KR100622295B1 - Preparation method of polyaluminiumchloride - Google Patents
Preparation method of polyaluminiumchloride Download PDFInfo
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- KR100622295B1 KR100622295B1 KR1020040104717A KR20040104717A KR100622295B1 KR 100622295 B1 KR100622295 B1 KR 100622295B1 KR 1020040104717 A KR1020040104717 A KR 1020040104717A KR 20040104717 A KR20040104717 A KR 20040104717A KR 100622295 B1 KR100622295 B1 KR 100622295B1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
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- C—CHEMISTRY; METALLURGY
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- C01P2006/32—Thermal properties
Abstract
본 발명은 폴리염화알루미늄(Ploy Aluminum Chloride, PAC)의 제조방법에 관한 것으로 보다 상세하게는 수산화알루미늄(Al2(OH)3)과 염산(HCl)을 반응시킨 후 붕사(borax), 규산나트륨(Sodium silicate), 제올라이트(zeolite) 중에서 선택된 어느 하나의 수분희석제를 첨가하여 하기 구조식(1)의 폴리염화알루미늄을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing poly aluminum chloride (Ploy Aluminum Chloride, PAC), and more specifically, after reacting aluminum hydroxide (Al 2 (OH) 3 ) and hydrochloric acid (HCl) borax (borax), sodium silicate ( The present invention relates to a method for preparing polyaluminum chloride of the following structural formula (1) by adding any one of water diluents selected from sodium silicate) and zeolite.
[Al2(OH)nCl6-n]m......구조식(1)(1≤n≤5, m≤10) [Al 2 (OH) n Cl 6-n ] m ... Structural formula (1) (1≤n≤5, m≤10)
본 발명은 수산화알루미늄과 염산을 반응시켜 폴리염화알루미늄 제조시 이산화탄소의 영향이 없는 붕사, 규산나트륨, 제올라이트 중에서 선택된 어느 하나의 수분희석제를 첨가하여 OH 인자를 증가시켜 염기도가 45％ 이상이 되도록 하고, 외부의 고온이나 저온의 혹독한 환경에서도 안정한 폴리염화알루미늄의 제조방법 제공을 목적으로 한다.In the present invention, aluminum hydroxide and hydrochloric acid are reacted to prepare a polyaluminum chloride, thereby adding a water diluent selected from borax, sodium silicate, and zeolite without the influence of carbon dioxide to increase the OH factor so that the basicity is 45% or more. An object of the present invention is to provide a method for producing polyaluminum chloride that is stable even in harsh environments at high temperatures and low temperatures.
Description
본 발명은 폴리염화알루미늄(Ploy Aluminum Chloride, PAC)의 제조방법에 관한 것으로 보다 상세하게는 수산화알루미늄(Al2(OH)3)과 염산(HCl)을 반응시킨 후 붕사(borax), 규산나트륨(Sodium silicate), 제올라이트(zeolite) 중에서 선택된 어느 하나의 수분희석제를 첨가하여 하기 구조식(1)의 폴리염화알루미늄을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing poly aluminum chloride (Ploy Aluminum Chloride, PAC), and more specifically, after reacting aluminum hydroxide (Al 2 (OH) 3 ) and hydrochloric acid (HCl) borax (borax), sodium silicate ( The present invention relates to a method for preparing polyaluminum chloride of the following structural formula (1) by adding any one of water diluents selected from sodium silicate) and zeolite.
[Al2(OH)nCl6-n]m......구조식(1)(1≤n≤5, m≤10) [Al 2 (OH) n Cl 6-n ] m ... Structural formula (1) (1≤n≤5, m≤10)
폴리염화알루미늄은 수산화알루미늄(Aluminium Hydroxide)과 염산(hydrochloric acid)을 반응시켜 제조되는 다염기성염화알루미늄으로써 일반식[Al2(OH)nCl6-n]m으로 표시되며, (단 1≤n≤5, m≤10) 수용액에서는 아코착이온[Al(H2O)6]을 가지는 배위화합물이기 때문에 OH기를 가교로 해서 다핵착체가 되고 핵은 증가해서 거대화한 무기고분자화합물을 형성하고 있다. Polyaluminum chloride is a polybasic aluminum chloride prepared by reacting aluminum hydroxide with hydrochloric acid, represented by the general formula [Al 2 (OH) n Cl 6-n ] m , where 1 ≦ n ≤ 5, m ≤ 10) In the aqueous solution, it is a coordination compound having an azo complex [Al (H 2 O) 6 ], so that the OH group is crosslinked to form a multinuclear complex, and the nucleus is increased to form a large inorganic polymer compound.
폴리염화알루미늄은 수(水)처리시의 응집제로 주로 사용되고 있다. 응집제는 무기응집제와 유기응집제로 크게 나눌 수 있는데 무기응집제에는 2가, 3가의 금속양이온염, 폴리염화알루미늄염(PAC), 활성규산 등이 있으며, 1가 금속양이온도 사용되고 있다. 유기응집제 중 공업상 가치가 있는 것은 그 대부분이 고분자 응집제이며, 약간의 계면활성제, 기타 유기성 저분자이온이 사용될 때가 있다. Polyaluminum chloride is mainly used as a flocculant in water treatment. Coagulants can be broadly divided into inorganic coagulants and organic coagulants. Inorganic coagulants include divalent, trivalent metal cation salts, polyaluminum chloride salts (PAC), active silicic acid, and the like. Industrially, most of the organic coagulants are polymer coagulants, and some surfactants and other organic low molecular ions are sometimes used.
폴리염화알루미늄은 응집제로 사용할 수 있는 다른 무기약품에 비해 대부분의 오폐수 처리시 일을 효율적으로 처리해 주고 부산물로써 슬러지 양도 훨씬 적어 오폐수처리 뿐만 아니라 상수도 정수처리, 각종 폐수처리 및 도시하수처리 등에 널리 이용되고 있다. Compared to other inorganic chemicals that can be used as flocculants, polyaluminum chloride is more efficient in treating wastewater and has less sludge as a by-product, so it is widely used for wastewater treatment, wastewater treatment, various wastewater treatment and urban sewage treatment. have.
이처럼 다양한 수(水)처리의 응집제로 사용할 수 있는 폴리염화알루미늄을 일반적으로 수산화알루미늄(Al2O3 57∼60％ 함유) 1몰(mole)과 염산(HCl)(32∼35％) 2몰을 혼합한 후 130∼140℃에서 7∼8시간 교반하여 반응시킨 다음 물을 희석하여 염기도가 42∼43％인 폴리염화알루미늄(Al2(OH)nCl6-n)(Al2O 3 10∼17％ 함유)을 얻고 있다.Such polyaluminum chloride, which can be used as a coagulant for various water treatments, generally includes 1 mole of aluminum hydroxide (containing 57 to 60% of Al 2 O 3 ) and 2 moles of hydrochloric acid (HCl) (32 to 35%). After mixing, the mixture was stirred and reacted at 130-140 ° C. for 7-8 hours, followed by dilution of water to give polyaluminum chloride (Al 2 (OH) n Cl 6-n ) (Al 2 O 3 10 having a basicity of 42-43%). To 17%).
이때 염기도가 45％ 이하의 폴리염화알루미늄은 높은 온도나 낮은 온도 조건에서 화합물이 파괴되어 안정하지 못하기 때문에 이러한 문제를 해결하기 위해 수분을 희석시 탄산나트륨(Na2CO3), 탄산칼슘(CaCO3) 중에서 선택된 어느 하나를 첨가하여 OH를 추가로 올려 염기도가 45％ 유지하도록 하고 있다. 그러나 탄산나트륨, 탄산칼슘의 첨가로 인하여 발생하는 이산화탄소(CO2)의 영향으로 폴리염화알루미늄 의 구조가 약화되어 외부의 높은 온도나 낮은 온도에서 폴리염화알루미늄의 구조가 변형되고, 수산화알루미늄(Al(OH)3) 등의 침전물이 발생하여 수처리시 효율이 떨어지고 저장탱크의 침전물을 제거해야 하는 문제가 있다. At this time, polyaluminium chloride having a basicity of 45% or less is not stable due to compound destruction at high or low temperature conditions. So, to solve this problem, sodium carbonate (Na 2 CO 3 ) and calcium carbonate (CaCO 3 ) are diluted when water is diluted. OH is further raised by adding any one selected from) to maintain the basicity at 45%. However, due to the effect of carbon dioxide (CO 2 ) generated by the addition of sodium carbonate and calcium carbonate, the structure of the polyaluminum chloride is weakened and the structure of the polyaluminum chloride is deformed at an external high or low temperature. 3 ) There is a problem that the sediment such as 3 ) occurs to reduce the efficiency of water treatment and to remove the deposit from the storage tank.
본 발명은 상기에서 언급한 문제를 해결하기 위해 수산화알루미늄(Al2(OH)3)과 염산(HCl)을 반응시켜 폴리염화알루미늄 제조시 이산화탄소의 영향이 없는 붕사(borax), 규산나트륨(Sodium silicate), 제올라이트(zeolite) 중에서 선택된 어느 하나의 수분희석제를 첨가하여 OH 인자를 증가시켜 염기도가 45％ 이상이 되도록 하고, 외부의 고온이나 저온의 혹독한 환경에서도 안정한 폴리염화알루미늄의 제조방법 제공을 목적으로 한다.
The present invention is to solve the above-mentioned problems by reacting aluminum hydroxide (Al 2 (OH) 3 ) with hydrochloric acid (HCl) borax (borax), sodium silicate without the influence of carbon dioxide in the production of polyaluminum chloride ), To increase the OH factor by adding any one of the water diluents selected from zeolites to have a basicity of 45% or more, and to provide a method for producing polyaluminum chloride that is stable even in harsh environments of high temperature and low temperature do.
본 발명은 수산화알루미늄(Al2(OH)3)과 염산(HCl)를 반응시킨 후 수분희석제를 첨가하여 하기 구조식(1)의 폴리염화알루미늄을 제조하는 방법을 제공한다.The present invention provides a method of preparing polyaluminum chloride of formula (1) by reacting aluminum hydroxide (Al 2 (OH) 3 ) with hydrochloric acid (HCl) and then adding a water diluent.
[Al2(OH)nCl6-n]m......구조식(1)(1≤n≤5, m≤10) [Al 2 (OH) n Cl 6-n ] m ... Structural formula (1) (1≤n≤5, m≤10)
본 발명에서 수산화알루미늄과 염산을 반응시킨 후 첨가하는 수분희석제는 폴리염화알루미늄을 제조시 외부의 높은 온도나 낮은 온도에서 폴리염화알루미늄의 결합력을 약하게 하지 않아 결과적으로 폴리염화알루미늄의 구조 변형을 일으키지 않도록 하는 물질로 정의한다.In the present invention, the water diluent added after reacting aluminum hydroxide with hydrochloric acid does not weaken the binding strength of polyaluminum chloride at high or low temperature when manufacturing polyaluminum chloride, so as not to cause structural deformation of polyaluminum chloride. It is defined as a substance.
본 발명에서 이러한 수분희석제는 이산화탄소를 발생시키지 않아 폴리염화알루미늄의 안정성을 저해하지 않는 것이라면 어떠한 것이라도 사용할 수 있다. 본 발명에서 이러한 수분희석제의 일예로서 붕사(borax), 규산나트륨(Sodium silicate), 제올라이트(zeolite) 중에서 선택된 어느 하나를 사용할 수 있다.In the present invention, any of these water diluents can be used as long as they do not generate carbon dioxide and do not impair the stability of polyaluminum chloride. In the present invention, as one example of such a water diluent, any one selected from borax, sodium silicate, and zeolite may be used.
본 발명에서 수산화알루미늄(Al2(OH)3)과 염산(HCl)를 반응시킨 후 수분희석제를 첨가하여 폴리염화알루미늄을 제조시 수분희석제는 수산화알루미늄 중량 대비 0.5∼2％ 첨가할 수 있다. In the present invention, when the aluminum hydroxide (Al 2 (OH) 3 ) and hydrochloric acid (HCl) is reacted to prepare a polyaluminum chloride by adding a water diluent, the water diluent may be added 0.5 to 2% relative to the weight of aluminum hydroxide.
본 발명에서 폴리염화알루미늄을 제조시 수분희석제를 수산화알루미늄 중량 대비 0.5％ 미만 사용하면 최종 반응물인 폴리염화알루미늄이 외부의 높은 온도나 낮은 온도에서 안정화하지 못하고, 수산화알루미늄 중량 대비 2％ 초과하여 사용하면 외부의 높은 온도나 낮은 온도에서 폴리염화알루미늄의 안정성에 대한 뚜렷한 향상이 없다. 따라서 본 발명에서 폴리염화알루미늄을 제조시 수분희석제를 수산화알루미늄 중량 대비 0.5∼2％ 첨가하는 것이 바람직하다.In the present invention, when the water diluent is used less than 0.5% by weight of aluminum hydroxide in the production of polyaluminum chloride, when the final reactant polyaluminum chloride is not stabilized at an external high or low temperature, it is used in excess of 2% by weight of aluminum hydroxide. There is no obvious improvement in the stability of polyaluminum chloride at high or low external temperatures. Therefore, in the present invention, it is preferable to add 0.5 to 2% of the water diluent with respect to the weight of aluminum hydroxide when preparing the aluminum aluminum chloride.
본 발명에서 수산화알루미늄(Al2(OH)3)과 염산(HCl)은 80∼150℃에서 5∼15시간 동안 반응시킨 후 수분희석제를 첨가하여 폴리염화알루미늄을 제조할 수 있다. In the present invention, aluminum hydroxide (Al 2 (OH) 3 ) and hydrochloric acid (HCl) may be reacted at 80 to 150 ° C. for 5 to 15 hours, and then polyaluminum chloride may be prepared by adding a water diluent.
본 발명의 폴리염화알루미늄 제조시 원료인 수산화알루미늄의 입자크기를 작게 하거나, 염산의 농도를 높이거나, 반응조건중에서 압력과 온도를 높이면 폴리염 화알루미늄 제조시 반응은 가속화될 수 있으나, 이러한 방법들은 폴리염화알루미늄의 생산비용을 증가시키므로 본 발명에서 반응조건은 80∼150℃에서 5∼15시간 동안 실시하는 것이 바람직하다.Reducing the particle size of the aluminum hydroxide as a raw material in the production of polyaluminum chloride of the present invention, increasing the concentration of hydrochloric acid, or increasing the pressure and temperature under the reaction conditions may accelerate the reaction during the production of polyaluminum chloride. Since the production cost of polyaluminum chloride is increased, the reaction conditions in the present invention are preferably performed at 80 to 150 ° C. for 5 to 15 hours.
한편 본 발명에 의해 제조한 폴리염화알루미늄은 Al2O3가 5∼25％ 정도 함유할 수 있다.On the other hand, the polyaluminum chloride manufactured by the present invention may contain about 5 to 25% of Al 2 O 3 .
이하 본 발명의 내용을 비교예, 실시예 및 시험예를 통하여 구체적으로 설명한다. 그러나, 이들은 본 발명을 보다 상세하게 설명하기 위한 것으로 본 발명의 권리범위가 이들에 의해 한정되는 것은 아니다.Hereinafter, the contents of the present invention will be described in detail through comparative examples, examples, and test examples. However, these are intended to explain the present invention in more detail, and the scope of the present invention is not limited thereto.
<비교예>Comparative Example
수산화알루미늄(Al2O3 60％ 함유) 3,000kg과 염산(HCl)(32％) 6,000kg을 혼합한 후 140℃에서 8시간 반응시킨 다음 탄산나트륨 100kg과 탄산칼슘 100kg을 첨가하여 물을 희석하여 염기도가 45％인 폴리염화알루미늄(Al2(OH)2.7Cl3.3)(Al 2O3 17％ 함유) 10,400kg을 제조하였다. After mixing 3,000 kg of aluminum hydroxide (containing 60% of Al 2 O 3 ) and 6,000 kg of hydrochloric acid (HCl) (32%), the mixture was reacted at 140 ° C for 8 hours, and then diluted with water by adding 100 kg of sodium carbonate and 100 kg of calcium carbonate. 10,400 kg of polyaluminum chloride (Al 2 (OH) 2.7 Cl 3.3 ) containing 17% Al 2 O 3 having 45% was prepared.
<실시예 1><Example 1>
수산화알루미늄(Al2O3 60％ 함유) 3,000kg과 염산(HCl)(32％) 6,000kg을 혼합한 후 140℃에서 8시간 반응시킨 다음 붕사(borax) 45kg(수산화알루미늄 중량 대 비 1％)을 첨가하여 물을 희석하여 염기도가 45％인 폴리염화알루미늄(Al2(OH)2.7Cl3.3)(Al2O3 17％ 함유) 10,400kg을 제조하였다. 3,000 kg of aluminum hydroxide (containing 60% of Al 2 O 3 ) and 6,000 kg of hydrochloric acid (HCl) (32%) were mixed and reacted at 140 ° C. for 8 hours, followed by 45 kg of borax (1% by weight of aluminum hydroxide). Water was diluted to prepare 10,400 kg of polyaluminum chloride (Al 2 (OH) 2.7 Cl 3.3 ) (containing 17% Al 2 O 3 ) having a basicity of 45%.
<실시예 2><Example 2>
수산화알루미늄(Al2O3 60％ 함유) 3,000kg과 염산(HCl)(32％) 6,000kg을 혼합한 후 140℃에서 8시간 반응시킨 다음 규산나트륨(Sodium silicate) 45kg(수산화알루미늄 중량 대비 1％)을 첨가하여 물을 희석하여 염기도가 45％인 폴리염화알루미늄(Al2(OH)2.7Cl3.3)(Al2O3 17％ 함유) 10,400kg을 제조하였다.After mixing 3,000 kg of aluminum hydroxide (containing 60% of Al 2 O 3 ) and 6,000 kg of hydrochloric acid (HCl) (32%), the mixture was reacted at 140 ° C. for 8 hours, followed by 45 kg of sodium silicate (1% by weight of aluminum hydroxide). ) Was added to dilute water to prepare 10,400 kg of polyaluminum chloride (Al 2 (OH) 2.7 Cl 3.3 ) (containing 17% Al 2 O 3 ) having a basicity of 45%.
<실시예 3><Example 3>
수산화알루미늄(Al2O3 60％ 함유) 3,000kg과 염산(HCl)(32％) 6,000kg을 혼합한 후 140℃에서 8시간 반응시킨 다음 제올라이트(zeolite) 45kg(수산화알루미늄 중량 대비 1％)을 첨가하여 물을 희석하여 염기도가 45％인 폴리염화알루미늄(Al2(OH)2.7Cl3.3)(Al2O3 17％ 함유) 10,400kg을 제조하였다.After mixing 3,000 kg of aluminum hydroxide (containing 60% of Al 2 O 3 ) and 6,000 kg of hydrochloric acid (HCl) (32%), the mixture was reacted at 140 ° C. for 8 hours, followed by 45 kg of zeolite (1% by weight of aluminum hydroxide). Water was diluted to prepare 10,400 kg of polyaluminum chloride (Al 2 (OH) 2.7 Cl 3.3 ) (containing 17% Al 2 O 3 ) having a basicity of 45%.
<시험예 1><Test Example 1>
상기 비교예 및 실시예 1, 실시예 2, 실시예 3에서 제조한 폴리염화알루미늄(Al2(OH)2.7Cl3.3)을 3개월 동안 -20℃에서 보관시켜 폴리염화알루미늄의 동결발생, 침전물발생, 상태, 동결여부를 측정하고 그 결과를 아래의 표 1에 나타내었다.The poly aluminum chloride (Al 2 (OH) 2.7 Cl 3.3 ) prepared in Comparative Examples and Examples 1, 2, and 3 was stored at -20 ° C. for 3 months to freeze and precipitate precipitates of polyaluminum chloride. , Status, freezing was measured and the results are shown in Table 1 below.
표 1. 동결 시험Table 1. Freezing Tests
<시험예 2><Test Example 2>
상기 비교예 및 실시예 1, 실시예 2, 실시예 3에서 제조한 폴리염화알루미늄(Al2(OH)2.7Cl3.3)을 1개월 동안 50℃에서 보관시켜 폴리염화알루미늄의 침전물발생, 상태를 측정하고 그 결과를 아래의 표 2에 나타내었다.The poly aluminum chloride (Al 2 (OH) 2.7 Cl 3.3 ) prepared in Comparative Examples and Examples 1, 2, and 3 was stored at 50 ° C. for 1 month to measure the occurrence of precipitates of polyaluminum chloride. The results are shown in Table 2 below.
표 2. 고온 시험Table 2. High Temperature Test
상기 시험예 1,2의 결과에서처럼 본 발명에 의해 제조한 실시예 1 내지 실시예 3의 폴리염화알루미늄은 종래의 방법에 의해 제조한 비교예의 폴리염화알루미늄에 비해 저온(-20℃) 또는 고온에서 침전물이 발생하지 않았으며, 상태가 보다 안정화되어 있음을 알 수 있었다. 한편 저온에서는 동결발생 여부를 확인한바 본 발명에 의해 제조한 실시예 1 내지 실시예 3의 폴리염화알루미늄은 종래의 방법에 의 해 제조한 비교예의 폴리염화알루미늄과 달리 동결이 발생하지 않았음을 알 수 있었다. As in the results of Test Examples 1 and 2, the polyaluminum chlorides of Examples 1 to 3 prepared according to the present invention are at a low temperature (-20 ° C) or a high temperature compared to the polyaluminum chloride of Comparative Example prepared by a conventional method. A precipitate did not occur, and the state was found to be more stable. On the other hand, it was confirmed that the freezing occurs at low temperatures, the poly aluminum chloride of Examples 1 to 3 prepared according to the present invention, unlike the poly aluminum chloride of the comparative example prepared by the conventional method did not occur freezing Could.
따라서 본 발명에 의해 제조한 폴리염화알루미늄 종래의 방법에 의해 제조한 것보다 저온 또는 고온의 혹독한 외부의 환경에 보다 안정함을 알 수 있다.Therefore, it can be seen that the polyaluminum chloride produced according to the present invention is more stable to the harsh external environment at low temperature or high temperature than that produced by the conventional method.
상술한 바와 같이, 본 발명의 바람직한 실시예를 참조하여 설명하였지만 해당 기술 분야의 숙련된 당업자라면 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.
As described above, although described with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and modified within the scope of the present invention without departing from the spirit and scope of the invention described in the claims below. It will be appreciated that it can be changed.
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| WO2008150211A1 (en) * | 2007-06-08 | 2008-12-11 | Kemira Kemi Ab | Process for the production of polyaluminium salts |
| KR101113178B1 (en) | 2011-10-05 | 2012-03-13 | 삼구화학공업 주식회사 | Basic polyaluminum chloride and its manufacturing method for preparing a basic polyaluminum chloride prepared by |
| CN103482666A (en) * | 2013-09-07 | 2014-01-01 | 郴州四方立投资有限公司 | Method for preparing polyalumnium chloride water purifying agent by using low-grade kaolin |
| KR101374191B1 (en) * | 2013-10-30 | 2014-03-13 | 미주엔비켐 주식회사 | Preparing method of poly aluminum chloride inorganic coagulant with high basicity for water treatment |
| KR102017114B1 (en) | 2018-04-02 | 2019-09-02 | 한국건설기술연구원 | Manufacturing method of polyaluminum chloride |
| KR102017116B1 (en) | 2018-04-02 | 2019-09-03 | 한국건설기술연구원 | Polyaluminum chloride and water treatment method using same |
| KR20190115336A (en) | 2018-04-02 | 2019-10-11 | 한국건설기술연구원 | Manufacturing apparatus of polyaluminum chloride |
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| CN103482666A (en) * | 2013-09-07 | 2014-01-01 | 郴州四方立投资有限公司 | Method for preparing polyalumnium chloride water purifying agent by using low-grade kaolin |
| KR101374191B1 (en) * | 2013-10-30 | 2014-03-13 | 미주엔비켐 주식회사 | Preparing method of poly aluminum chloride inorganic coagulant with high basicity for water treatment |
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| KR102017116B1 (en) | 2018-04-02 | 2019-09-03 | 한국건설기술연구원 | Polyaluminum chloride and water treatment method using same |
| KR20190115336A (en) | 2018-04-02 | 2019-10-11 | 한국건설기술연구원 | Manufacturing apparatus of polyaluminum chloride |
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