KR101923536B1 - Substituted material composition for admixture - Google Patents
Substituted material composition for admixture Download PDFInfo
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- KR101923536B1 KR101923536B1 KR1020180081116A KR20180081116A KR101923536B1 KR 101923536 B1 KR101923536 B1 KR 101923536B1 KR 1020180081116 A KR1020180081116 A KR 1020180081116A KR 20180081116 A KR20180081116 A KR 20180081116A KR 101923536 B1 KR101923536 B1 KR 101923536B1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
- C04B18/0481—Other specific industrial waste materials not provided for elsewhere in C04B18/00
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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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators or shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
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- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators or 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 or 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
- C04B22/147—Alkali-metal sulfates; Ammonium sulfate
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- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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Abstract
본 발명은 발연황산 제조시 발생되는 삼산화황 증기를 채집한 산업부산물을 포함하는 것을 특징으로 하는 혼화제용 치환재 조성물에 관한 것이다. The present invention relates to a replacement material composition for an admixture, which comprises an industrial by-product obtained by collecting sulfur trioxide vapor generated in the production of fuming sulfuric acid.
Description
본 발명은 산업부산물을 이용하여 혼화제 중 일부를 치환하여도 분산성, 유지성, 압축강도 등을 향상시킬 수 있어 친환경적이며 경제적인 혼화제용 치환재 조성물에 관한 것이다. The present invention relates to an environmentally friendly and economical replacement material composition for an admixture, which can improve dispersibility, retainability, compressive strength and the like even when a part of the admixture is replaced with industrial byproducts.
콘크리트용 화학혼화제는 그 화학 성분에 따라 리그닌계(리그닌설폰산염), 나프탈렌계(나프탈렌 술폰산 포르말린 축합물), 멜라민계(멜라민술폰산 포르말린 축합물),및 폴리카본산계(폴리카르본산염)로 분류되어 사용되고 있다.Chemical admixtures for concrete are classified into lignin type (lignin sulfonate), naphthalene type (naphthalene sulfonic acid formalin condensate), melamine type (melamine sulfonic acid formalin condensate), and polycarbonate type (polycarboxylate) depending on the chemical composition thereof. Has been used.
리그닌계, 멜라민계 및 나프탈렌계 화학혼화제의 경우에는 감수성 및 유동성이 우수하여 고강도, 고유동 및 고내구성 콘크리트 제조가 가능하였으나, 슬럼프로스가 크다는 단점을 가지고 있다. 이에 비하여 폴리카르본산계의 화학혼화제의 경우에는 기존에 사용하던 화학혼화제에 비하여 우수한 감수성능을 발휘할 뿐만 아니라, 슬럼프 로스가 적고, 또한 우수한 혼련성을 가진다.In the case of lignin-based, melamine-based and naphthalene-based chemical admixtures, it is possible to manufacture high-strength, high-dynamic and high-durability concrete with excellent sensitivity and fluidity, but has a disadvantage of large slump loss. On the other hand, the polycarboxylic acid-based chemical admixture exhibits excellent water-reducing performance as compared with the chemical admixture used in the past, has less slump loss, and has excellent kneading ability.
한편 화학혼화제만을 첨가하는 경우 비경제적인 문제가 있어 이를 해결하기 위해 산업부산물을 이용하여 혼화제를 제조하는 방법 등에 대한 기술이 다양하게 제시되고 있는 바, 일 예로 대한민국 특허등록 제10-0754610호에서는 i) 테레프탈산 제조과정에서 발생하는 폐기물에 염기성 용액을 가하여 pH 5.0 내지 7.0으로 중화시키는 단계 및 ii) 상기 폐기물에 펜톤시약, H2O2, KMnO4, K2Cr2O7, O3 및 K2S2O8로 이루어진 군으로부터 선택되는 산화제를 첨가하여 교반함으로써 상기 폐기물을 산화시키는 단계를 포함하는 콘크리트용 분산제 제조방법에 대해서 개시하고 있다.On the other hand, in the case of adding only a chemical admixture, there are unexpected problems, and techniques for manufacturing an admixture using industrial byproducts have been proposed in various ways. For example, in Korean Patent Registration No. 10-0754610, i) Adding a basic solution to the waste generated in the production of terephthalic acid to neutralize the solution to pH 5.0 to 7.0 and ii) adding an oxidant selected from the group consisting of Fenton's reagent, H 2 O 2, KMnO 4, K 2 Cr 2 O 7, O 3 and K 2 S 2 O 8 to the waste, And oxidizing the wastes to produce a dispersion for concrete.
상기 기술의 경우 산업부산물을 이용하여 친환경적이면서 경제적인 잇점은 있으나 단순히 분산에 초점이 맞춰진 것으로 이외에 강도 등의 면에서도 물성을 향상시킬 수 있는 혼화제의 치환재 개발의 필요성이 있다. In the case of the above-mentioned technology, there is a need to develop a replacement material of an admixture which can improve physical properties in terms of strength and the like, besides merely focusing on dispersion, although it has advantages of being environmentally friendly and economical using industrial byproducts.
따라서, 본 발명은 산업부산물을 이용하면서도 분산성, 유지성 등은 물론 강도면에서도 유리한 효과가 발현될 수 있는 혼화제 치환재를 제공하고자 함이다. Accordingly, it is an object of the present invention to provide an admixture replacement material which can exhibit advantageous effects in terms of dispersibility, maintainability, and strength, while using industrial byproducts.
상기 목적을 달성하기 위해 본 발명의 혼화제용 치환재 조성물은, 발연황산 제조시 발생되는 삼산화황 증기를 채집한 산업부산물을 포함하는 것을 특징으로 한다. In order to achieve the above object, the replacement material composition for an admixture of the present invention is characterized by including industrial by-products obtained by collecting sulfur trioxide vapor generated in the production of fuming sulfuric acid.
하나의 예로 티오황산나트륨을 가열하여 얻어지는 개질 티오황산나트륨이 더 포함되는 것을 특징으로 한다. One example is further characterized by comprising modified sodium thiosulfate obtained by heating sodium thiosulfate.
하나의 예로 상기 개질 티오황산나트륨에는 황산나트륨(Na2SO4), 황화나트륨(Na2S), 이산화황(SO2) 및 물(H2O)이 포함되는 것을 특징으로 한다. As one example, the modified sodium thiosulfate includes sodium sulfate (Na 2 SO 4 ), sodium sulfide (Na 2 S), sulfur dioxide (SO 2 ), and water (H 2 O).
하나의 예로 고형분비 100중량%를 기준으로 발연황산 제조시 발생되는 삼산화황 증기를 채집한 산업부산물 5 내지 30중량%; 티오황산나트륨을 가열하여 얻어지는 개질 티오황산나트륨 20 내지 90중량%; 분산제, 유기계 안정화제, 무기계 안정화제로 이루어지는 그룹으로부터 선택되는 하나 이상 0.5 내지 10중량%를 포함하는 것을 특징으로 한다. As an example, 5 to 30% by weight of industrial by-products collected from sulfur trioxide vapor generated in the production of fuming sulfuric acid based on 100% by weight of solid content; 20 to 90% by weight of modified sodium thiosulfate obtained by heating sodium thiosulfate; At least one selected from the group consisting of a dispersant, an organic stabilizer and an inorganic stabilizer.
본 발명은 혼화제의 일부를 치환함으로써 경화 전 콘크리트의 초기 감수성, 분산성, 유지력 개선 및 경화 후 콘크리트의 압축강도가 증진되는 효과를 나타낼 수 있는 장점이 있다. The present invention is advantageous in that it can exhibit the effect of improving the initial sensitivity, dispersibility, maintenance force and compressive strength of concrete after curing by substituting a part of the admixture.
또한 산업부산물을 주재로 함으로써 친환경적이며 경제적인 장점이 있다.In addition, it is environmentally friendly and economical because it is based on industrial byproducts.
도 1은 본 발명의 일 실시 예에 따른 각 시료에 대한 실험결과 그래프.FIG. 1 is a graph showing an experimental result of each sample according to an embodiment of the present invention. FIG.
이하 본 발명의 실시 예 및 실험 예를 첨부되는 도면을 통해 보다 상세히 설명하도록 한다.BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which:
본 발명의 혼화제용 치환재 조성물은, 발연황산 제조시 발생되는 삼산화황 증기를 채집한 산업부산물(이하 "삼산화황 산업부산물"이라함)을 포함하는 것을 특징으로 한다.The replacement material composition for an admixture of the present invention is characterized by including an industrial by-product (hereinafter referred to as a "sulfur trioxide industrial by-product") obtained by collecting sulfur trioxide vapor generated in the production of fuming sulfuric acid.
상기 삼산화황 산업부산물은 물에 삼산화황이 개략적으로 20~30% 녹아있는 수용액으로서 주성분이 삼산화황(SO3)으로 이러한 삼산화황 성분은 하기 작용기작에서 보는 바와 같이 산화칼슘과 반응하면서 황산이온이 형성되고, 황산이온이 시멘트 성분 중 C3A와 반응하여 콘크리트의 압축강도를 증진시키는 기능을 한다. The sulfur trioxide industrial by-product is an aqueous solution in which approximately 20 to 30% of sulfur trioxide is dissolved in water, and the main component thereof is sulfur trioxide (SO 3 ). This sulfur trioxide component reacts with calcium oxide to form sulfate ions, Ions react with C 3 A in the cement component to enhance the compressive strength of the concrete.
이를 더욱 상세히 설명하면 C3A와 CaSO4가 반응하여 Ettringite가 생성되고 액상속 SO4 2- 소진됨에 따라 미수화 C3A와 Ettringite가 반응을 하여 Monosulfate(3CaO·Al2O3·CaSO4·12H2O)와 C3A·Ca(OH)2·12H2O의 고용체를 생성하게 된다. More specifically, when C 3 A reacts with CaSO 4 to form ettringite and disappearance of SO 4 2- in liquid phase, unreacted C 3 A and Ettringite react to form monosulfate (3CaO · Al 2 O 3 · CaSO 4 · 12H 2 O) and a solid solution of C 3 A · Ca (OH) 2 · 12H 2 O.
상기 과정은 물-시멘트비 0.4에서 5~48시간에 종료되며, Ettringite의 결정상은 침상으로 Monosulfate의 판상형 보다 강도 개선에 유리하다. 따라서 초기 삼산화황의 적절한 공급은 Ettringite 생성에 유리하며, Monosulfate 상으로 전이되는 량을 적게하여 초기강도 개선에 효과적이다. The above process is terminated at a water-cement ratio of 0.4 to 5 to 48 hours, and the crystalline phase of Ettringite is an acicular phase, which is more advantageous than the monosulfate plate-like type. Therefore, proper supply of the initial sulfur trioxide is advantageous for the production of ettringite, and it is effective for improving initial strength by reducing the amount of transition to monosulfate phase.
한편 상기 삼산화황 산업부산물의 삼산화황에 의해 콘크리트의 초기 압축강도를 증진시키게 되는 것인데 이러한 초기 압축강도 증진에 따라 저감될 수 있는 작업성 등을 본 발명에서는 티오황산나트륨을 가열하여 얻어지는 개질 티오황산나트륨(이하 "개질 티오황산나트륨"이라함)이 더 첨가되도록 함으로써 이러한 점을 보완토록 하는 것이다. On the other hand, the initial compressive strength of the concrete is increased by the sulfur trioxide of the sulfur trioxide industrial by-product. In the present invention, the modified sodium thiosulfate obtained by heating sodium thiosulfate (hereinafter referred to as & Sodium thiosulfate ") is added in order to compensate for this point.
상기 개질 티오황산나트륨은 티오황산나트륨(Na2S2O3)을 50~120℃로 가열하여 얻어지는 결과물로서 액상의 결과물이다. The modified sodium thiosulfate is a product obtained by heating sodium thiosulfate (Na2S2O3) to 50 to 120 占 폚, and is a liquid product.
무색의 단사결정형 티오황산나트륨(Sodium tiosulfate, Na2S2O3)을 공기 중 또는 공기를 차단한 상태에서 상기 온도로 가열하면 산화되어 황산나트륨(Na2SO4), 황화나트륨(Na2S), 이산화황(SO2) 및 물(H2O)로 분해되는 바, 이러한 높은 온도의 황산화합물 수용액에 안정화제를 첨가하여 상온에서의 결정화(석출)를 억제토록 하는 것이다. Colorless monoclinic sodium thiosulfate (Na 2 S 2 O 3 ) is oxidized by heating to the above temperature in the air or in the air-shielded state to form sodium sulfate (Na 2 SO 4 ), sodium sulfide (Na 2 S) (SO 2 ) and water (H 2 O). By adding a stabilizer to the aqueous solution of the sulfuric acid compound at such a high temperature, crystallization (precipitation) at room temperature is suppressed.
이러한 황산화합물 중 황산나트륨(CaSO4, 석고)은 pH 11~12에서 C3A와 CaSO4 사이에서 반응이 일어나 C3A-CaSO4-H2O계 복염(염기성)이 신속하게 생성되고 그 생성층이 C3A를 감싸기 때문에 초기(물 접촉 0~30분) C3A의 수화를 억제하여 콘크리트의 Slump Loss를 줄이고 유지력을 개선하게 되는 것이다. In this sulfuric acid compound, sodium sulfate (CaSO 4 , gypsum) reacts between C 3 A and CaSO 4 at a pH of 11 to 12, resulting in rapid formation of C 3 A-CaSO 4 -H 2 O complex salt (basic) C 3 A is wrapped around the initial (water contact for 0 ~ 30 minutes) to suppress the hydration of C 3 A, thereby reducing the slump loss of concrete and improving the holding power.
즉 삼산화황 산업부산물의 첨가에 의해 초기 압축강도가 증진되도록 하면서 초기 압축강도의 증진에 따라 작업성이 저하될 수 있는 문제를 개질 티오황산나트륨이 첨가되도록 하여 보완토록 하는 것이다. That is, the initial compressive strength is increased by the addition of the by-product of sulfur trioxide industry, and the problem that the workability is lowered due to the improvement of the initial compressive strength is supplemented by adding the reformed sodium thiosulfate.
이에 더하여 유지력 등을 더욱 개선 하기 위해 상기 삼산화황 산업부산물과 상기 개질 티오황산나트륨 외에 분산제, 유기계 안정화제, 무기계 안정화제로 이루어지는 그룹으로부터 선택되는 하나 이상이 더 혼합되도록 하는 것이 타당하다. In order to further improve the holding power and the like, it is appropriate that at least one selected from the group consisting of a dispersant, an organic stabilizer and an inorganic stabilizer is further mixed in addition to the sulfur trioxide industrial by-product and the modified sodium thiosulfate.
바람직하게는 고형분비 100중량%를 기준으로 발연황산 제조시 발생되는 삼산화황 증기를 채집한 산업부산물 5 내지 30중량%, 티오황산나트륨을 가열하여 얻어지는 개질 티오황산나트륨 20 내지 90중량%, 분산제, 유기계 안정화제, 무기계 안정화제로 이루어지는 그룹으로부터 선택되는 하나 이상 0.5 내지 10중량%를 포함하도록 배합하는 것이 타당하다. Preferably 5 to 30% by weight of industrial by-products obtained by collecting sulfur trioxide vapor generated in the production of fuming sulfuric acid based on 100% by weight of solid content, 20 to 90% by weight of modified sodium thiosulfate obtained by heating sodium thiosulfate, , And an inorganic stabilizer, based on the total weight of the composition.
이하에서는 실험 예에 의해 본 발명에 대해 설명한다. Hereinafter, the present invention will be described with reference to experimental examples.
<슬럼프 실험><Slump Experiment>
하기 표 1에서 보는 바와 같이 각 시료를 배합하여 6개의 시료를 제작하였다. 각 시료에 대해 슬럼프를 측정하였다. 본 실험에서 사용되는 본 발명의 치환재는 전체 100중량부에 대해 삼산화황 산업부산물 30중량부, 개질 티오황산나트륨 65중량부, 당류 5중량부를 배합하여 제조되었다. As shown in Table 1, six samples were prepared by blending each sample. The slump was measured for each sample. The replacement material of the present invention used in this experiment was prepared by blending 30 parts by weight of the sulfur trioxide industrial by-product, 65 parts by weight of modified sodium thiosulfate, and 5 parts by weight of saccharides, based on 100 parts by weight of the whole.
(%)Water-cement ratio
(%)
(%)Fine aggregate rate
(%)
(시멘트×%)Admixture
(Cement ×%)
각각 시료에 대한 실험결과가 도 1에 도시되고 있는 바, 도 1에서 보는 바와 같이 혼화제 치환율이 20 내지 30중량%인 경우 분산성 및 감수성이 커지는 것을 알 수 있고 유지력도 향상되는 것을 알 수 있다. 이는 치환재 중 당류는 물론 상기에서 언급한 개질 티오황산나트륨 성분에 기인한 것으로 판단된다. As shown in FIG. 1, when the admixture replacement ratio is 20 to 30% by weight, the dispersibility and the sensitivity are increased, and the retention is improved. It is considered that this is due to the above-mentioned sodium thiosulfate component as well as sugars in the substitute.
<압축강도 실험><Compressive Strength Test>
하기 표 2에서 보는 바와 같이 각 시료를 배합하여 4개의 시료를 제작하였다. 각 시료에 대해 각 재령에 따른 압축강도를 측정하였다. 본 실험에서 사용되는 본 발명의 치환재는 전체 100중량부에 대해 삼산화황 산업부산물 30중량부, 개질 티오황산나트륨 65중량부, 당류 5중량부를 배합하여 제조되었다. As shown in Table 2, each sample was blended to prepare four samples. The compressive strength of each sample was measured according to each age. The replacement material of the present invention used in this experiment was prepared by blending 30 parts by weight of the sulfur trioxide industrial by-product, 65 parts by weight of modified sodium thiosulfate, and 5 parts by weight of saccharides, based on 100 parts by weight of the whole.
감수제 100%Substituent 0%
감수제 80%
감수제 70%
유지제 15%
감수제 70%
상기 표 3에 압축강도 실험결과를 개시하고 있는 바, 혼화제(감수제)만을 사용한 경우보다 치환재를 치환한 경우가 대체적으로 압축강도면에서 유리한 효과가 발현되는 것을 알 수 있다. 이는 상기 삼산화황 산업부산물 성분에 의해 기존 혼화제만을 첨가한 경우보다 압축강도면에서 유리한 효과가 발현되는 것으로 판단된다. The results of the compressive strength test are shown in Table 3. It can be seen that the effect of substituting the substitution material is more advantageous in terms of compressive strength than the case of using only the admixture (water reducing agent). It is considered that this advantageous effect is exhibited in terms of compressive strength compared to the case where only the conventional admixture is added due to the sulfur trioxide industrial byproduct component.
이상 설명한 내용을 통해 당업자라면 본 발명의 기술사상을 일탈하지 아니하는 범위에서 다양한 변경 및 수정이 가능함을 알 수 있을 것이다. 따라서, 본 발명의 기술적 범위는 명세서의 상세한 설명에 기재된 내용으로 한정되는 것이 아니라 특허 청구의 범위에 의해 정하여 져야만 할 것이다. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Therefore, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be defined by the claims.
Claims (4)
An industrial by-product obtained by collecting sulfur trioxide vapor generated in the production of fuming sulfuric acid, and a modified sodium thiosulfate obtained by heating sodium thiosulfate.
상기 개질 티오황산나트륨에는 황산나트륨(Na2SO4), 황화나트륨(Na2S), 이산화황(SO2) 및 물(H2O)이 포함되는 것을 특징으로 하는 혼화제용 치환재 조성물.
The method according to claim 1,
Wherein the modified sodium thiosulfate comprises sodium sulfate (Na 2 SO 4 ), sodium sulfide (Na 2 S), sulfur dioxide (SO 2 ) and water (H 2 O).
고형분비 100중량%를 기준으로 발연황산 제조시 발생되는 삼산화황 증기를 채집한 산업부산물 5 내지 30중량%; 티오황산나트륨을 가열하여 얻어지는 개질 티오황산나트륨 20 내지 90중량%; 분산제, 유기계 안정화제, 무기계 안정화제로 이루어지는 그룹으로부터 선택되는 하나 이상 0.5 내지 10중량%를 포함하는 것을 특징으로 하는 혼화제용 치환재 조성물. The method according to claim 1,
5 to 30% by weight of industrial by-products collected from sulfur trioxide vapor generated in the production of fuming sulfuric acid based on 100% by weight of solid content; 20 to 90% by weight of modified sodium thiosulfate obtained by heating sodium thiosulfate; At least one selected from the group consisting of an inorganic stabilizer, a dispersant, an organic stabilizer, and an inorganic stabilizer.
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| JP2000008029A (en) | 1998-06-19 | 2000-01-11 | Asahi Denka Kogyo Kk | Latent heat storage material composition and heat storage method |
| KR101601967B1 (en) * | 2015-05-12 | 2016-03-21 | (주)한필이엔지 | cement mortar compositon for Block and cement mortar for Block comprising the same |
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| JP2000008029A (en) | 1998-06-19 | 2000-01-11 | Asahi Denka Kogyo Kk | Latent heat storage material composition and heat storage method |
| KR101601967B1 (en) * | 2015-05-12 | 2016-03-21 | (주)한필이엔지 | cement mortar compositon for Block and cement mortar for Block comprising the same |
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