oxide powder; environmentally friendly cement additive composition for fixing heavy metal ions.
상기 유동층상 보일러 애시는 유동층상 보일러에서 연소 후 발생하는 것으로서 free-CaO의 함량이 5 내지 45 중량%인 것을 특징으로 하는 친환경 중금속 이온 고정용 시멘트 첨가제 조성물.According to claim 1,
The fluidized bed boiler ash is generated after combustion in a fluidized bed boiler, and the environmentally friendly cement additive composition for fixing heavy metal ions, characterized in that the content of free-CaO is 5 to 45% by weight.
상기 무수석고 분말은 CaSO4의 함량이 30 중량% 이상인 것을 특징으로 하는 친환경 중금속 이온 고정용 시멘트 첨가제 조성물.According to claim 1,
The anhydrite powder is an eco-friendly cement additive composition for fixing heavy metal ions, characterized in that the content of CaSO 4 is 30% by weight or more.
상기 고로슬래그는 급냉 고로 수쇄슬래그인 것을 특징으로 하는 친환경 중금속 이온 고정용 시멘트 첨가제 조성물.According to claim 1,
The blast furnace slag is an eco-friendly cement additive composition for fixing heavy metal ions, characterized in that quenched blast furnace granulated slag.
상기 산화철 분말은 Fe2O3의 함량이 60 중량% 이상인 것을 특징으로 하는 친환경 중금속 이온 고정용 시멘트 첨가제 조성물.According to claim 1,
The iron oxide powder is an eco-friendly cement additive composition for fixing heavy metal ions, characterized in that the content of Fe 2 O 3 is 60% by weight or more.
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| KR101840470B1 (en) * | 2016-10-20 | 2018-05-04 | 주식회사 지안산업 | Grouting agent and method |
| CN111548034B (en) * | 2020-06-19 | 2022-01-11 | 中山大学 | Auxiliary cementing material utilizing circulating fluidized bed fly ash and preparation method thereof |
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| KR100373461B1 (en) | 2000-03-06 | 2003-02-25 | 임범관 | A stabilization composition for preparing of cement concrete to treat heavy metals |
| KR20110070048A (en) | 2009-12-18 | 2011-06-24 | (주)제이엔티아이엔씨 | Cement mixture for filling |
| KR20110072929A (en) | 2009-12-23 | 2011-06-29 | 유진기업 주식회사 | Eco-friendly low cement-based solidifying composition for weak ground and method of solidifying soil using the same |
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| KR101990870B1 (en) * | 2018-09-18 | 2019-06-19 | (주)보경아이앤씨 | Composite of soil solidification materials with salt resistance property |
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