KR101721307B1 - Modified sulfur binder production method for the reaction process improvement and colorizing - Google Patents
Modified sulfur binder production method for the reaction process improvement and colorizing Download PDFInfo
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- KR101721307B1 KR101721307B1 KR1020150013185A KR20150013185A KR101721307B1 KR 101721307 B1 KR101721307 B1 KR 101721307B1 KR 1020150013185 A KR1020150013185 A KR 1020150013185A KR 20150013185 A KR20150013185 A KR 20150013185A KR 101721307 B1 KR101721307 B1 KR 101721307B1
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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
- C04B28/36—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 sulfur, sulfides or selenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/14—Producing shaped prefabricated articles from the material by simple casting, the material being neither forcibly fed nor positively compacted
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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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/54—Pigments; Dyes
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Abstract
콘크리트의 주원료인 시멘트는 1t 생산에 약 0.9t의 이산화탄소를 배출해 지구 온난화를 야기하는 오염원 중 하나로 지적되고 있는데, 포틀랜드 시멘트를 사용하는 일반적인 칼라콘크리트를 칼라개질유황바인더 기반의 소재로 대체할 경우 CO2 저감 효과를 나타내 저탄소. 녹색성장 구현이 가능하며 공업적 폐기물, 부산물을 활용하는 측면에서 경제적이다. 그리고 현재 개질유황바인더를 제조할 때 140℃이상의 고온에서 합성을 하므로 공정상에 열에너지의 소모가 심하다. 이를 반응촉진제를 첨가하여 공정시간을 단축시킴으로써 원가절감을 도모하고자 한다.
또한, 칼라유황바인더를 제조하여 다양한 친환경 녹색 건축자재로 활용함과 동시에 강도를 향상시키고 수축에 의한 crack 발생을 완화시켜 외관불량 및 강도저하 발생을 줄여 개질유황바인더 콘크리트 구조물의 내구성을 높이기 위한 것이다.
발명의 바람직한 실시예에 따르면 개질유황바인더 합성 시 안료 첨가하는 방법과 개질유황바인더로 블록 제조 시 안료를 첨가해 칼라개질유황바인더 블록을 제조하는 방법이 제공된다.Cement, which is the main material of concrete, is reported to be one of the pollutants causing global warming by emitting 0.9t of carbon dioxide to 1t production. When replacing common color concrete using portland cement with collar-modified sulfur binder based material, CO 2 Low carbon effect. It is possible to implement green growth and it is economical in terms of utilizing industrial waste and by-products. At present, when the modified sulfur binder is manufactured, the synthesis is performed at a high temperature of 140 ° C or more, so that the heat energy is consumed in the process. And to reduce the cost by shortening the process time by adding a reaction accelerator thereto.
In addition, a color sulfur binder is manufactured to be used as various green green building materials, and the strength is improved and the occurrence of cracks caused by shrinkage is alleviated, thereby reducing appearance defects and strength reduction, thereby enhancing the durability of the modified sulfur binder concrete structure.
According to a preferred embodiment of the present invention, there is provided a method of adding a pigment in the synthesis of a modified sulfur binder and a method of producing a color modified sulfur binder block by adding a pigment in the production of a block with a modified sulfur binder.
Description
본 발명은 원유의 정제과정에서 발생되는 산업 부산물인 유황을 기존 보다 빠르게 개질하여 칼라유황바인더를 개발하는 것으로 기존 개질유황바인더 제조방법에서 반응촉진제 첨가로 반응공정시간을 단축시켜 생산성을 향상시키며, 무기안료를 첨가해 바인더 칼라화와 동시에 강도향상, 수축저감 등 화학적·물리적으로도 기존의 유황바인더 보다 더 우수한 특성을 갖도록 개선하여 다양한 분야에서 친환경 녹색 건축자재를 활용할 수 있게 하기 위한 것이다.The present invention is to develop a color sulfur binder by rapidly reforming sulfur, which is an industrial by-product produced in the refining process of crude oil, to improve the productivity by shortening the reaction process time by adding a reaction promoter in the existing method of producing a modified sulfur binder, It is intended to improve the chemical and physical properties such as strength, shrinkage and reduction of binder color by adding pigments, so as to have better characteristics than existing sulfur binders, thereby utilizing environmentally friendly green building materials in various fields.
콘크리트 산업이 지속가능한 사회발전 및 녹색성장에 대한 사회적 요구에 부응하기 위해서는 시멘트 제조과정에서 발생하는 막대한 이산화탄소 발생과 사용되는 자원을 최소화하는 기술혁신이 필요하다. 이에 전세계적으로도 이산화탄소 감축 노력이 진행되고 있다.In order to meet the social demands for sustainable social development and green growth, concrete industry needs huge technological innovation to minimize carbon dioxide generation and resources used in cement manufacturing process. Therefore, efforts are being made to reduce CO2 globally.
또한 정유생산 설비의 증가 및 원유정제 고도화시설 등으로 인해 앞으로 더 많은 양의 유황이 부생적으로 만들어질 것으로 예측되며 부생황의 대량 수요처 확보와 활용성 증대에 대한 노력이 지속적으로 필요한 상황에서 유황을 활용한 새로운 부가가치 제품 개발의 필요성은 매우 크다고 할 수 있다.In addition, due to the increase in refinery production facilities and the upgrading of crude oil refining facilities, it is predicted that more sulfur will be formed in the future, and in the future, The need for the development of new value-added products is very high.
이러한 세계 각국의 환경보존과 부생황의 활용성 증대에 대한 관심 증가에 발맞추어 포틀랜드 시멘트를 사용하지 않고 유황을 개질하여 바인더로 사용하는 친환경 건설자재 사용에 대한 기술들이 개발되고 있는 실정이며, 기존의 석유화학 부산물인 아스팔트를 활용한 아스콘 분야와 시멘트의 2차 가공 산업 전 분야에 적용하기 위하여 유황바인더 2차 제품에 다양한 색상을 구현함으로서 활용도를 높이고, 내구성이 향상된 친환경적인 칼라개질유황바인더 개발이 요구된다.In order to meet the increasing interest in environmental preservation and utilization of natural resources in the world, technologies for the use of eco-friendly construction materials, which use sulfur cement as a binder without using Portland cement, have been developed. It is necessary to develop eco-friendly color-modified sulfur binder which improves utilization and improves durability by implementing various colors in secondary products of sulfur binder for secondary application of asphalt field and cement secondary industry by using asphalt which is a byproduct of petrochemical do.
더 나아가, 기존 개질부생유황바인더를 이용한 제품의 시장성을 높이기 위하여 생산성을 향상시키는 공정기술의 개발이 필요한 실정이다.Furthermore, in order to improve the marketability of products using existing modified secondary by-product sulfur binders, it is necessary to develop a process technology for improving productivity.
등록번호 제10-0632609호에는 개질유황결합재 및 이의 제조방법을 개시하고 있다.Registration No. 10-0632609 discloses modified sulfur binders and methods for their preparation.
출원번호 제10-2013-0026138호에는 개질유황바인더를 활용하여 시멘트를 대체할 친환경 보도용 SPB 블록을 성형하는 방법을 개시하고 있다.Japanese Patent Application No. 10-2013-0026138 discloses a method of molding an environmentally-friendly press-formed SPB block to replace cement using a modified sulfur binder.
등록번호 제10-1232072호에는 칼라 폴리머 시멘트 콘크리트 조성물, 이를 이용한 콘크리트 포장공법 및 콘크리트 구조물의 유지보수공법이 공개되어 포틀랜드 시멘트를 포함하는 칼라 폴리머 시멘트 콘크리트 조성물에 대한 방법을 개시하고 있다. No. 10-1232072 discloses a color polymer cement concrete composition, a concrete paving method using the same, and a maintenance method of a concrete structure, and discloses a method for a color polymer cement concrete composition including Portland cement.
출원번호 제 10-2007-0107576호에는 내구성 및 강도가 우수하고 시인성이 우수한 포틀랜드 시멘트를 포함하는 칼라 콘크리트 제조방법을 개시하고 있다. Japanese Patent Application No. 10-2007-0107576 discloses a method of manufacturing a color concrete including portland cement having excellent durability and strength and excellent visibility.
그러나 유황바인더 2차제품은 시간 경과에 따라 수축 변형이 일어나는데, 이로 인해 균열이 발생해 기체 및 액체가 침투되어 철근부식과 열화 촉진의 문제점을 가지고 있다. 이러한 철근 부식현상이 심해지면 유황바인더 구조물은 결국 붕괴될 수 있고, 상기 종래기술들은 기존 개질유황바인더의 제조에 있어, 기존 시멘트 콘크리트 제품보다 가격경쟁력이 떨어져 상용화가 원활히 이루어지지 않은 단점이 있다. However, shrinkage deformation occurs in the secondary product of the sulfur binder over time, which causes cracks and permeation of gas and liquid, which causes problems of corrosion and deterioration of the steel bars. When such a rebar corrosion phenomenon becomes severe, the sulfur binder structure may eventually collapse, and the above-mentioned conventional techniques have a disadvantage in that commercialization of the conventional modified sulfur binder is not achieved because of lower price competitiveness than conventional cement concrete products.
콘크리트는 시간 경과에 따라 수축 변형이 일어나는데, 이로 인해 균열이 발생해 기체 및 액체가 침투되어 철근부식과 열화 촉진의 문제점을 가지고 있다. 이러한 철근 부식현상이 심해지면 콘크리트 구조물은 결국 붕괴될 수 있다. Concrete undergoes shrinkage deformation with time, which causes cracks, gas and liquid penetration, and has problems of corrosion and deterioration of reinforcing steel. If these rebar corrosion phenomena become severe, the concrete structure may eventually collapse.
안료가 첨가된 칼라개질유황바인더는 이런 자기 수축을 저하시켜 초기 균열을 억제하면서도 강도 및 내구성이 개선되어 개질유황바인더 2차제품의 성능을 향상시키는 방법을 제공하며, 다양한 칼라 연출이 가능한 칼라개질유황바인더를 제조함으로써 제품의 시인성과 활용성을 높일 수 있어 건물 주변 및 조경 공간, 체육시설 주변광장, 자전거도로, 공원, 인도, 차도, 화장실 타일, 바닥재용 타일 등 우리 생활에 직접적으로 활용되는 공사에 적용되게 하여 유황바인더 2차 제품의 시장가치를 높이고 유황바인더 브랜드 이미지 향상에 도움을 주어 시장 진입을 용이하게 하는데 그 목적이 있다.The color-modified sulfur binder to which the pigment is added has the effect of improving the strength and the durability of the modified sulfur binder, while suppressing the initial shrinkage, thereby improving the performance of the secondary product of the modified sulfur binder. The color- It is possible to improve the visibility and usability of products by manufacturing binders, and thus it is possible to improve the visibility and usability of the products by using a binder which is used directly in our daily life, such as surrounding buildings, landscaping spaces, sports facilities, squares, bicycle roads, parks, To increase the market value of the secondary product of sulfur binder and to help improve the image of sulfur binder brand, thereby facilitating entry into the market.
즉, 시인성과 활용성이 우수하면서도 강도 및 내구성에 문제가 없는 적정 첨가량을 선정하여 적용함으로써 강도발현과 내구성이 우수한 고강도 칼라개질유황바인더를 제조하고자 하였다.That is, the present inventors made attempts to prepare a high strength color modified sulfur binder having excellent strength and durability by selecting an appropriate amount of the additive which is excellent in visibility and usability, and has no problem in strength and durability.
또한, 기존 개질유황바인더의 제조에 있어, 기존 시멘트 콘크리트 제품보다 우수한 성능과 친환경적인 장점이 있지만 가격경쟁력이 떨어지며 개질에 소요되는 공정 시간이 길어 상용화가 원활히 이루어지지 않은 단점이 있으며,이를 개선하고 자 반응촉진제를 첨가하여 공정시간을 단축시켜 생산성 향상을 도모하였다.In addition, although the conventional modified sulfur binder is superior in performance and environmental friendliness to existing cement concrete products, it is inferior in price competitiveness and has a disadvantage in that commercialization is not smooth due to a long process time required for modification. A reaction accelerator was added to shorten the processing time, thereby improving the productivity.
본 발명은 상기와 같은 문제점을 해결하고 목적을 달성하고자 안출된 것으로서 개질유황바인더 제조 시 무기안료를 첨가하여 2차 가공 산업 전반에 적용 가능한 칼라개질유황바인더를 제조하며, 개질반응시 반응이 빠르게 진행될 수 있도록 하는 반응 촉진제를 사용하여 합성공정의 시간을 단축시켜 생산성을 향상시키는 기술을 제공하는 것이다.Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems and to achieve the object thereof, and it is an object of the present invention to provide a color modified sulfur binder which is applicable to the secondary processing industry by adding an inorganic pigment in the production of a modified sulfur binder, A reaction promoter capable of reducing the time required for the synthesis process to improve the productivity.
또한, 무기안료를 첨가하여 제조한 칼라개질유황바인더는 수축저감 및 강도향상 등 내구성 향상의 효과를 보여 기본 유황바인더보다 우수한 내화학적 성능과 기계적 강도를 발현하여 고기능성 소재로 사용할 수 있는 제조 방법을 제공하는 것이다. In addition, the color-modified sulfur binder prepared by adding an inorganic pigment exhibits an effect of improving durability such as shrinkage reduction and strength enhancement, thereby exhibiting an excellent chemical resistance and mechanical strength superior to that of a basic sulfur binder, .
상세하게는, 유황바인더 합성 시 반응촉진제를 첨가하여 공정시간을 축소하고, 안료첨가 또는 블록 제조 시 골재와 함께 유황바인더와 안료를 가열하여 혼합하는 것으로 유황바인더는 유황에 DCPD계를 사용하여 합성된 개질유황바인더를 사용한다. In detail, in the synthesis of a sulfur binder, a reaction accelerator is added to reduce the processing time, and the sulfur binder and the pigment are heated and mixed together with the aggregate during pigment addition or block production. The sulfur binder is synthesized by using a DCPD system in sulfur Use a modified sulfur binder.
그러므로 본발명은 칼라 유황바인더 제조방법에 관한 것으로, 반응기에 Sulfur를 넣은 후 일정온도로 유지하여 Sulfur를 완전히 용해시키는 용해단계;Accordingly, the present invention relates to a method for producing a color sulfur binder, comprising: a step of dissolving a sulfuride completely by maintaining a sulfuric acid in a reactor at a predetermined temperature;
용해된 Sulfur에 DCPD(Dicyclopentadiene)를 첨가하고, 이후 일정시간 반응시키는 반응단계;를 포함하되, A reaction step of adding DCPD (Dicyclopentadiene) to the dissolved Sulfur and then reacting for a predetermined time,
반응단계에서 반응이 종료되기 일정시간 이전 무기안료를 첨가하여 섞어주는 단계;를 더 포함하는 것을 특징으로 한다.And adding an inorganic pigment to the reaction mixture before a certain period of time to complete the reaction in the reaction step.
현재 시멘트, 콘크리트에 칼라안료를 첨가하여 콘크리트 자체에 별도의 색상을 갖게 하는 칼라시멘트, 칼라콘크리트가 있지만 보통 포틀랜드 시멘트를 포함하기 때문에 제조과정 중 CO2가 다량으로 발생된다. 하지만 본 발명에서 제조하는 칼라개질유황바인더는 정유공장에서 부산물로 발생되는 유황을 개질하여 만드는 개질유황바인더에 무기안료를 첨가함으로서 CO2 발생을 억제하여 저탄소·녹색성장 구현이 가능하며 공업적 폐기물 즉, 부산물을 활용하는 측면에서 경제적이며, 다양한 칼라를 믹싱해 제조 가능하므로 다양한 종류의 친환경 녹색 건축자재 생산이 가능하다.Currently, there are color cements and color concrete that add color pigments to cement and concrete to give concrete color itself, but it usually contains portland cement, so CO 2 is generated in a large amount during the manufacturing process. However, the color-modified sulfur binders produced in the present invention is adding an inorganic pigment to the modified sulfur binder is created by modifying the sulfur generated in refinery by-product CO 2 by It is possible to realize low carbon and green growth by suppressing the generation of waste. It is economical in terms of utilizing industrial waste, that is, by-products, and can be manufactured by mixing various colors.
동시에 압축강도, 휨강도가 향상되며 작업성이 좋아지고 블록의 자기수축이 저감되기 때문에 콘크리트 구조물의 성능 저하 및 사용 수명 단축을 야기하는 균열에 대한 문제를 개선하여 콘크리트의 하자를 줄일 수 있는 효과가 있다.At the same time, the compressive strength and bending strength are improved, workability is improved, and the magnetic shrinkage of the block is reduced, thereby reducing the defects of the concrete caused by degradation of the concrete structure and cracks .
그리고 현재 개질유황바인더를 제조할 때 140℃이상의 고온에서 합성을 하므로 공정상에 열에너지의 소모가 심하다. 이를 반응촉진제를 첨가하여 공정시간을 단축시킴으로써 생산성 향상을 도모하고 자 한다.At present, when the modified sulfur binder is manufactured, the synthesis is performed at a high temperature of 140 ° C or more, so that the heat energy is consumed in the process. And a reaction accelerator is added thereto to shorten the processing time, thereby improving the productivity.
도 1은 본 발명의 제조방법으로 제조된 칼라개질유황바인더 블록이다.
도 2는 본 발명의 실시예에 의해 제조된 칼라유황바인더 시편의 압축강도 측정결과이다.(한국화학융합시험연구원)
도 3은 본 발명의 실시예에 의해 제조된 칼라유황바인더블록의 휨강도 측정결과이다. (한국화학융합시험연구원)
도 4는 본 발명의 실시예에 의해 제조된 유황바인더의 촉진제 첨가 및 미첨가시 반응률을 나타내는 Toluene 불용분 함량 비교 그래프이다.
도 5는 본 발명의 실시예에 의해 진행된 칼라유황바인더블록의 길이변화율 측정결과이다.1 is a color modified sulfur binder block produced by the production method of the present invention.
2 shows the results of measurement of the compressive strength of a color sulfur binder specimen produced according to an embodiment of the present invention. (Korean Chemical Fusion Test Institute)
3 is a graph showing the results of measurement of the flexural strength of the color sulfur binder block manufactured according to the embodiment of the present invention. (Korea Chemical Fusion Test Institute)
FIG. 4 is a comparative graph showing the content of toluene insoluble matter in the sulfur binder prepared according to the embodiment of the present invention, which shows the reaction rate when the accelerator is added or not.
FIG. 5 is a graph illustrating a measurement result of the rate of change of the length of a color sulfur binder block according to an embodiment of the present invention.
본 발명은 칼라 유황바인더 제조방법에 관한 것으로, 반응기에 Sulfur를 넣은 후 일정온도로 유지하여 Sulfur를 완전히 용해시키는 용해단계;The present invention relates to a method for producing a color sulfur binder, comprising: dissolving a sulfur in a reactor to maintain a constant temperature to completely dissolve the sulfur;
용해된 Sulfur에 DCPD(Dicyclopentadiene)를 첨가하고, 이후 일정시간 반응시키는 반응단계;를 포함하되,A reaction step of adding DCPD (Dicyclopentadiene) to the dissolved Sulfur and then reacting for a predetermined time,
반응단계에서 반응이 종료되기 일정시간 이전 무기안료를 첨가하여 섞어주는 단계;를 더 포함하는 것을 특징으로 한다.And adding an inorganic pigment to the reaction mixture before a certain period of time to complete the reaction in the reaction step.
또한, 상기 반응기내에 혼합되는 원료는 Sulfur 85~99중량부에 대하여, DCPD 0.1~10중량부, 무기안료 0.5~10중량부의 비율로 혼합되는 것을 특징으로 한다.The raw materials to be mixed in the reactor are mixed in a ratio of DCPD of 0.1 to 10 parts by weight and inorganic pigment of 0.5 to 10 parts by weight based on 85 to 99 parts by weight of sulfur.
또한, 상기 무기안료는 산화티탄안료 또는 산화철안료인 것을 특징으로 한다.The inorganic pigment is characterized by being a titanium oxide pigment or an iron oxide pigment.
또한, 상기 반응단계에서는 DCPD와 함께 반응촉진제를 첨가하되, 반응촉진제는 2,2-Dithiobis(benzothiazole), Zinc salt of 2-mercapto-benzothiazole을 포함하는 benzothiazole계열, 또는 Zinc dimethyl dithiocarbamate, zinc di-n-butyl dithiocarbamate을 포함하는 dithiocarbamate계열, 또는 Tetramethyl thiuram disulfide, Tetraethyl thiuram disulfide을 포함하는 disulfide계열인 것을 특징으로 한다.Also, in the above reaction step, a reaction promoter is added together with DCPD, and the reaction promoter is a benzothiazole series including 2-Dithiobis (benzothiazole), Zinc salt of 2-mercapto-benzothiazole, or Zinc dimethyl dithiocarbamate, zinc di-n -butyl dithiocarbamate, or a disulfide series including Tetramethyl thiuram disulfide and Tetraethyl thiuram disulfide.
또한, 상기 반응단계를 거쳐 합성된 칼라 유황바인더에 굵은골재, 잔골재, 필러를 첨가한 후, 압축성형하여 칼라유황바인더블록을 제조하는 것을 특징으로 한다.
Further, the coarse aggregate, the fine aggregate and the filler are added to the color sulfur binder synthesized through the reaction step, and then compression molding is performed to produce a color sulfur binder block.
본발명을 첨부도면에 의해 상세히 설명하면 다음과 같다.The present invention will be described in detail with reference to the accompanying drawings.
도 1은 본 발명의 제조방법으로 제조된 칼라개질유황바인더 블록이다.1 is a color modified sulfur binder block produced by the production method of the present invention.
도 2는 본 발명의 실시예에 의해 제조된 칼라유황바인더 시편의 압축강도 측정결과이다.(한국화학융합시험연구원)2 shows the results of measurement of the compressive strength of a color sulfur binder specimen produced according to an embodiment of the present invention. (Korean Chemical Fusion Test Institute)
도 3은 본 발명의 실시예에 의해 제조된 칼라유황바인더블록의 휨강도 측정결과이다. (한국화학융합시험연구원)3 is a graph showing the results of measurement of the flexural strength of the color sulfur binder block manufactured according to the embodiment of the present invention. (Korea Chemical Fusion Test Institute)
도 4는 본 발명의 실시예에 의해 제조된 유황바인더의 촉진제 첨가 및 미첨가시 반응률을 나타내는 Toluene 불용분 함량 비교 그래프이다.FIG. 4 is a comparative graph showing the content of toluene insoluble matter in the sulfur binder prepared according to the embodiment of the present invention, which shows the reaction rate when the accelerator is added or not.
도 5는 본 발명의 실시예에 의해 진행된 칼라유황바인더블록의 길이변화율 측정결과이다.
FIG. 5 is a graph illustrating a measurement result of the rate of change of the length of a color sulfur binder block according to an embodiment of the present invention.
본 발명은 부생자원인 유황을 건설자재로서 가치 있는 자원으로 활용하고자 유황바인더에 무기안료를 첨가하여 칼라유황바인더를 제조해 강도향상과 수축저감을 도모하고, 시장성 및 생산성을 고려하여 유황바인더의 활용 범위를 점차 넓혀가기 위한 것으로, 용해된 Sulfur와 DCPD 합성 시 무기안료를 일정량 첨가하여 칼라유황바인더를 합성한다. 또한, 합성된 유황바인더와 굵은 골재, 잔골재, 무기안료를 함께 혼합한 후 가열, 압축성형하여 칼라유황바인더 블록을 제조한다. 이 때, 원료의 제조과정에서 2,2-Dithiobis(benzothiazole)등과 같은 촉진제를 첨가하여 합성공정을 단축시켜 공정상의 생산성과 경제성을 향상시킨다.In order to utilize sulfur, a by-product, as a valuable resource as a construction material, an inorganic pigment is added to a sulfur binder to produce a color sulfur binder to improve strength and reduce shrinkage, and to utilize a sulfur binder in consideration of marketability and productivity In order to widen the range gradually, a certain amount of inorganic pigment is added to synthesize dissolved sulfur and DCPD to synthesize a color sulfur binder. Also, the synthesized sulfur binder is mixed with coarse aggregate, fine aggregate, and inorganic pigment, followed by heating and compression molding to produce a colored sulfur binder block. At this time, a promoter such as 2,2-Dithiobis (benzothiazole) is added during the production of the raw material to shorten the synthesis process, thereby improving the productivity and economy of the process.
본 발명에서는 백색(산화티탄안료, TiO2), 청색(산화철안료, Fe2O3), 암갈색 안료(산화철안료, Fe2O3)를 사용하였고, 안료는 원하는 색에 따라 다양한 색의 안료를 사용할 수 있으며 시인성과 경제성, 강도 등을 고려하여 적절한 색, 사용양, 성분의 안료를 선정하여야 한다. 안료 사용량은 활용성과 시인성을 확보하면서 콘크리트의 강도 및 내구성에 악영향을 미치지 않는 범위에서 결정되어야 한다.In the present invention, white (titanium oxide pigment, TiO 2 ), blue (iron oxide pigment, Fe 2 O 3 ) and dark brown pigment (iron oxide pigment, Fe 2 O 3 ) were used. It is necessary to select appropriate color, usage amount, and ingredient pigment in consideration of visibility, economy and strength. The pigment usage should be determined within a range that does not adversely affect the strength and durability of the concrete while ensuring utility and visibility.
또한, 안료는 원료의 성분에 따라 크게 무기안료와 유기안료로 나눌 수 있는데 유기안료는 무기안료에 비해 선명하고 맑은 색상이 많고 착색력이 크나 자외선이나 열 및 유기용제에 의한 변색, 분해 등이 발생하여 도로 포장용 안료로 사용하기에는 부적절하다. 이에 비해 무기안료는 내열성, 내광성, 내용제성, 내약품성 등 내성이 우수하고 가격이 싸다는 장점이 있다. 또한 무기안료는 유기 안료에 비해 친환경적인 안료이기 때문에 본 발명에서는 무기 안료 사용이 바람직하다.
In addition, pigments can be roughly divided into inorganic pigments and organic pigments depending on the ingredient of the raw material. Organic pigments have a clear and clear color tone and coloring power compared with inorganic pigments. However, they are discolored or decomposed by ultraviolet rays, It is not suitable for use as road paving pigment. In contrast, inorganic pigments have an advantage of being excellent in resistance to heat, light resistance, solvent resistance, chemical resistance, and inexpensive price. Further, since the inorganic pigment is an environmentally friendly pigment as compared with the organic pigment, the use of the inorganic pigment is preferable in the present invention.
본 발명에 따른 칼라유황바인더 블록은 아래의 실시예의 방법에 따른다.
The color sulfur binder block according to the present invention follows the method of the following embodiment.
[실시예 1][Example 1]
반응기에 Sulfur를 넣은 후 반응기 내부 온도를 140℃로 유지하여 Sulfur를 완전히 용해시킨 후, 용해된 Sulfur에 DCPD(Dicyclopentadiene)를 첨가한다. 이 때, Sulfur와 DCPD의 혼합비는 Sulfur 90~99중량부에 대하여, DCPD 1~10중량부로 하며, 반응촉진제로 2,2-Dithiobis(benzothiazole)을 0.1~0.5중량부 첨가하였으며, 무기안료는 0.5~10중량부 첨가한다. 이후 1~4시간 반응시킨다. 이 때, 교반속도는 200~300RPM으로 조절하였다. Sulfur is added to the reactor, the temperature of the reactor is maintained at 140 ° C to completely dissolve the Sulfur, and DCPD (Dicyclopentadiene) is added to the dissolved Sulfur. In this case, the mixture ratio of sulfur and DCPD is 1 to 10 parts by weight of DCPD relative to 90 to 99 parts by weight of sulfuric acid, 0.1 to 0.5 parts by weight of 2,2-dithiobis (benzothiazole) is added as a reaction accelerator, To 10 parts by weight. Then, react for 1 to 4 hours. At this time, the stirring speed was adjusted to 200 to 300 RPM.
이 때, 합성이 된 분말 2g을 비이커에 넣고 톨루엔 1L를 넣은 후 200rpm으로 4시간 교반시킨 후 필터링하여 Toluene을 완전히 건조시킨 후의 불용분의 질량을 측정하여 합성률을 평가하였다. 반응촉진제가 첨가 된 분말과 미첨가 된 분말의 불용분 수치를 비교하면 표1과 같으며, 시간에 따른 합성속도의 차이를 그래프로 도 4에 나타내었다.At this time, 2 g of the synthesized powder was put in a beaker, and 1 L of toluene was added thereto. The mixture was stirred at 200 rpm for 4 hours, filtered, and the toluene was completely dried to measure the mass of the insoluble matter. Table 1 shows the results of comparing the insolubles of the powder containing the reaction promoter and the powder not added, and FIG. 4 is a graph showing the difference in the rate of synthesis with time.
표 1. 촉진제 첨가/미첨가 Toluene 불용분 비교Table 1. Comparison of insoluble Toluene with / without accelerator
반응이 종료되기 30분~1시간 전 무기안료를 0.5~10중량부 첨가하여 섞어주어 칼라유황바인더 합성을 완료하였다. 0.5 to 10 parts by weight of an inorganic pigment was added for 30 minutes to 1 hour before the completion of the reaction, followed by mixing to complete the synthesis of a color sulfur binder.
무기안료는 백색(산화티탄안료, TiO2), 청색(산화철안료, Fe2O3), 암갈색 안료(산화철안료, Fe2O3)가 사용되었고, 굵은골재, 잔골재, 무기안료가 포함된 개질유황바인더를 130~140℃에서 가열 및 혼합공정을 거쳐 압축강도 시편을 제작하여 압축강도를 측정하였다.The inorganic pigments used were white (titanium oxide pigment, TiO 2 ), blue (iron oxide pigment, Fe 2 O 3 ), dark brown pigment (iron oxide pigment, Fe 2 O 3 ), modified with coarse aggregate, fine aggregate, Compressive strength specimens were prepared by heating and mixing the sulfur binder at 130 ~ 140 ℃.
안료를 첨가하지 않은 시편의 압축강도 평균은 41.1 MPa였고, 청색, 백색, 암갈색 안료가 첨가된 시편의 압축강도 평균은 45.52 MPa로 안료가 첨가된 시편의 강도가 4.42 MPa 만큼 더 높은 값을 보였다.
The average compressive strength of specimens without pigments was 41.1 MPa. The average compressive strength of specimens with blue, white and dark brown pigments was 45.52 MPa. The strength of specimens with pigment was higher by 4.42 MPa.
[실시예 2][Example 2]
합성된 개질유황바인더를 사용하여 혼합 시 굵은 골재, 잔골재, 개질유황바인더, 무기안료를 130~140℃에서 가열 및 혼합공정을 거쳐 압축성형하여 블록을 제조하였다. 이 때, 개질유황바인더는 상온에서 초속경화되기 때문에 혼합된 재료를 빠르게 몰딩하는 것이 중요하며 성형 시 5~10초 가량 진동을 가해주어 몰드 내의 골재와 유황바인더와 안료가 더 잘 혼합될 수 있게 한다. Using the modified modified sulfur binder, coarse aggregate, fine aggregate, modified sulfur binder, and inorganic pigment were mixed at 130 ~ 140 ℃ for heating to mix. In this case, since the modified sulfur binder hardens at a very low speed at room temperature, it is important to mold the mixed material quickly, and vibration is applied for 5 to 10 seconds during molding, so that the aggregate in the mold and the sulfur binder and the pigment can be better mixed .
탈형은 블록의 성형이 끝나고 10분정도 경과 후에 진행하였고, 탈형 후 색 발현, 휨강도 그리고 길이변화율(블록의 수축률) 등 물성을 평가하였다.
Deformations proceeded after 10 minutes of block molding, and color properties, bending strength, and percent change in length (shrinkage of block) were evaluated after demolding.
골재는 8mm~50mm의 굵은골재와 8mm미만의 모래와 같은 잔골재로 이루어진다.The aggregate consists of coarse aggregate of 8mm ~ 50mm and fine aggregate of less than 8mm.
본발명의 개질유황바인더 콘크리트 블록 내의 혼합물의 함량은 굵은 골재 30 ~ 40 중량부에 대하여, 잔골재 30~ 40중량부, 개질유황바인더 17 ~ 30중량부, 필러 15 중량부 이하(0은 제외)이다.The content of the mixture in the modified sulfur binder concrete block of the present invention is 30 to 40 parts by weight of the fine aggregate, 17 to 30 parts by weight of the modified sulfur binder and 15 parts by weight or less (excluding 0) of the filler, relative to 30 to 40 parts by weight of the coarse aggregate .
굵은 골재가 30중량부 미만이 되면 강도가 떨어지고, 40중량부를 초과하면, 강도는 강해지나 결합력이 상대적으로 나빠진다. 잔골재는 개질유황바인더와 무기안료에 의해 접착되며, 또한 접착된 잔골재들은 굵은 골재와 굵은 골재 사이의 빈공간을 채우는 것으로, 30중량부 미만이 되면 결합력이 떨어지며 40중량부를 초과하면 강도가 상대적으로 나빠진다. 개질유황바인더가 17중량부 미만이면, 결합력이 떨어지며, 개질유황바인더가 30중량부를 초과하면, 강도가 상대적으로 저하된다. 그리고 필러가 너무 적을 경우 결합력이 떨어지나, 필러가 15중량부를 초과하면, 강도가 상대적으로 저하된다. 그러므로 필러는 15 중량부 이하(0은 제외)로 혼합한다. 상기 필러는 플라이애쉬, 실리카흄, 고로슬래그 미분말중 어느 하나를 사용한다.When the coarse aggregate is less than 30 parts by weight, the strength is lowered. When the coarse aggregate is more than 40 parts by weight, the strength is strengthened but the bonding strength is relatively poor. The fine aggregate is bonded by the modified sulfur binder and the inorganic pigment, and the fine aggregated materials fill the empty space between the coarse aggregate and the coarse aggregate. When the amount of the fine aggregate is less than 30 parts by weight, It falls out. When the modified sulfur binder is less than 17 parts by weight, the bonding strength is lowered, and when the modified sulfur binder is more than 30 parts by weight, the strength is relatively lowered. When the filler is too small, the bonding strength is lowered, but when the filler is more than 15 parts by weight, the strength is relatively lowered. Therefore, the filler is mixed at 15 parts by weight or less (excluding 0 parts). The filler may be any one of fly ash, silica fume and blast furnace slag fine powder.
무기안료는 백색(산화티탄안료, TiO2), 청색(산화철안료, Fe2O3), 암갈색 안료(산화철안료, Fe2O3)가 0.5~10중량부 사용되었고 안료 첨가하지 않은 블록과 물성을 비교하였다. The inorganic pigment used was 0.5 to 10 parts by weight of white (titanium oxide pigment, TiO 2 ), blue (iron oxide pigment, Fe 2 O 3 ) and dark brown pigment (iron oxide pigment, Fe 2 O 3 ) Were compared.
본 실시예에 의해 제조된 청색, 백색, 암갈색 안료가 첨가된 블록의 평균 휨강도는 7.995 MPa이고, 안료를 첨가하지 않은 블록의 평균 휨강도는 6.71 MPa로 안료를 첨가한 블록이 1.285 MPa 만큼 더 높은 값을 보였다.The average flexural strength of the block added with the blue, white and dark brown pigments prepared according to this example was 7.995 MPa and the average flexural strength of the block without pigment was 6.71 MPa and the block with pigment was higher by 1.285 MPa Respectively.
블록의 길이변화율(블록의 수축률) 측정 시 디지털 캘리퍼스를 사용하여 안료첨가에 따른 블록의 높이와 세로의 길이변화를 10분 단위, 1일 단위로 10일까지 측정하였다.The change of block height and block length were measured by digital caliper and the change of length and height of block according to pigment addition were measured in 10 minute increments and 10 days in 1 day increments.
본 실시예에 의해 블록의 세로와 높이의 길이변화율을 측정한 결과 안료첨가량이 증가함에 따라 블록의 세로 수축률은 0.26%에서 0.23%로 줄어들었고, 높이 수축률은 0.26%에서 0.17%로 줄어들었다. As a result of measuring the change rate of the length and height of the block according to this embodiment, the longitudinal shrinkage ratio of the block was reduced from 0.26% to 0.23% and the height shrinkage ratio was decreased from 0.26% to 0.17% as the pigment addition amount was increased.
Claims (5)
용해된 Sulfur에 DCPD(Dicyclopentadiene)를 첨가하고, 이후 일정시간 반응시키는 반응단계;를 포함하되,
반응단계에서 반응이 종료되기 일정시간 이전 무기안료를 첨가하여 혼합하는 단계;를 더 포함하는 반응공정개선 및 컬러화를 위한 개질유황바인더 제조방법에 있어서,
상기 반응기 내에 혼합되는 원료는 Sulfur 85~99중량부에 대하여, DCPD 0.1~10중량부, 반응촉진제 0.1~0.5중량부, 무기안료 0.5~10중량부의 비율로 혼합되는 것으로,
상기 반응촉진제는 2,2-Dithiobis(benzothiazole), Zinc salt of 2-mercapto-benzothiazole을 포함하는 benzothiazole계열, 또는 Zinc dimethyl dithiocarbamate, zinc di-n-butyl dithiocarbamate을 포함하는 dithiocarbamate계열, 또는 Tetramethyl thiuram disulfide, Tetraethyl thiuram disulfide을 포함하는 disulfide계열인 것이며,
상기 무기안료는 산화티탄안료 또는 산화철안료인 것으로, 성형 시 5~10초 가량 진동을 가해주어 몰드 내의 골재와 유황바인더와 안료가 더 잘 혼합될 수 있게 하는 것이며,
상기 단계를 거쳐 합성된 개질 유황바인더에 굵은골재, 잔골재, 필러혼합물을 첨가한 후, 압축성형하여 개질유황바인더블록을 제조하되,
상기 혼합물의 함량은 굵은 골재 30 ~ 40 중량부에 대하여, 잔골재 30~ 40중량부, 개질유황바인더 17 ~ 30중량부, 필러 15 중량부 이하(0은 제외)인 것을 특징으로 하는 반응공정개선 및 컬러화를 위한 개질유황바인더 제조방법
A step of dissolving the sulfuride and the reaction promoter completely by keeping the sulfuric acid in the reactor at a constant temperature;
A reaction step of adding DCPD (Dicyclopentadiene) to the dissolved Sulfur and then reacting for a predetermined time,
And adding and mixing an inorganic pigment before a certain period of time to terminate the reaction in the reaction step, the method comprising the steps of:
The raw materials to be mixed in the reactor are mixed in a proportion of 0.1 to 10 parts by weight of DCPD, 0.1 to 0.5 parts by weight of a reaction promoter, and 0.5 to 10 parts by weight of an inorganic pigment, relative to 85 to 99 parts by weight of the sulfur.
The reaction promoter may be a benzothiazole series including 2,2-Dithiobis (benzothiazole), a Zinc salt of 2-mercapto-benzothiazole, a dithiocarbamate series including Zinc dimethyl dithiocarbamate, zinc di-n-butyl dithiocarbamate, or Tetramethyl thiuram disulfide, Tetraethyl thiuram disulfide, including disulfide series,
The inorganic pigments are titanium oxide pigments or iron oxide pigments. The inorganic pigments are subjected to vibration for 5 to 10 seconds at the time of molding, so that the aggregate in the mold, the sulfur binder and the pigment can be better mixed.
After adding the coarse aggregate, the fine aggregate, and the filler mixture to the modified sulfur binder synthesized through the above steps, the modified sulfur binder block is produced by compression molding,
Wherein the content of the mixture is 30 to 40 parts by weight of fine aggregate, 17 to 30 parts by weight of modified sulfur binder, 15 parts by weight or less of filler (excluding 0), based on 30 to 40 parts by weight of coarse aggregate, Manufacturing method of modified sulfur binder for colorization
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