KR101016392B1 - Coagulant compositions for water/wastewater treatment by using zirconium compounds and water/wastewater treatment method using the same - Google Patents

Coagulant compositions for water/wastewater treatment by using zirconium compounds and water/wastewater treatment method using the same Download PDF

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KR101016392B1
KR101016392B1 KR1020100086998A KR20100086998A KR101016392B1 KR 101016392 B1 KR101016392 B1 KR 101016392B1 KR 1020100086998 A KR1020100086998 A KR 1020100086998A KR 20100086998 A KR20100086998 A KR 20100086998A KR 101016392 B1 KR101016392 B1 KR 101016392B1
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zirconium
coagulant
water
component
sulfate
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KR1020100086998A
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Korean (ko)
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한승우
최영근
최기충
강임석
송광섭
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주식회사 수엔텍
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    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5209—Regulation methods for flocculation or precipitation
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

PURPOSE: A coagulant composition for the water treatment, and a water treatment method using thereof are provided to improve the coagulating efficiency during a water treatment process by applying the coagulant composition for water purifying and sewage processing processes. CONSTITUTION: A coagulant composition for the water treatment contains the following: an aluminum salt based inorganic coagulant selected from the group consisting of aluminum sulfate, poly aluminum chloride silicate, and poly aluminum silicate sulfate; a ferric salt based inorganic coagulant; and a zirconium compound.

Description

지르코늄을 이용한 수처리용 응집제 조성물 및 이를 이용한 수처리 방법{Coagulant compositions for water/wastewater treatment by using zirconium compounds and water/wastewater treatment method using the same}Coagulant compositions for water / wastewater treatment by using zirconium compounds and water / wastewater treatment method using the same}

본 발명은 수처리용 응집제 조성물 및 이를 이용한 수처리 방법에 관한 것으로, 구체적으로는 알루미늄염계 무기응집제 또는 철염계 무기응집제에 지르코늄화합물이 함유된 수처리용 응집제 조성물 및 이를 이용한 수처리 방법에 관한 것이다.The present invention relates to a flocculant composition for water treatment and a water treatment method using the same, and more particularly, to a flocculant composition for water treatment containing a zirconium compound in an aluminum salt-based inorganic coagulant or an iron salt-based inorganic coagulant and a water treatment method using the same.

일반적으로 상수처리, 하수처리 및 제지산업의 수처리 등의 폐수처리를 위하여 무기응집제인 철염계 무기응집제 또는 알루미늄염계 무기응집제가 널리 사용되고 있으며, 철염계 또는 알루미늄염계 등 무기응집제들을 단독으로 사용되는 경우 그 사용량을 증가시켜도 응집공정에서 부유물, 용존 유기물질 등이 적절하게 제거되지 않는 경우가 있어 이를 해결하기 위해서는 고도 정수처리의 부하량을 증가시켜야하기 때문에 수돗물 가격의 인상효과가 커지는 부작용이 발생한다는 점 외에도 홍수나 기타 다른 원인에 의해 일시적으로 원수의 탁도가 높아지거나 pH의 변화가 심한 여름철의 경우에는 무기응집제 단독으로는 효과적인 응집이 어려운 문제점이 있다.Generally, inorganic salt coagulant or aluminum salt inorganic coagulant, which is inorganic coagulant, is widely used for waste water treatment such as water treatment, sewage treatment and water treatment in paper industry. Increasing the amount of use does not properly remove suspended solids and dissolved organic substances in the flocculation process.In order to solve this problem, it is necessary to increase the load of advanced water purification treatment. In addition, in the summer, when the turbidity of the raw water is temporarily increased due to other causes or when the pH change is severe, the effective aggregation of the inorganic coagulant alone is difficult.

그리고, 최근 발표된 논문들에 의하면 정수처리에 있어서 알루미늄계 무기응집제의 과다 사용으로 인한 처리수 내의 높은 잔류알루미늄 농도는 알츠하이머병(Alzheimer's disease)이라 불리는 노인성 치매와 같은 뇌 질환을 일으키는 한 원인으로 보고되고 있어, 이에 따라 알루미늄의 유해성을 인식한 유럽공동체는 음용수 중에 알루미늄의 허용치를 0.05㎎/ℓ로 규제할 것을 권고하고 있고, 세계 보건기구(WHO)는 0.2㎎/ℓ이하로, 그리고 미국의 경우는 제 2종 음용수 기준에서 0.1㎎/ℓ 이하로 잔류하게 할 것을 권장하고 있으며, 우리나라의 경우는 1996년부터 0.2㎎/ℓ 이하로 규제하고 있다.And recently published papers report that high residual aluminum concentration in treated water due to overuse of aluminum-based inorganic coagulant in water treatment is one cause of brain disease such as senile dementia called Alzheimer's disease. As a result, the European Community, which is aware of the hazards of aluminum, recommends a limit of 0.05 mg / l for drinking water, while the World Health Organization (WHO) has below 0.2 mg / l and the United States. Recommend to remain less than 0.1mg / ℓ in the second type of drinking water standards, and in 1996, Korea has been regulated to less than 0.2mg / ℓ.

또 철염계 무기 응집제의 경우는 과다 사용시 처리수가 벌겋게 되는 착색현상과 많은 양의 슬러지가 발생하는 문제점이 있으며 또 철 박테리아(Iron bacteria)에 의해 냄새를 유발시키거나 Fe(OH)₃을 형성하여 관 내부에 침전·부착되어 스케일(scale)을 유발시키는 문제가 있고, 국내에서 철염의 응집제는 대부분이 제철 또는 제강공장에서 부산물로 생산되는 제일철을 원료로 사용하여 생산된 제품이므로 정수처리에 부적합한 현실에 따라 정수용으로 사용은 되지 않고 주로 폐수처리에 많이 사용되고 있다.In the case of the iron salt-based inorganic flocculant, there is a problem in that the treated water is excessively colored and a large amount of sludge is generated.In addition, the iron salt-based inorganic flocculant causes an odor by iron bacteria or forms Fe (OH) ₃. There is a problem of causing scale due to sedimentation and adhesion inside, and the coagulant of iron salt in Korea is mostly produced by using ferrous iron, which is produced as a by-product of steelmaking or steel mills, as a raw material. Therefore, it is not used for water purification but is mainly used for wastewater treatment.

일반적으로 알루미늄 혹은 철염계 무기 응집제들은 주로 흡착(adsorption)과 전하중화(charge neutralization)에 의해 콜로이드 입자를 불안정화시키므로 3가 이온으로서 그 작용에는 한계가 있다.In general, aluminum or iron salt-based inorganic flocculant destabilizes colloidal particles mainly by adsorption and charge neutralization, so the function of trivalent ions is limited.

이러한 문제점을 개선한 응집제 관련 기술로 국내 등록특허공보 등록번호 10-0497992호에 폴리규산화염화황산알루미늄을 개시하고 있으며, 국내 등록특허공보 등록번호 10-0310785호에 황산알루미늄, 폴리염화알루미늄, 폴리염화알루미늄규산, 폴리황산규산, 알루미늄(PASS)으로부터 선택되는 1종의 무기응집제에 폴리아민계 고분자응집제 혼합한 폴리아민계 고분자응집제를 이용한 정수처리방법을 개시하고 있다.As a flocculant-related technology that improves these problems, Korean Patent Publication No. 10-0497992 discloses polysilicate aluminum sulfate, and Korean Patent Publication No. 10-0310785 discloses aluminum sulfate, polyaluminum chloride, and poly Disclosed is a water treatment method using a polyamine polymer coagulant, in which a polyamine polymer coagulant is mixed with one inorganic coagulant selected from aluminum chloride silicate, polysulfite silicate, and aluminum (PASS).

본 발명은 기존의 무기응집제보다 응집효율이 우수하고, 특히 하ㆍ폐수처리에서 유기물 및 질소, 인 등을 동시에 제거하기 위하여 지르코늄화합물을 병용 사용하는 응집제 조성물에 관한 기술로서, 질소, 인 등을 동시에 제거하는 선행기술로는 국내 등록특허공보 등록번호 10-0342171호에 칼슘형 인공 제올라이트가용성 알루미늄계 또는 철염계 화합물 천연 또는 합성 고분자응집제, 알칼리금속의 탄산염분립체 및 칼슘화합물, 알칼리토류금속의 탄산염류, 이산화티탄 및 분말활성탄으로 이루어진 군으로부터 2종 이상을 선택한 응집제를 개시하고 있으나 흡착제 및 고분자응집제 등 복수의 응집성분을 조합하고 있는 기술이며, 또 대한환경공학회지, 제31권 제3호, p.203~207에 지르코늄 실리케이트를 응집보조제로 사용한 연구결과에 대한 논문이 개재되어 있으나, 질소와 인에 대한 제거능력에 대하여 어떠한 언급도 없다.The present invention is superior to the existing inorganic coagulant, and more particularly, and a technology for coagulant composition using zirconium compound in combination to remove organic matter, nitrogen and phosphorus at the same time in sewage and wastewater treatment. As a prior art to remove, in Korean Patent Publication No. 10-0342171, calcium-type artificial zeolite soluble aluminum- or iron salt-based compound natural or synthetic polymer coagulant, carbonate granules and alkali compounds of alkali metals, carbonates of alkaline earth metals , A coagulant selected from the group consisting of titanium dioxide and powdered activated carbon is disclosed, but it is a technology combining a plurality of agglomerates such as adsorbents and polymer coagulants, and Journal of Korean Society of Environmental Engineers, Vol. 31, No. 3, p. In 203 ~ 207, a paper about the results of the research using zirconium silicate as coagulant aid is published. However, no mention is made of the ability to remove nitrogen and phosphorus.

본 발명은 종래의 제반 문제점을 해소하고 정수 및 하ㆍ폐수처리에 있어서 응집효율을 증대시키기 위한 수처리용 응집제 조성물 및 이를 이용한 수처리 방법을 제공하는 것에 목적이 있으며, 보다 상세하게는 정수 및 하ㆍ폐수처리에 알루미늄염계 응집제 또는 철염계 무기응집제에 지르코늄 화합물을 포함하는 응집제를 적용하여 수처리 공정 중 응집공정에서의 응집효율 개선에 따른 수질개선과 유기물 및 질소와 인을 동시에 제거 가능한 응집제 조성물 및 이를 이용한 수처리 방법을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a flocculant composition for water treatment and a water treatment method using the same to solve the conventional problems and to increase the flocculation efficiency in water and sewage and wastewater treatment. Coagulant composition which can remove water quality and organic matter, nitrogen and phosphorus at the same time by applying coagulant containing zirconium compound to aluminum salt coagulant or iron salt inorganic coagulant in the treatment process. It is an object to provide a method.

또한, 본 발명은 음용수의 정수처리 시에는 응집과정에서의 응집효율 개선에 따른 수질개선과 발생되는 슬러지의 부피를 감소시키고, 잔류알루미늄의 감소, 착색현상을 방지하며, 고탁도시에도 원활한 응집능력을 발휘하며, 조류 제거에도 효과가 있는 응집제 조성물 및 이를 이용한 정수처리방법을 제공하는 것을 목적으로 한다.In addition, the present invention is to improve the water quality and the volume of sludge generated by the improvement of the flocculation efficiency in the coagulation process during drinking water purification, to prevent the reduction of residual aluminum, coloration, and smooth cohesion ability even in high turbidity It is an object of the present invention to provide a flocculant composition which is effective in removing algae and a water treatment method using the same.

본 발명은 상기한 목적 달성을 위한 해결수단으로 (a)성분으로 황산알루미늄(Alum), 폴리염화알루미늄(PAC), 폴리염화규산알루미늄(PACS) 및 폴리황산규산알루미늄(PASS)으로 구성된 군으로부터 선택되는 1종 이상의 알루미늄계 무기응집제 또는 (b)성분으로 염화제이철(Ferric chloride, FeCl₃), 염화제일철(Ferrous chloride, FeCl₂), 황산제이철(Ferric sulfate, Fe₂(SO₄)₃), 황산제일철(Ferrous sulfate, Fe(SO)₄), 폴리염화철(polyferric chloride, PFC), 폴리황산철(polyferric sulfate, PFS) 및 폴리규산철(polysilicate iron)로 구성된 군으로부터 선택되는 1종 이상의 철염계 무기응집제에, (c)성분으로 지르코늄 화합물을 조합하는 것으로 이루어진다.The present invention is selected from the group consisting of aluminum sulfate (Alum), polyaluminum chloride (PAC), polyaluminum silicate chloride (PACS) and polyaluminum silicate silicate (PASS) as a solution for achieving the above object (a) component Ferric chloride (Ferric chloride, FeCl₃), ferrous chloride (FeCl₂), ferric sulfate (Ferric sulfate, Fe₂ (SO₄) ₃), ferrous sulfate , At least one iron salt-based inorganic coagulant selected from the group consisting of Fe (SO) ₄), polyferric chloride (PFC), polyferric sulfate (PFS) and polysilicate iron, c) a zirconium compound as a component.

상기한 (c)성분인 지르코늄 화합물은 수산화지르코늄, 규산지르코늄, 산화지르코늄 및 지르코늄의 화합물로 구성된 군으로부터 선택되며, 또 상기한 (a)성분인 알루미늄계 무기응집제, (b)성분인 철염계 무기응집제 및 (c)성분인 지르코늄 화합물의 배합량은 (a)성분 또는 (b)성분의 부피에 대하여 100㎎/ℓ 내지 5,000㎎/ℓ 범위로 배합되며, 이때 100mg/ℓ 미만인 경우에는 응집효과를 발현하기 어렵고, 5,000㎎/ℓ를 초과하는 경우에는 지르코늄화합물의 초과량에 따라 비례적으로 응집효과가 나타나는 것이 아니므로 본 발명에서 제시하는 범위 내로 혼합하는 것이 경제적인 측면이나 효율성 면에서도 가장 바람직하다.The zirconium compound as the component (c) is selected from the group consisting of a compound of zirconium hydroxide, zirconium silicate, zirconium oxide and zirconium, and the aluminum-based inorganic coagulant as the component (a), and the iron salt inorganic as the (b) component. The blending amount of the coagulant and the zirconium compound as the component (c) is in the range of 100 mg / L to 5,000 mg / L based on the volume of the component (a) or (b), and when less than 100 mg / L, the coagulation effect is expressed. In case of exceeding 5,000 mg / l, the coagulation effect does not occur proportionally according to the excess amount of the zirconium compound, so it is most preferable in terms of economics and efficiency to mix within the range suggested by the present invention.

예를 들면, 정수처리의 경우에 있어서는 원수의 탁도가 100NTU 이상인 고탁도의 경우, 상기한 (a)성분 또는 (b)성분인 무기응집제 1ℓ당 규산지르코늄을 500㎎/ℓ 내지 1,000㎎/ℓ의 비율로 사용되며, 또 원수의 pH가 8에서 10까지 높은 경우, 규산지르코늄을 100㎎/ℓ 내지 500㎎/ℓ의 비율로 사용한다. 또 하ㆍ폐수처리의 경우에 있어서는 원수의 SS가 3,000㎎/ℓ 이상이거나 질소와 인이 다량 함유된 경우에는 규산지르코늄은 1,000㎎/ℓ 내지 5,000㎎/ℓ의 비율로 사용된다.For example, in the case of water treatment, in the case of high turbidity of 100 NTU or more of turbidity of raw water, 500 mg / L to 1,000 mg / L of zirconium silicate per liter of inorganic coagulant of (a) component or (b) component It is used in a ratio, and when the pH of raw water is high from 8 to 10, zirconium silicate is used in a ratio of 100 mg / L to 500 mg / L. In the case of sewage and wastewater treatment, zirconium silicate is used at a rate of 1,000 mg / l to 5,000 mg / l when SS of raw water is 3,000 mg / l or more or when nitrogen and phosphorus are contained in a large amount.

또한, 본 발명은 상기한 (a)성분 또는 (b)성분에 (c)성분을 조합한 수처리용 응집제 조성물은 정수 및 하ㆍ폐수처리수의 부피기준으로 약 10 내지 100㎎/ℓ로 투입하며, 20 ~ 60㎎/ℓ 로 투입하는 것이 바람직하며, 본 발명의 투입량은 통상 사용되는 응집제 사용량의 약 1/3 ~ 1/2수준으로 투입하여도 유기물 및 질소와 인이 동시에 제거되는 수처리 방법으로 이루어진다.In addition, the present invention is a coagulant composition for water treatment combining the (a) component or the component (b) with the component (c) in about 10 to 100mg / l based on the volume of purified water and sewage and wastewater treatment water , 20 ~ 60mg / L is preferably added, the input amount of the present invention is a water treatment method to remove the organic matter and nitrogen and phosphorus at the same time even if the input to the level of about 1/3 to 1/2 of the amount of flocculant used commonly Is done.

일반적으로 상수 및 하ㆍ폐수에 분산되어 부유하고 있는 물질의 대부분은 0.1㎛ 내지 100㎛의 입자크기를 가지는 침전하기 어려운 부유물질로 구성되어 있으며, 1㎛ 내지 100㎛의 입자크기를 가지는 부유입자는 침전 불가능한 콜로이드상 미립자이며, 상수 내의 고형물들은 콜로이드 입자의 범위를 벗어나는 입자크기를 갖음에도 불구하고 역시 콜로이드 입자처럼 대부분은 침전속도를 무시해도 좋을 만큼 느린 침전특성을 가진다는 것이다.In general, most of the suspended solids dispersed in water and wastewater are composed of suspended solids which have a particle size of 0.1 μm to 100 μm and suspended particles having a particle size of 1 μm to 100 μm. It is colloidal fine particles that cannot be precipitated, and the solids in the constant have a particle size that is out of the range of the colloidal particles, but, like colloidal particles, most of them have precipitation characteristics that are negligible.

콜로이드상 용수나 폐수가 응집제(coagulant)에 의해 응집되는 대표적인 메커니즘으로는 (1)전기 2중층의 감소(double-layer compression), (2)흡착과 충전 전하중화(adsorption and chargeneutralization), (3)체거름 응집(enmeshment in precipitate), (4)흡착과 입자상호 간의 가교작용(adsorption and interparticle bridging)과 같은 4가지의 형태를 들 수 있으며, 철염계 혹은 알루미늄계 무기응집제들은 3가 이온으로서 흡착(adsorption)과 전하중화 (charge neutralization)에 의해 콜로이드 입자를 불안정화시키는 작용에 한계가 있다.Representative mechanisms in which colloidal water or wastewater are coagulated by coagulants include (1) double-layer compression, (2) adsorption and chargeneutralization, (3) (4) Adsorption and interparticle bridging. Four types of iron salt or aluminum inorganic coagulants are adsorbed as trivalent ions. There is a limit to the action of destabilizing colloidal particles by adsorption and charge neutralization.

상기한 본 발명에 따른 수처리용 응집제 조성물 및 수처리 방법은 4가의 지르코늄 화합물을 혼합하여 3가의 양이온과 4가의 양이온을 공존시켜 3가의 한계를 넘어 우수한 흡착(adsorption)과 전하중화(charge neutralization)에 의한 상승된 응집효율을 나타낼 뿐 아니라 각 정수장에서 사용하고 있는 무기응집제 주입량의 약 1/3 ~ 1/2 수준으로 사용할 수 있는 유리한 점에 의해 여름철이나 겨울철 등 계절에 따라 적절하게 선택되어 수중의 콜로이드 입자들을 응집하여 플럭을 형성시켜 유기물 제거 및 수질개선에 큰 역할을 하게 된다.The coagulant composition for water treatment and the water treatment method according to the present invention are mixed with a trivalent zirconium compound to coexist trivalent cations and tetravalent cations, resulting in excellent adsorption and charge neutralization beyond the limits of trivalent. Not only does it show an increased cohesive efficiency, it is also appropriately selected according to the season, such as summer or winter, by the advantage that it can be used at about 1/3 to 1/2 of the amount of inorganic coagulant injected in each water treatment plant. By flocculating these flocs, they play a big role in organic matter removal and water quality improvement.

또한, 본 발명은 지르코늄이 갖는 질소를 흡수하는 특성을 이용하여 알루미늄염 및 철염계 무기 응집제와 지르코늄 화합물을 혼합한 응집제에 의해 폐수에서 문제시되는 유기물과 부영양화의 원인물질인 질소와 인을 동시에 제거할 수 있으므로 정수 및 하폐수 처리장에서의 응집능력을 더욱 극대화시킬 수 있게 된다.In addition, the present invention utilizes the property of absorbing nitrogen of zirconium to simultaneously remove nitrogen and phosphorus, which are problematic substances in wastewater, by flocculant mixed with aluminum salt, iron salt-based inorganic flocculant and zirconium compound. As a result, it is possible to further maximize the flocculation capacity of the purified and sewage treatment plants.

상기한 본 발명에서 사용되는 지르코늄 화합물은 수산화지르코늄, 규산지르코늄 및 산화지르코늄으로 구성된 군으로부터 선택되며, 바람직하게는 규산지르코늄을 사용한다. 지르코늄화합물 1종을 왕수(aqua regia)나 플루오르수소(HF)에 용해시켜 수용액 상태로 사용하며, 구체적인 용해방법은 유리로 코팅된 용해조에 상온조건하에서 염산 3부피에 질산 1부피를 천천히 투입하면서 왕수를 조제하여 조제된 왕수에 일정량의 규산지르코늄을 용해조의 투입구를 통해 투입하여 용해시켜 수용액 상태의 규산지르코늄을 얻는다.The zirconium compound used in the present invention described above is selected from the group consisting of zirconium hydroxide, zirconium silicate and zirconium oxide, preferably zirconium silicate is used. One zirconium compound is dissolved in aqua regia or hydrogen fluoride (HF) and used as an aqueous solution.A specific dissolution method is to slowly add one volume of nitric acid to three volumes of hydrochloric acid under normal temperature in a glass-coated dissolution tank. To prepare a predetermined amount of zirconium silicate into the prepared aqua regia through the inlet of the dissolution tank to dissolve to obtain zirconium silicate in the form of an aqueous solution.

본 발명에 따른 수처리용 응집제 조성물 및 이를 이용한 수처리 방법은 지르코늄 화합물을 특정 비율로 함께 사용함으로써 pH변화에 따른 응집효율의 저하문제를 해결하면서, 3가 이온의 알루미늄계 또는 철염계 응집제의 응집한계를 넘어 우수한 흡착(adsorption)과 전하중화(charge neutralization)에 의한 상승된 응집효과를 나타낼 뿐 아니라 무기응집제 사용량을 통상의 응집제 사용량에 비하여 약 1/3 ~ 1/2 수준으로 사용하여도 우수한 응집효과를 나타내므로 응집제 사용량을 현저하게 줄일 수 있고, 색도, 냄새유발 및 다량의 슬러지 발생의 문제를 해결하는 효과가 있다.The coagulant composition for water treatment and the water treatment method using the same according to the present invention solve the problem of lowering the coagulation efficiency according to the pH change by using the zirconium compound in a specific ratio, and the coagulation limit of the aluminum-based or iron salt-based coagulant of trivalent ions In addition, it exhibits an increased coagulation effect due to excellent adsorption and charge neutralization, and an excellent coagulation effect even when the amount of inorganic coagulant is used at about 1/3 to 1/2 of that of the conventional coagulant. As a result, the amount of flocculant used can be remarkably reduced, and the effect of solving the problems of chromaticity, odor induction and generation of sludge is large.

또한, 하ㆍ폐수처리 시에 문제가 되는 유기물과 부영양화의 원인물질인 질소와 인을 동시에 제거하는 장점을 지니고 있으므로 정수 및 하ㆍ폐수처리장에서의 응집능력을 더욱 극대화시킬 수가 있다.In addition, it has the advantage of simultaneously removing nitrogen and phosphorus, which are the causes of eutrophication and eutrophication, in the sewage and wastewater treatment, thereby further maximizing the flocculation capacity in the purified and sewage and wastewater treatment plants.

도 1은 [표 3]의 응집제 주입량에 대한 응집효율 결과를 나타낸 그래프
도 2는 [표 6]의 응집제 주입량에 대한 응집효율 결과를 나타낸 그래프
도 3은 [표 7]의 응집제 주입량에 대한 응집효율 결과를 나타낸 그래프
도 4는 [표 8]의 응집제 주입량에 대한 응집효율 결과를 나타낸 그래프1 is a graph showing the flocculation efficiency of the flocculant injection amount of [Table 3]
2 is a graph showing the results of the flocculation efficiency of the flocculant injection amount of [Table 6]
Figure 3 is a graph showing the results of the flocculation efficiency of the flocculant injection amount of [Table 7]
Figure 4 is a graph showing the results of the flocculation efficiency of the flocculant injection amount of [Table 8]

이하에서는 실시예 및 실험예를 통해 본 발명을 더욱 구체적으로 설명하기로 한다. 그러나 하기에 설명하고 있는 실시예 및 실험예에 의해 본 발명의 범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the scope of the present invention is not limited by the Examples and Experimental Examples described below.

본 발명에 따른 실시예 및 실험예에 있어서 정수처리는 채수한 원수(raw water)를 Jar-tester를 이용하여 250rpm의 속도로 약 1분 정도의 급속교반 및 약 30rpm에서 30분 정도 완속교반한 후 30분간 정치하고, 정치가 끝난 처리수를 채취하여 탁도와 총유기물 함량(total orgarnic carbon, TOC)을 측정한 것이며, 또 하ㆍ폐수처리는 채수한 원수(raw water)를 Jar-tester를 이용하여 250rpm의 속도로 약 1분 정도의 급속교반 및 약 30rpm에서 30분 정도 완속교반한 후 30분간 정치하고, 정치가 끝난 처리수를 채취하여 SS, COD, TN, TP를 측정한 것이다.
In the Examples and Experimental Examples according to the present invention, the purified water was rapidly stirred for about 1 minute at a speed of 250 rpm using a Jar-tester, and then slowly stirred for about 30 minutes at about 30 rpm. After standing for a minute, the treated water was collected and the turbidity and total organic matter (TOC) were measured, and the sewage and waste water treatment was performed using a jar tester at 250rpm. Rapid stirring at about 1 minute and slow stirring at about 30 rpm for 30 minutes, and then left to stand for 30 minutes. The treated water was collected and the SS, COD, TN, and TP were measured.

[[ 실시예Example 1] One]

A. A. 규산지르코늄Zirconium Silicate 조제 pharmacy

상온의 조건에서 유리로 코팅된 반응조에 염산 3부피와 질산 1부피를 순차적으로 천천히 투입하면서 왕수를 조제하고, 조제된 왕수에 규산지르코늄을 반응조의 투입구를 통해 투입하여 수용액 상태의 규산지르코늄을 얻었다(시료 1).
At room temperature, 3 volumes of hydrochloric acid and 1 volume of nitric acid were slowly added to the glass-coated reaction tank in order to prepare aqua regia, and zirconium silicate was added to the prepared aqua regia through the inlet of the reactor to obtain zirconium silicate in aqueous solution. Sample 1).

B. B. 알루미늄염계Aluminum salt system -지르코늄 응집제 제조-Zirconium flocculant

상온의 조건에서 폴리염화알루미늄(PAC)을 반응조에 투입하고 90 내지 180rpm으로 교반하면서 반응조의 투입구를 통해 폴리염화알루미늄(PAC) 1리터당 규산지르코늄(시료 1) 2,000mg/ℓ를 투입하고 2~3시간 혼합하여 지르코늄화합물이 혼합된 알루미늄염계-지르코늄 응집제를 제조하였다(시료 2).
At room temperature, polyaluminum chloride (PAC) was added to the reactor and stirred at 90 to 180 rpm, and 2,000 mg / l of zirconium silicate (sample 1) was added per liter of polyaluminum chloride (PAC) through the inlet of the reactor. Mixing with time to prepare an aluminum salt-zirconium flocculant mixed with a zirconium compound (sample 2).

C. 철염계-지르코늄 응집제 제조C. Iron Salt-Zirconium Coagulant Preparation

상온의 조건에서 염화제이철(Ferric chloride, FeCl₃)을 반응조에 투입하고 90 내지 180rpm으로 교반하면서 반응조의 투입구를 통해 염화제이철(Ferric chloride, FeCl₃) 1리터당 규산지르코늄(시료 1) 2,000mg/ℓ를 투입하고 2~3시간 혼합하여 지르코늄화합물이 혼합된 알루미늄염계-지르코늄 응집제를 제조하였다(시료 3).
At room temperature, ferric chloride (FeCl₃) was added to the reactor and stirred at 90 to 180 rpm, and 2,000 mg / ℓ of zirconium silicate (sample 1) was added per liter of ferric chloride (Ferric chloride) through the inlet of the reactor. 2 to 3 hours to prepare an aluminum salt-zirconium flocculant mixed with a zirconium compound (sample 3).

[[ 실험예Experimental Example 1] One]

A. A. 알루미늄염계Aluminum salt system -지르코늄 혼합물(시료 2)의 정수처리 응집특성-Coagulation Characteristics of Water Treatment of Zirconium Mixture (Sample 2)

본 발명에 따른 지르코늄화합물이 혼합된 응집제조성물(시료 2)을 하기 [표 1]의 수질조건을 갖는 낙동강 강물에 적용하여 Jar-tester(Phipps & Bird 社)에 의한 응집실험을 실시하였다.The coagulant composition (sample 2) mixed with the zirconium compound according to the present invention was applied to the Nakdong river river having the water quality conditions of the following [Table 1] to perform a coagulation experiment by Jar-tester (Phipps & Bird).

응집의 교반조건은 교반속도(rpm)에 따른 평균속도경사 (G) 값을 사용하여 예비실험을 통하여 결정하여 사용하였다. 예비실험 결과 도출된 최적 G 값 및 교반시간은 급속 및 완속의 교반조건에서 각각 250rpm(G=550sec-1 at 20℃)과 30rpm (G=22 sec-1 at 20℃)이었으며, 교반시간은 각각 1min과 30min으로 나타났으며, 응집실험은 도출된 교반조건과 교반시간에서 실시하였다. 이때 급속혼합 및 완속혼합에서의 Gt 값은 각각 33,000과 39,600으로 AWWA(1998)의 급속혼합 기준범위(24,000~84,000) 내에 해당하였다. 완속교반 후 침전시간은 30분으로 하였으며, 침전 후 상징액을 수표면 밑 10㎝ 지점에서 채취하여 수질분석을 실시하였다(Standard methods(AWWA, 2005)에 의해 수행되었으며, 수질분석에 사용된 분석방법 및 기기를 아래 [표 2]에 나타내었다).Agitation conditions of coagulation were determined through preliminary experiments using the average speed gradient (G) value according to the stirring speed (rpm). Each was 250rpm (G = 550sec -1 at 20 ℃) and 30rpm (G = 22 sec -1 at 20 ℃) in the stirring conditions of the preliminary test results derived optimal value G and the stirring time is rapid and slow stirring time were 1min and 30min appeared, and the coagulation experiment was carried out under the derived stirring conditions and stirring time. At this time, Gt values in rapid mixing and slow mixing were 33,000 and 39,600, respectively, and were within the AWWA (1998) range of rapid mixing (24,000 ~ 84,000). After slow stirring, the settling time was 30 minutes. After settling, the supernatant was collected from 10 cm below the surface of the water and analyzed by water quality (Standard methods (AWWA, 2005)). The instrument is shown in Table 2 below).

본 실험예에 응집실험장치로 사용된 Jar-tester(Phipps & Bird 社)는 6개의 교반장치를 갖춘 것으로 교반장치에 연결된 paddle(two-blade)의 크기는 2.54W × 7.6Lcm이고, 교반속도의 조절이 가능한 장치이다. 또한, 응집실험에 사용된 Jar는 2ℓ 용량의 사각형을 이용하였으며, 사각형 Jar의 사용에 있어서 장점으로는 ① 교반에 의한 vortex의 감소, ② 시료 채취구가 수면 아래 10cm에 고정되어 floc 침전속도 계산이 용이, ③ Jar는 두꺼운 아크릴의 재질로서 낮은 열의 전달로 온도 변화가 작다는 것 등이 있다.Jar-tester (Phipps & Bird Co., Ltd.) used in this experiment was equipped with six stirring devices. The size of the paddle (two-blade) connected to the stirring device was 2.54 W × 7.6 L cm. The device is adjustable. In addition, the jar used for the coagulation experiment used a square of 2 liter capacity. The advantages of using the square jar include ① reduction of vortex by stirring and ② a sampling port fixed at 10cm below the water surface to calculate the floc precipitation rate. Easy, ③ Jar is a thick acrylic material, and the temperature change is small due to low heat transfer.

아래 [표 3]은 본 발명의 시료 2와 정수처리 현장에서 통상적으로 사용되고 있는 알루미늄염계 무기응집제인 황산알루미늄(Alum), 폴리염화알루미늄(PAC), 폴리염화규산알루미늄(PACS) 및 폴리황산규산알루미늄(PASS) 각각의 응집특성에 따른 응집효율을 나타낸 것으로서, 본 발명에 따른 지르코늄화합물이 혼합된 응집제 조성물(시료 2, 알루미늄염계-지르코늄 혼합물)의 경우, 타 알루미늄염계 응집제보다 우수한 응집효율을 나타내고 있으며, 특히 수중의 유기물 제거에 우수한 효과를 나타내고 있다.[Table 3] below is aluminum sulfate-based inorganic coagulant, aluminum sulfate (Alum), polyaluminum chloride (PAC), polyaluminum silicate (PACS), and polysulfate aluminum, which are commonly used in Sample 2 of the present invention and water purification treatment sites. (PASS) shows the coagulation efficiency according to the coagulation characteristics of each, the coagulant composition (Sample 2, aluminum salt-zirconium mixture) mixed with the zirconium compound according to the present invention shows a better cohesive efficiency than other aluminum salt coagulant In particular, it shows an excellent effect on the removal of organic matter in water.

Figure 112010057782745-pat00001
Figure 112010057782745-pat00001

[표 1]에서 TOC치는 수중에 존재하는 유기물의 농도를 정량화하기 위해 측정하는 것이며, UV-254는 유기물질의 변화상태를 간접적으로 측정하는데 많이 이용된다(Ezdwald et al., 1985).In Table 1, the TOC value is measured to quantify the concentration of organic matter present in water, and UV-254 is widely used to indirectly measure the state of change of organic matter (Ezdwald et al., 1985).

Figure 112010057782745-pat00002
Figure 112010057782745-pat00002

Figure 112010057782745-pat00003
Figure 112010057782745-pat00003

B. B. 알루미늄염계Aluminum salt system -지르코늄 혼합물(시료 2)의 하ㆍ폐수처리 응집특성-Agglomeration Characteristics of Sewage and Wastewater Treatment of Zirconium Mixture (Sample 2)

실험에 이용된 폐수는 아래 [표 4]에 나타낸 바와 같은 하수처리장의 생물학적 처리에 의해 처리되어 소독조로 유입되기 전의 침전지 유출수를 채수하여 Jar-test를 이용한 응집실험을 실시하였다. The wastewater used in the experiment was treated by biological treatment of sewage treatment plant as shown in Table 4 below, and the sedimentation basin effluent was collected before entering the sterilization tank, and a coagulation experiment using Jar-test was performed.

응집실험장치는 상기 ‘지르코늄화합물이 혼합된 응집제 조성물(시료 2, 알루미늄염계-지르코늄 혼합물)의 정수처리 응집특성’에서 사용한 Jar-tester (Phipps & Bird 社)를 이용하고 응집실험조건도 동일하게 이용하였으며, 응집실험에서의 수질분석은 COD, 탁도, TN과 TP를 실시하였으며, 분석방법은 Standard methods(AWWA, 2005)와 수질오염공정시험법(환경부)에 의해 수행되었다. 수질분석에 사용된 분석방법 및 기기를 아래 [표 5]에 나타내었다.The coagulation test apparatus uses Jar-tester (Phipps & Bird Co., Ltd.) used in the 'coagulation characteristics of water treatment treatment of the coagulant composition (Sample 2, aluminum salt-zirconium mixture) mixed with zirconium compound' and the coagulation test conditions are used in the same way. COD, turbidity, TN and TP were used for the water quality analysis in the flocculation experiment, and the analysis method was performed by the standard methods (AWWA, 2005) and the water pollution process test method (Ministry of Environment). The analytical methods and instruments used for water quality analysis are shown in Table 5 below.

또한, 본 발명에 따른 지르코늄화합물이 혼합된 응집제조성물(시료 2)과 정수처리 현장에서 많이 사용되고 있는 알루미늄염계 무기응집제인 황산알루미늄(Alum), 폴리염화알루미늄(PAC), 폴리염화규산알루미늄(PACS) 및 폴리황산규산알루미늄(PASS)을 이용하여 응집제 각각의 응집특성에 따른 응집효율을 아래 [표 6]에 나타내었으며, [표 6]에 나타난 바와 같이 본 발명에 따른 지르코늄화합물이 혼합된 응집제 조성물(시료 2, 알루미늄염계-지르코늄 혼합물)의 경우, 타 알루미늄염계 응집제보다 우수한 응집효율을 나타내고 있으며, 특히 수중의 유기물 제거와 질소제거에 우수한 효과를 나타내고 있다.In addition, the coagulant composition mixed with the zirconium compound according to the present invention (Sample 2) and the aluminum salt-based inorganic coagulant, aluminum sulfate (Alum), polyaluminum chloride (PAC), polyaluminum silicate chloride (PACS) And coagulation efficiency according to the coagulation characteristics of the coagulant using polyaluminum silicate (PASS) is shown in [Table 6] below, and the coagulant composition in which the zirconium compound according to the present invention is mixed as shown in [Table 6] ( Sample 2, an aluminum salt-zirconium mixture), exhibited better cohesive efficiency than other aluminum salt-based coagulants, and particularly exhibited excellent effects in removing organic matter and nitrogen in water.

Figure 112010057782745-pat00004
Figure 112010057782745-pat00004

Figure 112010057782745-pat00005
Figure 112010057782745-pat00005

Figure 112010057782745-pat00006
Figure 112010057782745-pat00006

[[ 실험예Experimental Example 2] 2]

A. 철염계-지르코늄 혼합물(시료 3)의 정수처리 응집특성A. Coagulation Characteristics of Water Treatment of Iron Salt-Zirconium Mixture (Sample 3)

정수시료(낙동강 강물) 및 실험장치는 상기 [실험예 1]의 시료 2의 정수처리 응집특성 실험과 동일한 조건에서 실시하였다.The purified water sample (Nakdong River) and the experimental apparatus were carried out under the same conditions as the hydrostatic treatment flocculation characteristics experiment of Sample 2 of [Experimental Example 1].

본 발명에 따른 지르코늄화합물이 혼합된 응집제조성물(시료 3) 정수처리 현장에서 많이 사용되고 있는 철염계 무기응집제인 염화제이철(Ferric chloride, FeCl₃), 염화제일철(Ferrous chloride, FeCl₂), 황산제이철(Ferric sulfate, Fe₂(SO₄)₃), 황산제일철(Ferrous sulfate, Fe(SO)₄), 폴리염화철(polyferric chloride, PFC), 폴리황산철(polyferric sulfate, PFS), 폴리규산철(polysilicate iron)을 이용하여 응집제 각각의 응집특성에 따른 응집효율을 아래 [표 7]에 나타내었으며, [표 7]에 나타난 바와 같이 본 발명에 따른 지르코늄화합물이 혼합된 응집제 조성물(시료 3, 철염계-지르코늄 혼합물)의 경우, 타 철염계 응집제보다 우수한 응집효율을 나타내고 있으며, 특히 수중의 유기물 제거에 우수한 효과를 나타내고 있다. Coagulant composition mixed with zirconium compound according to the present invention (Sample 3) Ferric chloride, FeCl₃, ferrous chloride (Ferrous chloride, FeCl₂), ferric sulfate (Ferric sulfate) , Fe₂ (SO₄) ₃), Ferrous sulfate (Fe (SO) ₄), polyferric chloride (PFC), polyferric sulfate (PFS), polysilicate iron The coagulation efficiency according to the coagulation properties of each coagulant is shown in [Table 7] below, and as shown in [Table 7], in the case of the coagulant composition (sample 3, iron salt-zirconium mixture) mixed with the zirconium compound according to the present invention. It shows a better flocculation efficiency than other iron salt coagulants, and particularly shows the effect of removing organic matter in water.

Figure 112010057782745-pat00007
Figure 112010057782745-pat00007

B. 철염계-지르코늄 혼합물(시료 3)의 하ㆍ폐수처리 응집특성B. Coagulation Characteristics of Sewage and Wastewater Treatment of Iron Salt-Zirconium Mixture (Sample 3)

폐수시료(하수처리장의 생물학적 처리에 의해 처리되어 소독조로 유입되기 전의 침전지 유출수) 및 실험장치는 상기 [실험예 1]의 시료 2의 하ㆍ폐수처리 응집특성실험과 동일한 조건에서 실시하였다.The wastewater sample (the sedimentation basin effluent before being treated by biological treatment of the sewage treatment plant and introduced into the disinfection tank) and the experimental apparatus were carried out under the same conditions as the sewage and wastewater treatment coagulation characteristics test of Sample 2 of [Example 1].

본 발명에 따른 지르코늄화합물이 혼합된 응집제조성물(시료 3)과 정수처리 현장에서 많이 사용되고 있는 철염계 무기응집제인 염화제이철(Ferric chloride, FeCl₃), 염화제일철(Ferrous chloride, FeCl₂), 황산제이철(Ferric sulfate, Fe₂(SO₄)₃), 황산제일철(Ferrous sulfate, Fe(SO)₄), 폴리염화철(polyferric chloride, PFC), 폴리황산철(polyferric sulfate, PFS), 폴리규산철(polysilicate iron)을 이용하여 응집제 각각의 응집특성에 따른 응집효율을 아래 [표 8]에 나타내었으며, [표 8]에 나타난 바와 같이 본 발명에 따른 지르코늄화합물이 혼합된 응집제 조성물(시료 3, 철염계-지르코늄 혼합물)의 경우, 타 철염계 응집제보다 우수한 응집효율을 나타내고 있으며, 특히 수중의 유기물 제거에 우수한 효과를 나타내고 있다.Coagulant composition mixed with the zirconium compound according to the present invention (Sample 3) and ferric chloride, FeCl₃, ferrous chloride, ferrous chloride (Ferrous chloride, FeCl₂), ferric sulfate (Ferric) sulfate, Fe₂ (SO₄) ₃), ferrous sulfate (Fe (SO) ₄), polyferric chloride (PFC), polyferric sulfate (PFS), polysilicate iron Coagulation efficiency according to the coagulation properties of each coagulant is shown in [Table 8] below, and as shown in [Table 8] of the coagulant composition (sample 3, iron salt-zirconium mixture) mixed with the zirconium compound according to the present invention In this case, the coagulation efficiency is better than that of other iron salt coagulants, and in particular, it is excellent in removing organic matter in water.

Figure 112010057782745-pat00008
Figure 112010057782745-pat00008

Claims (8)

삭제delete (a)성분으로 황산알루미늄(Alum), 폴리염화규산알루미늄(PACS) 및 폴리황산규산알루미늄(PASS)으로 이루어진 군으로부터 선택되는 1종 이상의 알루미늄계 무기응집제, 또는 (b)성분으로 철염계 무기응집제에, (c)성분으로 지르코늄화합물을 조합하되, (a)성분 또는 (b)성분의 부피기준으로 100㎎/ℓ 내지 5,000㎎/ℓ 범위로 (c)성분을 포함하는 것을 특징으로 하는 지르코늄을 이용한 정수 또는 하ㆍ폐수처리용 응집제 조성물.(a) At least one aluminum inorganic coagulant selected from the group consisting of aluminum sulfate (Alum), polyaluminum silicate silica (PACS) and aluminum polysilicate silicate (PASS), or (b) an iron salt inorganic coagulant as a component To the zirconium compound as a component (c), zirconium comprising a component (c) in the range of 100mg / l to 5,000mg / l based on the volume of the component (a) or (b) Coagulant composition for purified water or sewage and wastewater treatment. 제2항에 있어서, (b)성분인 철염계 무기응집제는 염화제이철(Ferric chloride, FeCl₃), 염화제일철(Ferrous chloride, FeCl₂), 황산제이철(Ferric sulfate, Fe₂(SO₄)₃), 황산제일철(Ferrous sulfate, Fe(SO)₄), 폴리염화철(polyferric chloride, PFC), 폴리황산철(polyferric sulfate, PFS) 및 폴리규산철(polysilicate iron)로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 지르코늄을 이용한 정수 또는 하ㆍ폐수처리용 응집제 조성물.According to claim 2, wherein the iron salt-based inorganic coagulant (b) component Ferric chloride (FeCl₃), Ferrous chloride (Ferrous chloride, FeCl₂), Ferric sulfate (Fe₂ (SO₄) ₃), Ferrous sulfate ( Zirconium, characterized in that at least one member selected from the group consisting of ferrous sulfate, Fe (SO) ₄), polyferric chloride (PFC), polyferric sulfate (PFS) and polysilicate iron Coagulant composition for purified water or wastewater treatment using. 제2항 또는 제3항에 있어서, (c)성분인 지르코늄 화합물이 수산화지르코늄, 규산지르코늄 및 산화지르코늄으로 이루어진 군으로부터 선택되는 어느 하나인 것을 특징으로 하는 지르코늄을 이용한 정수 또는 하ㆍ폐수처리용 응집제 조성물.The coagulant for water purification or wastewater treatment using zirconium according to claim 2 or 3, wherein the zirconium compound as the component (c) is any one selected from the group consisting of zirconium hydroxide, zirconium silicate, and zirconium oxide. Composition. 삭제delete (a)성분으로 황산알루미늄(Alum), 폴리염화규산알루미늄(PACS) 및 폴리황산규산알루미늄(PASS)으로 이루어진 군으로부터 선택되는 1종 이상의 알루미늄계 무기응집제, 또는 (b)성분으로 철염계 무기응집제에, (c)성분으로 지르코늄 화합물을 조합하되, (a)성분 또는 (b)성분의 부피기준으로 100㎎/ℓ 내지 5,000㎎/ℓ 범위로 (c)성분을 포함하는 응집제 조성물을 정수 또는 하ㆍ폐수의 부피기준으로 10 ~ 100㎎/ℓ 범위로 정수 또는 하ㆍ폐수에 투입하여 수중의 유기물, 질소 및 인을 동시에 제거하는 것을 특징으로 하는 정수 또는 하ㆍ폐수 처리방법.(a) At least one aluminum inorganic coagulant selected from the group consisting of aluminum sulfate (Alum), polyaluminum silicate silica (PACS) and aluminum polysilicate silicate (PASS), or (b) an iron salt inorganic coagulant as a component To the (c) component, the zirconium compound is combined, but the coagulant composition comprising the component (c) in the range of 100 mg / L to 5,000 mg / L based on the volume of the component (a) or (b) is purified or ㆍ A method for treating purified water or sewage and wastewater, characterized by simultaneously removing organic matter, nitrogen and phosphorus from water by adding water to wastewater or sewage and wastewater in the range of 10 to 100 mg / L based on the volume of wastewater. 제6항에 있어서, (b)성분인 철염계 무기응집제는 염화제이철(Ferric chloride, FeCl₃), 염화제일철(Ferrous chloride, FeCl₂), 황산제이철(Ferric sulfate, Fe₂(SO₄)₃), 황산제일철(Ferrous sulfate, Fe(SO)₄), 폴리염화철(polyferric chloride, PFC), 폴리황산철(polyferric sulfate, PFS) 및 폴리규산철(polysilicate iron)로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 정수 또는 하ㆍ폐수 처리방법.According to claim 6, wherein the iron salt-based inorganic coagulant (b) component Ferric chloride (FeCl₃), Ferrous chloride (Ferrous chloride, FeCl₂), Ferric sulfate (Fe₂ (SO₄) ₃), Ferrous sulfate ( Integer, characterized in that at least one selected from the group consisting of ferrous sulfate, Fe (SO) ₄), polyferric chloride (PFC), polyferric sulfate (PFS) and polysilicate iron (polysilicate iron) Or sewage and wastewater treatment method. 제6항 또는 제7항에 있어서, (c)성분인 지르코늄 화합물이수산화지르코늄, 규산지르코늄 및 산화지르코늄으로 이루어진 군으로부터 선택되는 어느 하나인 것을 특징으로 하는 정수 또는 하ㆍ폐수 처리방법.The method for treating purified water or sewage or wastewater according to claim 6 or 7, wherein the zirconium compound as the component (c) is any one selected from the group consisting of zirconium hydroxide, zirconium silicate, and zirconium oxide.
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CN104291419A (en) * 2014-08-25 2015-01-21 河南鼎鑫冶金科技有限公司 Compound polymerization aluminum ferric chloride water treatment agent
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KR101270211B1 (en) 2012-01-10 2013-05-31 주식회사 크린켐 Composition for treatment of wastewater containing fluorine
CN104291419A (en) * 2014-08-25 2015-01-21 河南鼎鑫冶金科技有限公司 Compound polymerization aluminum ferric chloride water treatment agent
CN104445546A (en) * 2014-11-05 2015-03-25 阳原县仁恒精细粘土有限责任公司 Coagulant for processing coating waste water and production process of coagulant
CN104445441A (en) * 2014-11-14 2015-03-25 河南省煤气（集团）有限责任公司 Method for producing polymeric aluminium ferric sulfate solution from industrial waste sulfuric acid generated during purification of acetylene gas and red mud
CN105712451A (en) * 2014-12-05 2016-06-29 郭杰 Clearing sewage treatment agent and preparation method thereof
CN104591364A (en) * 2015-02-15 2015-05-06 陆燕 Composite flocculant and preparation method thereof
CN105967295A (en) * 2016-06-27 2016-09-28 安徽世绿环保科技有限公司 Electroplating wastewater synchronous dephosphorization-defluorination compound flocculant and preparation method thereof
CN105967295B (en) * 2016-06-27 2018-12-04 安徽世绿环保科技有限公司 Synchronous dephosphorization fluorine removal built-up flocculant of a kind of electroplating wastewater and preparation method thereof
CN106186233A (en) * 2016-08-18 2016-12-07 桂林市春晓环保科技有限公司 A kind of efficiently waste water flocculant and preparation method thereof
WO2019119475A1 (en) * 2017-12-21 2019-06-27 北京工业大学 Method for enhancing coagulation in stages
KR101973986B1 (en) 2018-06-01 2019-08-23 염선화 Method of preparation for coagulant and treating method of water/wastewater using the same
KR20210144617A (en) 2020-05-22 2021-11-30 삼구화학공업 주식회사 Water treatment method to reduce residual aluminum
CN112093873A (en) * 2020-09-15 2020-12-18 中山大学 Composite flocculant and preparation method and application thereof
KR20220106716A (en) 2021-01-22 2022-07-29 삼구화학공업 주식회사 A method to reduce residual aluminum

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