KR101222109B1 - Body containing fulvic acid and humin for water purification - Google Patents

Body containing fulvic acid and humin for water purification

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Publication number
KR101222109B1
KR101222109B1 KR1020120090607A KR20120090607A KR101222109B1 KR 101222109 B1 KR101222109 B1 KR 101222109B1 KR 1020120090607 A KR1020120090607 A KR 1020120090607A KR 20120090607 A KR20120090607 A KR 20120090607A KR 101222109 B1 KR101222109 B1 KR 101222109B1
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South Korea
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humin
weight
fulvic acid
water
water purification
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KR1020120090607A
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Korean (ko)
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강정용
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석성기업주식회사
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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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/009—Porous or hollow ceramic granular materials, e.g. microballoons
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • 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
    • B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
    • B28B3/02—Producing shaped articles from the material by using presses; Presses specially adapted therefor wherein a ram exerts pressure on the material in a moulding space; Ram heads of special form

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Microbiology (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Biological Treatment Of Waste Water (AREA)

Abstract

PURPOSE: A formed block for water purification is provided to improve absorption performance of a heavy metal in the water and decomposition performance of an organic material in the water. CONSTITUTION: A manufacturing method of a formed block for water purification(100) comprises: a step of compression molding 10-20 weight% of a water-purifying material(40), 35-50 weight% of a crushed stone aggregate(60), 20-42 weight% of an inorganic binder(50), and 10-20 weight% of water. A manufacturing method of the water-purifying material comprises a step of mixing 10-30 parts by weight of humin into 100.0 parts by weight of allophane to charge and absorb humin into pores of the allophane; and a step of adding 5-15 part by weight of liquid fulvic acid(300) into the humin-absorbed allophone, to coat the surface of the allophane with the fulvic acid.

Description

풀빅산 및 휴민이 함유된 수질정화체를 이용한 수질정화용 블록성형체{Body containing fulvic acid and humin for water purification}Body containing fulvic acid and humin for water purification using water purifier containing fulvic acid and humin

본 발명은 풀빅산 및 휴민을 이용한 수질정화용 블록성형체에 관한 것으로, 앨러페인, 휴민 및 액상 풀빅산으로 이루어진 수질정화체와 무기질 바인더 및 쇄석골재를 혼합성형한 블록성형체에 관한 것이다.
The present invention relates to a block molded body for water purification using fulvic acid and humin, and to a block molded body mixed with an aqueous binder composed of allerpine, humin and liquid fulvic acid, and an inorganic binder and crushed aggregate.

인구가 도시로 집중하고 산업이 발달함에 따라 대규모의 인구 밀집지역과 공장 밀집단지가 형성되어 막대한 양의 하수와 폐수를 배출하게 되었으며, 산업의 발전과 인구의 증가로 인해 많은 양의 각종 생활하수 및 공업용수가 하천이나 호수, 바다 등으로 유입되어 수질오염이 심해져 오고 있다. As the population concentrates into cities and the industry develops, large-scale population centers and factory clusters are formed, which generates huge amounts of sewage and wastewater, and due to the development of the industry and the increase of population, Industrial water has flowed into rivers, lakes and the sea, and water pollution has been increasing.

이러한 원인은 자연 스스로의 정화능력을 넘어서는 유기물, 질소 화합물 등 수질을 오염시키는 유해성분들에 의해 하천이 오염되고, 오염된 시냇물이나 하천수가 그대로 강으로 유입되어, 강을 오염시킬 뿐 아니라, 해양오염을 발생하게 된다. This is caused by contamination of rivers by harmful substances which pollute the water quality such as organic matter and nitrogen compounds beyond the purification ability of the natural self, and contaminated streams and river water are directly introduced into the river and pollute the river. .

최근에는 환경오염에 대한 인식이 제고되어, 공업용 폐수나 양어장의 오수 등과 같은 오,폐수는 반드시 오,폐수 정화처리시설을 설치하여 수질을 정화시킨 후 방류하도록 되어 있어 수질오염을 어느정도 방지할 수 있으나, 빗물이 흐르는 수로 및 일반 하천 등에는 별도의 수질정화시설이 없어 오염지역을 통과한 우수 등이 그대로 하천으로 유입되어 흐르게 되는 문제점이 있었다. Recently, awareness of environmental pollution has been raised, and wastewater, such as industrial wastewater or sewage from fish farms, must be equipped with a wastewater purification treatment facility to purify the water and discharge it to prevent water pollution. In other words, there is a problem that rainwater flows through rainwater, and general rivers do not have a separate water purification facility, and rainwater flowing through the polluted area flows into the river.

하천의 수질을 정화하기 위하여 하천의 호안 또는 바닥에 설치되는 장치 또는 구조물로는, 폭기의 유도에 의해 용존산소량을 증가시키는 방식, 식생이 가능하도록 하여 오염물질의 자연 저감을 유도하는 방식, 구조물에 미생물을 함침시켜 미생물로 하여금 오염물을 저감하도록 하는 생물학적 방식 등이 개발되어 있다.In order to purify the water quality of the river, the device or structure installed on the shore or the bottom of the river includes a method of increasing the amount of dissolved oxygen by inducing aeration, a method of inducing natural reduction of pollutants by allowing vegetation, and Biological methods have been developed to impregnate microorganisms so that they can reduce contaminants.

이들 중 미생물을 이용하는 생물학적 방식은 정화 효율이 높고, 유지관리가 편하여 높은 효용성을 인정받고 있으며, 현재 개발된 기술은 다공성 블록에 직접 미생물을 함침시키고, 이러한 블록을 하천 내에 설치하여 정화를 유도하는 방식을 취하고 있다.Among them, the biological method using microorganisms has high purification efficiency, easy maintenance, and high utility, and currently developed technology impregnates microorganisms directly in porous blocks and installs them in rivers to induce purification. The way it is.

그런데, 이러한 종래의 방식은 미생물의 유실이 쉽다는 점, 미생물이 다공성 블록에 직접 함침되므로 활성도가 저하된다는 점, 다공성 블록에 침사물이 누적되면 기능이 저하된다는 점 등의 문제점이 지적되어 왔다. 특히, 접촉여제나 기능성 구조물을 설치하더라도 즉각적으로 수중미생물이 흡착되어 정착하거나 수생 동식물이 정착하는 것이 아니기 때문에 수중 및 수변의 자연 정화력이 완전히 복원되기 까지 흘러가는 오염원은 그대로 방치될 수밖에 없었다.However, such conventional methods have been pointed out such that the loss of microorganisms, microorganisms are directly impregnated in the porous block, the activity is lowered, and the function is reduced when the deposit is accumulated in the porous block. In particular, the installation of a contact filter or a functional structure does not immediately adsorb and settle the aquatic microorganisms or settle the aquatic flora and fauna, so the pollutant flowing until the natural purification of the water and waterside is completely restored, has to be left as it is.

또한, 미생물이 흡착되더라도 유속등에 따른 미생물의 빠른 탈리 현상으로 인해 미생물의 분해 및 정화 능력의 지속성이 저하되는 등의 문제점이 여전히 남게 되어, 종래의 구조물로는 효과의 지속성 및 범용성, 편의성 등의 측면에서 미흡한 점이 많은 문제점이 있었다.
In addition, even if the microorganisms are adsorbed, problems such as deterioration of the microbial decomposition and purification ability due to the rapid desorption of microorganisms due to the flow rate, etc. still remain. There were many problems with the lack.

등록특허공보 등록번호 10-0948556(2010.03.12)Registered Patent Publication No. 10-0948556 (2010.03.12) 등록특허공보 등록번호 10-0632249(2006.09.28)Registered Patent Publication No. 10-0632249 (September 28, 2006) 공개특허공보 공개번호 2008-0036785(2008.04.29)Published Patent Publication No. 2008-0036785 (2008.04.29) 공개특허공보 공개번호 2011-0083885(2011.07.21)Korean Laid-Open Patent Publication No. 2011-0083885 (2011.07.21)

본 발명의 목적은 앨러페인내에 휴민과 풀빅산이 안정적으로 담지된 수질정화체에 의해 수중 유기물의 분해성능 및, 수중 중금속의 흡착성능을 향상시켜 수질을 정화할 수 있는 풀빅산 및 휴민을 이용한 수질정화용 블록성형체를 제공하는 것이다.
An object of the present invention is to improve the decomposition performance of organic matter in water and adsorption performance of heavy metals in water by purifying humine and fulvic acid stably supported in allergy to water purification using fulvic acid and humin It is to provide a block molded body.

본 발명에 따른 수질정화용 블록성형체는 휴민 및 풀빅산이 함유된 수질정화체 10∼20중량%, 쇄석골재 35∼50중량%, 무기바인더 20∼42중량% 및, 물 10∼20중량%를 압축성형하여 형성하되,상기 수질정화체는 앨러페인 100 중량부에, 휴민 10∼30중량부를 혼합하여 앨러페인에 휴민을 흡착시키고, 상기 휴민이 흡착된 앨러페인에 액상 풀빅산 5∼15중량부를 첨가하여 앨러페인의 표면을 코팅하도록 되어 있다.
Water-purifying block molding according to the present invention is a water-purifying water containing humin and fulvic acid 10 to 20% by weight, crushed aggregate 35 to 50% by weight, inorganic binder 20 to 42% by weight, water 10 to 20% by weight compression molding The water purifier is mixed with 100-30 parts by weight of allergy, 10-30 parts by weight of humin to adsorb the humin to allergy, and add 5-15 parts by weight of liquid fulvic acid to the allergy to which the humin is adsorbed. It is intended to coat the surface of allergy.

본 발명은 앨러페인, 휴민 및 풀빅산으로 이루어진 수질정화체가 쇄석골재 및 무기바인더에 의해 소정형상의 블록성형체로 압축성형하도록 되어 있어, 블록성형체의 표면 및 내부에 위치하는 수질정화체에 의해 미생물이 안정적으로 정착될 수 있으며, 이와 같은 미생물의 정착에 의해 우수한 수질정화능력을 구비하게 된다. In the present invention, the water purification body consisting of allerpine, humin, and fulvic acid is compressed and molded into a block shaped body by a crushed aggregate and an inorganic binder. It can be stably settled, and has excellent water purification ability by the settlement of such microorganisms.

본 발명은 앨러페인(allophane)내에 휴민이 흡착 또는 충전되고, 그 표면이 액상 풀빅산에 의해 코팅되도록 되어 있어, 포틀랜드 시멘트 등의 무기바인더에 의한 블록성형체의 압축성형시에도 엘러페인내에 휴민 및 풀빅산을 안정적으로 유지할 수 있으며, 이를 통해, 수질정화효율을 향상시킬 수 있다. In the present invention, the humin is adsorbed or filled in the allophane, and the surface thereof is coated with liquid fulvic acid, so that even when the block molded product is compressed by an inorganic binder such as portland cement, the humin and the grass It is possible to maintain the Big Mountain stably, thereby improving the water purification efficiency.

본 발명은 무수히 많은 기공을 구비하는 앨러페인의 분말도를 무기바인더와 거의 동일하게 하여 시멘트와 배합함으로써, 블록성형체내에 앨러페인이 균일하게 분포되고, 이와 같은 앨러페인의 분포에 의해 블록성형체내에 수질정화체가 균일하게 분포되어 수중에서의 휴민 및 풀빅산 분해 및 분리에 의해 연속적인 공극이 형성되도록 하여, 미생물의 자유로운 이동이 가능하며, 미생물의 생존효율을 향상시킬 수 있다. According to the present invention, by mixing the powder of allergy having numerous pores with the same amount as that of the inorganic binder, the allergy is uniformly distributed in the block molded body. Water purifiers are uniformly distributed in the water so that continuous pores are formed by decomposition and separation of humin and fulvic acid in water, allowing free movement of microorganisms and improving survival efficiency of microorganisms.

본 발명은 수질정화체가 휴민 및 풀빅산을 포함하고 있어, 시멘트 독성 및 하천내의 중금속이 휴민 및 풀빅산에 의해 제거되어 수질을 정화하는 효과를 구비한다.According to the present invention, since the water purification body contains humin and fulvic acid, cement toxicity and heavy metals in the stream are removed by the humin and fulvic acid to purify the water quality.

본 발명은 다량의 풀빅산이 앨러페인의 표면에 코팅처리되어 있어, 별도의 고정수단없이도, 앨러페인내에 휴민과 풀빅산의 고정이 가능하다. In the present invention, a large amount of fulvic acid is coated on the surface of the allergy, so that the fixing of humin and fulvic acid in the allergy is possible without a separate fixing means.

본 발명은 풀빅상을 함유하고 있어, 수중생물의 생육을 향상시키고, 미생물의 활성화를 높이며, 용존산소량을 증대시키는 효과가 있다. The present invention contains a full-bic phase, has the effect of improving the growth of aquatic organisms, increase the activation of microorganisms, and increase the amount of dissolved oxygen.

본 발명은 비결정성 앨러페인이 내에 미생물 세포가 흡착되어 있어, 다당류, 단백질 및 지방질로 구성된 미생물 세포벽의 카르복실레이트(carboxylate), 하이드로실(hydroxyl), 설페이트(sulfate), 포스페이트(phosphate), 아미노(amino)기에 의해 중금속의 생물흡착이 이루어진다. In the present invention, the microorganism cells are adsorbed in the amorphous allergy, and the carboxylate, hydroxyl, sulfate, phosphate, and amino of the microbial cell wall composed of polysaccharides, proteins and fats. Bio-adsorption of heavy metals occurs by (amino) groups.

본 발명은 앨러페인내에 미생물이 고정화되는 생화학적 정화방식을 취하면서도, 미생물의 유실이 적고, 활성도가 높아, 장기간이 경과하더라도 기능 저하의 우려가 적은 효과가 있다. The present invention takes the biochemical purification method in which microorganisms are immobilized in allergy, while the loss of microorganisms is high, the activity is high, and there is little effect of deterioration of function even after a long period of time.

본 발명은 다양한 형상으로 성형이 가능하여, 자연에 존재하는 하천이나 호수 뿐만 아니라 양어장, 수족관 등의 수자원 오염을 적은 비용으로 쉽고 용이하게 해결함으로써, 효과적으로 자연의 자정능력을 되살려, 쾌적한 자연 환경을 유지하는데 도움을 주는 등 많은 효과가 있다.
The present invention can be molded into a variety of shapes, by easily and easily solve the pollution of water resources, such as fish farms, aquariums, as well as rivers and lakes existing in nature, and effectively restore the self-cleaning ability of nature, maintaining a pleasant natural environment There are many effects such as to help.

도 1 은 본 발명에 따른 수질정화용 블록성형체의 구성을 보인 예시도
도 2 는 본 발명에 따른 수질정화체의 구성을 보인 예시도
도 3 은 본 발명에 따른 다양한 형태의 블록성형체 구성을 보인 예시도
도 4 는 본 발명에 따른 수질정화용 블록성형체의 설치상태를 보인 예시도
도 5 는 본 발명에 따른 또다른 블록성형체 구성을 보인 예시도1 is an exemplary view showing the configuration of a block molded body for water purification according to the present invention
Figure 2 is an exemplary view showing the configuration of the water purification body according to the present invention
Figure 3 is an exemplary view showing the configuration of various types of block molded body according to the present invention
Figure 4 is an exemplary view showing the installation state of the block for molding water purification according to the present invention
5 is an exemplary view showing another block molded body configuration according to the present invention

도 1 은 본 발명에 따른 수질정화용 블록성형체의 구성을 보인 예시도를, 도 2 는 본 발명에 따른 수질정화체의 구성을 보인 예시도를, 도 3 은 본 발명에 따른 다양한 형태의 블록성형체 구성을 보인 예시도를, 도 4 는 본 발명에 따른 수질정화용 블록성형체의 설치상태를 보인 예시도를, 도 5 는 본 발명에 따른 또다른 블록성형체 구성을 보인 예시도를 도시한 것으로, 1 is an exemplary view showing the configuration of the water purification block according to the present invention, Figure 2 is an exemplary view showing the configuration of the water purification body according to the present invention, Figure 3 is a block molding of various forms according to the present invention 4 is an exemplary view showing an installation state of a water purification block molded product according to the present invention, Figure 5 is an illustration showing another block molded body configuration according to the present invention,

본 발명에 따른 수질정화용 블록성형체(100)는 휴민 및 풀빅산이 함유된 수질정화체 10∼20중량%, 쇄석골재 35∼50중량%, 무기바인더 20∼42중량% 및, 물 10∼20중량%를 압축성형하여 블록성형체를 형성하도록 되어 있다. The water purification block molded body 100 according to the present invention comprises 10-20% by weight of water-purifying substances containing humin and fulvic acid, 35-50% by weight of crushed aggregate, 20-42% by weight of inorganic binder, and 10-20% by weight of water. Is compression molded to form a block molded body.

상기 수질정화체(40)는 블록성형체(100)내의 시멘트 독성제거 및, 수중의 오염물질과 중금속을 흡착제거하여 수질을 정화시키기 위한 것으로, 앨러페인 100 중량부에, 휴민 10∼30중량부를 혼합하여 앨러페인의 다공내에 휴민을 충전 및 흡착시키고, 상기 휴민이 충전 및 흡착된 앨러페인에 액상 풀빅산 5∼15중량부를 첨가하여 앨러페인의 표면을 코팅처리한 것이다. 도 1 은 수질정화체의 분포도를 보이기 위한 것으로, 상기 수질정화체는 시멘트의 입도와 큰 차이를 구비하지 않아 균일하게 혼합되게 된다.
The water purification body 40 is to purify the water quality by removing the toxicity of cement in the block molding body 100, and removing the pollutants and heavy metals in the water, by mixing 10-30 parts by weight of Humin with 100 parts by weight of allergy. Humin is filled and adsorbed in the pores of allergy, and the surface of the allergy is coated by adding 5-15 parts by weight of liquid fulvic acid to the allergy to which the humin is filled and adsorbed. 1 is to show the distribution of the water purification body, the water purification body does not have a large difference in the particle size of the cement is to be uniformly mixed.

상기 앨러페인(allophane,10)은 유효수분 함량이 우수하고, 공극율 약 70%의 결정구조를 갖지 않는 비정질 다공성 광물로, 표면적이 넓고, 수분 ·유기물, 중금속 등의 흡수력이 강한 특성을 구비하며, 특히, 풀빅산과 결합하기 쉬운 특성을 구비한다. The allophane (allophane, 10) is an amorphous porous mineral having excellent effective moisture content and no crystalline structure of about 70% of porosity, having a wide surface area, and having strong absorption ability of moisture, organic matter, heavy metals, etc. In particular, it has the characteristic of easy to combine with fulvic acid.

즉, 상기 앨러페인(10)은 휴민(20)과의 혼합에 의해 휴민(20)이 다공내로 충전 및 흡착된 상태를 유지하게 되고, 액상 풀빅산에 의해 앨러페인의 표면이 코팅됨과 동시에, 앨러페인이 풀빅산(30)과 결합되어 앨러페인(10)내에 휴민(20)과 풀빅산(30)이 안정적으로 유지되게 된다.That is, the allerphane 10 maintains the state in which the humin 20 is charged and adsorbed into the pores by mixing with the humin 20, and at the same time the surface of the allerphane is coated by the liquid fulvic acid, Payne is combined with fulvic acid 30 to maintain the humin 20 and fulvic acid 30 in the allerfein 10 stably.

이때, 상기 앨러페인(10)과 풀빅산(30)의 결합은 영구적인 결합이 아닌 일시적인 결합을 이루게 된다. 즉, 상기 풀빅산(30)은 표면장력 및 점성이 낮은 특성을 구비하는데 반하여, 비정질 다공성 광물인 앨러페인(10)은 풀빅산과 결합하기 쉬운 특성을 구비하고 있어, 액상 풀빅산에 의한 앨러페인의 표면코팅시 앨러페인에 풀빅산이 일시적으로 결합되는 상태를 구비하게 되며, 이와 같은 결합은 블록성형 후, 수중내에 설치시, 미생물에 의해 쉽게 분해되어지게 된다.
At this time, the combination of the allergy 10 and the fulvic acid 30 is to form a temporary bond rather than a permanent bond. That is, the fulvic acid 30 has low surface tension and low viscosity, whereas the allerphane 10, which is an amorphous porous mineral, has a property that is easy to bind with fulvic acid, and thus the Fulvic acid is temporarily bonded to the allergy during surface coating, such a bond is easily decomposed by microorganisms when installed in water after block molding.

상기 휴민(20)은 산성과 알칼리성의 모든 pH 조건에서 불용성을 띠고 있으며, 분자량이 크고 안정화된 물질로, 높은 중금속 흡착능력을 구비한다. The humin 20 is insoluble in all acidic and alkaline pH conditions, and has a high molecular weight and stabilized material, and has a high heavy metal adsorption capacity.

상기 휴민(20)은 화산회토(한라산 주변토양)를 CHCl3/MeOH(1:3,v/v) 혼합용매와 20∼30시간동안 반응시켜 free Lipid 성분을 추출 분리하고, 이를 염산으로 세척한 후, 수산화나트륨(NaOH)을 가하고 질소(N2)분위기하에서 20∼30시간동안 분리(shaking)한 침전물을 동결건조시킨 것이다.The Humin 20 reacted with volcanic ash (Hallasan surrounding soil) with CHCl 3 / MeOH (1: 3, v / v) mixed solvent for 20-30 hours to extract and separate the free Lipid component, which was washed with hydrochloric acid After that, sodium hydroxide (NaOH) was added and the precipitate which was shaken for 20-30 hours under nitrogen (N 2 ) atmosphere was lyophilized.

상기와 같이 이루어진 휴민(20)은 앨러페인(20)과의 혼합시, 앨러페인의 다공내로 충전 및 흡착되어, 블록성형체 및 수중내의 중금속을 흡착제거하게 된다. 또한, 상기 앨러페인의 특성 즉, 유기물 흡착능에 의해 휴민이 안정적으로 충전된 상태를 구비하게 된다.
Humin 20 made as described above is filled and adsorbed into the pores of the allergy, when mixed with the allergy, 20 to adsorb and remove the block and the heavy metal in the water. In addition, it has a state in which the humin is stably charged by the characteristics of the allergy, that is, the organic material adsorption capacity.

상기 액상 풀빅산은 휴믹산으로부터 추출한 과포화농축액으로, 풀빅산 20∼50중량%를 함유하는 진한 황갈색반투명 (Translucent)의 액체로서 pH는 2.5 ~ 4.5를 구비한다. 이와 같은 앨러페인의 표면코팅 및, 수계에 녹아있는 미량의 중금속 이온들과 착화합반응을 하여, 중금속을 제거하거나 운송하는 기능을 구비한다. The liquid fulvic acid is a supersaturated concentrate extracted from humic acid, and is a dark yellow translucent liquid containing 20 to 50% by weight of fulvic acid, and has a pH of 2.5 to 4.5. The surface coating of the allergy is combined with a small amount of heavy metal ions dissolved in the water system to have a function of removing or transporting heavy metals.

상기 액상 풀빅산은 토양(풀빅산 함유 토양)으로부터 추출된 액상 풀빅산을 발효숙성시켜 농축하거나, 토양(풀빅산 함유 토양)으로 부터 추출된 액상 풀빅산을 이산화탄소에 의해 처리하여 농도를 향상시킨 것을 사용한다. The liquid fulvic acid is concentrated by fermentation of the liquid fulvic acid extracted from the soil (pulvic acid containing soil), or the liquid fulvic acid extracted from the soil (pulvic acid containing soil) by using carbon dioxide to improve the concentration. do.

또한, 상기 액상 풀빅산은 15중량부를 초과하여 첨가될 경우, 오염물질의 흡착성능이 오히려 저하되는 현상이 발생되고, 5중량부 미만으로 첨가될 경우, 미생물 생육성능이 저하되는 문제점이 있다.
In addition, when the liquid fulvic acid is added in excess of 15 parts by weight, a phenomenon that the adsorption performance of the contaminants is rather reduced, when added to less than 5 parts by weight, there is a problem that the microbial growth performance is lowered.

상기 휴민 및 액상 풀빅산은 산성을 구비하나, 미생물 생육이 가능한 특성을 구비하고 있으며, 수분흡수성이 높아 자기중량의 약4.5배의 수분을 흡착한다.
The humin and the liquid fulvic acid have acidity, but have the property of growing microorganisms, and absorb water of about 4.5 times its own weight due to its high water absorption.

또한, 상기 휴민 및 풀빅산은 활성탄소보다 높은 흡착작용을 갖고 있어, 물리적인 표면흡착이 아니라 유기화학적으로 공중의 오염물질, 취기물질을 전리분해 하여 수질 뿐 아니라 공기 정화기능을 함께 구비한다.
In addition, the humin and fulvic acid has a higher adsorption action than activated carbon, and not only physical surface adsorption, but also organic chemically ionized decomposition of pollutants and odorous substances in the air, as well as water quality and air purification function.

또한, 상기 휴민 및 풀빅산은 공기중 및 수중내의 산소, 질소, 이산화탄소의 고정화작용이 강하여, 중금속 흡착제거 및 미생물에 영양소를 공급하는 기능을 동시에 구비한다.
In addition, the humin and fulvic acid has a strong immobilization action of oxygen, nitrogen, carbon dioxide in the air and in water, and has the function of simultaneously removing the heavy metal adsorption and supplying nutrients to microorganisms.

상기와 같이 이루어지는 본 발명은 수질정화체 10∼20중량%, 쇄석골재 45∼60중량%, 무기바인더 30∼45중량% 및, 물 10∼20중량%를 배합하고, 이를 60∼80㎏/㎠ 로 압축 성형하여 블록성형체(100)를 형성하며, 이와 같이 성형된 블록성형체는 압축강도(재령28일) 180∼200㎏f/㎠ 를 구비하게 되고, pH 8.0∼10.0 정도의 약알카리성을 구비한다.
The present invention made as described above is blended 10 to 20% by weight of water purification body, 45 to 60% by weight of crushed aggregate, 30 to 45% by weight of inorganic binder, and 10 to 20% by weight of water, which is 60 to 80 kg / cm 2 The block molded body 100 is formed by compression molding with a block molded body having a compressive strength (age 28 days) of 180 to 200 kg f / cm 2, and having weak alkalinity of about pH 8.0 to 10.0. .

상기 쇄석골재(60)는 3∼12㎜의 크기의 골재이고, 무기바인더는 포틀랜드 시멘트 등의 무기질 바인더를 사용한다.
The crushed aggregate 60 is an aggregate having a size of 3 to 12 mm, and an inorganic binder uses an inorganic binder such as portland cement.

또한, 본 발명은 수질정화체에 휴면포자된 미생물이 더 담지되도록 되어 있다. 즉, 본 발명은 미생물 배양탱크에 유해성분으로 철화합물을 첨가한 후 멸균처리된 블록성형체를 24시간 이상 함침시켜 수질정화체내에 미생물을 고정화시킴과 동시에 고정화된 미생물이 수질정화체내에서 휴면포자시켜, 블록성형체내에 미생물이 휴면포자된 상태로 고정화되도록 한다. In addition, the present invention is to further support the dormant spores in the water purification body. That is, the present invention impregnates the sterilized block molded body after adding iron compound as a harmful component to the microbial culture tank for more than 24 hours to immobilize the microorganisms in the water purification body and at the same time, the immobilized microorganisms dormant spores in the water purification body. The microorganisms are immobilized in dormant spores in the block molded body.

상기 철화합물은 황산철 또는 폴리황산철을 사용하고, 미생물 배양탱크내 배양액 100 중량부에 대하여 2∼4 중량부 첨가한다. 이와 같이 황산철 또는 폴리황산철이 첨가된 미생물 배양탱크내로 수질정화체가 침지되면, 수질정화체내의 기공내로 미생물이 고정화됨과 동시에, 첨가된 철화합물의 영향에 의해 수질정화체내 기공에서 일시적으로 휴면포자되게 된다. The iron compound uses iron sulfate or polyiron sulfate, and is added in an amount of 2 to 4 parts by weight based on 100 parts by weight of the culture solution in the microbial culture tank. As such, when the water purification body is immersed in the microbial culture tank to which the iron sulfate or the iron polysulfate is added, the microorganisms are immobilized into the pores of the water purification body, and at the same time, the doped spores are temporarily dormant in the pores of the water purification body under the influence of the added iron compound. do.

상기 철화합물은 4중량부를 초과하여 첨가될 경우, 미생물의 휴면포자화가 신속하게 진행되어 미생물고정화에 좋지 않은 영향을 줄 수 있으며, 2중량부 미만으로 첨가될 경우, 미생물의 휴면포자 진행속도가 느리게 되므로, 적정범위내로 첨가하여야 한다. When the iron compound is added in excess of 4 parts by weight, the dormant spores of the microorganisms are rapidly progressed and may adversely affect the microbial fixation. When the iron compound is added in an amount less than 2 parts by weight, the dormant spores of the microorganisms are slowed. Therefore, it should be added within an appropriate range.

상기 미생물은 Bacillus solisalsi(KCTC 13181), Bacillus alkalitelluris(KCTC 3947), Paenibacillus alkaliterrae(KCTC 3956), Cohnella laeviribosi(KCTC 3987), Streptomyces mexicanus(KCTC 9981), Streptomyces thermocarboxydus(KCTC 19532)으로 이루어진 미생물 군에서 하나 이상을 선택 혼합한다. The microorganism is composed of Bacillus solisalsi (KCTC 13181), Bacillus alkalitelluris (KCTC 3947), Paenibacillus alkaliterrae (KCTC 3956), Cohnella laeviribosi (KCTC 3987), Streptomyces mexicanus (KCTC 9981), Streptomyces thermocarboxydus (KCTC 19532) Select and mix more.

상기 Bacillus solisalsi(KCTC 13181)는 saline soil에서 분리되며, ellipsoidal endospore 형성하고, 생육가능온도 15∼53℃, 생육가능 pH 5∼13, NaCl tolerance : up to 15%을 구비하며, starch, casein, 저분자 지질(Tween 20) 분해 기능 및, 질산염 환원기능을 구비한다. The Bacillus solisalsi (KCTC 13181) is separated from the saline soil, forms ellipsoidal endospore, growth possible temperature 15 ~ 53 ℃, growth possible pH 5 ~ 13, NaCl tolerance: up to 15%, starch, casein, low molecular weight Lipid (Tween 20) decomposition function and nitrate reduction function.

상기 Bacillus alkalitelluris(KCTC 3947)는 폐광의 토양에서 분리되며, ellipsoidal endospore 형성하고, 생육가능온도 15∼40℃, 생육가능 pH 7∼11 (최적 조건이 pH 9.0), NaCl tolerance : up to 4% 및, starch 분해 기능을 구비한다. The Bacillus alkalitelluris (KCTC 3947) is isolated from the soil of the abandoned mine, forms ellipsoidal endospore, growth possible temperature 15-40 ℃, growth possible pH 7-11 (optimum condition pH 9.0), NaCl tolerance: up to 4% and , starch decomposition function.

상기 Paenibacillus alkaliterrae(KCTC 3956)는 soil에서 분리되며, ellipsoidal endospore 형성하고, 생육가능온도 10∼37℃, 생육가능 pH 7∼9.5 를 구비한다.The Paenibacillus alkaliterrae (KCTC 3956) is separated from the soil, forms ellipsoidal endospore, and has a growthable temperature of 10 to 37 ° C and a growthable pH of 7 to 9.5.

상기 Cohnella laeviribosi(KCTC 3987)는 volcanic soil에서 분리되며, ellipsoidal endospore 형성하고, 생육가능온도 30∼60℃, 생육가능 pH 5∼8 을 구비한다. The Cohnella laeviribosi (KCTC 3987) is separated from volcanic soil, forms ellipsoidal endospore, and has a growth possible temperature of 30 to 60 ° C and a growthable pH of 5 to 8.

상기 Streptomyces mexicanus(KCTC 9981)는 사탕수수밭의 soil에서 분리되고, green smooth spore을 형성(spherical or oval)하며, 생육가능온도 20∼55℃, 생육가능 pH 4.3∼8.0를 구비한다. The Streptomyces mexicanus (KCTC 9981) is separated from the soil of the sugar cane field, forms a green smooth spore (spherical or oval), and has a growth possible temperature of 20 to 55 ℃, a pH of 4.3 to 8.0.

상기 Streptomyces thermocarboxydus(KCTC 19532)는 grey, warty spore 형성하고, 생육가능온도 20∼55℃, 생육가능 pH 6∼8 를 구비한다.
Streptomyces thermocarboxydus (KCTC 19532) forms a grey, warty spore, and has a growthable temperature of 20 to 55 ° C and a growthable pH of 6 to 8.

상기 미생물은 모두 pH 5∼9 사이에서 활발하게 생육하는 특성을 구비하고 있어, pH 8.0∼10.0 을 구비하는 본 발명에 따른 블록성형체내에서 생육이 가능하다.All of the microorganisms have a characteristic of actively growing between pH 5 and 9, and are capable of growing in a block molded body according to the present invention having a pH of 8.0 to 10.0.

또한, 상기 수질정화체에는 풀빅산 및 휴민이 함유되어 있어, 미생물의 생육을 촉진시킴으로써, 수질정화를 더욱 향상시키게 된다.
In addition, the water purification body contains fulvic acid and humin, thereby promoting the growth of microorganisms, thereby further improving the water purification.

또한, 본 발명에 따른 수질정화용 블록성형체는 다중꼬임 혼합사(70) 3∼5 중량%를 더 포함한다. In addition, the water purification block molding according to the present invention further comprises 3 to 5% by weight of the multi-twist mixed yarn 70.

상기 다중꼬임 혼합사(70)는 10∼30㎜ 길이를 구비하고, 콘크리트 블록의 강도를 유지하면서 수질정화체 사이를 연결하여 휴믹 및 풀빅산의 수중분해 및 분리효율을 높이고, 미생물의 서식공간을 제공하기 위한 것으로, 폴리섬유, 합성섬유, 목질섬유 및 면섬유 등이 첨가되며, 다중꼬임을 구비하도록 2가닥 이상의 혼합사가 꼬임을 이루도록 되어 있다.
The multi-twist mixed yarn 70 has a length of 10 ~ 30㎜, while maintaining the strength of the concrete block is connected between the water purification body to increase the hydrolysis and separation efficiency of the humic and fulvic acid, and the habitat space of the microorganism To provide, poly fibers, synthetic fibers, wood fibers and cotton fibers, etc. are added, and two or more mixed yarns are twisted to have multiple twists.

이하, 본 발명을 실시예에 의해 상세히 설명하면 다음과 같다. Hereinafter, the present invention will be described in detail by way of examples.

실시예 1Example 1

앨러페인 100 중량부에, 휴민 20중량부를 혼합하고, 앨러페인에 액상 풀빅산 20중량부를 첨가하여 앨러페인의 표면을 코팅한 후, 이를 자연건조하여 수질정화체를 형성하였다. 20 parts by weight of humin was mixed with 100 parts by weight of allergy, and 20 parts by weight of liquid fulvic acid was added to the allergy to coat the surface of the allergy, and then it was naturally dried to form a water purification body.

상기와 같이 제조된 수질정화체 15중량%, 쇄석골재 45중량%, 무기바인더 20중량% 및, 물 20중량%를 배합하고, 이를 압축성형하여 블록성형체(190×90×57)를 형성하였다.15% by weight of the water purification product prepared as described above, 45% by weight of crushed aggregate, 20% by weight of inorganic binder, and 20% by weight of water were combined and compression molded to form a block molded product (190 × 90 × 57).

상기와 같이 제조된 블록성형체를 수로(가로 15.0ｍ, 세로 1.0ｍ, 높이 0.5ｍ)의 바닥면 2층으로 포개어 설치하고, 블록성형체로의 유입 및 블록성형체를 통과하여 유출되는 물에 대한 총질소(TN), 총인(TP), 유기물(COD)을 측정하였으며, 그 결과는 아래의 [표1]과 같다. The block molded body manufactured as described above is installed in two layers of the bottom surface of a water channel (15.0 m long, 1.0 m long, 0.5 m high), and the total nitrogen of the water flowing into and out of the block molded body. (TN), total phosphorus (TP) and organic matter (COD) were measured, and the results are shown in Table 1 below.

이때, 상기 수로는 평균유속 80㎝/sec의 흐름을 구비하도록 형성하였으며, 약 60일간의 변화에 대하여 측정하였다. At this time, the channel was formed to have an average flow rate of 80 cm / sec, was measured for a change of about 60 days.

[표1]Table 1

Figure 112012066392687-pat00001
Figure 112012066392687-pat00001

위의 [표1]에서, 본 발명에 따른 블록성형체의 설치 후 약 2주 경과시, 총질소(TN), 총인(TP), 유기물(COD)을 유출량이 급격히 감소되고 있음을 알 수 있으며, 설치 4주후 총질소(TN) 및 총인(TP)의 유출량은 2급수 수준으로 나타났다.
In the above [Table 1], after about two weeks after the installation of the block molding according to the present invention, it can be seen that the total nitrogen (TN), total phosphorus (TP), organic matter (COD) flow rate is rapidly reduced, Four weeks after installation, the total nitrogen (TN) and total phosphorus (TP) outflows were at the second level.

실시예 2Example 2

앨러페인 100 중량부에, 휴민 20중량부를 혼합하고, 앨러페인에 액상 풀빅산 20중량부를 첨가하여 앨러페인의 표면을 코팅한 후, 이를 자연건조하여 수질정화체를 형성하였다. 20 parts by weight of humin was mixed with 100 parts by weight of allergy, and 20 parts by weight of liquid fulvic acid was added to the allergy to coat the surface of the allergy, and then it was naturally dried to form a water purification body.

상기와 같이 제조된 수질정화체 15중량%, 쇄석골재 45중량%, 무기바인더 20중량% 및, 물 20중량%를 배합하고, 이를 압축성형하여 블록성형체(190×90×57)를 형성하였으며, 15% by weight of the water purification product prepared as described above, 45% by weight of crushed aggregate, 20% by weight of inorganic binder, and 20% by weight of water were combined and compression molded to form a block molded product (190 × 90 × 57).

상기 블록성형체를 철화합물이 첨가된 미생물 배양탱크내에 24시간 함침시킨 후, 48시간 건조하여, 수로(가로 15.0ｍ, 세로 1.0ｍ, 높이 0.5ｍ)의 바닥면 2층으로 포개어 설치하고, 블록성형체로의 유입 및 블록성형체를 통과하여 유출되는 물에 대한 총질소(TN), 총인(TP), 유기물(COD)을 측정하였으며, 그 결과는 아래의 [표2]와 같다. The block molded product was impregnated in a microorganism culture tank to which iron compound was added for 24 hours, and then dried for 48 hours. The block molded product was stacked on two floors of a water channel (15.0 m long, 1.0 m long and 0.5 m high), and the block molded body was installed. The total nitrogen (TN), total phosphorus (TP), and organic matter (COD) of the inflow into the furnace and the outflow through the block molded product were measured, and the results are shown in [Table 2] below.

이때, 상기 수로는 평균유속 80㎝/sec의 흐름을 구비하도록 형성하였으며, 약 60일간의 변화에 대하여 측정하였다. At this time, the channel was formed to have an average flow rate of 80 cm / sec, was measured for a change of about 60 days.

[표2][Table 2]

Figure 112012066392687-pat00002

Figure 112012066392687-pat00002

실시예 3Example 3

실시예1 에 따른 블록성형체를 수로(가로 10ｍ, 세로 2ｍ, 높이 1ｍ)의 내로 바닥면에 설치하고, 카드뮴, 구리, 납, 아연 등이 함유된 오염수를 수로로 12시간 연속 순환시킨 후, 중금속 함유량을 분석하였다. 그 결과는 중금속이 전체적으로 약 35∼62% 제거됨을 확인할 수 있었다.
After the block molded body according to Example 1 was installed at the bottom of a channel (10 m in width, 2 m in height, 1 m in height), and contaminated water containing cadmium, copper, lead, zinc and the like was continuously circulated for 12 hours in a water channel. Heavy metal content was analyzed. As a result, it was confirmed that about 35-62% of the heavy metals were removed as a whole.

본 발명은 상술한 특정의 바람직한 실시예에 한정되지 아니하며, 청구범위에서 청구하는 본 발명의 요지를 벗어남이 없이 당해 발명이 속하는 기술분야에서 통상의 지식을 가진 자라면 누구든지 다양한 변형실시가 가능한 것은 물론이고, 그와 같은 변경은 청구범위 기재의 범위내에 있게 된다.
The present invention is not limited to the above-described specific preferred embodiments, and various modifications can be made by any person having ordinary skill in the art without departing from the gist of the present invention claimed in the claims. Of course, such changes will fall within the scope of the claims.

(10) : 앨러페인 (20) : 휴민
(30) : 풀빅산 (40) : 수질정화체
(50) : 무기바인더 (60) : 쇄석골재
(70) : 다중꼬임 혼합사 (100) : 블록성형체(10): Alpine Pain (20): Humin
(30): fulvic acid (40): water purification body
(50): Inorganic Binder (60): Crushed Aggregate
(70): multi-twist mixed yarn (100): block molding

Claims (7)

휴민 및 풀빅산이 함유된 수질정화체 10∼20중량%,
쇄석골재 35∼50중량%,
무기바인더 20∼42중량% 및,
물 10∼20중량%를 압축성형하여 형성하되,
상기 수질정화체는 앨러페인 100 중량부에, 휴민 10∼30중량부를 혼합하여 앨러페인의 다공내에 휴민을 충전 및 흡착시키고, 상기 휴민이 충전 및 흡착된 앨러페인에 액상 풀빅산 5∼15중량부를 첨가하여 앨러페인의 표면을 풀빅산에 의해 코팅처리한 것을 특징으로 하는 풀빅산 및 휴민이 함유된 수질정화체를 이용한 수질정화용 블록성형체.
10-20% by weight of water purification bodies containing humin and fulvic acid,
Crushed aggregate 35-50% by weight,
Inorganic binder 20 to 42% by weight,
10 to 20% by weight of water is formed by compression molding,
The water purifier is mixed with 100-30 parts by weight of allahine and 10-30 parts by weight of humin to fill and adsorb the humin in the pores of the allergy, and 5-15 parts by weight of liquid fulvic acid to the allergy to which the humin is filled and adsorbed. A block molded product for water purification using a water purification substance containing fulvic acid and humin, which is added and coated with a fulvic acid surface.
삭제delete 청구항 1 에 있어서;
상기 휴민은 화산회토를 CHCl3/MeOH(1:3,v/v) 혼합용매와 20∼30시간동안 반응시켜 free Lipid 성분을 추출 분리하고, 이를 염산으로 세척한 후, 수산화나트륨(NaOH)을 가하고 질소(N2)분위기하에서 20∼30시간동안 분리(shaking)한 침전물을 동결건조시킨 것을 특징으로 하는 풀빅산 및 휴민이 함유된 수질정화체를 이용한 수질정화용 블록성형체.
The method of claim 1,
The Humin reacted volcanic ash with CHCl 3 / MeOH (1: 3, v / v) mixed solvent for 20-30 hours to extract and separate free Lipid components, washed with hydrochloric acid, and then sodium hydroxide (NaOH) A block molded product for water purification using water purifiers containing fulvic acid and humin, wherein the precipitate is lyophilized after being added and shaken for 20 to 30 hours in a nitrogen (N 2 ) atmosphere.
청구항 1 에 있어서;
상기 액상 풀빅산은 휴믹산으로부터 추출한 과포화농축액으로, 풀빅산 20∼50중량%를 함유하는 것을 특징으로 하는 풀빅산 및 휴민이 함유된 수질정화체를 이용한 수질정화용 블록성형체.
The method of claim 1,
The liquid fulvic acid is a supersaturated concentrate extracted from a humic acid, and the block molding for water purification using a qualic acid containing fulvic acid and humin, characterized in that it contains 20 to 50% by weight.
청구항 4 에 있어서;
상기 액상 풀빅산은 토양(풀빅산 함유 토양)으로부터 추출된 액상 풀빅산을 발효숙성시켜 농축하거나, 토양(풀빅산 함유 토양)으로 부터 추출된 액상 풀빅산을 이산화탄소에 의해 처리하여 농도가 높도록 조절한 것을 풀빅산 및 휴민이 함유된 수질정화체를 이용한 수질정화용 블록성형체.
The method of claim 4,
The liquid fulvic acid is concentrated by fermentation of the liquid fulvic acid extracted from the soil (pulvic acid containing soil), or adjusted to have a high concentration by treating the liquid fulvic acid extracted from the soil (pulvic acid containing soil) with carbon dioxide. A block molded product for water purification using a water purifier containing fulvic acid and humin.
청구항 1 에 있어서;
상기 수질정화체내에는 미생물이 휴면포자된 상태로 고정화되고,
미생물의 고정화는 유해성분으로 철화합물이 첨가된 미생물 배양탱크내에 블록성형체를 24시간 이상 함침시켜 블록성형체내에서 미생물을 휴면포자된 상태로 고정화되도록 한 것을 특징으로 하는 풀빅산 및 휴민이 함유된 수질정화체를 이용한 수질정화용 블록성형체.
The method of claim 1,
The microorganism is immobilized in a dormant spore state in the water purification body,
Immobilization of microorganisms is water quality containing fulvic acid and humin, which impregnates the block molded body in a dormant spore state in the block molded body by impregnating the block molded body in the microbial culture tank to which the iron compound is added as a harmful component for 24 hours or more. Block forming body for water purification using purified body.
청구항 1 에 있어서;
다중꼬임 혼합사 3∼5 중량%를 더 포함하는 것을 특징으로 하는 풀빅산 및 휴민이 함유된 수질정화체를 이용한 수질정화용 블록성형체.The method of claim 1,
A water molding for water purification using fulvic acid and humin-containing water purification body, characterized in that it further comprises 3 to 5% by weight of multi-twist mixed yarn.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103936088A (en) * 2014-04-25 2014-07-23 大连金海湾养殖科技有限公司 Precious marine product aquaculture ecological water quality modifier as well as preparation method and application thereof
JP2015147702A (en) * 2014-02-05 2015-08-20 株式会社Ａｏｉ Method of producing activated fulvic acid and aqueous solution comprising activated fulvic acid
KR101563401B1 (en) * 2013-09-10 2015-10-26 최부섭 Organic waste treatment agent and fuelization method of organic waste using the same
KR102255933B1 (en) 2020-09-07 2021-05-26 (주)주원산업 Concrete product composition containing water purification ingredients and manufacturing method of concrete product using the same
KR102274556B1 (en) * 2021-02-02 2021-07-07 허교 Composition for removing harmful algae and block manufactured using the same

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KR100766555B1 (en) 2007-06-08 2007-10-12 (주)한국바이오콘 Bioecological mixture, bio products and manufacture method thereof

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KR100766555B1 (en) 2007-06-08 2007-10-12 (주)한국바이오콘 Bioecological mixture, bio products and manufacture method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101563401B1 (en) * 2013-09-10 2015-10-26 최부섭 Organic waste treatment agent and fuelization method of organic waste using the same
JP2015147702A (en) * 2014-02-05 2015-08-20 株式会社Ａｏｉ Method of producing activated fulvic acid and aqueous solution comprising activated fulvic acid
CN103936088A (en) * 2014-04-25 2014-07-23 大连金海湾养殖科技有限公司 Precious marine product aquaculture ecological water quality modifier as well as preparation method and application thereof
KR102255933B1 (en) 2020-09-07 2021-05-26 (주)주원산업 Concrete product composition containing water purification ingredients and manufacturing method of concrete product using the same
KR102274556B1 (en) * 2021-02-02 2021-07-07 허교 Composition for removing harmful algae and block manufactured using the same

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