KR100849395B1 - Reducing agent for crvi with high stability - Google Patents

Reducing agent for crvi with high stability Download PDF

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Publication number
KR100849395B1
KR100849395B1 KR1020070030124A KR20070030124A KR100849395B1 KR 100849395 B1 KR100849395 B1 KR 100849395B1 KR 1020070030124 A KR1020070030124 A KR 1020070030124A KR 20070030124 A KR20070030124 A KR 20070030124A KR 100849395 B1 KR100849395 B1 KR 100849395B1
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South Korea
Prior art keywords
reducing agent
hexavalent chromium
zeolite
cement
chromium reducing
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KR1020070030124A
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Korean (ko)
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권우택
김수룡
김영희
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요업기술원
주식회사 케미콘
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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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • 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
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C04B22/142—Sulfates
    • C04B22/149—Iron-sulfates
    • 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
    • C04B14/047—Zeolites
    • 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
    • C04B2103/0004—Compounds chosen for the nature of their cations
    • C04B2103/0017—Refractory metal compounds
    • C04B2103/0018—Cr
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1075—Chromium-free or very low chromium-content materials
    • C04B2111/1081—Chromium VI, e.g. for avoiding chromium eczema

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

A six-valent chrome reducing agent for cement is provided to maintain reduction characteristics stably during the manufacture and storage steps of cement. A six-valent chrome reducing agent for cement includes 20-80wt% of a six-valent chrome reductant which is at least one compound selected from the group comprising iron, tin, and zinc compounds, and 20-80wt% of zeolite, wherein at least a part of the six-valent chrome reductant is substituted into the zeolite crystal. The zeolite contains at least one selected from the group comprising zeolite A, zeolite X, zeolite Y, analcime, bikitaite, clinoptilolite, fujasite, and ZSM5. Further, the substitution is performed by mixing and heating.

Description

산화 안정성이 우수한 시멘트 6가 크롬 저감제{Reducing Agent for CrVI with high stability}Reducing Agent for CrVI with high stability

본 발명은 시멘트 중에 존재하는 6가 크롬 환원제에 관한 것으로, 보다 상세하게는 6가 크롬 함량을 효율적으로 감소시키고 시멘트의 물성에 영향을 미치지 않는 6가 크롬 환원제에 관한 것이다.The present invention relates to a hexavalent chromium reducing agent present in cement, and more particularly to a hexavalent chromium reducing agent that effectively reduces the hexavalent chromium content and does not affect the properties of the cement.

일반적으로 크롬은 시멘트를 제조하는 과정에서 혼입되게 되며, 특히 고온의 킬른 분위기에서 시멘트 원료중의 3가 크롬이 6가 크롬으로 전환된다. 시멘트에 함유된 6가 크롬은 수용성으로서, 피부와 접촉되었을 경우에 피부를 자극하여 알러지 및 피부염을 야기시킨다. 상기 6가 크롬을 감소시키기 위하여 예를 들어 공개특허 10-2006-0036459에 개시된 바와 같은 황산철 화합물은 오래전부터 시멘트 산업에서 사용되었으며, 최근들어 황산 주석 화합물을 6가 크롬 환원제로 사용하고 있기도 하며(공개특허 10-2007-0000400), 또 염화주석의 6가 크롬 환원제로서의 사용도 보고되고 있다(공개특허 10-2006-0127116). In general, chromium is incorporated in the process of manufacturing cement, and trivalent chromium in the cement raw material is converted to hexavalent chromium, especially in a high temperature kiln atmosphere. Hexavalent chromium contained in cement is water soluble and irritates skin when contacted with skin, causing allergies and dermatitis. In order to reduce the hexavalent chromium, for example, iron sulfate compounds as disclosed in JP 10-2006-0036459 have been used in the cement industry for a long time, and recently, tin sulfate compounds have been used as hexavalent chromium reducing agents ( In addition, the use of tin chloride as a hexavalent chromium reducing agent has also been reported (Patent Publication 10-2006-0127116).

그러나, 이와 같은 6가 크롬 환원제를 시멘트에 적용할 경우에는 문제점이 생긴다. 이것은 주로 시멘트 제조 및 보관 또는 사용과정에서 6가 크롬 환원제가 산화되기 때문에 6가 크롬 환원제 효과가 급속히 저하되는 것에 기인한다. 따라서 시멘트에서의 6가크롬 용출량을 일정수준으로 유지하기 위해서는 6가 크롬 저감제의 량을 증가시킬 수밖에 없다. However, there is a problem when such a hexavalent chromium reducing agent is applied to cement. This is mainly due to the rapid deterioration of the hexavalent chromium reducing effect because the hexavalent chromium reducing agent is oxidized during cement production and storage or use. Therefore, in order to maintain the hexavalent chromium elution in the cement level, the amount of hexavalent chromium reducing agent must be increased.

그러나, 시멘트에 첨가되는 6가 크롬 환원제의 특성변화 및 첨가량 증가에 따라서 시멘트에서의 6가 크롬 함량 증가와 시멘트 품질이 저하된다. However, as the properties of the hexavalent chromium reducing agent added to the cement and the amount of the additive are increased, the hexavalent chromium content and the quality of the cement are degraded.

본 발명은 상기한 문제점을 해결하기 위해, 시멘트 제조 및 저장과정에서 안정적으로 환원특성을 유지할 수 있는 6가 크롬 저감제를 제공하는 것을 목적으로 한다. In order to solve the above problems, an object of the present invention is to provide a hexavalent chromium reducing agent that can stably maintain reducing properties during cement production and storage.

상기한 기술적 과제를 달성하기 위하여 본 발명은, 6가 크롬 환원제 20~80 중량%; 및 제올라이트 20~80 중량%를 포함하는 시멘트용 6가 크롬 저감제를 제공한다. The present invention, 20 to 80% by weight of a hexavalent chromium reducing agent to achieve the above technical problem; And it provides a hexavalent chromium reducing agent for cement comprising 20 to 80% by weight zeolite.

본 발명에서, 상기 제올라이트는 제올라이트 A, 제올라이트 X, 제올라이트 Y, 방비석(Analcime), 비키타이트(Bikitaite), 클리놉틸로라이트(Clinoptilolite), 푸자사이트(Fujasite) 및 ZSM5으로 이루어진 그룹 중에서 선택된 1종 이상을 포함할 수 있다. In the present invention, the zeolite is at least one selected from the group consisting of zeolite A, zeolite X, zeolite Y, anticime, bikitite, clinoptilolite, fujasite and ZSM5. It may include.

또한, 본 발명에서 상기 6가 크롬 환원제는 철, 주석 또는 아연 화합물인 것이 바람직하다.In the present invention, the hexavalent chromium reducing agent is preferably an iron, tin or zinc compound.

이하 본 발명의 바람직한 실시예를 통해 본 발명을 더욱 상세히 설명한다. Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the present invention.

본 발명의 6가 크롬 저감제는 제올라이트 및 6가 크롬 환원제를 포함한다.Hexavalent chromium reducing agents of the present invention include zeolites and hexavalent chromium reducing agents.

본 발명에서 사용되는 제올라이트는 일반적으로 알칼리 및 알칼리토금속의 규산알루미늄 수화물을 지칭하는 것으로서, 본 발명에서 제올라이트는 이온 교환체로 작용한다. 본 발명에서 제올라이트는 6가 크롬 환원제의 금속 이온 예컨대 철 또는 주석 이온과 결합하여 시멘트 제조 과정 및 사용 과정에서 6가 크롬 환원제를 안정화 시키고, 결합된 6가 크롬 환원제의 금속 이온이 시멘트 시공시 칼슘 이온과 이온 교환하여 수화물로 용출된단. 용출된 6가 크롬 환원제의 금속 이온은 시멘트 내의 6가 크롬을 3가 크롬으로 환원한다. 본 발명에서 상기 제올라이트는 높은 비표면적을 제공하여 우수한 이온 교환 특성을 나타내도록 다공성인 것이 바람직하다. Zeolites used in the present invention generally refer to aluminum silicate hydrates of alkali and alkaline earth metals, in which the zeolite acts as an ion exchanger. In the present invention, the zeolite is combined with metal ions of the hexavalent chromium reducing agent, such as iron or tin ions, to stabilize the hexavalent chromium reducing agent during cement production and use, and the combined metal ions of the hexavalent chromium reducing agent are calcium ions during cement construction. Eluted with hydrate by ion exchange with The metal ions of the eluted hexavalent chromium reducing agent reduce the hexavalent chromium in the cement to trivalent chromium. In the present invention, the zeolite is preferably porous to provide a high specific surface area and exhibit excellent ion exchange properties.

본 발명의 제올라이트로는 6가 크롬 환원제를 안정화 시킬 수 있는 다양한 종류의 천연 및 인공 제올라이트가 사용될 수 있다. 예를 들면 제올라이트 A, 제올라이트 X, 제올라이트 Y, 방비석(Analcime), 비키타아이트(Bikitaite), 클리놉틸로라이트(Clinoptilolite), 퓨자사이트(Fujasite), ZSM5 등이 사용될 수 있으며, 제올라이트는 2종 이상이 혼합되어 사용될 수도 있다. As the zeolite of the present invention, various kinds of natural and artificial zeolites capable of stabilizing a hexavalent chromium reducing agent may be used. For example, zeolite A, zeolite X, zeolite Y, analcime, bikitaite, clinoptilolite, fujasite, ZSM5, and the like may be used. The above may be mixed and used.

본 발명에서 6가 크롬 환원제는 통상의 시멘트 6가 크롬 환원제, 예컨대 철 또는 주석 화합물이 사용될 수 있다. 본 발명에서 상기 철 화합물로서는 황산철 제1수화물, 황산철 제7수화물과 같은 황산철 화합물 또는 철강산업체에서 부산물로 발생하는 황산철 화합물이 사용될 수도 있다. 물론, 본 발명에서 사용가능한 철 화 합물은 위에 열거된 것에 한정되지 않는다. In the present invention, the hexavalent chromium reducing agent may be a conventional cement hexavalent chromium reducing agent such as iron or tin compounds. In the present invention, as the iron compound, an iron sulfate compound such as iron sulfate monohydrate, iron sulfate seventh hydrate or an iron sulfate compound generated as a by-product from an iron and steel industry may be used. Of course, the iron compounds usable in the present invention are not limited to those listed above.

또한 본 발명에서 6가 크롬 환원제로 사용가능한 주석 화합물로서는 황산 주석, 염화 주석 등이 사용될 수 있으며, 여기에 한정되지 않는다. 예컨대 아연 화합물도 6가 크롬 환원제로서 사용가능하다. In addition, tin sulfate, tin chloride, and the like may be used as the tin compound usable as the hexavalent chromium reducing agent in the present invention, but is not limited thereto. Zinc compounds, for example, can also be used as hexavalent chromium reducing agents.

본 발명에서 제올라이트가 6가 크롬 환원제와 결합하는 메커니즘은 다양하게 설명 가능하다. 예를 들어, 제올라이트가 6가 크롬 환원제와 반응하여 6가 크롬 환원제가 제올라이트의 결정 구조 내로 편입될 수도 있으며, 이와 달리 6가 크롬 환원제는 제올라이트 표면에 흡착 등의 메커니즘에 의해 결합될 수도 있다. 본 발명에서 흡착은 화학적 또는 물리적 흡착을 불문한다. In the present invention, the mechanism by which the zeolite binds with the hexavalent chromium reducing agent can be variously described. For example, the zeolite may react with the hexavalent chromium reducing agent so that the hexavalent chromium reducing agent may be incorporated into the crystal structure of the zeolite, whereas the hexavalent chromium reducing agent may be bound to the zeolite surface by a mechanism such as adsorption. Adsorption in the present invention, whether chemical or physical adsorption.

본 발명에서 6가 크롬 저감제는 상기 6가크롬 환원제 20∼80중량% 및 산화안정제로서 제올라이트 20∼80중량%를 혼합하여 제조할 수 있다. 이 때, 상기 배합비율로 배합된 6가크롬 환원제는 철 또는 주석 화합물과 제올라이트를 건식 또는 습식 혼합한 후, 약 20~100℃의 온도 바람직하게는 60℃ 이상의 온도로 가열하여 약 0.5~5시간동안 교반하면서 반응시켜 제조될 수 있다. 본 발명의 6가 크롬 저감제는 사용 방법에 따라 액상 상태로 사용하거나 농축하여 사용하거나, 건조하여 고상 상태로 사용할 수도 있다. 또 혼합시 첨가제가 추가로 혼합될 수도 있다. In the present invention, the hexavalent chromium reducing agent may be prepared by mixing 20 to 80% by weight of the hexavalent chromium reducing agent and 20 to 80% by weight of zeolite as an oxidative stabilizer. At this time, the hexavalent chromium reducing agent blended in the above mixing ratio is dry or wet mixed with the iron or tin compound and zeolite, and then heated to a temperature of about 20 to 100 ° C, preferably 60 ° C or more, for about 0.5 to 5 hours. Can be prepared by reacting with stirring. The hexavalent chromium reducing agent of the present invention may be used in a liquid state, used in a concentrated state, or dried to be used in a solid state. In addition, additives may be further mixed during mixing.

본 발명에서 제올라이트는 산화안정제로 작용한다. 본 발명에 따른 6가 크롬 저감용 제올라이트는 시멘트 제조 과정에서 투입될 수 있으며, 제조된 시멘트의 사용 과정에서 투입될 수도 있다. 본 발명의 제올라이트는 사용의 용이성 및 특성 향상을 위하여 고상 또는 액상으로 제공될 수 있다. In the present invention, zeolite acts as an oxidative stabilizer. The zeolite for reducing hexavalent chromium according to the present invention may be added during the cement manufacturing process, or may be added during the use of the manufactured cement. The zeolites of the present invention may be provided in solid or liquid form for ease of use and improved properties.

본 발명의 제올라이트가 사용 가능한 시멘트로는 수경성 물질인 1종 보통 시멘트뿐만 아니라 고로슬래그 시멘트, 플라이애쉬 혼합시멘트, 초속경 시멘트 및 중용열 시멘트 등의 특수시멘트를 포함한다. The cement which can be used in the zeolite of the present invention includes not only one type of ordinary cement, which is a hydraulic material, but also special cements such as blast furnace slag cement, fly ash mixed cement, superhard cement, and medium heat cement.

본 발명에 따른 6가 크롬 저감제는 시멘트의 분쇄, 저장, 포장 과정에서 고상으로 투입되거나 시멘트를 물과 함께 페이스트, 몰탈 또는 레미콘으로 사용되는 도중에 액체나 고체상태로 투입될 수 있다. The hexavalent chromium reducing agent according to the present invention may be added to the solid phase in the process of crushing, storing, and packing the cement, or in the liquid or solid state while the cement is used as a paste, mortar or ready-mixed concrete with water.

본 발명에서 6가 크롬 저감제는 시멘트 중량에 대해 0.2~4% 사용되는 것이 바람직하다.In the present invention, the hexavalent chromium reducing agent is preferably used 0.2 to 4% by weight of the cement.

실시예Example

본 실시예에서는 6가 크롬 환원제로서 황산철을 사용하였다.본 실시예의 6가 크롬 저감제는, 황산철 화합물과 제올라이트를 50 : 50의 비율로 반응을 위한 수용액에 투입하고 수용액을 80℃에서 1시간동안 가열하여 철 이온이 제올라이트 결정내로 치환하도록 하여 제조하였다. 본 실시예에서 사용된 시멘트는 보통 포틀랜드 시멘트였다. 본 실시예에서 사용된 6가 크롬 저감제의 대표적인 화학성분을 표 1에 나타내었다 In the present embodiment, iron sulfate was used as the hexavalent chromium reducing agent. The hexavalent chromium reducing agent of the present example was charged with an iron sulfate compound and zeolite in an aqueous solution for the reaction at a ratio of 50:50, and the aqueous solution was added at 80 ° C. Prepared by heating for a time to allow iron ions to substitute into the zeolite crystals. The cement used in this example was usually Portland cement. Representative chemical constituents of the hexavalent chromium reducing agent used in this example are shown in Table 1.

[표 1]  TABLE 1

(단위 : 중량%)(Unit: weight%)

Figure 112007024164705-pat00001
Figure 112007024164705-pat00001

본 실시예에서는 6가 크롬 저감제의 함량에 따른 영향을 알아보기 위해 아래 표 2와 같이 6가 크롬 저감제의 함량을 달리하여 시험하였다. 또, 본 실시예의 6가 크롬 저감제와 종래의 6가 크롬 환원제의 비교를 위해 황산철 6가 크롬 환원제를 시멘트에 혼합한 것과 비교하였다. 또, 시멘트 분쇄 등과 같이 실제 사용 환경에서의 영향을 알아보기 위해 6가 크롬 환원제 및 저감제를 단순 혼합한 것과 200℃로 60분 동안 분쇄한 것과의 특성을 비교 측정하였다. 이때 시멘트중의 수용성 ６가 크롬 정량 방법은, 일본 시멘트 협회의 JCASI-51-1981「시멘트 및 시멘트 원료중의 미량 성분의 정량 방법」중의 「흡광 광도법에 따르는 시멘트중의 수용성 6가 크롬 정량 방법」을 이용하여 측정하였다. In this embodiment, to determine the effect of the content of the hexavalent chromium reducing agent was tested by varying the content of the hexavalent chromium reducing agent as shown in Table 2 below. In addition, in order to compare the hexavalent chromium reducing agent of this example with the conventional hexavalent chromium reducing agent, the iron sulfate hexavalent chromium reducing agent was compared with cement. In addition, in order to determine the effect in the actual use environment, such as cement grinding, the characteristics of a simple mixture of a hexavalent chromium reducing agent and a reducing agent and a grinding for 60 minutes at 200 ℃ was measured. At this time, the method for quantifying water-soluble hexavalent chromium in cement is the method for quantifying water-soluble hexavalent chromium in cement according to the absorbance photometric method in JCASI-51-1981 "Method for Determination of Trace Components in Cement and Cement Raw Materials" of the Japan Cement Association. Measured using.

[표 2]TABLE 2

Figure 112007024164705-pat00002
Figure 112007024164705-pat00002

위 표로부터 알 수 있는 바와 같이, 6가 크롬 환원제로서 황산철 화합물을 단독으로 사용하였을 경우에는 가열분쇄와 같이 산화조건에 노출되었을 경우에 6가 크롬 환원제가 산화되어 시멘트중의 6가 크롬 저감 효과가 급격히 저하되지만 본 발명에 의한 제올라이트 함유 6가 크롬 환원제의 경우에 6가 크롬 환원제가 제올라이트 결정 내에서 안정하게 존재하여 가열 분쇄와 같은 산화조건에서도 6가 크롬 환원제 특성을 유지하여 시멘트에서의 6가 크롬 함량을 급격히 저하시킬 수 있음을 알 수 있다.As can be seen from the above table, when the iron sulfate compound alone was used as the hexavalent chromium reducing agent, the hexavalent chromium reducing agent was oxidized when exposed to oxidizing conditions such as heating crushing, thereby reducing the hexavalent chromium in the cement. However, in the case of the zeolite-containing hexavalent chromium reducing agent according to the present invention, the hexavalent chromium reducing agent is stably present in the zeolite crystals to maintain the hexavalent chromium reducing agent properties even under oxidizing conditions such as heat pulverization. It can be seen that the chromium content can be drastically lowered.

다음 표 3은 6가 크롬 저감제를 상기의 배합비로 혼합하여 제조된 시멘트의 모르터 압축강도와 색상을 비교하여 나타내었다.Table 3 shows mortar compressive strength and color of cement prepared by mixing the hexavalent chromium reducing agent in the above mixing ratio.

[표 3]TABLE 3

Figure 112008043587582-pat00003
Figure 112008043587582-pat00003

상기 표의 결과에서 알 수 있는 바와 같이 황산철 제7수염을 6가 크롬 환원제로 사용하였을 경우에는 첨가량이 증가할수록 시멘트 몰탈 응결이 증가하며, 압축강도가 급격히 저하되어 시멘트 품질이 저하됨을 알 수 있으나, 본 발명에의한 제올라이트 함유 6가 크롬 환원제를 첨가하였을 경우에는 6가 크롬 환원제 첨가량이 2%까지는 응결변화가 거의 없으며, 압축강도는 보통 포틀랜드 시멘트의 경우보다 증가하여 오히려 향상됨을 확인할 수 있다. 따라서, 본 발명에 따른 저감제가 시멘트 품질에 미치는 악영향은 없는 것으로 판단된다. As can be seen from the results of the above table, when the ferric sulfate is used as a hexavalent chromium reducing agent, the cement mortar condensation increases as the amount added, and the compressive strength is sharply lowered, thereby decreasing the cement quality. When the zeolite-containing hexavalent chromium reducing agent according to the present invention is added, the amount of hexavalent chromium reducing agent added hardly changes up to 2%, and the compressive strength increases rather than that of ordinary portland cement. Therefore, it is judged that the reducing agent according to the present invention does not adversely affect the cement quality.

이상에서 설명한 본 발명은 전술한 실시예에 의해 한정되는 것이 아니고 본 발명의 기술적 사상에서 벗어나지 않는 범위 내에서 여러 가지 변형 및 응용이 가능하다.  The present invention described above is not limited to the above-described embodiments, and various modifications and applications can be made without departing from the technical spirit of the present invention.

이상 설명한 바와 같이 본 발명에 의해 기존의 철 화합물, 주석 화합물 또는 아연 혼합물과 같은 6가 크롬 환원제를 단독으로 사용하였을 경우에 시멘트 제조 및 보관 과정에서의 산화 과정에 의한 6가 크롬 환원제 특성저감 및 이로 인해 시멘트 내에 6가 크롬 환원제의 과량첨가에 의한 시멘트 품질저하의 문제점을 근본적으로 해결할 수 있다. As described above, when the hexavalent chromium reducing agent such as an iron compound, tin compound, or zinc mixture is used alone according to the present invention, the properties of the hexavalent chromium reducing agent are reduced by oxidation during the cement production and storage process, and thus Due to the excessive addition of hexavalent chromium reducing agent in the cement it is possible to fundamentally solve the problem of deterioration of cement quality.

Claims (5)

철, 주석 및 아연 화합물로 이루어진 그룹 중에서 선택된 최소한 1종의 화합물인 6가 크롬 6가 크롬환원제 20~80 중량%; 및 제올라이트 20~80 중량%를 포함하고, 상기 6가 크롬 6가 크롬환원제의 최소한 일부는 상기 제올라이트 결정내로 치환된 것인 시멘트용 6가 크롬 저감제.20 to 80% by weight of a hexavalent chromium hexavalent chromium reducing agent which is at least one compound selected from the group consisting of iron, tin and zinc compounds; And 20 to 80% by weight of zeolite, wherein at least a portion of the hexavalent chromium hexavalent chromium reducing agent is substituted into the zeolite crystals. 제1항에 있어서, 제올라이트는 제올라이트 A, 제올라이트 X, 제올라이트 Y, 방비석(Analcime), 비키타이트(Bikitaite), 클리놉틸로라이트(Clinoptilolite), 푸자사이트(Fujasite) 및 ZSM5으로 이루어진 그룹 중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 시멘트용 6가 크롬 저감제.The zeolite of claim 1, wherein the zeolite is one selected from the group consisting of zeolite A, zeolite X, zeolite Y, analcime, bikitite, clinoptilolite, fujasite and ZSM5. A hexavalent chromium reducing agent for cement, comprising the above. 삭제delete 삭제delete 제1항에 있어서, The method of claim 1, 상기 제올라이트내로 치환은 혼합 및 가열에 의해 이루어지는 것을 특징으로 하는 시멘트 6가 크롬 저감제.The substitution into the zeolite is a cement hexavalent chromium reducing agent, characterized in that by mixing and heating.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2363386A1 (en) * 2010-02-23 2011-09-07 Mig Material Innovative Gesellschaft MBH Reduction of CR(VI) ions in cement or products containing cement
KR20230045396A (en) 2021-09-28 2023-04-04 정찬일 Reducing Agent for Cr+6 using Bio sulfur and Method for manufacturing the same

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Publication number Priority date Publication date Assignee Title
KR19980039042A (en) * 1996-11-27 1998-08-17 우덕창 How to remove hexavalent chromium in cement
JP2003093538A (en) * 2001-09-26 2003-04-02 Taiheiyo Cement Corp Reduction method of hexavalent chrome by particle-size control of silicon
KR20070000400A (en) * 2003-11-21 2007-01-02 더블유.알. 그레이스 앤드 캄파니-콘. Sulfate dispersion chromate reducer

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19980039042A (en) * 1996-11-27 1998-08-17 우덕창 How to remove hexavalent chromium in cement
JP2003093538A (en) * 2001-09-26 2003-04-02 Taiheiyo Cement Corp Reduction method of hexavalent chrome by particle-size control of silicon
KR20070000400A (en) * 2003-11-21 2007-01-02 더블유.알. 그레이스 앤드 캄파니-콘. Sulfate dispersion chromate reducer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2363386A1 (en) * 2010-02-23 2011-09-07 Mig Material Innovative Gesellschaft MBH Reduction of CR(VI) ions in cement or products containing cement
KR20230045396A (en) 2021-09-28 2023-04-04 정찬일 Reducing Agent for Cr+6 using Bio sulfur and Method for manufacturing the same

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