KR20210144617A - Water treatment method to reduce residual aluminum - Google Patents

Water treatment method to reduce residual aluminum Download PDF

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KR20210144617A
KR20210144617A KR1020210117722A KR20210117722A KR20210144617A KR 20210144617 A KR20210144617 A KR 20210144617A KR 1020210117722 A KR1020210117722 A KR 1020210117722A KR 20210117722 A KR20210117722 A KR 20210117722A KR 20210144617 A KR20210144617 A KR 20210144617A
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South Korea
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coagulant
aluminum
group
chloride
water treatment
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KR1020210117722A
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Korean (ko)
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염복철
박민자
김지은
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삼구화학공업 주식회사
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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
    • 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
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment

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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

The present invention relates to a water treatment method for reducing residual aluminum, wherein a coagulant is manufactured by mixing hydrochloric acid, aluminum hydroxide and water in a certain ratio to solve problems such as residual unreacted substances, additional facilities and the like, and residual aluminum can be minimized without additional materials or additional facilities by treating the same alone or in combination with inorganic and/or organic coagulants.

Description

잔류알루미늄 저감을 위한 수처리방법{Water treatment method to reduce residual aluminum}Water treatment method to reduce residual aluminum

본 발명은 잔류알루미늄 저감을 위한 수처리방법에 관한 것으로, 염산, 수산화알루미늄 및 물을 일정비율로 혼합 반응하여 응집제를 제조하고, 이를 원수에 단독으로 처리하거나 알루미늄계 응집제와 병용 처리하여 잔류알루미늄을 최소화하는 방법에 관한 것이다.The present invention relates to a water treatment method for reducing residual aluminum. A coagulant is prepared by mixing and reacting hydrochloric acid, aluminum hydroxide, and water in a certain ratio, and the raw water is treated alone or in combination with an aluminum-based coagulant to minimize residual aluminum. it's about how to

알루미늄은 토양성분의 약 8 중량%를 차지하며, 암석, 동식물의 조직을 구성하는 은백색의 부드러운 금속으로, 알칼리에 녹아 수소를 발생시켜 알루민산 염 형성이 가능한 금속이다. 알루미늄은 물 속에서 침전물을 형성하거나 수산화물, 탄산염 등의 형태로 흡착되는 경향이 있어 정수장에서 응집제로 알루미늄을 사용하고 있다.Aluminum accounts for about 8% by weight of soil components, and is a silvery-white soft metal constituting the tissues of rocks and animals and plants. It is a metal capable of forming aluminate by dissolving in alkali to generate hydrogen. Aluminum tends to form precipitates in water or is adsorbed in the form of hydroxides and carbonates, so aluminum is used as a coagulant in water purification plants.

알루미늄을 포함하는 응집제로서 단분자 무기 응결제로 염산알루미늄(Aluminum Sulphate), 알루민산 나트륨(Sodium Aluminate), 염산알루미늄 암모늄(Aluminum ammonium Sulphate), 칼리 백반(Potash alum) 등이 있고, 고분자형 무기 응결제로 폴리염화알루미늄(Poly Aluminium Chloride), 폴리염산알루미늄(Poly Alumium Sulfate), 폴리염산알루미늄규산(Poly Aluminium Sulfate Silicate), 폴리수산화염화염산알루미늄 (Poly Aluminium Hydroxy Chloro Sulfate)등이 있다.As a coagulant containing aluminum, there are aluminum hydrochloride (Aluminum Sulphate), sodium aluminate (Sodium Aluminate), aluminum ammonium Sulphate, potassium alum, etc. as a single-molecular inorganic coagulant, Poly Aluminum Chloride, Poly Aluminum Sulfate, Poly Aluminum Sulfate Silicate, Poly Aluminum Hydroxy Chloro Sulfate, and the like.

알루미늄과 관련하여, 논쟁의 여지는 있으나 치매의 일종인 알츠하이머(Alzheimer’s disease)와 연관이 있다는 보고가 있다. 이에 따라 물 속의 단량체 알루미늄과 다른 형태의 알루미늄을 포함한 전체 알루미늄 수치가 리터당 200 mg 이하여야 한다는 지적이 있어왔으나, 현재는 심미적 영향에 따라 유럽공동체 음용수수질기준지침, 세계보건기구 음용수수질기준지침, 미국 음용수수질기준 등에서 음용수중의 최대 알루미늄 권장치는 리터당 0.2 mg으로 설정되어 있으며, 우리나라의 경우 먹는물관리법에 의해 위와 같은 기준을 설정된 상태이다. Regarding aluminum, there are reports that it is linked to Alzheimer's disease, a type of dementia, although controversial. Accordingly, it has been pointed out that the total aluminum level, including monomer aluminum and other forms of aluminum in water, should be less than 200 mg per liter. In drinking water quality standards, etc., the maximum recommended value of aluminum in drinking water is set at 0.2 mg per liter.

우리나라의 경우 최근 5년 전부터 비가 적게 내려 전국적으로 원수의 pH가 상승하여 봄이나 가을철의 경우 pH가 9.5까지도 상승하는 현상이 발생하여 고염기도를 사용하는 정수장에서 잔류알루미늄이 다소 많이 발생하는 문제가 발생하고 있다. 정수시설에서 염산알루미늄 등의 알루미늄계 응집제를 이용하는 것이 불가피한 실정이며, 탁도, 유기물제거 등의 효율적인 수처리를 위하여 고염기도 응집제를 다수 사용하고 있으며, 잔류알루미늄의 문제로 인해 염산, 염산을 단순히 투입하거나 CO2 처리설비를 통하는 방식에 의하고 있으나, 유해화학물질의 미반응, 설계비용, 설계용량 등에 의해 한계가 있다. 특히 염산, 염산의 경우 10% 이상일 경우 유해화학물질로서 수처리에 사용할 경우 작업자의 안전에 대한 문제가 발생할 수 있기에 대부분의 수처리장에서는 9% 염산과 염산을 사용하여 pH를 낮추고 있다. 낮은 농도의 염산 염산을 사용함에따라 투입량이 많아지며, 그에 따라 탱크관리 등의 많은 어려움을 겪고 있다.In the case of Korea, since there has been little rain for the past 5 years, the pH of raw water has risen nationwide, and in the spring and autumn, the pH rises to 9.5. are doing It is unavoidable to use aluminum-based coagulants such as aluminum hydrochloride in water purification facilities, and many high-basic coagulants are used for efficient water treatment such as turbidity and organic matter removal. 2 It is based on the method through the treatment facility, but there are limitations due to non-reacting of hazardous chemicals, design cost, and design capacity. In particular, in the case of hydrochloric acid and hydrochloric acid, if it is 10% or more, it is a hazardous chemical and when used for water treatment, there may be a problem for worker safety. Therefore, most water treatment plants use 9% hydrochloric acid and hydrochloric acid to lower the pH. As the low concentration of hydrochloric acid is used, the input amount increases, and accordingly, there are many difficulties such as tank management.

통상적인 폴리염화알루미늄(Poly Aluminium chloride)는 중합정도에 따라 염기도가 상이하고 제조공정에 따라 특성이 다르나, 주로 산화알루미늄의 함량은 10~18 중량%, 염기도는 35% 이상인 것을 사용한다. 폴리염화알루미늄은 전기적 중화능력와 OH 가교작용이 우수하여 탁월한 응집능력을 가지고 있는 것으로 알려져있으며, 응집반응은 하기와 같은 식으로 이루어진다.Conventional poly aluminum chloride (Poly Aluminum chloride) has different basicity depending on the degree of polymerization and different properties depending on the manufacturing process, but mainly the content of aluminum oxide is 10 to 18% by weight, and the basicity is 35% or more. Polyaluminum chloride is known to have excellent aggregation ability due to its excellent electrical neutralization ability and OH crosslinking action, and the aggregation reaction is performed in the following manner.

[Al2(OH)3Cl3]n + 2H2PO4 - + HCO3 - → 2AlPO4 + 3Cl- + +2H2O + H2CO3 [Al 2 (OH) 3 Cl 3 ] n + 2H 2 PO 4 - + HCO 3 - → 2AlPO 4 + 3Cl - + +2H 2 O + H 2 CO 3

*이와 관련하여, 탄산칼슘 및 염화칼슘을 포함하는 하폐수 처리제에 관한 국내등록특허 제10-0318661호, 지르코늄을 함유한 수처리용 응집제 조성물 관한 국내 등록특허 제10-1016392호 등이 있으며, 국내등록특허 제10-1661179호에서는 고염기성 폴리염화알루미늄 응집제의 제조방법으로 Al2O3 함량이 10~15 중량%이고 염기도가 60~75 중량%인 폴리염화알루미늄을 개시하고 있으며, 국내등록특허 제10-1159236호에서는 저염기도 폴리염화알루미늄 응집제의 제조방법 및 이를 이용한 수처리 방법으로서, 녹조현상 등의 부영양화를 방지할 수 있고 장기간 저장이 가능한 염기도 10~20 %, Al2O3 8~15 %인 저염기도 폴리염화알루미늄(PACB) 응집제를 개시하고 있으며, 국내등록특허 제10-1640368호에서는 Al2O3 7~15 중량%, Fe 함량이 1~5 중량%인 저염기도를 유지하는 응집제의 제조방법 및 이를 통한 하폐수 처리방법을 개시하고 있다.* In this regard, there are domestic registered patent No. 10-0318661 regarding a wastewater treatment agent containing calcium carbonate and calcium chloride, domestic registered patent No. 10-1016392 regarding a coagulant composition for water treatment containing zirconium, etc. No. 10-1661179 discloses polyaluminum chloride having an Al 2 O 3 content of 10 to 15% by weight and a basicity of 60 to 75% by weight as a method for manufacturing a highly basic polyaluminum chloride coagulant, and Korean Patent Registration No. 10-1159236 the arc low salt airway polyvinyl chloride as a manufacturing method and a water treatment method using the same of the aluminum coagulants, can be prevented from eutrophication, such as algal blooms and basicity 10% to 20% are possible long-term storage, Al 2 O 3 8 ~ 15 % of low sodium airway poly Disclosed is an aluminum chloride (PACB) coagulant, and in Korean Patent No. 10-1640368, a method for producing a coagulant maintaining a low basicity of Al 2 O 3 7 to 15 wt% and Fe content 1 to 5 wt%, and the same Disclosed is a method for treating wastewater through

일반적으로 무기응집제가 대부분 알루미늄계열의 응집제로서, 실제 원수에 들어있는 알루미늄보다 응집제가 투입됨에 따라 콜로이드와 결합한 후 남은 알루미늄이 물에 용해되어 알루미늄을 용출시키기에 문제가 된다.In general, inorganic coagulants are mostly aluminum-based coagulants, and as coagulants are added rather than aluminum contained in raw water, aluminum remaining after binding with colloids is dissolved in water, causing a problem in eluting aluminum.

특히 이러한 알루미늄 용출 문제는 원수의 pH가 7.5 이상에서 생기기 시작하며, 원수의 pH가 높을수록 알루미늄 용출문제는 더 커진다. 응집을 위해 최소한의 응집제 투입을 하여도 원수의 pH가 높으면 응집은 이루어졌어도 처리수 내에 알루미늄은 기준치 이상이 검출되며, 투입량이 많아질수록 잔류알루미늄은 더 높게 검출되기에 상기 선행문헌과 같은 잔류알루미늄 저감을 위한 노력이 있으나 pH가 높은 원수에서는 잔류알루미늄 저감효과가 없다.In particular, the problem of aluminum elution starts to occur when the pH of the raw water is 7.5 or higher, and the higher the pH of the raw water, the bigger the problem of aluminum elution. If the pH of the raw water is high even when the minimum amount of coagulant is added for coagulation, aluminum is detected above the standard value in the treated water even if coagulation is achieved, and the higher the input amount, the higher the residual aluminum is detected. Efforts are made to reduce aluminum, but there is no effect of reducing residual aluminum in raw water with high pH.

또한, 알루미늄 용출의 문제를 해결을 위한 pH 조절방법으로, 이산화탄소를 이용하거나 과량의 응집제를 주입하는 방법을 시도하고 있으나, 이산화탄소를 주입하는 경우 실 공정에서 운영관리, 비용, 효율 등의 측면에서 어려움이 있으며, 과량의 응집제를 이용하는 경우 슬러지 발생량 증가하며 투입량이 증가함에따라 잔류알루미늄이 더 증가할 수 있는 문제점이 있다.In addition, as a pH control method to solve the problem of aluminum dissolution, a method using carbon dioxide or injecting an excessive amount of coagulant is tried, but when carbon dioxide is injected, it is difficult in terms of operation management, cost, efficiency, etc. in the actual process There is a problem that, when an excessive amount of coagulant is used, the amount of sludge generated increases and the amount of residual aluminum may further increase as the input amount increases.

본 발명은 위의 선행문헌의 알루미늄계열의 응집제 혹은 다른 알루미늄계열의 응집제를 사용하여도 본 발명품을 일정량 투입하여 pH를 7.5이하로 낮추면 잔류알루미늄이 발생이 저감된다.In the present invention, even if the aluminum-based coagulant of the prior literature or other aluminum-based coagulant is used, the generation of residual aluminum is reduced when the pH is lowered to 7.5 or less by adding a certain amount of the present invention.

이에 본 발명자들은 상기 문제를 해결하기 위해 노력한 결과, 종래 응집제를 사용하더라도 본 발명에 따른 조성물을 일정량 투입하여 pH를 7.5 이하로 낮추면 잔류알루미늄 발생이 저감되는 효과가 있고, 염산이나 염산에 비하여 적게 투입함에도 pH를 7.5 이하로 낮출 수 있으며, 잔류알루미늄이 더 낮게 검출되고, 단독으로 투입하여도 잔류알루미늄을 저감시키면서 응집효율도 나타낼 수 있음을 밝힘으로써, 본 발명을 완성하였다.As a result of the present inventors' efforts to solve the above problem, even if a conventional coagulant is used, if a certain amount of the composition according to the present invention is added to lower the pH to 7.5 or less, the generation of residual aluminum is reduced, and less input than hydrochloric acid or hydrochloric acid However, the present invention was completed by revealing that the pH can be lowered to 7.5 or less, the residual aluminum is detected lower, and the aggregation efficiency can also be exhibited while reducing the residual aluminum even when added alone.

대한민국등록특허 제10-1016392호Republic of Korea Patent No. 10-1016392 대한민국등록특허 제10-1661179호Republic of Korea Patent No. 10-1661179 대한민국등록특허 제10-0318661호Republic of Korea Patent No. 10-0318661 대한민국등록특허 제10-1640368호Republic of Korea Patent No. 10-1640368

건국대학교 석사학위논문, 고영송 외, 1993.02, 정수처리시 잔류알루미늄 농도를 최소화하기 위한 영향인자 고찰 Konkuk University master's thesis, Youngsong Ko et al., 1993.02, A study on factors affecting the minimization of residual aluminum concentration in water treatment

본 발명에서는 종래의 응집제를 사용할 경우 pH가 높은 원수에서 응집제를 투입함에 따라 잔류알루미늄이 증가하는 문제를 해결하고자 무기응집제 및/또는 유기응집제를 그대로 사용하면서 알루미늄 저감이 가능한 잔류알루미늄 저감용 수처리방법을 제공한다.In the present invention, when using a conventional coagulant, in order to solve the problem of an increase in residual aluminum as a coagulant is added in raw water with a high pH, a water treatment method for reducing aluminum residual aluminum by using an inorganic coagulant and/or an organic coagulant as it is. to provide.

상기 목적을 달성하기 위하여, a) 염산, 수산화알루미늄 및 물을 혼합하여 응집제를 제조하되, 응집제 총 중량대비 염산 25 내지 90 중량%, 수산화알루미늄 0.5 내지 12 중량% 및 물 0.01 내지 70 중량%로 혼합 반응하여 응집제를 제조하는 단계; 및 b1) 단계 a)의 응집제를 단독으로 투입하는 단계 또는 b2) 단계 a)의 응집제를 무기응집제 및 유기응집제로 구성된 그룹으로부터 선택되는 1종 이상의 응집제와 병용하여 원수에 투입하는 단계;를 포함하고, 여기에서, 상기 단계 a)의 응집제는 산화알루미늄, 염화이온을 포함하는 것인 알루미늄 저감용 수처리방법을 제공한다.In order to achieve the above object, a) hydrochloric acid, aluminum hydroxide and water are mixed to prepare a coagulant, but 25 to 90% by weight of hydrochloric acid, 0.5 to 12% by weight of aluminum hydroxide and 0.01 to 70% by weight of water, based on the total weight of the coagulant, are mixed. reacting to prepare a coagulant; and b1) adding the coagulant of step a) alone or b2) adding the coagulant of step a) to raw water in combination with one or more coagulants selected from the group consisting of inorganic coagulants and organic coagulants; and , Here, the coagulant of step a) provides a water treatment method for reducing aluminum that includes aluminum oxide and chloride ions.

본 발명의 일 양태에서, 단계 a)의 응집제는 응집제 총 중량대비 염화이온 함량은 10 내지 40 %이고, 산화알루미늄 함량은 0.5 내지 5 %이다.In one aspect of the present invention, the coagulant in step a) has a chloride ion content of 10 to 40% and an aluminum oxide content of 0.5 to 5% relative to the total weight of the coagulant.

본 발명의 일 양태에서, 단계 a)의 응집제는 황화물, 염화물, 규산화물, 산화물; 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함한다. In one aspect of the present invention, the flocculant of step a) is selected from the group consisting of sulfides, chlorides, silicates, oxides; and at least one compound selected from the group consisting of salts thereof.

본 발명의 일 양태에서, 단계 a)의 응집제는 2A족 화합물, 3A족 화합물, 4A족 화합물, 3B족 화합물, 4B족 화합물 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함한다. 구체적인 본 발명의 일 양태에서, 단계 a)의 응집제는 2A족 염화물, 2A족 황화물, 3B족 염화물, 3B족 황화물, 4B족 염화물, 4B족 황화물, 규산나트륨(Na2SiO3) 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함한다. In one embodiment of the present invention, the coagulant of step a) further comprises at least one compound selected from the group consisting of a group 2A compound, a group 3A compound, a group 4A compound, a group 3B compound, a group 4B compound, and salts thereof. In a specific aspect of the present invention, the coagulant of step a) is a group 2A chloride, a group 2A sulfide, a group 3B chloride, a group 3B sulfide, a group 4B chloride, a group 4B sulfide, sodium silicate (Na 2 SiO 3 ) and salts thereof. It further comprises one or more compounds selected from the group consisting of.

또한, 본 발명의 일 양태에서, 단계 b2)의 무기응집제는 알루미늄계 응집제, 철염계 응집제 또는 이들의 혼합 응집제이다. Further, in one aspect of the present invention, the inorganic coagulant in step b2) is an aluminum-based coagulant, an iron salt-based coagulant, or a mixed coagulant thereof.

본 발명의 일 양태에서, 단계 b2)의 알루미늄계 응집제는 염화알루미늄, 황산알루미늄, 폴리염산알루미늄, 폴리염화알루미늄, 폴리염산규산알루미늄, 폴리염화규산알루미늄, 폴리수산화염화규산알루미늄, 폴리염산규산알루미늄 및 폴리수산화염화염산알루미늄로 구성된 그룹으로부터 선택된 1종 이상이다.In one aspect of the present invention, the aluminum-based coagulant of step b2) is aluminum chloride, aluminum sulfate, polyaluminum hydrochloride, polyaluminum chloride, polyaluminum silicate hydrochloride, polyaluminum chloride silicate, polyhydroxychloride aluminum silicate, polyhydrochloride aluminum silicate and It is at least one selected from the group consisting of aluminum polyhydroxychloride hydrochloride.

구체적인 본 발명의 일 양태에서, 단계 b2)의 무기응집제는 무기응집제 총 중량대비 산화알루미늄 함량이 5 내지 25%이다.In a specific aspect of the present invention, the inorganic coagulant of step b2) has an aluminum oxide content of 5 to 25% based on the total weight of the inorganic coagulant.

본 발명의 일 양태에서, 단계 b2)의 유기응집제는 폴리아크릴아마이드계, 폴리비닐아민계, 폴리알릴아민계, 폴리에틸렌아민계, 폴리아민계, 폴리아크릴에스테르계, 폴리에틸렌이민계, 폴리데드막 및 이들의 혼합응집제로 구성된 그룹으로부터 선택된 1종 이상이다.In one aspect of the present invention, the organic coagulant of step b2) is polyacrylamide-based, polyvinylamine-based, polyallylamine-based, polyethyleneamine-based, polyamine-based, polyacrylic ester-based, polyethyleneimine-based, polydead film, and these It is at least one selected from the group consisting of a mixed coagulant of

본 발명의 일 양태에서, 수처리방법은 처리 후 처리수의 탁도가 2NTU 이하이다. 구체적인 본 발명의 일 양태에서, 수처리방법은 처리 후 처리수의 탁도가 1 NTU 이하이다.In one aspect of the present invention, in the water treatment method, the turbidity of the treated water after treatment is 2NTU or less. In a specific aspect of the present invention, in the water treatment method, the turbidity of the treated water after treatment is 1 NTU or less.

본 발명의 일 양태에서, 수처리방법은 처리 후 처리수의 pH가 8.5이하이다. 구체적인 본 발명의 일 양태에서, 수처리방법은 처리 후 처리수의 pH가 7.0 내지 8.0이다.In one aspect of the present invention, in the water treatment method, the pH of the treated water after treatment is 8.5 or less. In a specific aspect of the present invention, in the water treatment method, the pH of the treated water after treatment is 7.0 to 8.0.

본 발명의 일 양태에서, 수처리방법은 상기 단계 a)의 응집제를 미투입한 경우와 비교하여 잔류알루미늄이 5 내지 90 %로 저감되는 것이다.In one aspect of the present invention, in the water treatment method, the residual aluminum is reduced to 5 to 90% compared to the case where the coagulant of step a) is not added.

또한, 본 발명의 단계 a)에서 제조된 응집제는 하기 [화학식 1]로 표현되는 화합물 및 산화알루미늄을 포함하고, 여기에서 산화알루미늄 함량은 응집제 총 중량대비 0.5 내지 5 중량%인 알루미늄 저감용 수처리 응집제를 제공한다.In addition, the coagulant prepared in step a) of the present invention includes a compound and aluminum oxide represented by the following [Formula 1], wherein the aluminum oxide content is 0.5 to 5% by weight relative to the total weight of the coagulant. provides

[화학식 1][Formula 1]

Al2(OH)nCl6-n 또는 Al(OH)nCl3-n (여기에서, n은 0 내지 1 사이의 값)Al 2 (OH) n Cl 6-n or Al(OH) n Cl 3-n (where n is a value between 0 and 1)

본 발명의 일 양태에서, 알루미늄 저감용 수처리 응집제는 염화이온을 포함하고, 염화이온은 응집제 총 중량대비 10 내지 30 중량%이다.In one aspect of the present invention, the water treatment coagulant for reducing aluminum includes chloride ions, and the chloride ions are 10 to 30% by weight based on the total weight of the coagulant.

본 발명의 일 양태에서, 알루미늄 저감용 수처리 응집제는 황화물, 염화물, 규산화물, 산화물; 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함한다. In one aspect of the present invention, the water treatment coagulant for aluminum reduction is sulfide, chloride, silicate, oxide; and at least one compound selected from the group consisting of salts thereof.

본 발명의 일 양태에서, 알루미늄 저감용 수처리 응집제는 2A족 화합물, 3A족 화합물, 4A족 화합물, 3B족 화합물, 4B족 화합물 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함한다. 구체적인 본 발명의 일 양태에서, 알루미늄 저감용 수처리 응집제는 2A족 염화물, 2A족 황화물, 3B족 염화물, 3B족 황화물, 4B족 염화물, 4B족 황화물, 규산나트륨(Na2SiO3) 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함한다.In one aspect of the present invention, the water treatment coagulant for reducing aluminum further comprises at least one compound selected from the group consisting of a group 2A compound, a group 3A compound, a group 4A compound, a group 3B compound, a group 4B compound, and salts thereof. In one specific aspect of the present invention, the water treatment coagulant for aluminum reduction is a group 2A chloride, a group 2A sulfide, a group 3B chloride, a group 3B sulfide, a group 4B chloride, a group 4B sulfide, sodium silicate (Na 2 SiO 3 ) and salts thereof It further comprises one or more compounds selected from the group consisting of.

또한, 본 발명의 일 양태에서, 알루미늄 저감용 수처리 응집제는 무기응집제 또는 유기응집제를 더 포함한다.In addition, in one aspect of the present invention, the water treatment coagulant for reducing aluminum further comprises an inorganic coagulant or an organic coagulant.

본 발명은 염산, 수산화알루미늄을 포함하는 응집제를 통해 수처리시 잔류알루미늄이 최소화 가능한 처리방법으로, 응집제를 단독으로 투입하는 방식, 무기 및/또는 유기 응집제와 병용하여 투입하는 방식 모두에 의해 잔류알루미늄이 저감될 수 있으며, 추가 물질이나 설비 등이 필요하지 않다는 이점이 있다.The present invention is a treatment method in which residual aluminum can be minimized during water treatment through a coagulant containing hydrochloric acid and aluminum hydroxide, and the residual aluminum It can be reduced and has the advantage that no additional materials or equipment are required.

또한, 본 발명은 pH, 알칼리도 저감효과를 가지고 있으므로, 종래 pH를 저감하기 위한 황산, 염산 대용으로 사용이 가능하다. 종래 황산, 염산의 농도가 10% 이상일 경우 유해화학물질로서 인체에 매우 유독하다는 문제가 있으나, 본 발명은 적은 투입량으로도 pH, 알칼리도를 낮출 수 있고, 인체에 유해하지 않으며, 알루미늄이 포함되어 수처리 효율을 증대할수 있는 이점이 있다.In addition, since the present invention has an effect of reducing pH and alkalinity, it can be used as a substitute for sulfuric acid and hydrochloric acid for reducing conventional pH. Conventionally, when the concentration of sulfuric acid and hydrochloric acid is 10% or more, there is a problem that it is very toxic to the human body as a hazardous chemical, but the present invention can lower the pH and alkalinity even with a small amount of input, is not harmful to the human body, and contains aluminum for water treatment It has the advantage of increasing efficiency.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명은 a) 염산, 수산화알루미늄 및 물을 혼합하여 응집제를 제조하되, 응집제 총 중량대비 염산 25 내지 90 중량%, 수산화알루미늄 0.5 내지 12 중량% 및 물 0.01 내지 70 중량%로 혼합하여 응집제를 제조하는 단계; 및 b1) 단계 a)의 응집제를 단독으로 투입하는 단계 또는 b2) 단계 a)의 응집제를 무기응집제 및/또는 유기응집제와 병용하여 투입하는 단계;를 포함하고, 여기에서, 상기 응집제는 산화알루미늄, 염화이온을 포함하는 것인 알루미늄 저감용 수처리방법에 관한 것이다.According to the present invention, a) hydrochloric acid, aluminum hydroxide and water are mixed to prepare a coagulant, but 25 to 90 wt% of hydrochloric acid, 0.5 to 12 wt% of aluminum hydroxide and 0.01 to 70 wt% of water, relative to the total weight of the coagulant, are mixed to prepare a coagulant to do; and b1) adding the coagulant of step a) alone or b2) adding the coagulant of step a) in combination with an inorganic coagulant and/or an organic coagulant, wherein the coagulant is aluminum oxide, It relates to a water treatment method for reducing aluminum that contains chloride ions.

본 명세서에서 염산과 같은 물질은 본 발명이 속하는 기술 분야에서 통상적으로 이해되는 것과 동일한 의미를 갖는다. 또한, 본 명세서에서 원수 처리는 하수 또는 폐수로서 내에 있는 오염물질을 제거하는 과정으로서, 본 발명이 속하는 기술 분야에서 통상적으로 이해되는 것과 동일한 의미를 갖는다.In this specification, a substance such as hydrochloric acid has the same meaning as commonly understood in the technical field to which the present invention pertains. In addition, in the present specification, raw water treatment is a process of removing contaminants in the sewage or wastewater, and has the same meaning as commonly understood in the technical field to which the present invention pertains.

본 발명에서 상기 단계 b1) 및 b2)는 순차적으로 진행되거나 b1) 또는 b2) 단계를 단독 또는 함께 진행될 수 있고 b1), b2) 단계의 순서에 한정되지 않는다. 본 발명에서 단계 b2)의 무기응집제를 단독으로 사용하는 경우 잔류알루미늄이 현저하게 높게 나타나므로 본 발명 응집제와 병용하여 사용되어 인, 황 제거 등의 수처리 효율이 높으면서도 잔류알루미늄이 낮은 효과를 나타낼 수 있다.In the present invention, the steps b1) and b2) may be performed sequentially, or the steps b1) or b2) may be performed alone or together, and the order of steps b1) and b2) is not limited. In the present invention, when the inorganic coagulant of step b2) is used alone, the residual aluminum appears remarkably high, so it can be used in combination with the coagulant of the present invention to exhibit a low residual aluminum effect while high water treatment efficiency such as phosphorus and sulfur removal. have.

본 발명에서 상기 단계 b2)의 무기응집제 및 유기응집제로 구성된 그룹으로부터 선택되는 1종 이상의 응집제와 병용하여 사용한다고 할 때, 이는 단계 a)의 응집제와 무기응집제 및 유기응집제를 병용하여 사용하는 경우, 및 단계 a)의 응집제와 무기응집제, 또는 단계 a)의 응집제와 유기응집제를 병용하여 사용하는 경우를 모두 포함한다.In the present invention, when used in combination with at least one coagulant selected from the group consisting of the inorganic coagulant and the organic coagulant of step b2), this is when the coagulant of step a) and the inorganic coagulant and the organic coagulant are used in combination, and the case of using the coagulant and the inorganic coagulant of step a) or the coagulant and the organic coagulant of step a) in combination.

또한, 본 발명에서 병용하여 사용한다고 할 때, 별도의 응집제 각각을 분리하여 사용하는 경우뿐만 아니라 각 응집제가 혼합되어 하나의 응집제 형태로서 사용하는 것을 포함한다. 예를 들어, 단계 a)의 응집제와 폴리수산화염화알루미늄이 혼합되어 하나의 용액 또는 분말 형태로서 존재할 수 있고, 이를 원수에 투입하는 경우, 및 각각의 성분이 분리되어 있고 사용 시 함께 사용하는 것이 모두 병용하여 사용하는 것에 해당한다.In addition, when used in combination in the present invention, it includes not only the case of using separate flocculants separately, but also mixing each flocculant and using it as a single flocculant. For example, the coagulant of step a) and aluminum hydroxide chloride may be mixed and present as one solution or powder form, and when it is added to raw water, each component is separated and used together at the time of use It corresponds to use in combination.

본 발명에서 응집제는 알루미늄 저감효과 이 외에도 KMnO4, 탁도 개선, pH 조절 등의 효과를 더 가지는 것으로 본 발명의 수처리방법을 알루미늄 저감효과에 한정하는 것은 아니다. 따라서, pH, 알칼리도가 높을 때 pH를 낮추기 위한 용도로서, 황산, 염산 대용으로도 사용이 가능할 수 있다.In the present invention, the coagulant has effects such as KMnO 4 , turbidity improvement, and pH control in addition to the aluminum reduction effect, and the water treatment method of the present invention is not limited to the aluminum reduction effect. Therefore, as a use for lowering the pH when the pH and alkalinity are high, it may be used as a substitute for sulfuric acid or hydrochloric acid.

본 발명에서, 단계 a)의 염산은 농도 30 내지 40 중량%, 수산화알루미늄은 농도 55 내지 65 중량%일 수 있다. 본 발명에서 염산, 수산화알루미늄을 물과 혼합하여 사용할 수 있으며, 염산 또는 수산화알루미늄을 물에 용해시킨 상태로 물과 혼합하는 경우 상기 농도 이외의 범위를 사용할 수 있다.In the present invention, the concentration of silver hydrochloric acid in step a) may be 30 to 40% by weight, and the concentration of aluminum hydroxide may be 55 to 65% by weight. In the present invention, hydrochloric acid and aluminum hydroxide can be mixed with water, and when hydrochloric acid or aluminum hydroxide is mixed with water in a state in which it is dissolved in water, a range other than the above concentration can be used.

본 발명의 일 양태에서, 단계 a)의 응집제는 응집제 총 중량대비 염화이온 함량은 10 내지 40 %이고, 산화알루미늄 함량은 0.5 내지 5 %이다. 구체적인 본 발명의 일 양태에서, 단계 a)의 응집제는 염화이온 함량 10 내지 30 중량%, 산화알루미늄 함량 1 내지 3 중량%이다. 본 발명에서 응집제의 염화이온 및 산화알루미늄의 함량이 주요한 특징을 가지는 것으로, 염화이온이 9% 이하인 경우 산화알루미늄을 녹이기에 충분하지 않아 응집제가 만들어지지 않으며 염화이온이 40 % 초과인 경우 미 반응된 염화이온이 잔류하여 유독성이 있을 수 있고, 추가적인 처리과정이 필요할 수 있다. 또한, 산화알루미늄의 농도가 0.5 % 미만인 경우 응집능력이 없으며, 6% 이상인 경우 잔류알루미늄이 증가하여 본 발명의 목적과 달리하는 효과가 발생할 수 있다.In one aspect of the present invention, the coagulant in step a) has a chloride ion content of 10 to 40% and an aluminum oxide content of 0.5 to 5% relative to the total weight of the coagulant. In a specific aspect of the present invention, the coagulant of step a) has a chloride ion content of 10 to 30 wt% and an aluminum oxide content of 1 to 3 wt%. In the present invention, the content of chloride ions and aluminum oxide in the coagulant is a major characteristic. If the chloride ion is 9% or less, the coagulant is not made because it is not sufficient to dissolve the aluminum oxide, and if the chloride ion is more than 40%, the unreacted Residual chloride ions may be toxic and may require additional treatment. In addition, when the concentration of aluminum oxide is less than 0.5%, there is no agglomeration ability, and when it is 6% or more, the residual aluminum increases, and an effect different from the object of the present invention may occur.

또한, 본 발명에서 상기 단계 a)의 응집제는 염화이온과 산화알루미늄 이외의 물질, 예를 들면 2A족 금속의 황화물, 3B족 금속의 염화물, 4B족 금속의 황화물 등과 같은 다른 종류의 화합물을 더 포함할 수 있다. 2A족 금속의 염화물로 염화칼슘(CaCl2), 3A족 화합물로 황산갈륨(Ga2(SO4)3), 4A족 화합물로 규산나트륨(Na2SiO3), 4A족 화합물로 규산칼륨(K2SiO3), 제올라이트 등이 있으며, 이는 예시적인 것으로 이에 한정되는 것은 아니다.In addition, in the present invention, the coagulant of step a) further includes other types of compounds such as chloride ions and materials other than aluminum oxide, for example, sulfides of Group 2A metals, chlorides of Group 3B metals, and sulfides of Group 4B metals. can do. Calcium chloride (CaCl 2 ) as a chloride of a group 2A metal, gallium sulfate (Ga 2 (SO 4 ) 3 ) as a group 3A compound, sodium silicate (Na 2 SiO 3 ) as a group 4A compound, potassium silicate (K 2 ) as a group 4A compound SiO 3 ), zeolite, and the like, which are exemplary and not limited thereto.

본 발명의 일 양태에서 상기 단계 a)의 응집제는 황화물, 염화물, 규산화물, 산화물; 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함할 수 있고, 더 구체적으로 2A족 화합물, 3A족 화합물, 4A족 화합물, 3B족 화합물, 4B족 화합물 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함할 수 있으며. 보다 더 구체적으로 2A족 염화물, 2A족 황화물, 3B족 염화물, 3B족 황화물, 4B족 염화물, 4B족 황화물, 규산나트륨(Na2SiO3) 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함할 수 있다.In one aspect of the present invention, the coagulant of step a) is sulfide, chloride, silicate, oxide; and one or more compounds selected from the group consisting of salts thereof, and more specifically, from the group consisting of a group 2A compound, a group 3A compound, a group 4A compound, a group 3B compound, a group 4B compound, and salts thereof. It may further include one or more selected compounds. More specifically, at least one compound selected from the group consisting of Group 2A chloride, Group 2A sulfide, Group 3B chloride, Group 3B sulfide, Group 4B chloride, Group 4B sulfide, sodium silicate (Na 2 SiO 3 ) and salts thereof may include more.

또한, 본 발명에서 상기 단계 a)의 응집제는 상기 2A족 화합물, 3A족 화합물 등의 화합물 뿐만 아니라 폴리아크릴아마이드계, 폴리비닐아민계 등의 유기응집제 및/또는 알루미늄계 등의 무기응집제를 더 포함한 형태일 수 있다.In addition, in the present invention, the coagulant of step a) includes not only compounds such as the group 2A compound and the group 3A compound, but also an organic coagulant such as polyacrylamide and polyvinylamine and/or an inorganic coagulant such as aluminum. may be in the form

본 발명에서, 단계 b2)의 무기응집제는 알루미늄계 응집제, 철염계 응집제 또는 이들의 혼합응집제일 수 있다. 알루미늄계 응집제는 예를 들면, 황산알루미늄(Alum), 폴리염화알루미늄(Poly aluminium chloride) 등이 있고, 철염계 응집제는 염화제이철(Ferric chloride, FeCl3), 염화제일철(Ferrouschloride, FeCl2), 황산제이철(Ferric sulfate, Fe2(SO4)3), 황산제일철(Ferrous sulfate, Fe(SO)4), 폴리염화철(polyferric chloride, PFC), 폴리황산철(polyferric sulfate, PFS), 폴리규산철(polysilicate iron) 등이 있으며, 본 발명에서 알루미늄계 응집제 및 철염계 응집제는 상기 예시에 한정되지 않는다. 또한, 이들의 혼합응집제는 알루미늄계와 철염계를 모두 가지고 있는 응집제를 의미하며, 예를 들면, 폴리염화알루미늄철, 알루미늄철, 폴리염화황산알루미늄철 등이 있다.In the present invention, the inorganic coagulant in step b2) may be an aluminum-based coagulant, an iron salt-based coagulant, or a mixed coagulant thereof. The aluminum-based coagulant is, for example, aluminum sulfate (Alum), poly aluminum chloride, etc., and the iron salt-based coagulant is ferric chloride (FeCl 3 ), ferrous chloride (FeCl 2 ), sulfuric acid. Ferric sulfate (Fe 2 (SO 4 ) 3 ), ferrous sulfate (Fe(SO) 4 ), polyferric chloride (PFC), polyferric sulfate (PFS), polyferric silicate ( polysilicate iron) and the like, and in the present invention, the aluminum-based coagulant and the iron salt-based coagulant are not limited to the above examples. In addition, these mixed coagulants refer to coagulants having both aluminum-based and iron salt-based systems, and for example, polyaluminum iron, aluminum iron, polychlorinated aluminum sulfate, and the like.

구체적인 본 발명의 일 양태에서, 단계 b2)의 알루미늄계 응집제는 염화알루미늄, 황산알루미늄, 폴리염산알루미늄, 폴리염화알루미늄, 폴리염산규산알루미늄, 폴리염화규산알루미늄, 폴리수산화염화규산알루미늄, 폴리염산규산알루미늄 및 폴리수산화염화염산알루미늄로 구성된 그룹으로부터 선택된 1종 이상이다. 보다 구체적인 본 발명의 일 양태에서, 단계 b2)의 무기응집제는 폴리염화알루미늄 또는 폴리수산화염화황산알루미늄이다.In a specific aspect of the present invention, the aluminum-based coagulant of step b2) is aluminum chloride, aluminum sulfate, It is at least one selected from the group consisting of polyaluminum hydrochloride, polyaluminum chloride, polyaluminum silicate hydrochloride, polyaluminum chloride silicate, aluminum polyhydroxychloride silicate, aluminum polyhydrochloride silicate and polyaluminum hydrochloride hydrochloride. In a more specific aspect of the present invention, the inorganic coagulant in step b2) is polyaluminum chloride or polyaluminum chloride hydrochloride sulfate.

본 발명의 일 양태에서, 단계 b2)의 알루미늄계 응집제는 알루미늄계 응집제 총 중량대비 산화알루미늄 함량이 5 내지 25%이다. 구체적인 본 발명의 일 양태에서, 알루미늄계 응집제는 총 중량대비 산화알루미늄 함량이 7 내지 20 %이다.In one aspect of the present invention, the aluminum-based coagulant of step b2) has an aluminum oxide content of 5 to 25% based on the total weight of the aluminum-based coagulant. In a specific aspect of the present invention, the aluminum-based coagulant has an aluminum oxide content of 7 to 20% based on the total weight.

본 발명에서, 단계 b2)의 유기응집제는 폴리아크릴아마이드계, 폴리비닐아민계, 폴리알릴아민계, 폴리에틸렌아민계, 폴리아민계, 폴리아크릴에스테르계, 폴리에틸렌이민계, 폴리데드막 및 이들의 혼합응집제로 구성된 그룹으로부터 선택된 1종 이상일 수 있다.In the present invention, the organic coagulant of step b2) is polyacrylamide-based, polyvinylamine-based, polyallylamine-based, polyethyleneamine-based, polyamine-based, polyacrylic ester-based, polyethyleneimine-based, polydead film, and mixed coagulants thereof. It may be at least one selected from the group consisting of.

본 발명의 일 양태에서, 수처리방법은 처리 후 처리수의 탁도가 2 NTU 이하이다. 구체적인 본 발명의 일 양태에서, 수처리방법은 처리 후 처리수의 탁도가 1.5 NTU 이하일 수 있다. 더 구체적인 본 발명의 일 양태에서, 단계 b1) 또는 단계 b2)에 의한 수처리방법은 처리 후 처리수의 탁도가 1.5 NTU 이하일 수 있다. 더 구체적인 본 발명의 일 양태에서, 단계 b1) 또는 단계 b2)에 의한 수처리방법은 처리 후 처리수의 탁도가 1.0 NTU 이하일 수 있다.In one aspect of the present invention, in the water treatment method, the turbidity of the treated water after treatment is 2 NTU or less. In a specific aspect of the present invention, in the water treatment method, the turbidity of the treated water after treatment may be 1.5 NTU or less. In a more specific aspect of the present invention, in the water treatment method according to step b1) or step b2), the turbidity of the treated water after treatment may be 1.5 NTU or less. In a more specific aspect of the present invention, in the water treatment method according to step b1) or step b2), the turbidity of the treated water after treatment may be 1.0 NTU or less.

본 발명의 일 양태에서, 수처리방법은 pH를 8.5 이하까지 투입하는 것이다. 또한, 본 발명에서 단계 b1) 또는 b2)에서 pH를 8.5 이하까지 투입할 수 있다. 구체적인 본 발명의 일 양태에서, 수처리방법은 처리 후 처리수의 pH가 8.0 이하이다. 보다 구체적인 본 발명의 일 양태에서, 수처리방법은 처리 후 처리수의 pH가 7.0 내지 8.0이다. In one aspect of the present invention, the water treatment method is to input the pH to 8.5 or less. In addition, in the present invention, the pH may be added up to 8.5 or less in step b1) or b2). In a specific aspect of the present invention, in the water treatment method, the pH of the treated water after treatment is 8.0 or less. In a more specific aspect of the present invention, in the water treatment method, the pH of the treated water after treatment is 7.0 to 8.0.

본 발명 수처리방법을 통해 탁도와 pH 조건을 동시에 달성할 수 있으며, 이와 동시에 알루미늄처리도 가능함으로써 우수한 효과를 나타낸다. 또한, 본 발명 수처리방법은 통상 pH를 저하시키기 위해 투입되는 염산, 황산의 투입량보다 적은 양을 투여하더라도 원하는 pH 조건을 달성할 수 있다.Through the water treatment method of the present invention, turbidity and pH conditions can be achieved at the same time, and at the same time, aluminum treatment is also possible, thereby exhibiting an excellent effect. In addition, in the water treatment method of the present invention, a desired pH condition can be achieved even when an amount less than the amount of hydrochloric acid and sulfuric acid that is usually added to lower the pH is administered.

본 발명의 일 양태에서, 본 발명 수처리방법은 상기 단계 a)의 응집제를 미투입한 경우와 비교하여 잔류알루미늄이 5 내지 90 %로 저감될 수 있다. 보다 구체적인 본 발명의 일 양태에서, 잔류알루미늄이 10 내지 70%로 저감될 수 있다.In one aspect of the present invention, in the water treatment method of the present invention, the residual aluminum can be reduced by 5 to 90% compared to the case where the coagulant of step a) is not added. In a more specific aspect of the present invention, residual aluminum may be reduced to 10 to 70%.

또한, 본 발명의 단계 a)에서 제조된 응집제는 하기 [화학식 1]로 표현되는 화합물 및 산화알루미늄을 포함하고, 여기에서 산화알루미늄 함량은 응집제 총 중량대비 0.5 내지 5 중량%인 알루미늄 저감용 수처리 응집제를 제공한다.In addition, the coagulant prepared in step a) of the present invention includes a compound and aluminum oxide represented by the following [Formula 1], wherein the aluminum oxide content is 0.5 to 5% by weight relative to the total weight of the coagulant. provides

[화학식 1][Formula 1]

Al2(OH)nCl6-n 또는 Al(OH)nCl3-n (여기에서, n은 0 내지 1 사이의 값)Al 2 (OH) n Cl 6-n or Al(OH) n Cl 3-n (where n is a value between 0 and 1)

본 발명의 일 양태에서, 알루미늄 저감용 수처리 응집제는 염화이온을 포함하고, 염화이온은 응집제 총 중량대비 10 내지 30 중량%이다.In one aspect of the present invention, the water treatment coagulant for reducing aluminum includes chloride ions, and the chloride ions are 10 to 30% by weight based on the total weight of the coagulant.

본 발명의 일 양태에서, 알루미늄 저감용 수처리 응집제는 황화물, 염화물, 규산화물, 산화물; 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함할 수 있고, 더 구체적으로 2A족 화합물, 3A족 화합물, 4A족 화합물, 3B족 화합물, 4B족 화합물 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함할 수 있으며. 보다 더 구체적으로 2A족 염화물, 2A족 황화물, 3B족 염화물, 3B족 황화물, 4B족 염화물, 4B족 황화물, 규산나트륨(Na2SiO3) 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함할 수 있다.In one aspect of the present invention, the water treatment coagulant for aluminum reduction is sulfide, chloride, silicate, oxide; and one or more compounds selected from the group consisting of salts thereof, and more specifically, from the group consisting of a group 2A compound, a group 3A compound, a group 4A compound, a group 3B compound, a group 4B compound, and salts thereof. It may further include one or more selected compounds. More specifically, at least one compound selected from the group consisting of Group 2A chloride, Group 2A sulfide, Group 3B chloride, Group 3B sulfide, Group 4B chloride, Group 4B sulfide, sodium silicate (Na 2 SiO 3 ) and salts thereof may include more.

또한, 본 발명의 일 양태에서, 상기 알루미늄 저감용 수처리 응집제는 무기응집제 또는 유기응집제를 더 포함할 수 있다. 구체적인 본 발명의 일 양태에서, 상기 무기응집제는 염화알루미늄, 황산알루미늄, 폴리황산알루미늄, 폴리염화알루미늄, 폴리황산규산알루미늄, 폴리염화규산알루미늄, 폴리수산화염화규산알루미늄, 폴리황산규산알루미늄 및 폴리수산화염화황산알루미늄로 구성된 그룹으로부터 선택된 1종 이상일 수 있고, 구체적인 본 발명의 일 양태에서, 상기 유기응집제는 폴리아크릴아마이드계, 폴리비닐아민계, 폴리알릴아민계, 폴리에틸렌아민계, 폴리아민계, 폴리아크릴에스테르계, 폴리에틸렌이민계, 폴리데드막 및 이들의 혼합응집제로 구성된 그룹으로부터 선택된 1종 이상일 수 있다.In addition, in one aspect of the present invention, the water treatment coagulant for reducing aluminum may further include an inorganic coagulant or an organic coagulant. In a specific aspect of the present invention, the inorganic coagulant is aluminum chloride, aluminum sulfate, polyaluminum sulfate, polyaluminum chloride, polyaluminum silicate polysulfate, polyaluminum chloride silicate, polyhydroxychloride aluminum silicate, polyaluminum silicate sulfate and polyhydroxychloride chloride. It may be at least one selected from the group consisting of aluminum sulfate, and in a specific aspect of the present invention, the organic coagulant is polyacrylamide-based, polyvinylamine-based, polyallylamine-based, polyethyleneamine-based, polyamine-based, polyacrylic ester It may be at least one selected from the group consisting of a polyvinyl chloride-based, polyethyleneimine-based, poly-dead film, and a mixed coagulant thereof.

또한, 본 발명에서 상기 알루미늄 저감용 응집제는 상기 2A족 화합물, 3A족 화합물 등의 화합물 뿐만 아니라 폴리아크릴아마이드계, 폴리비닐아민계 등의 유기응집제 및/또는 알루미늄계 등의 무기응집제를을 더 포함한 형태일 수 있다.In addition, in the present invention, the coagulant for aluminum reduction includes not only compounds such as the group 2A compound and the group 3A compound, but also an organic coagulant such as polyacrylamide and polyvinylamine and/or an inorganic coagulant such as aluminum. may be in the form

이하, 본 발명을 실시예 및 실험예에 의해 상세히 설명한다.Hereinafter, the present invention will be described in detail by way of Examples and Experimental Examples.

단, 하기 실시예 및 실험예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예 및 실험예에 한정되는 것은 아니다.However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following Examples and Experimental Examples.

<실시예 1> 염산계열 응집제의 제조<Example 1> Preparation of hydrochloric acid-based coagulant

하기 표 1와 같이, 수산화알루미늄, 염산 및 물의 조성비율을 조절하여 염산계열 응집제를 제조하였다. 구체적으로, 제조원료의 성상은 수산화알루미늄 63%, 염산(HCl) 농도 35%를 사용하였으며, 제조비율을 달리하여 염화이온 농도 10 내지 30 %, 산화알루미늄 농도 0.5 내지 7 %가 되도록 응집제를 제조하였다.As shown in Table 1 below, a hydrochloric acid-based coagulant was prepared by adjusting the composition ratio of aluminum hydroxide, hydrochloric acid, and water. Specifically, the properties of the raw material used were aluminum hydroxide 63%, hydrochloric acid (HCl) concentration of 35%, and the production ratio was changed to prepare a coagulant so that the chloride ion concentration was 10 to 30% and the aluminum oxide concentration was 0.5 to 7%. .

실시예Example S 0.5S 0.5 S 1S 1 S 3S 3 S 5S 5 S 6S 6 S 7S 7 1) 염화이온 농도 10%1) Chloride ion concentration 10% 성상appearance Al2O3 (%)Al 2 O 3 (%) 0.50.5 1One 33 55 66 77 염소이온 (%)Chloride ion (%) 1010 제조비율production rate 수산화 알루미늄aluminum hydroxide 88 1717 5050 8383 100100 117117 염산Hydrochloric acid 294294 물water 698698 689689 656656 623623 606606 589589 2) 염화이온 농도 20%2) Chloride ion concentration 20% 성상appearance Al2O3 (%)Al 2 O 3 (%) 0.50.5 1One 33 55 66 77 염소이온 (%)Chloride ion (%) 2020 제조비율production rate 수산화 알루미늄aluminum hydroxide 88 1717 5050 8383 100100 117117 염산Hydrochloric acid 588588 물water 404404 395395 362362 329329 312312 295295 3) 염화이온 농도 30%3) Chloride ion concentration 30% 성상appearance Al2O3 (%)Al 2 O 3 (%) 0.50.5 1One 33 55 66 77 염소이온 (%)Chloride ion (%) 3030 제조비율production rate 수산화 알루미늄aluminum hydroxide 88 1717 5050 8383 100100 117117 염산Hydrochloric acid 882882 물water 110110 101101 6868 3535 1818 1One

<실험예 1> 염산계열 응집제의 잔류알루미늄 저감효과<실험예 1-1> 염화이온 농도 10% 응집제의 저감효과<Experimental Example 1> Effect of reducing residual aluminum of hydrochloric acid-based coagulant <Experimental Example 1-1> Reducing effect of 10% chloride ion concentration of coagulant

실시예 1에서 제조된 염산계열 응집제를 D 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 응집실험에 사용된 원수의 성상, 응집제 투입량 및 투입결과는 표 2와 같다.The hydrochloric acid-based coagulant prepared in Example 1 was collected in water from the D water purification plant, and a coagulation experiment using Jar-test was performed. Table 2 shows the properties of raw water used in the coagulation experiment, the amount of coagulant input, and the input results.

9% 염산9% hydrochloric acid 실시예Example S 0.5S 0.5 S 1S 1 S 3S 3 S 5S 5 S 6S 6 S 7S 7 성상appearance Al2O3 (%)Al 2 O 3 (%) -- 0.50.5 1One 33 55 66 77 염소이온 (%)Chloride ion (%) -- 1010 투입량 (ppm)Dosage (ppm) 7070 6565 pHpH 7.177.17 7.167.16 7.157.15 7.167.16 7.137.13 7.137.13 7.157.15 탁도 (NTU)Turbidity (NTU) 1.971.97 1.371.37 1.251.25 1.241.24 1.101.10 0.9570.957 0.8920.892 알칼리도 (mg/l)Alkalinity (mg/l) 14.814.8 14.814.8 14.814.8 14.714.7 14.514.5 14.614.6 14.714.7 KMnO4 (mg/l)KMnO 4 (mg/l) 17.517.5 14.714.7 14.214.2 12.512.5 11.211.2 9.49.4 8.78.7 Al (mg/l)Al (mg/l) 0.0230.023 0.0200.020 0.0180.018 0.0170.017 0.0220.022 0.0470.047 0.0580.058 원수성상foe constellation pH 8.32, 탁도 2.28NTU, 알칼리도 18.7mg/l, KMnO4 17.9mg/l, Al 0.023mg/lpH 8.32, turbidity 2.28NTU, alkalinity 18.7mg/l, KMnO 4 17.9mg/l, Al 0.023mg/l

<실험예 1-2> 염화이온 농도 20% 응집제의 저감효과실시예 1에서 제조된 염산계열 응집제를 D 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 응집실험에 사용된 원수의 성상, 응집제 투입량 및 투입결과는 표 3과 같다. <Experimental Example 1-2> Reduction effect of 20% chloride ion concentration of the coagulant The hydrochloric acid-based coagulant prepared in Example 1 was collected in water from the D water purification plant, and a coagulation experiment using Jar-test was performed. Table 3 shows the properties of raw water used in the coagulation experiment, the amount of coagulant input, and the input results.

9% 염산9% hydrochloric acid 실시예Example S 0.5S 0.5 S 1S 1 S 3S 3 S 5S 5 S 6S 6 S 7S 7 성상appearance Al2O3 (%)Al 2 O 3 (%) -- 0.50.5 1One 33 55 66 77 염소이온 (%)Chloride ion (%) -- 2020 투입량 (ppm)Dosage (ppm) 7070 3030 pHpH 7.157.15 7.177.17 7.167.16 7.147.14 7.157.15 7.137.13 7.157.15 탁도 (NTU)Turbidity (NTU) 1.951.95 1.451.45 1.421.42 1.271.27 1.141.14 1.011.01 0.9410.941 알칼리도 (mg/l)Alkalinity (mg/l) 14.614.6 14.814.8 14.714.7 14.614.6 14.514.5 14.414.4 14.614.6 KMnO4 (mg/l)KMnO 4 (mg/l) 17.117.1 14.314.3 14.114.1 12.412.4 10.810.8 9.29.2 8.58.5 Al (mg/l)Al (mg/l) 0.0250.025 0.0210.021 0.0160.016 0.0170.017 0.0230.023 0.0350.035 0.0460.046 원수성상foe constellation pH 8.42, 탁도 2.11NTU, 알칼리도 18.5mg/l, KMnO4 17.8mg/l, Al 0.026mg/lpH 8.42, turbidity 2.11NTU, alkalinity 18.5mg/l, KMnO 4 17.8mg/l, Al 0.026mg/l

<실험예 1-3> 염화이온 농도 30% 응집제의 저감효과실시예 1에서 제조된 염산계열 응집제를 D 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 응집실험에 사용된 원수의 성상, 응집제 투입량 및 투입결과는 표 4와 같다. <Experimental Example 1-3> Reducing effect of the coagulant with a chloride ion concentration of 30% The hydrochloric acid-based coagulant prepared in Example 1 was collected from water at the D water purification plant and a coagulation experiment using Jar-test was performed. Table 4 shows the properties of raw water used in the coagulation experiment, the amount of coagulant input, and the input results.

9% 염산9% hydrochloric acid 실시예Example S 0.5S 0.5 S 1S 1 S 3S 3 S 5S 5 S 6S 6 S 7S 7 성상appearance Al2O3 (%)Al 2 O 3 (%) -- 0.50.5 1One 33 55 66 77 염소이온 (%)Chloride ion (%) -- 3030 투입량 (ppm)Dosage (ppm) 7070 3030 pHpH 7.137.13 7.107.10 7.127.12 7.107.10 7.117.11 7.137.13 7.127.12 탁도 (NTU)Turbidity (NTU) 1.901.90 1.591.59 1.551.55 1.461.46 1.281.28 1.131.13 1.021.02 알칼리도 (mg/l)Alkalinity (mg/l) 14.614.6 14.414.4 14.514.5 14.414.4 14.614.6 14.614.6 14.314.3 KMnO4 (mg/l)KMnO 4 (mg/l) 17.317.3 14.714.7 14.514.5 12.712.7 11.611.6 9.99.9 9.29.2 Al (mg/l)Al (mg/l) 0.0220.022 0.0190.019 0.0170.017 0.0180.018 0.0210.021 0.0370.037 0.0480.048 원수성상foe constellation pH 8.14, 탁도 2.12NTU, 알칼리도 18.5mg/l, KMnO4 18.0mg/l, Al 0.022mg/lpH 8.14, turbidity 2.12NTU, alkalinity 18.5mg/l, KMnO 4 18.0mg/l, Al 0.022mg/l

표 2, 3 및 4에 나타난 바와 같이, 염산 9%인 경우 알루미늄이 없기에 응집능력이 없어, 탁도, KMnO4, Al 등이 제거되지 않았으며, 산화알루미늄의 농도가 높을수록 수처리효율이 우수하게 나타났다. 또한, 산화알루미늄의 농도가 0.5 내지 5 %에서는 잔류 알루미늄이 원수보다 낮게 검출되어 잔류알루미늄 저감효과가 우수함을 확인하였으나, 산화알루미늄 농도가 6% 이상인 경우 원수보다 높은 잔류 알루미늄이 검출되어 잔류알루미늄 저감효과가 없음을 확인하였다.As shown in Tables 2, 3 and 4, in the case of 9% hydrochloric acid, there was no aggregation ability because there was no aluminum, turbidity, KMnO 4 , Al, etc. were not removed, and the higher the concentration of aluminum oxide, the better the water treatment efficiency. . In addition, when the concentration of aluminum oxide was 0.5 to 5%, the residual aluminum was detected lower than the raw water, and it was confirmed that the residual aluminum reduction effect was excellent, but when the aluminum oxide concentration was 6% or more, the residual aluminum was detected higher than the raw water It was confirmed that there is no

<실험예 2> 첨가제를 더 포함한 염산계열 응집제의 잔류알루미늄 저감효과<Experimental Example 2> Residual aluminum reduction effect of hydrochloric acid-based coagulant containing additives

실시예 1의 방법에 의해 제조된 염산계열 응집제에 첨가제(2A족, 3A족, 4A족, 3B족, 4B족 물질)를 더 포함시킨 후, H 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 응집실험에 사용된 원수의 성상, 응집제 투입량, 첨가제의 종류 및 투입결과는 표 5에 나타난 바와 같다.After adding an additive (group 2A, group 3A, group 4A, group 3B, group 4B material) to the hydrochloric acid-based coagulant prepared by the method of Example 1, water was collected from the H water purification plant and coagulation using Jar-test An experiment was conducted. Table 5 shows the properties of raw water used in the coagulation test, the amount of coagulant input, the type of additive, and the input result.

9% 염산9% hydrochloric acid 실시예 (+첨가제)Example (+additives) 미첨가unadded 2A족2A group 3A족3A group 4A족4A group 3B족3B group 4B족4B group 투입량 (ppm)Dosage (ppm) 9595 4545 pHpH 7.157.15 7.097.09 7.057.05 7.117.11 7.107.10 7.087.08 7.117.11 탁도 (NTU)Turbidity (NTU) 2.982.98 0.9170.917 0.9060.906 0.9110.911 0.9030.903 0.9080.908 0.9050.905 Al (mg/l)Al (mg/l) 0.0240.024 0.0210.021 0.0190.019 0.0170.017 0.0180.018 0.0180.018 0.0190.019 비고note 1) 원수성상 : pH 8.62, 탁도 3.13NTU, Al 0.026mg/l
2) 염산계열 응집제 성상: Al2O3 4% 염소이온 19%
3) 첨가제 성상
- 2A족 물질 : CaCl2 0.5중량부% 첨가
- 3A족 물질 : Ga2(SO4)3 0.5중량부% 첨가
- 4A족 물질 : Na2SiO3 0.5중량부% 첨가
- 3B족 물질 : YCl3·6H2O 0.5중량부% 첨가
- 4B족 물질 : ZrCl4 0.5중량부% 첨가1) Raw water phase: pH 8.62, turbidity 3.13NTU, Al 0.026mg/l
2) Hydrochloric acid-based coagulant properties: Al 2 O 3 4% Chloride ion 19%
3) Additive properties
- Group 2A material: CaCl 2 0.5 parts by weight added
- Group 3A material: Ga 2 (SO 4 ) 3 0.5 parts by weight added
- Group 4A material: Na 2 SiO 3 0.5 parts by weight added
- Group 3B material: YCl 3 6H 2 O 0.5 parts by weight added
- Group 4B material: ZrCl 4 0.5 parts by weight added

표 5에 나타난 바와 같이, 염산 9%의 경우 응집능력이 없어, 탁도, 알루미늄 등이 저감되지 않았다. 또한, 염산계열 응집제에 첨가제를 더 포함한 경우 첨가제를 포함하지 않는 경우와 비교하여 탁도제거효율 및 잔류알루미늄 저감효과가 더 우수하게 나타난 것을 확인하였다. 또한, 첨가제의 종류가 상이하더라도 수처리효율에 큰 변화가 없음을 확인하였다.<실험예 3> 첨가제를 더 포함한 염산계열 응집제의 잔류알루미늄 저감효과 As shown in Table 5, in the case of 9% hydrochloric acid, there was no aggregation ability, and turbidity, aluminum, etc. were not reduced. In addition, it was confirmed that the turbidity removal efficiency and the effect of reducing residual aluminum were more excellent when the hydrochloric acid-based coagulant was further included as compared to the case where the additive was not included. In addition, it was confirmed that there was no significant change in the water treatment efficiency even if the types of additives were different. <Experimental Example 3> Residual aluminum reduction effect of hydrochloric acid-based coagulant containing additives

실시예 1의 방법에 의해 염산계열 응집제에 첨가제(유기응집제로서 폴리아민)를 더 포함시킨 후, I 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 응집실험에 사용된 원수의 성상, 응집제 투입량, 첨가제의 혼합비율 및 투입결과는 표 6에 나타난 바와 같다.After adding an additive (polyamine as an organic coagulant) to the hydrochloric acid-based coagulant according to the method of Example 1, water from the I water purification plant was collected and an agglomeration experiment using Jar-test was performed. The properties of the raw water used in the flocculation experiment, the amount of coagulant input, the mixing ratio of the additives and the input results are as shown in Table 6.

9% 염산9% hydrochloric acid 실시예 (+ Polymer 혼합비율)Example (+ Polymer mixing ratio) 0%0% 0.5%0.5% 1%One% 3%3% 5%5% 7%7% 투입량 (ppm)Dosage (ppm) 7575 3535 3535 3535 3535 3535 3535 pHpH 7.117.11 7.067.06 7.097.09 7.117.11 7.127.12 7.147.14 7.257.25 탁도 (NTU)Turbidity (NTU) 3.863.86 1.211.21 1.021.02 0.9710.971 0.8610.861 0.7910.791 0.7420.742 Al (mg/l)Al (mg/l) 0.0250.025 0.0240.024 0.0240.024 0.0220.022 0.0200.020 0.0210.021 0.0250.025 비고note 1) 원수성상: pH 8.37, 탁도 4.01NTU, Al 0.025mg/l
2) 염산계열 응집제 성상: Al2O3 2% 염소이온 25%
3) 첨가제 성상: Polymer - 폴리아민(Polyamine)1) Raw water phase: pH 8.37, turbidity 4.01NTU, Al 0.025mg/l
2) Hydrochloric acid-based coagulant properties: Al 2 O 3 2% Chloride ion 25%
3) Additive properties: Polymer - Polyamine

표 6에 나타난 바와 같이, 염산 9%의 경우 응집능력이 없어, 탁도, 알루미늄 등이 저감되지 않았다. 또한, 염산계열 응집제에 폴리머를 혼합한 제품의 경우 폴리머의 혼합비율이 상승할수록 탁도제거효율은 우수하였으나, 7%이상을 초과하여 혼합하는 경우 잔류알루미늄 저감효과가 떨어지는 것을 확인하였다. 산화알루미늄의 농도가 높을수록 수처리효율이 우수하게 나타났다. 또한, 염산이온의 농도가 높을수록 pH 조절시 필요한 응집제의 양이 적어졌음을 확인하였다.<실험예 4> 첨가제를 더 포함한 염산계열 응집제의 잔류알루미늄 저감효과 As shown in Table 6, in the case of 9% hydrochloric acid, there was no aggregation ability, and turbidity, aluminum, etc. were not reduced. In addition, in the case of a product in which a polymer was mixed with a hydrochloric acid-based coagulant, the turbidity removal efficiency was excellent as the mixing ratio of the polymer increased. The higher the concentration of aluminum oxide, the better the water treatment efficiency. In addition, it was confirmed that the higher the concentration of hydrochloric acid ions, the less the amount of coagulant required for pH adjustment. <Experimental Example 4> Residual aluminum reduction effect of hydrochloric acid-based coagulant containing additives

실시예 1의 방법에 의해 염산계열 응집제에 첨가제(2A족, 4B족 물질, Polymer)를 더 포함시킨 후, J 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 응집실험에 사용된 원수의 성상, 응집제 투입량, 첨가제의 종류 및 투입결과는 표 7에 나타난 바와 같다.After adding an additive (group 2A, group 4B material, polymer) to the hydrochloric acid-based coagulant according to the method of Example 1, water was collected from the J water purification plant and an agglomeration experiment using Jar-test was performed. Table 7 shows the properties of raw water used in the coagulation test, the amount of coagulant input, the type of additive, and the input result.

9% 염산9% hydrochloric acid 실시예 (+ 첨가제)Examples (+ Additives) 미첨가unadded 2A족2A group 4B족4B group 투입량 (ppm)Dosage (ppm) 190190 8585 8585 8585 pHpH 7.137.13 7.057.05 7.147.14 7.087.08 탁도 (NTU)Turbidity (NTU) 2.952.95 0.9230.923 0.9180.918 0.9150.915 Al (mg/l)Al (mg/l) 0.0220.022 0.0190.019 0.0150.015 0.0170.017 비고note 1) 원수성상 : pH 9.01, 탁도 3.11NTU, Al 0.022mg/l
2) 염산계열 응집제 성상: Al2O3 3% 염소이온 21%
3) 첨가제 성상
- 2A족 물질 : CaCl2 0.5중량부% 첨가
- 4B족 물질 : ZrCl4 0.5중량부% 첨가
- Polymer : 폴리데드막(PolyDADMAC) 3 중량부% 첨가1) Raw water phase: pH 9.01, turbidity 3.11NTU, Al 0.022mg/l
2) Hydrochloric acid-based coagulant properties: Al 2 O 3 3% Chloride ion 21%
3) Additive properties
- Group 2A material: CaCl 2 0.5 parts by weight added
- Group 4B material: ZrCl 4 0.5 parts by weight added
- Polymer: 3 parts by weight of PolyDADMAC added

표 7에 나타난 바와 같이, 염산 9%의 경우 응집능력이 없어, 탁도, 알루미늄 등이 저감되지 않았다. 또한, 염산계열 응집제에 첨가제를 더 포함한 경우 첨가제를 포함하지 않는 경우와 비교하여 탁도제거효율 및 잔류알루미늄 저감효과가 더 우수하게 나타난 것을 확인하였다. 또한, 첨가제의 종류가 상이하더라도 수처리효율에 큰 변화가 없음을 확인하였다.<실험예 5> 염산계열 응집제의 병용사용시 잔류알루미늄 저감효과 As shown in Table 7, in the case of 9% hydrochloric acid, there was no aggregation ability, and turbidity, aluminum, etc. were not reduced. In addition, it was confirmed that the turbidity removal efficiency and the effect of reducing residual aluminum were more excellent when the hydrochloric acid-based coagulant was further included as compared to the case where the additive was not included. In addition, it was confirmed that there was no significant change in the water treatment efficiency even if the types of additives were different. <Experimental Example 5> Residual aluminum reduction effect when using hydrochloric acid-based coagulant in combination

<실험예 5-1> 염화이온 농도 10% 응집제의 저감효과<Experimental Example 5-1> Reduction effect of 10% chloride ion concentration of coagulant

*실시예 1에서 제조된 염산계열 응집제를 F 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 폴리수산화염화염산알루미늄과 병용하여 투입하여 잔류알루미늄 저감효과를 확인하였으며, 응집실험에 사용된 원수의 성상, 응집제 성상, 응집제 투입량 및 투입결과는 표 8에 나타난 바와 같다.* The hydrochloric acid-based coagulant prepared in Example 1 was collected in water from the F water purification plant, and a coagulation experiment using Jar-test was performed. The effect of reducing aluminum residual was confirmed by using it in combination with aluminum polyhydroxychloride hydrochloride.

병행투입 시 알루미늄계열의 응집제 중 폴리수산화염화염산알루미늄을 선택한 것은 pH 저하가 적을수록 알루미늄이 더 높게 검출되므로 염기도 70%의 고염기도 응집제군을 선택하여 실험하였다.Among the aluminum-based coagulants, aluminum polyhydroxychloride hydrochloride was detected as aluminum was higher as the pH decreased. Therefore, a high basicity coagulant group having a basicity of 70% was selected and tested.

미투입not input 9% 염산9% hydrochloric acid 실시예Example S 0.5S 0.5 S 1S 1 S 3S 3 S 5S 5 S 6S 6 S 7S 7 성상appearance Al2O3 (%)Al 2 O 3 (%) -- -- 0.50.5 1One 33 55 66 77 염소이온 (%)Chloride ion (%) -- -- 1010 투입량 (ppm)Dosage (ppm) -- 7070 6565 응집제flocculant 폴리수산화염화염산알루미늄Aluminum polyhydroxychloride hydrochloride 투입량 (ppm)Dosage (ppm) 15ppm15ppm pHpH 7.987.98 7.097.09 7.077.07 7.057.05 7.047.04 7.057.05 7.067.06 7.037.03 탁도 (NTU)Turbidity (NTU) 0.6330.633 0.4250.425 0.2750.275 0.2670.267 0.2520.252 0.2450.245 0.2460.246 0.2430.243 알칼리도 (mg/l)Alkalinity (mg/l) 17.417.4 14.214.2 14.214.2 14.114.1 14.314.3 14.214.2 14.114.1 14.314.3 KMnO4 (mg/l)KMnO 4 (mg/l) 7.37.3 5.25.2 4.44.4 4.34.3 4.14.1 4.04.0 4.04.0 3.83.8 Al (mg/l)Al (mg/l) 0.1630.163 0.1190.119 0.0820.082 0.0880.088 0.0940.094 0.01010.0101 0.1310.131 0.1450.145 비고note 1) 원수 성상: pH 8.34, 탁도 2.28NTU, 알칼리도 18.2mg/l, KMnO4 17.8mg/l, Al 0.022mg/l
2) 응집제 성상: 폴리수산화염화염산알루미늄 Al2O3 10.5%, Basicity 70.3%1) Raw water properties: pH 8.34, turbidity 2.28NTU, alkalinity 18.2mg/l, KMnO 4 17.8mg/l, Al 0.022mg/l
2) Coagulant properties: polyhydroxychloride aluminum Al 2 O 3 10.5%, Basicity 70.3%

<실험예 5-2> 염화이온 농도 20% 응집제의 저감효과실시예 1에서 제조된 염산계열 응집제를 F 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 폴리수산화염화염산알루미늄과 병용하여 투입하여 잔류알루미늄 저감효과를 확인하였으며, 응집실험에 사용된 원수의 성상, 응집제 성상, 응집제 투입량 및 투입결과는 표 9에 나타난 바와 같다. <Experimental Example 5-2> Reducing effect of the 20% chloride ion concentration of the coagulant The hydrochloric acid-based coagulant prepared in Example 1 was collected from water at the F water purification plant, and a coagulation experiment using Jar-test was performed. The effect of reducing aluminum residual was confirmed by using it in combination with aluminum polyhydroxychloride hydrochloride.

미투입not input 9% 염산9% hydrochloric acid 실시예Example S 0.5S 0.5 S 1S 1 S 3S 3 S 5S 5 S 6S 6 S 7S 7 성상appearance Al2O3 (%)Al 2 O 3 (%) -- -- 0.50.5 1One 33 55 66 77 염소이온 (%)Chloride ion (%) -- -- 2020 투입량 (ppm)Dosage (ppm) -- 7070 3030 응집제flocculant 폴리수산화염화염산알루미늄Aluminum polyhydroxychloride hydrochloride 투입량 (ppm)Dosage (ppm) 15ppm15ppm pHpH 7.987.98 7.097.09 7.077.07 7.057.05 7.047.04 7.057.05 7.067.06 7.037.03 탁도 (NTU)Turbidity (NTU) 0.6210.621 0.4110.411 0.02880.0288 0.2710.271 0.2590.259 0.2510.251 0.2480.248 0.2450.245 알칼리도 (mg/l)Alkalinity (mg/l) 17.917.9 14.114.1 14.214.2 14.214.2 14.114.1 14.114.1 14.314.3 14.214.2 KMnO4 (mg/l)KMnO 4 (mg/l) 7.67.6 5.55.5 4.84.8 4.54.5 4.34.3 4.04.0 4.14.1 3.93.9 Al (mg/l)Al (mg/l) 0.1660.166 0.1210.121 0.0820.082 0.0850.085 0.0900.090 0.0990.099 0.1290.129 0.1410.141 비고note 1) 원수성상: pH 8.38, 탁도 2.31NTU, 알칼리도 18.4mg/l, KMnO4 18.0mg/l, Al 0.023mg/l
2) 응집제 성상: 폴리수산화염화염산알루미늄 Al2O3 10.5%, Basicity 70.3%1) Raw water phase: pH 8.38, turbidity 2.31NTU, alkalinity 18.4mg/l, KMnO 4 18.0mg/l, Al 0.023mg/l
2) Coagulant properties: polyhydroxychloride aluminum Al 2 O 3 10.5%, Basicity 70.3%

<실험예 5-3> 염화이온 농도 30% 응집제의 저감효과실시예 1에서 제조된 염산계열 응집제를 F 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 폴리수산화염화염산알루미늄과 병용하여 투입하여 잔류알루미늄 저감효과를 확인하였으며, 응집실험에 사용된 원수의 성상, 응집제 성상, 응집제 투입량 및 투입결과는 표 10에 나타난 바와 같다. <Experimental Example 5-3> Reducing effect of the coagulant with a chloride ion concentration of 30% The hydrochloric acid-based coagulant prepared in Example 1 was drained from water at the F water purification plant and a coagulation experiment using Jar-test was performed. The effect of reducing aluminum residual was confirmed by using it with aluminum polyhydroxychloride hydrochloride.

미투입not input 9% 염산9% hydrochloric acid 실시예Example S 0.5S 0.5 S 1S 1 S 3S 3 S 5S 5 S 6S 6 S 7S 7 성상appearance Al2O3 (%)Al 2 O 3 (%) -- -- 0.50.5 1One 33 55 66 77 염소이온 (%)Chloride ion (%) -- -- 3030 투입량 (ppm)Dosage (ppm) -- 7070 2020 응집제flocculant 폴리수산화염화염산알루미늄Aluminum polyhydroxychloride hydrochloride 투입량 (ppm)Dosage (ppm) 15ppm15ppm pHpH 7.957.95 7.077.07 7.057.05 7.067.06 7.057.05 7.037.03 7.077.07 7.027.02 탁도 (NTU)Turbidity (NTU) 0.6250.625 0.4020.402 0.3010.301 0.2830.283 0.2640.264 0.2550.255 0.2500.250 0.2470.247 알칼리도 (mg/l)Alkalinity (mg/l) 17.817.8 14.214.2 14.114.1 14.314.3 14.214.2 14.214.2 14.114.1 14.314.3 KMnO4 (mg/l)KMnO 4 (mg/l) 7.77.7 5.35.3 4.94.9 4.74.7 4.44.4 4.24.2 4.24.2 4.04.0 Al (mg/l)Al (mg/l) 0.1680.168 0.1230.123 0.0800.080 0.0810.081 0.0880.088 0.0920.092 0.1240.124 0.1380.138 비고note 1) 원수 성상: pH 8.32, 탁도 2.41NTU, 알칼리도 18.5mg/l, KMnO4 18.3mg/l, Al 0.022mg/l
2) 응집제 성상: 폴리수산화염화염산알루미늄 Al2O3 10.5%, Basicity 70.3%1) Raw water properties: pH 8.32, turbidity 2.41NTU, alkalinity 18.5mg/l, KMnO 4 18.3mg/l, Al 0.022mg/l
2) Coagulant properties: polyhydroxychloride aluminum Al 2 O 3 10.5%, Basicity 70.3%

표 8, 9 및 10에 나타난 바와 같이, 본 발명을 기존의 응집제인 폴리수산화염화염산알루미늄과 병용하여 사용하는 경우, 잔류알루미늄, 탁도, KMnO4 등의 저감효과가 우수한 것으로 나타나 수처리효율이 높다는 것을 확인하였다.또한, 산화알루미늄의 농도가 0.5 내지 5 %에서는 잔류 알루미늄이 낮게 검출되어 잔류알루미늄 저감효과가 우수함을 확인하였으나, 산화알루미늄 농도가 6% 이상인 경우 원수보다 높은 잔류 알루미늄이 검출되어 잔류알루미늄 저감효과가 없음을 확인하였다.As shown in Tables 8, 9 and 10, when the present invention is used in combination with the conventional coagulant, polyhydroxychloride aluminum, the reduction effect of residual aluminum, turbidity, KMnO 4, etc. is excellent, indicating that the water treatment efficiency is high. In addition, when the aluminum oxide concentration was 0.5 to 5%, the residual aluminum was detected low and it was confirmed that the residual aluminum reduction effect was excellent. It was confirmed that there was no effect.

<실험예 3> 염산계열 응집제의 병용사용시 잔류알루미늄 저감효과<Experimental Example 3> Residual aluminum reduction effect when using hydrochloric acid-based coagulant in combination

실시예 1의 방법에 의해 제조된 염산계열 응집제 중 염화이온농도 20 %, Al2O3 농도 1 내지 3 %인 응집제를 G 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 폴리수산화염화염산알루미늄과 병용하여 투입하여 잔류알루미늄 저감효과를 확인하였으며, 응집실험에 사용된 원수의 성상, 응집제 성상, 응집제 투입량 및 투입결과는 표 11에 나타난 바와 같다.Among the hydrochloric acid-based coagulants prepared by the method of Example 1, a coagulant having a chloride ion concentration of 20% and an Al 2 O 3 concentration of 1 to 3% was collected from water at the G water purification plant, and an agglomeration experiment using Jar-test was performed. The effect of reducing aluminum residual was confirmed by using it in combination with aluminum polyhydroxychloride hydrochloride.

또한, 채수위치는 원수는 폭기조 후단에서 측정하였고, pH, 탁도, 알칼리도 및 KMnO4는 침전지 후단, Al은 침전지 후단 및 여과 후단에서 각각 측정하였으며, CO2 설비는 pH가 7이 되도록하여 진행하였다.In addition, as for the water collection location, raw water was measured at the rear end of the aeration tank, pH, turbidity, alkalinity, and KMnO 4 were measured at the rear end of the settling basin, and Al was measured at the rear end of the settling basin and after filtration, respectively, and the CO 2 facility was carried out so that the pH was 7.

원수enemy 실시예Example 9% 염산9% hydrochloric acid CO2 설비CO 2 plant C 1C 1 C 3C 3 성상appearance Al2O3 (%)Al 2 O 3 (%) -- 1One 33 -- -- 염소이온 (%)Chloride ion (%) -- 2020 2020 -- -- 투입량 (ppm)Dosage (ppm) -- 3030 7070 -- 응집제flocculant -- 폴리수산화염화염산알루미늄Aluminum polyhydroxychloride hydrochloride 투입량 (ppm)Dosage (ppm) -- 15ppm15ppm 1 일차Day 1 pHpH 8.438.43 7.067.06 7.057.05 7.067.06 7.047.04 탁도 (NTU)Turbidity (NTU) 1.981.98 0.2550.255 0.2490.249 0.4310.431 0.4210.421 알칼리도 (mg/l)Alkalinity (mg/l) 18.218.2 14.214.2 14.114.1 14.014.0 13.913.9 KMnO4 (mg/l)KMnO 4 (mg/l) 17.117.1 4.84.8 4.74.7 6.16.1 6.16.1 Al (mg/l)Al (mg/l) 침전수sedimentation water 0.0250.025 0.0860.086 0.0910.091 0.1310.131 0.1280.128 여과수filtrate 0.0420.042 0.0460.046 0.0720.072 0.0760.076 2 일차Day 2 pHpH 8.478.47 7.047.04 7.037.03 7.047.04 7.027.02 탁도 (NTU)Turbidity (NTU) 2.212.21 0.2650.265 0.2580.258 0.4210.421 0.4100.410 알칼리도 (mg/l)Alkalinity (mg/l) 18.318.3 14.214.2 14.014.0 14.114.1 14.014.0 KMnO4 (mg/l)KMnO 4 (mg/l) 16.816.8 4.84.8 4.54.5 6.26.2 6.06.0 Al (mg/l)Al (mg/l) 침전수sedimentation water 0.0260.026 0.0890.089 0.0950.095 0.1250.125 0.1260.126 여과수filtrate 0.0400.040 0.0460.046 0.0760.076 0.0730.073 3 일차Day 3 pHpH 8.518.51 7.087.08 7.067.06 7.057.05 7.077.07 탁도 (NTU)Turbidity (NTU) 2.412.41 0.2710.271 0.2650.265 0.4710.471 0.4680.468 알칼리도 (mg/l)Alkalinity (mg/l) 18.318.3 14.314.3 14.114.1 14.214.2 14.314.3 KMnO4 (mg/l)KMnO 4 (mg/l) 17.317.3 4.54.5 4.34.3 6.06.0 5.95.9 Al (mg/l)Al (mg/l) 침전수sedimentation water 0.0220.022 0.0840.084 0.0890.089 0.1270.127 0.1220.122 여과수filtrate 0.0430.043 0.0460.046 0.0770.077 0.0790.079 4 일차Day 4 pHpH 8.618.61 7.057.05 7.047.04 7.037.03 7.027.02 탁도 (NTU)Turbidity (NTU) 2.182.18 0.2610.261 0.2550.255 0.4360.436 0.4290.429 알칼리도 (mg/l)Alkalinity (mg/l) 18.218.2 14.014.0 13.913.9 14.114.1 14.014.0 KMnO4 (mg/l)KMnO 4 (mg/l) 17.217.2 5.35.3 5.15.1 6.36.3 6.26.2 Al (mg/l)Al (mg/l) 침전수sedimentation water 0.0240.024 0.0880.088 0.0930.093 0.1220.122 0.1250.125 여과수filtrate 0.0390.039 0.0420.042 0.0780.078 0.0770.077 응집제 성상Flocculant properties 폴리수산화염화염산알루미늄 Al2O3 10.5%, Basicity 70.3%Aluminum polyhydroxychloride hydrochloride Al 2 O 3 10.5%, Basicity 70.3%

표 11에 나타난 바와 같이, 본 발명을 기존의 응집제인 폴리수산화염화염산알루미늄과 병용하여 사용하는 경우, 잔류알루미늄, 탁도, KMnO4 등의 저감효과가 우수한 것으로 나타나 수처리효율이 높은 것을 확인하였으며, 염산이나 CO2설비를 사용할때보다 잔류알루미늄이 약 40 %정도 저감됨을 확인할 수 있었다.<실험예 7> 첨가제를 더 포함한 염산계열 응집제의 병용사용시 잔류알루미늄 저감효과 As shown in Table 11, when the present invention is used in combination with aluminum polyhydroxychloride hydrochloride, which is a conventional coagulant, the effect of reducing residual aluminum, turbidity, KMnO 4, etc. is excellent, confirming that the water treatment efficiency is high, and hydrochloric acid However, it was confirmed that the residual aluminum was reduced by about 40% compared to when the CO 2 facility was used. <Experimental Example 7> Residual aluminum reduction effect when combined use of hydrochloric acid-based coagulant containing additives

실시예 1의 방법에 의해 제조된 염산계열 응집제에 첨가제(2A족, 3A족, 4A족, 3B족, 4B족 물질)를 더 포함시킨 후, H 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 폴리수산화염화염산알루미늄과 병용하여 투입하여 잔류알루미늄 저감효과를 확인하였으며, 응집실험에 사용된 원수의 성상, 응집제 성상, 응집제 투입량, 첨가제의 종류 및 투입결과는 표 12에 나타난 바와 같다.After adding an additive (group 2A, group 3A, group 4A, group 3B, group 4B material) to the hydrochloric acid-based coagulant prepared by the method of Example 1, water was collected from the H water purification plant and coagulation using Jar-test An experiment was conducted. The effect of reducing aluminum residual was confirmed by using it in combination with aluminum polyhydroxychloride hydrochloric acid.

-- 9% 염산9% hydrochloric acid 실시예 (+첨가제)Example (+additives) 미첨가unadded 2A족2A group 3A족3A group 4A족4A group 3B족3B group 4B족4B group 투입량 (ppm)Dosage (ppm) -- 9090 4040 응집제flocculant 폴리수산화염화황산알루미늄Aluminum polyhydroxychloride sulfate 투입량 (ppm)Dosage (ppm) 1313 pHpH 8.248.24 7.127.12 7.087.08 7.137.13 7.067.06 7.057.05 7.087.08 7.067.06 탁도 (NTU)Turbidity (NTU) 0.4170.417 0.3970.397 0.2260.226 0.2180.218 0.2230.223 0.2170.217 0.2230.223 0.2230.223 Al (mg/l)Al (mg/l) 0.1870.187 0.1180.118 0.0860.086 0.0790.079 0.0830.083 0.0800.080 0.0800.080 0.0830.083 비고note 1) 원수 성상: pH 8.67, 탁도 3.07NTU, Al 0.031mg/l
2) 응집제 성상: 폴리수산화염화염산알루미늄 Al2O3 10.5%, Basicity 70.3%
3) 염산계열 응집제 성상: Al2O3 2% 염소이온 23%
4) 첨가제 성상
- 2A족 물질 : CaCl2 0.5중량부% 첨가
- 3A족 물질 : Ga2(SO4)3 0.5중량부% 첨가
- 4A족 물질 : Na2SiO3 0.5중량부% 첨가
- 3B족 물질 : YCl3·6H2O 0.5중량부% 첨가
- 4B족 물질 : ZrCl4 0.5중량부% 첨가1) Raw water properties: pH 8.67, turbidity 3.07NTU, Al 0.031mg/l
2) Coagulant properties: polyhydroxychloride aluminum Al 2 O 3 10.5%, Basicity 70.3%
3) Hydrochloric acid-based coagulant properties: Al 2 O 3 2% Chloride ion 23%
4) Additive properties
- Group 2A material: CaCl 2 0.5 parts by weight added
- Group 3A material: Ga 2 (SO 4 ) 3 0.5 parts by weight added
- Group 4A material: Na 2 SiO 3 0.5 parts by weight added
- Group 3B material: YCl 3 6H 2 O 0.5 parts by weight added
- Group 4B material: ZrCl 4 0.5 parts by weight added

표 12에 나타난 바와 같이, 기존의 응집제와 병용투입하여 pH가 조절되지 않을 경우 잔류알루미늄의 수치가 매우 높았으며, 염산 9%을 병용하여 투입한 경우와 비교하여 본 발명의 응집제를 병용하여 투입하는 경우 탁도, 알루미늄 등이 저감효과가 더 우수한 것을 확인하였다. 또한, 염산계열 응집제에 첨가제를 더 포함한 경우 첨가제를 포함하지 않는 경우와 비교하여 탁도제거효율 및 잔류알루미늄 저감효과가 더 우수하게 나타난 것을 확인하였다. 또한, 첨가제의 종류가 상이하더라도 수처리효율에 큰 변화가 없음을 확인하였다.<실험예 8> 첨가제를 더 포함한 염산계열 응집제의 병용사용시 잔류알루미늄 저감효과 As shown in Table 12, when the pH was not adjusted by co-injection with the conventional coagulant, the level of residual aluminum was very high, and compared with the case of co-injection with 9% hydrochloric acid, the coagulant of the present invention was added in combination. In the case of turbidity and aluminum, it was confirmed that the reduction effect was more excellent. In addition, it was confirmed that the turbidity removal efficiency and the effect of reducing residual aluminum were more excellent when the hydrochloric acid-based coagulant was further included as compared to the case where the additive was not included. In addition, it was confirmed that there was no significant change in the water treatment efficiency even if the types of additives were different. <Experimental Example 8> Residual aluminum reduction effect when combined use of hydrochloric acid-based coagulant containing additives

실시예 1의 방법에 의해 제조된 염산계열 응집제에 첨가제(2A족, 4A족 물질, Polymer)를 더 포함시킨 후, H 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 폴리수산화염화염산알루미늄과 병용하여 투입하여 잔류알루미늄 저감효과를 확인하였으며, 응집실험에 사용된 원수의 성상, 응집제 성상, 응집제 투입량, 첨가제의 성상 및 투입결과는 표 13에 나타난 바와 같다.After adding an additive (group 2A, group 4A material, polymer) to the hydrochloric acid-based coagulant prepared by the method of Example 1, water was collected from the H water purification plant and agglomeration experiment using Jar-test was performed. The effect of reducing aluminum residual was confirmed by using it in combination with aluminum polyhydroxychloride hydrochloride, and the properties of raw water used in the coagulation experiment, properties of coagulant, amount of coagulant input, properties of additives and input results are as shown in Table 13.

-- 9% 염산9% hydrochloric acid 실시예 (+첨가제)Example (+additives) 미첨가unadded 2A족2A group 4A족4A group 성상appearance Al2O3 (%)Al 2 O 3 (%) -- -- 1.51.5 -- -- 염소이온 (%)Chloride ion (%) -- -- 1515 1414 1616 투입량 (ppm)Dosage (ppm) -- 100100 7070 7070 7070 응집제flocculant 폴리수산화염화염산알루미늄Aluminum polyhydroxychloride hydrochloride 투입량 (ppm)Dosage (ppm) 1313 응집제flocculant Polymerpolymer 투입량 (ppm)Dosage (ppm) 33 pHpH 8.588.58 7.117.11 7.087.08 7.097.09 7.107.10 탁도 (NTU)Turbidity (NTU) 0.3810.381 0.3670.367 0.1890.189 0.1830.183 0.1810.181 Al (mg/l)Al (mg/l) 0.1760.176 0.1020.102 0.0740.074 0.0700.070 0.0710.071 비고note 1) 원수성상 : pH 8.72, 탁도 3.14NTU, Al 0.039mg/l
2) 응집제 성상 : 폴리수산화염화염산알루미늄 Al2O3 10.5%, Basicity 70%
3) 염산계열 응집제 성상: Al2O3 1.5% 염소이온 16%
4) 첨가제 성상
- 2A족 물질: CaCl2 0.5중량부% 첨가
- 4A족 물질 : Na2SiO3 0.5중량부% 첨가
- Polymer: 폴리아민(Polyamine)1) Raw water phase: pH 8.72, turbidity 3.14NTU, Al 0.039mg/l
2) Coagulant properties: polyhydroxychloride aluminum Al 2 O 3 10.5%, Basicity 70%
3) Hydrochloric acid-based coagulant properties: Al 2 O 3 1.5% Chloride ion 16%
4) Additive properties
- Group 2A material: CaCl 2 0.5 parts by weight added
- Group 4A material: Na 2 SiO 3 0.5 parts by weight added
- Polymer: Polyamine

표 13에 나타난 바와 같이, 기존의 응집제와 병용투입하여 pH가 조절되지 않을 경우 잔류알루미늄의 수치가 매우 높았으며, 염산 9%을 병용하여 투입한 경우와 비교하여 본 발명의 응집제를 병용하여 투입하는 경우 탁도, 알루미늄 등이 저감효과가 더 우수한 것을 확인하였다. 또한, 염산계열 응집제에 첨가제를 더 포함한 경우 첨가제를 포함하지 않는 경우와 비교하여 탁도제거효율 및 잔류알루미늄 저감효과가 더 우수하게 나타난 것을 확인하였다. 또한, 첨가제의 종류가 상이하더라도 수처리효율에 큰 변화가 없음을 확인하였다.<실험예 9> 첨가제를 더 포함한 염산계열 응집제의 병용사용시 잔류알루미늄 저감효과 As shown in Table 13, when the pH was not adjusted by co-injection with the conventional coagulant, the residual aluminum level was very high. In the case of turbidity and aluminum, it was confirmed that the reduction effect was more excellent. In addition, it was confirmed that the turbidity removal efficiency and the effect of reducing residual aluminum were more excellent when the hydrochloric acid-based coagulant was further included as compared to the case where the additive was not included. In addition, it was confirmed that there was no significant change in the water treatment efficiency even if the types of additives were different. <Experimental Example 9> Residual aluminum reduction effect when combined use of hydrochloric acid-based coagulant containing additives

실시예 1의 방법에 의해 제조된 염산계열 응집제에 첨가제(유기응집제로서 폴리비닐아민)를 더 포함시킨 후, I 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 폴리염화알루미늄과 병용하여 투입하여 잔류알루미늄 저감효과를 확인하였으며, 응집실험에 사용된 원수의 성상, 응집제 성상, 응집제 투입량, 첨가제의 혼합비율 및 투입결과는 표 14에 나타난 바와 같다.After adding an additive (polyvinylamine as an organic coagulant) to the hydrochloric acid-based coagulant prepared by the method of Example 1, water was collected from the I water purification plant and agglomeration experiment using Jar-test was performed. The effect of reducing aluminum residual was confirmed by using it in combination with polyaluminum chloride, and the properties of raw water used in the coagulation experiment, properties of the coagulant, the amount of coagulant input, the mixing ratio of the additives, and the input results are shown in Table 14.

9% 염산9% hydrochloric acid 실시예 (+ Polymer 혼합비율)Example (+ Polymer mixing ratio) 0%0% 0.5%0.5% 1%One% 3%3% 5%5% 7%7% 투입량 (ppm)Dosage (ppm) 7070 3030 3030 3030 3030 3030 3030 응집제flocculant 폴리염화알루미늄poly aluminum chloride 투입량 (ppm)Dosage (ppm) 1313 pHpH 7.087.08 7.057.05 7.077.07 7.087.08 7.107.10 7.137.13 7.167.16 탁도 (NTU)Turbidity (NTU) 0.6810.681 0.5310.531 0.4870.487 0.4240.424 0.3970.397 0.3520.352 0.3210.321 Al (mg/l)Al (mg/l) 0.1060.106 0.0900.090 0.0870.087 0.0830.083 0.0810.081 0.0800.080 0.0950.095 비고note 1) 원수성상 : pH 8.31, 탁도 3.91NTU, Al 0.027mg/l
2) 응집제 성상: 폴리염화알루미늄 Al2O3 10.5% Basicity 40%
3) 염산계열 응집제 성상 : Al2O3 2% 염소이온 25%
4) 첨가제 성상: Polymer - 폴리비닐아민(Polyvinylamine)1) Raw water phase: pH 8.31, turbidity 3.91NTU, Al 0.027mg/l
2) Coagulant properties: polyaluminum chloride Al 2 O 3 10.5% Basicity 40%
3) Hydrochloric acid-based coagulant properties: Al 2 O 3 2% Chloride ion 25%
4) Additive properties: Polymer - Polyvinylamine

표 14에 나타난 바와 같이, 기존의 응집제와 염산 9%을 병용하여 투입한 경우와 비교하여 본 발명의 응집제를 병용하여 투입하는 경우 탁도, 알루미늄 등이 저감효과가 더 우수한 것을 확인하였다. 또한, 염산계열 응집제에 폴리머를 혼합한 제품의 경우 폴리머의 혼합비율이 상승할수록 탁도제거효율은 우수하였으나, 7%이상을 초과하여 혼합하는 경우 잔류알루미늄 저감효과가 떨어지는 것을 확인하였다.<실험예 10> 첨가제를 더 포함한 염산계열 응집제의 병용사용시 잔류알루미늄 저감효과 As shown in Table 14, it was confirmed that the reduction effect of turbidity, aluminum, etc. was more excellent when the coagulant of the present invention was added in combination compared to the case where the conventional coagulant and hydrochloric acid were added in combination. In addition, in the case of a product in which a polymer was mixed with a hydrochloric acid-based coagulant, the turbidity removal efficiency was excellent as the mixing ratio of the polymer increased. <Experimental Example 10> Residual aluminum reduction effect when combined use of hydrochloric acid-based coagulant containing additives

실시예 1의 방법에 의해 제조된 염산계열 응집제에 첨가제(2A족, 4B족 물질, Polymer)를 더 포함시킨 후, J 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 저염기성 폴리염화알루미늄과 병용하여 투입하여 잔류알루미늄 저감효과를 확인하였으며, 응집실험에 사용된 원수의 성상, 응집제 성상, 응집제 투입량, 첨가제의 성상 및 투입결과는 표 15에 나타난 바와 같다.After adding an additive (group 2A, group 4B material, polymer) to the hydrochloric acid-based coagulant prepared by the method of Example 1, water was collected from the J water purification plant and an agglomeration experiment using Jar-test was performed. The effect of reducing aluminum residual was confirmed by using it in combination with low-basic polyaluminum chloride, and the properties of raw water used in the coagulation experiment, properties of the coagulant, the amount of coagulant input, the properties of the additives, and the input results are as shown in Table 15.

-- 9% 염산9% hydrochloric acid 실시예 (+첨가제)Example (+additives) 미첨가unadded 2A족2A group 4B족4B group 투입량 (ppm)Dosage (ppm) -- 170170 7070 7070 7070 응집제flocculant 저염기성 폴리염화알루미늄Low base polyaluminum chloride 투입량 (ppm)Dosage (ppm) 1515 pHpH 8.758.75 7.127.12 7.077.07 7.137.13 7.097.09 탁도 (NTU)Turbidity (NTU) 0.8750.875 0.8510.851 0.5960.596 0.5910.591 0.5930.593 Al (mg/l)Al (mg/l) 0.2080.208 0.1250.125 0.0990.099 0.0940.094 0.0950.095 비고note 1) 원수성상: pH 8.97, 탁도 3.24NTU, Al 0.025mg/l
2) 응집제 성상: 저염기성 폴리염화알루미늄 Al2O3 11.5%, Basicity 15%
3) 염산계열 응집제 성상: Al2O3 3% 염소이온 21%
4) 첨가제 성상
- 2A족 물질 : CaCl2 0.5중량부% 첨가
- 4B족 물질: ZrCl4 0.5중량부% 첨가
- Polymer: 폴리에틸렌아민(Polyethyleneamine) 3 중량부% 첨가1) Raw water phase: pH 8.97, turbidity 3.24NTU, Al 0.025mg/l
2) Coagulant properties: Low basic polyaluminum chloride Al 2 O 3 11.5%, Basicity 15%
3) Hydrochloric acid-based coagulant properties: Al 2 O 3 3% Chloride ion 21%
4) Additive properties
- Group 2A material: CaCl 2 0.5 parts by weight added
- Group 4B material: ZrCl 4 0.5 parts by weight added
- Polymer: 3 parts by weight of polyethyleneamine added

표 15에 나타난 바와 같이, 기존의 응집제와 병용투입하여 pH가 조절되지 않을 경우 잔류알루미늄의 수치가 매우 높았으며, 염산 9%을 병용하여 투입한 경우와 비교하여 본 발명의 응집제를 병용하여 투입하는 경우 탁도, 알루미늄 등이 저감효과가 더 우수한 것을 확인하였다. 또한, 염산계열 응집제에 첨가제를 더 포함한 경우 첨가제를 포함하지 않는 경우와 비교하여 탁도제거효율 및 잔류알루미늄 저감효과가 더 우수하게 나타난 것을 확인하였다. 또한, 첨가제의 종류가 상이하더라도 수처리효율에 큰 변화가 없음을 확인하였다.<실험예 10> 염산계열 응집제의 병용사용 범위 As shown in Table 15, when the pH is not adjusted by co-injection with the conventional coagulant, the level of residual aluminum was very high, and compared with the case of co-injection with 9% hydrochloric acid, the coagulant of the present invention was added in combination. In the case of turbidity and aluminum, it was confirmed that the reduction effect was more excellent. In addition, it was confirmed that the turbidity removal efficiency and the residual aluminum reduction effect were more excellent when the hydrochloric acid-based coagulant was further included in comparison with the case where the additive was not included. In addition, it was confirmed that there was no significant change in the water treatment efficiency even if the types of additives were different. <Experimental Example 10> Range of combined use of hydrochloric acid-based coagulant

실시예 1의 방법에 의해 제조된 염산계열 응집제를 K 정수장의 물을 채수하여 Jar-test를 이용한 응집실험을 실시하였다. 폴리수산화염화염산알루미늄과 병용하여 투입하여 잔류알루미늄 저감효과를 확인하였으며, 응집실험에 사용된 원수의 성상, 응집제 성상, 응집제 투입량 및 투입결과는 표 16에 나타난 바와 같다.The hydrochloric acid-based coagulant prepared by the method of Example 1 was collected in water from the K water purification plant, and a coagulation experiment using Jar-test was performed. The effect of reducing aluminum residual was confirmed by using in combination with aluminum polyhydroxychloride hydrochloride.

-- 9% 염산9% hydrochloric acid 실시예Example 투입량 (ppm)Dosage (ppm) -- 220220 1212 2525 4040 7575 100100 응집제flocculant 폴리수산화염화염산알루미늄Aluminum polyhydroxychloride hydrochloride 투입량 (ppm)Dosage (ppm) 1414 pHpH 9.219.21 7.067.06 9.029.02 8.558.55 8.068.06 7.527.52 7.037.03 탁도 (NTU)Turbidity (NTU) 0.4270.427 0.3910.391 0.4000.400 0.3010.301 0.2560.256 0.2210.221 0.2070.207 Al (mg/l)Al (mg/l) 0.1970.197 0.1120.112 0.1860.186 0.1500.150 0.1310.131 0.0900.090 0.0850.085 비고note 1) 원수성상: pH 9.37, 탁도 4.12NTU, Al 0.020mg/l
2) 응집제 성상: 폴리수산화염화염산알루미늄 Al2O3 10.5% Basicity 70%
3) 염산계열 응집제 성상: Al2O3 2% 염소이온 28%, 1) Raw water phase: pH 9.37, turbidity 4.12NTU, Al 0.020mg/l
2) Coagulant properties: polyhydroxychloride aluminum Al 2 O 3 10.5% Basicity 70%
3) Hydrochloric acid-based coagulant properties: Al 2 O 3 2% chlorine ion 28%,

표 16에 나타난 바와 같이, 기존의 응집제와 병용투입한 후 처리수의 pH가 7.0~8.0인 경우, 탁도 및 잔류알루미늄 저감효과가 우수한 것으로 확인되었다.As shown in Table 16, when the pH of the treated water was 7.0 to 8.0 after co-injection with the conventional coagulant, it was confirmed that the turbidity and residual aluminum reduction effects were excellent.

Claims (15)

a) 염산, 수산화알루미늄 및 물을 혼합하여 응집제를 제조하되, 응집제 총 중량대비 염산 25 내지 90 중량%, 수산화알루미늄 0.5 내지 12 중량% 및 물 0.01 내지 70 중량%로 혼합 반응하여 응집제를 제조하는 단계; 및
b1) 단계 a)의 응집제를 단독으로 투입하는 단계 또는
b2) 단계 a)의 응집제를 무기응집제 및 유기응집제로 구성된 그룹으로부터 선택되는 1종 이상의 응집제와 병용하여 투입하는 단계;를 포함하고, 여기에서, 상기 단계 a)의 응집제는 산화알루미늄, 염화이온을 포함하고,
응집제는 염화이온 함량은 10 내지 40 중량%이고, 산화알루미늄 함량은 0.5 내지 5 중량%이며,
상기 단계 a)의 응집제를 미투입한 경우와 비교하여 잔류알루미늄이 5 내지 90%로 저감되고, 처리수의 pH가 8.5 이하인, 수처리를 함으로써 알루미늄을 저감시키는 방법.
a) preparing a coagulant by mixing hydrochloric acid, aluminum hydroxide and water, but mixing and reacting with 25 to 90 wt% of hydrochloric acid, 0.5 to 12 wt% of aluminum hydroxide and 0.01 to 70 wt% of water relative to the total weight of the coagulant to prepare a coagulant ; and
b1) adding the coagulant of step a) alone or
b2) adding the coagulant of step a) together with at least one coagulant selected from the group consisting of inorganic coagulants and organic coagulants; including,
The coagulant has a chloride ion content of 10 to 40% by weight, and an aluminum oxide content of 0.5 to 5% by weight,
A method of reducing aluminum by water treatment, wherein the residual aluminum is reduced to 5 to 90% and the pH of the treated water is 8.5 or less compared to the case where the coagulant of step a) is not added.
 제1항에 있어서,
상기 단계 a)의 응집제는 황화물, 염화물, 규산화물, 산화물; 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함하는 것인, 수처리를 함으로써 알루미늄을 저감시키는 방법.
According to claim 1,
The coagulant of step a) is sulfide, chloride, silicate, oxide; and one or more compounds selected from the group consisting of salts thereof. A method for reducing aluminum by water treatment.
 제1항에 있어서,
상기 단계 a)의 응집제는 2A족 화합물, 3A족 화합물, 4A족 화합물, 3B족 화합물, 4B족 화합물 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함하는 것인, 수처리를 함으로써 알루미늄을 저감시키는 방법.
According to claim 1,
The coagulant of step a) further comprises at least one compound selected from the group consisting of a group 2A compound, a group 3A compound, a group 4A compound, a group 3B compound, a group 4B compound, and salts thereof. how to reduce
 제1항에 있어서,
상기 단계 a)의 응집제는 2A족 염화물, 2A족 황화물, 3B족 염화물, 3B족 황화물, 4B족 염화물, 4B족 황화물, 규산나트륨(Na2SiO3) 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함하는 것인, 수처리를 함으로써 알루미늄을 저감시키는 방법.
According to claim 1,
The coagulant of step a) is one selected from the group consisting of Group 2A chloride, Group 2A sulfide, Group 3B chloride, Group 3B sulfide, Group 4B chloride, Group 4B sulfide, sodium silicate (Na 2 SiO 3 ) and salts thereof. The method of reducing aluminum by performing water treatment which further contains the above compound.
 제1항에 있어서,
상기 단계 b2)의 무기응집제는 알루미늄계 응집제, 철염계 응집제 또는 이들의 혼합응집제인, 수처리를 함으로써 알루미늄을 저감시키는 방법.
According to claim 1,
The inorganic coagulant of step b2) is an aluminum-based coagulant, an iron salt-based coagulant, or a mixed coagulant thereof, a method of reducing aluminum by water treatment.
 제1항에 있어서,
상기 단계 b2)의 무기응집제는 염화알루미늄, 황산알루미늄, 폴리황산알루미늄, 폴리염화알루미늄, 폴리황산규산알루미늄, 폴리염화규산알루미늄, 폴리수산화염화규산알루미늄, 폴리황산규산알루미늄 및 폴리수산화염화황산알루미늄로 구성된 그룹으로부터 선택된 1종 이상인, 수처리를 함으로써 알루미늄을 저감시키는 방법.
According to claim 1,
The inorganic coagulant of step b2) consists of aluminum chloride, aluminum sulfate, polyaluminum sulfate, polyaluminum chloride, polyaluminum silicate sulfate, polyaluminum chloride silicate, aluminum polyhydroxychloride silicate, aluminum polysulfate aluminum silicate and polyhydroxychlorinated aluminum sulfate. A method of reducing aluminum by performing water treatment, at least one selected from the group.
 제1항에 있어서,
상기 단계 b2)의 무기응집제는 무기응집제 총 중량대비 산화알루미늄 함량이 5 내지 25%인, 수처리를 함으로써 알루미늄을 저감시키는 방법.
According to claim 1,
The inorganic coagulant of step b2) has an aluminum oxide content of 5 to 25% based on the total weight of the inorganic coagulant, a method for reducing aluminum by water treatment.
 제1항에 있어서,
상기 단계 b2)의 유기응집제는 폴리아크릴아마이드계, 폴리비닐아민계, 폴리알릴아민계, 폴리에틸렌아민계, 폴리아민계, 폴리아크릴에스테르계, 폴리에틸렌이민계, 폴리데드막 및 이들의 혼합응집제로 구성된 그룹으로부터 선택된 1종 이상인, 수처리를 함으로써 알루미늄을 저감시키는 방법.
According to claim 1,
The organic coagulant of step b2) is a polyacrylamide-based, polyvinylamine-based, polyallylamine-based, polyethyleneamine-based, polyamine-based, polyacrylic ester-based, polyethyleneimine-based, polydead film, and mixed coagulant thereof. A method of reducing aluminum by performing water treatment of at least one selected from
 제1항에 있어서, 상기 수처리방법은 처리 후 처리수의 탁도가 2 NTU 이하인 것을 특징으로 하는, 수처리를 함으로써 알루미늄을 저감시키는 방법.
According to claim 1, wherein the water treatment method is characterized in that the turbidity of the treated water after treatment is 2 NTU or less, the method of reducing aluminum by water treatment.
 제1항의 단계 a)에서 제조된 응집제는 하기 [화학식 1]로 표현되는 화합물 및 산화알루미늄을 포함하고, 여기에서 산화알루미늄함량은 응집제 총 중량대비 0.5 내지 5 중량%이고,
여기에서, 염화이온은 응집제 총 중량대비 10 내지 40 중량%이며,
응집제를 미투입한 경우와 비교하여 잔류알루미늄이 5 내지 90%로 저감되고, 처리수의 pH가 8.5 이하인, 알루미늄 저감용 수처리 응집제:
[화학식 1]
Al2(OH)nCl6-n 또는 Al(OH)nCl3-n (여기에서, n은 0을 제외한 0 내지 1 사이의 값)
The coagulant prepared in step a) of claim 1 includes a compound represented by the following [Formula 1] and aluminum oxide, wherein the aluminum oxide content is 0.5 to 5% by weight relative to the total weight of the coagulant,
Here, the chloride ion is 10 to 40% by weight based on the total weight of the coagulant,
A water treatment coagulant for aluminum reduction, wherein the residual aluminum is reduced to 5 to 90% and the pH of the treated water is 8.5 or less compared to the case where the coagulant is not added:
[Formula 1]
Al 2 (OH) n Cl 6-n or Al(OH) n Cl 3-n (where n is a value between 0 and 1 excluding 0)
 제10항에 있어서,
상기 응집제는 황화물, 염화물, 규산화물, 산화물; 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함하는 것인, 알루미늄 저감용 수처리 응집제.
11. The method of claim 10,
The coagulant may include sulfides, chlorides, silicates, oxides; And one or more compounds selected from the group consisting of salts thereof, water treatment coagulant for reducing aluminum.
 제10항에 있어서,
상기 응집제는 2A족 화합물, 3A족 화합물, 4A족 화합물, 3B족 화합물, 4B족 화합물 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함하는 것인, 알루미늄 저감용 수처리 응집제.
11. The method of claim 10,
The flocculant further comprises at least one compound selected from the group consisting of a group 2A compound, a group 3A compound, a group 4A compound, a group 3B compound, a group 4B compound, and salts thereof, a water treatment flocculant for reducing aluminum.
 제10항에 있어서,
상기 응집제는 2A족 염화물, 2A족 황화물, 3B족 염화물, 3B족 황화물, 4B족 염화물, 4B족 황화물, 규산나트륨(Na2SiO3) 및 이들의 염으로 구성된 그룹으로부터 선택된 1종 이상의 화합물을 더 포함하는 것인, 알루미늄 저감용 수처리 응집제.
11. The method of claim 10,
The coagulant further comprises at least one compound selected from the group consisting of Group 2A chloride, Group 2A sulfide, Group 3B chloride, Group 3B sulfide, Group 4B chloride, Group 4B sulfide, sodium silicate (Na 2 SiO 3 ) and salts thereof. The water treatment coagulant for aluminum reduction which is included.
 제10항에 있어서,
상기 응집제는 무기응집제 또는 유기응집제를 더 포함하는 것인, 알루미늄 저감용 수처리 응집제.
11. The method of claim 10,
The coagulant further comprises an inorganic coagulant or an organic coagulant, a water treatment coagulant for reducing aluminum.
 a) 염산, 수산화알루미늄 및 물을 혼합하여 응집제를 제조하되, 응집제 총 중량대비 염산 25 내지 90 중량%, 수산화알루미늄 0.5 내지 12 중량% 및 물 0.01 내지 70 중량%로 혼합 반응하여 응집제를 제조하는 단계; 및
b1) 단계 a)의 응집제를 단독으로 투입하는 단계 또는
b2) 단계 a)의 응집제를 무기응집제 및 유기응집제로 구성된 그룹으로부터 선택되는 1종 이상의 응집제와 병용하여 투입하는 단계;를 포함하고,
여기에서, 상기 단계 a)의 응집제는 산화알루미늄, 염화이온을 포함하고,
응집제는 염화이온 함량은 10 내지 40 중량%이고, 산화알루미늄 함량은 0.5 내지 5 중량%이고, 처리수의 pH가 8.5 이하인, 수처리를 함으로써 pH를 저감시키는 방법.a) preparing a coagulant by mixing hydrochloric acid, aluminum hydroxide and water, but mixing and reacting with 25 to 90 wt% of hydrochloric acid, 0.5 to 12 wt% of aluminum hydroxide and 0.01 to 70 wt% of water relative to the total weight of the coagulant to prepare a coagulant ; and
b1) adding the coagulant of step a) alone or
b2) adding the coagulant of step a) in combination with at least one coagulant selected from the group consisting of inorganic coagulants and organic coagulants;
Here, the coagulant of step a) includes aluminum oxide and chloride ions,
A method for reducing pH by water treatment, wherein the coagulant has a chloride ion content of 10 to 40% by weight, an aluminum oxide content of 0.5 to 5% by weight, and a pH of the treated water of 8.5 or less.
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