KR101661179B1 - Preparation process of high basic polyaluminium chloride coagulants - Google Patents
Preparation process of high basic polyaluminium chloride coagulants Download PDFInfo
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- KR101661179B1 KR101661179B1 KR1020140040074A KR20140040074A KR101661179B1 KR 101661179 B1 KR101661179 B1 KR 101661179B1 KR 1020140040074 A KR1020140040074 A KR 1020140040074A KR 20140040074 A KR20140040074 A KR 20140040074A KR 101661179 B1 KR101661179 B1 KR 101661179B1
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- C—CHEMISTRY; METALLURGY
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
본 발명은 고염기성 폴리염화알루미늄 응집제의 제조방법에 관한 것으로, 수산화알루미늄(Al(OH)3) 100중량부를 기준으로 하여 10 ∼ 35중량％ 농도의 염산(HCl) 수용액 200 ∼ 300중량부를 140 ∼ 160℃의 온도 및 2 ∼ 5kgf/㎠의 압력 하에서 4 ∼ 9시간 동안 반응시키면서 숙성시켜 산화알루미늄(Al2O3) 함량이 15 ∼ 18중량％이고 염기도가 30 ∼ 40％인 저염기성 폴리염화알루미늄(LBPAC)을 제조하는 제1단계; 상기 반응이 완료된 저염기성 폴리염화알루미늄(PAC)을 20 ∼ 50℃의 온도로 냉각시킨 다음, 농도 조절을 위해 물을 800 ∼ 1200중량부 정도로 첨가하여 저염기성 폴리염화알루미늄(LBPAC) 수용액을 제조하는 제2단계; 상기 제2단계에서 제조된 저염기성 폴리염화알루미늄(LBPAC) 수용액 1000g을 기준으로 알루민산소다(NaAl(OH)4) 400g, 황산나트륨(Na2SO4) 60g 및 2중량％ 농도의 염산(HCl) 수용액 340g을 혼합하고 40 ∼ 70℃의 온도에서 8시간 동안 반응시켜 고염기성 폴리염화알루미늄(HBPAC)을 제조하는 제3단계로 이루어지는 것을 특징으로 한다.
본 발명의 제조방법으로 제조되는 고염기성 폴리염화알루미늄 응집제는 염기도가 60 ∼ 75％이고 산화알루미늄(Al2O3) 함량이 10 ∼ 15중량％로 조절되어 우수한 응집력과 pH조절 성능이 유지되며, 장기간 동안 고체상의 침전물이 석출되지 않는 등 우수한 저장 안정성을 나타낸다. 또한, 반응성과 응집능력이 우수하여 정수처리 과정에서 발생되는 슬러지의 부피와 응집제 사용량을 감소시키며, 이로 인하여 원수에 대한 잔류알루미늄의 감소와 탁도 개선 및 유기물과 부유물질 제거율 향상에 탁월한 효과가 있다.The invention and the basic poly relates to a method of producing aluminum chloride coagulant, aluminum hydroxide (Al (OH) 3) 100 parts by weight, based in the 10 to 35 wt% concentration hydrochloric acid (HCl) aqueous solution of 200 to 300 parts by weight of 140 to (Al 2 O 3 ) content of 15 to 18% by weight and a basicity of 30 to 40% by aging while reacting at a temperature of 160 ° C. and a pressure of 2 to 5 kgf / (LBPAC); After the completion of the reaction, the low-basic poly (aluminum chloride) (PAC) is cooled to a temperature of 20 to 50 ° C, and water is added in an amount of about 800 to 1200 parts by weight for controlling the concentration to prepare an aqueous solution of low basicity polychlorinated aluminum (LBPAC) A second step; 400 g of sodium aluminate (NaAl (OH) 4 ), 60 g of sodium sulfate (Na 2 SO 4 ) and 60 g of hydrochloric acid (HCl) at a concentration of 2% by weight were added to 1000 g of the aqueous low-basic polychlorinated aluminum (LBPAC) And 340 g of an aqueous solution are mixed and reacted at a temperature of 40 to 70 DEG C for 8 hours to produce high basic poly (aluminum chloride) (HBPAC).
The high basicity polychlorinated aluminum flocculant prepared by the production method of the present invention has a basicity of 60 to 75% and an aluminum oxide (Al 2 O 3 ) content of 10 to 15% by weight, And exhibits excellent storage stability such as precipitation of solid phase precipitates for a long period of time. In addition, it has excellent reactivity and cohesion ability, thereby reducing the volume of sludge and the amount of coagulant used in the water treatment process. Thus, there is an excellent effect in reducing residual aluminum, improving turbidity and removing organic matters and suspended matters in raw water.
Description
본 발명은 고염기도 폴리염화알루미늄 응집제의 제조방법에 관한 것으로, 더욱 상세하게는 원수 처리과정에 있어 일반적인 침전처리로 제거되지 않는 물질을 제거하는데 사용하기 위하여 수산화알루미늄(Al(OH)3)과 염산(HCl)을 투입하고 고온 고압반응에 의해 염기도가 30 ∼ 40％인 저염기성 폴리염화알루미늄(LBPAC)을 제조한 다음, 염기도 60 ∼ 75％ 정도의 고염기성 폴리염화알루미늄{HBPAC, High Basic Polyaluminum Chloride, (AL2(OH)nCl6-n)m, 1≤n≤5, m≤10} 응집제를 제조하는 방법에 관한 것이다.The present invention relates to a process for preparing highly salt-free polychlorinated aluminum flocculants and, more particularly, to a process for the preparation of aluminum chloride (Al (OH) 3 ) and hydrochloric acid (LBPAC) having a basicity of 30 to 40% by a high-temperature and high-pressure reaction, and then a high basic polyaluminum chloride (HBPAC) having a basicity of 60 to 75% , (AL 2 (OH) n Cl 6 -n ) m , 1? N? 5 , m ? 10} flocculants.
일반적으로, 원수 처리과정에 있어 일반적인 침전처리에 의해 제거되지 않는 미세한 점토, 유기물, 세균, 조류, 콜로이드 상태로 존재하는 물질을 제거하기 위해 응집제(coagulant) 및 응결제(flocculant)와 같은 화학약품을 첨가하여 콜로이드 성분들을 제거한다. 이러한 응집과정은 정수나 폐수처리에서 가장 중요한 과정 중의 일종으로 알루미늄계(황산알루미늄) 및 철염계(황산제1철, 염화제2철) 등과 같은 무기질 응집제가 오래 전부터 사용되어 왔다.In general, chemicals such as coagulants and flocculants are added to remove fine clay, organics, bacteria, algae, colloidal materials that are not removed by conventional precipitation treatment in raw water treatment To remove colloidal components. These coagulation processes are one of the most important processes in the treatment of water and wastewater, and inorganic coagulants such as aluminum (aluminum sulfate) and iron salts (ferrous sulfate, ferric chloride) have been used for a long time.
지금까지 이러한 저분자 무기응집제들은 가격이 비교적 저렴하다는 장점은 있으나, 수용액 중에서 분자입자의 크기가 작아 탁도 및 부유물질 등의 제거 능력이 충분하지 못하고 처리수의 pH 저하가 크다는 단점이 있다. 또한, 우리나라에서 많이 사용되고 있는 황산알루미늄은 철염계의 무기응집제에 비해 가격이 저렴하고 부식성 피해가 없기 때문에 원수의 수질에 따라 그 사용량을 달리하는데, 장마철과 같은 우수기에 일시적으로 탁도가 매우 높아지는 경우 그 처리능력이 현저하게 저하되며, 이를 과다 사용함으로 인하여 발생되는 잔류 알루미늄의 증가는 알츠하이머병을 일으키는 등 유해성 문제가 심각하게 제기되고 있다.Until now, such low molecular weight inorganic flocculants have a merit that they are relatively inexpensive. However, they are disadvantageous in that they have insufficient ability to remove turbidity and suspended substances due to a small molecular particle size in an aqueous solution and a large decrease in pH of the treated water. Aluminum sulphate, which is widely used in Korea, is inexpensive and does not cause corrosive damage compared to iron salt based coagulant. Therefore, the amount of aluminum sulfate used varies depending on the water quality of raw water. When turbidity is temporarily increased in high season such as rainy season, The processing ability is remarkably deteriorated, and the increase of residual aluminum caused by overuse of the aluminum has serious problems such as causing Alzheimer's disease.
최근에는 이러한 단점을 개선하기 위하여 폴리염화알루미늄(PAC)이 개발되어 전술한 저분자 무기질 응집제를 대체하게 되었으며, 상기 폴리염화알루미늄은 다염기성 무기응집제로서 수용액에서는 아쿠아 착이온을 가지는 배위물질이기 때문에 수산화기(-OH)를 가교로 하여 다핵 착체가 되고 핵은 증가하여 거대화된 무기 고분자화합물을 형성한다. 또한, 폴리염화알루미늄은 황산알루미늄에 비해 플록(floc)의 형성속도 및 침강속도가 빠르고 알칼리 조제 및 응집보조제를 거의 필요로 하지 않으며, 적정 응집량 및 pH 범위가 넓어 과량 주입에 의한 역효과가 적어 작업의 안정성이 높다. 그리고 저탁도 및 고탁도 모두에 대해서 1.2 내지 5배의 뛰어난 탁도 개선효과를 가지며, 저온에서도 응집효과가 좋은 장점을 가지고 있다.In recent years, poly (aluminum chloride) (PAC) has been developed to replace the above-mentioned low molecular weight inorganic flocculant to improve the above disadvantages. The polychlorinated aluminum is a polybasic inorganic flocculant, and since it is a coordination substance having an aqua complex ion in an aqueous solution, -OH) crosslinks to form a polynuclear complex and the nucleus is increased to form a macerated inorganic polymer compound. In addition, aluminum polychloride has a higher rate of floc formation and sedimentation rate than aluminum sulfate, requires almost no alkaline preparation and coagulation aid, has a small amount of pH, . It has an excellent turbidity improving effect of 1.2 to 5 times with respect to both low turbidity and high turbidity, and has an advantage of good flocculation effect even at low temperature.
이러한 폴리염화알루미늄은 일반적으로 산화알루미늄 함량이 58 내지 63％인 수산화알루미늄(Al(OH)3) 2몰(mole)과 농도가 32 내지 35％인 염산 3몰을 혼합한 후 130 내지 170℃에서 4시간 내지 8시간 동안 반응시킨 다음, 물에 의해 희석하여 염기도가 약 40％인 폴리염화알루미늄(산화알루미늄 함량: 10 내지 18％)을 제조하여 사용되고 있다.Such polychlorinated aluminum is generally prepared by mixing 2 moles of aluminum hydroxide (Al (OH) 3 ) having an aluminum oxide content of 58 to 63% and 3 moles of hydrochloric acid having a concentration of 32 to 35% For 4 hours to 8 hours, and then diluted with water to prepare polyaluminum chloride (aluminum oxide content: 10 to 18%) having a basicity of about 40%.
2Al(OH)3 + 3HCl → [Al2(OH)3Cl3]n + 3H2O 2Al (OH) 3 + 3HCl → [Al 2 (OH) 3 Cl 3] n + 3H 2 O
그런데, 상기 폴리염화알루미늄의 염기도는 조성, 구조, 이화학적 성질, 응집효과, 저장의 안정성 등과 매우 밀접한 관계가 있는 중요한 특성이며, 폴리염화알루미늄의 알루미늄(Al)의 당량과 알루미늄에 결합되어 있는 수산화기(-OH) 당량의 백분율로 나타낼 수 있다. 일반적인 정수용 폴리염화알루미늄의 염기도는 제품의 안정성 때문에 30 내지 60％ 정도로 제조되고 있으나, 이론적으로는 염기도가 높을수록 응집능력이 증가되므로 60％ 이상에서도 안정성을 갖는 응집제에 대한 수요가 꾸준히 증가하고 있는 실정이다.The basicity of the polychlorinated aluminum is an important characteristic closely related to the composition, structure, physicochemical properties, coagulation effect, storage stability and the like. The basicity of the aluminum chloride (Al) of the aluminum polychloride and the hydroxyl group (-OH) equivalents. In general, the basicity of polychlorinated aluminum for water purification is about 30 to 60% because of the stability of the product. However, theoretically, the higher the basicity, the more the flocculation ability is increased. Therefore, the demand for the flocculant having stability at 60% to be.
상기와 같은 이유로 고염기도 폴리염화알루미늄 응집제를 제조하기 위한 시도가 많이 있었는데, 대한민국 등록특허공보 제10-0733286호(공고일자 : 2007. 06. 29)에서 수처리용 염화알미늄계 응집제를 제조하는 방법을 보면, 염기도 30 ∼ 55％, Al2O3 농도가 8 ∼ 18％인 폴리염화알미늄 용액을 교반속도가 5,000 ∼ 15,000 rpm으로 유지되는 균질화반응기 중에서, 수산화알루미늄과 가성소다를 반응시켜 제조된 Al2O3함량 5 ∼ 25％, Na2O함량 4 ∼ 23％인 알민산소다와 3 ∼ 60분간 균질화 반응시킨 후, 40 ∼ 100℃에서 5 ∼ 15시간 안정화시켜 Al2O3 농도가 7 ∼ 15％이고, 염기도가 60 ∼ 70％인 고염기도 염화알미늄계 응집제를 제조하는 방법을 개시하고 있으나, 본 발명에서는 상기 선행기술보다 더욱 개선된 응집성능 및 저장 안정성을 나타낼 수 있는 고염기성 폴리염화알루미늄 응집제의 제조방법에 대한 공정상의 조건을 제시하고자 한다.There have been many attempts to produce highly salt-resistant polychlorinated aluminum flocculants for the above reasons, and a method for producing an aluminum chloride flocculant for water treatment in Korean Patent Registration No. 10-0733286 (publication date: 2007. 06. 29) In the homogenization reactor in which the aluminum chloride solution having a basicity of 30 to 55% and an Al 2 O 3 concentration of 8 to 18% is maintained at a stirring rate of 5,000 to 15,000 rpm, Al 2 O 3 content of 5 ~ 25% and Na 2 O content of 4 ~ 23% for 3 ~ 60 minutes, stabilized at 40 ~ 100 ℃ for 5 ~ 15 hours, and Al 2 O 3 concentration is 7 ~ 15 % And a basicity of 60 to 70%. However, in the present invention, a method of producing a highly basic polylactic acid-based coagulant having a high basicity poly And to present the conditions in the process for the preparation of the sum of aluminum coagulants.
또한, 대한민국 등록특허공보 제10-0730578호(공고일자 : 2007. 06. 20)에서는 염산(HCl)과 탄산나트륨(Na2CO3)을 반응시킨 후 탄산가스(CO2)를 제거시키고 수산화알루미늄(Al(OH)3)을 투입하여 150 ∼ 200℃의 온도로 8 ∼ 12시간 동안 반응에 의해 {Al2(OH)nCl6-n}m, 1≤n≤5, m≤10 으로 구성되는 고염기도 폴리염화알루미늄(Poly Aluminum Chloride)의 제조방법을 제공하고 있고, 동 등록특허공보 제10-0858633호(공고일자 : 2008. 09. 17)에서도 염산(HCl)과 수산화알루미늄(Al(OH)3)을 반응시킨 후, 140℃의 온도에서 8∼12시간 동안 혼합하고 냉각(60℃)시켜 탄산나트륨(Na2CO3)과 황산나트륨(Na2SO4)의 혼합물을 혼합한 후 물에 희석시켜 산화알루미늄(Al2O3)이 18％이고 염기도가 45％인 폴리염화알루미늄{2Al(OH)3 + HCl + Na2SO4 + Na2CO3} → {Al2(OH)nCl6-nSO4}m + CO2↑ 을 1≤n≤5, m≤10의 조건으로 형성된 제품을 고속으로 혼합시킨 다음, 산화나트륨(Na2O)의 농도가 20 ∼ 35％인 수산화나트륨(NaOH)을 투입하고 60 ∼ 110℃에서 3시간 동안 숙성시켜 10 ∼ 17％의 산화알루미늄(Al2O3)을 형성하고 55 ∼ 75％의 고염기도를 갖는 폴리염화알루미늄{Al2(OH)nCl6-nSO4}m + NaOH → {Al2(OH)nCl6-nSO4}m을 1≤n≤5, m≤10의 조건으로 제조하는 방법을 제공하고 있다.In addition, in Korean Patent Registration No. 10-0730578 (publication date: 2007. 06. 20), hydrochloric acid (HCl) and sodium carbonate (Na 2 CO 3 ) are reacted, carbonic acid gas (CO 2 ) Al (OH) 3) the charge and composed of 150 to a temperature of 8 to 12 hours by reacting {Al 2 (OH) n Cl 6-n} for m, 1≤n≤5, m≤10 of 200 ℃ (HCl) and aluminum hydroxide (Al (OH) 2) are also disclosed in this patent publication No. 10-0858633 (publication date: 2008.09.17) 3) after the reaction, then a solution for 8-12 hours at a temperature of 140 ℃ and mixing a mixture of sodium carbonate and cooling (60 ℃) (Na 2 CO 3) and sodium sulfate (Na 2 SO 4) was diluted in water, aluminum oxide (Al 2 O 3) is 18% and a basicity of 45% of poly aluminum chloride {2Al (OH) 3 + HCl + Na 2 SO 4 + Na 2 CO 3} → {Al 2 (OH) n Cl 6- n SO 4 } m + CO 2 ↑ is defined as 1? n? 5 , m ≤ 10 were mixed at a high speed and then sodium hydroxide (NaOH) having a concentration of 20 to 35% of sodium oxide (Na 2 O) was added thereto and aged at 60 to 110 ° C for 3 hours to obtain 10 to 17% of aluminum (Al 2 O 3) to form 55 - 75% polyaluminum chloride {Al 2 (OH) n Cl 6-n SO 4} with a high salt airway of m + NaOH → {Al 2 ( OH oxide ) n Cl 6-n SO 4 } m under the conditions of 1? n? 5 and m? 10.
그리고 대한민국 등록특허공보 제10-0748601호(공고일자 : 2007. 08. 06)에서는 (ⅰ) 100중량％를 기준으로 수산화알루미늄 10 내지 49.5중량％와, 염산 30 내지 50중량％ 및 물 0.5 내지 40중량％를 혼합하는 단계; (ⅱ) 단계 (ⅰ)의 혼합물을 120 내지 160℃의 온도범위에서 2 내지 5시간 동안 반응시키는 단계; (ⅲ) 100중량％를 기준으로 단계 (ⅱ)에 의해 생성된 염화알루미늄 35 내지 65중량％와, 수산화이온을 포함한 화합물 2 내지 10중량％와, 주기율표에 따른 1족 및 2족의 금속원소를 포함한 화합물 1 내지 8중량％ 및 물 30 내지 60중량％를 혼합하는 단계; (ⅳ) 단계 (ⅲ)를 통하여 제조된 혼합물을 교반기에 투입하고, 25 내지 70℃의 온도범위에서 8 내지 24시간 동안 혼합 반응시키는 단계를 포함하는 폴리염화알루미늄의 제조방법을 개시하고 있고, 상기 1족 및 2족의 금속원소를 포함한 화합물이 탄산나트륨 또는 탄산칼슘인 것을 특징으로 하고 있다.In addition, Korean Patent Registration No. 10-0748601 (Publication Date: 2007. 08. 06) discloses a process for producing a water-based coating composition comprising (i) 10 to 49.5% by weight of aluminum hydroxide, 30 to 50% by weight of hydrochloric acid, % By weight; (Ii) reacting the mixture of step (i) at a temperature in the range of 120 to 160 DEG C for 2 to 5 hours; (Iii) 35 to 65% by weight of aluminum chloride produced by step (ii) based on 100% by weight, 2 to 10% by weight of a compound containing a hydroxide ion, and metal elements of Group 1 and Group 2 according to the periodic table Mixing 1 to 8% by weight of the compound and 30 to 60% by weight of water; (Iv) introducing the mixture prepared through the step (iii) into a stirrer, and carrying out a mixing reaction at a temperature range of 25 to 70 ° C for 8 to 24 hours, And the compound containing Group 1 and Group 2 metal elements is sodium carbonate or calcium carbonate.
그러나 상기와 같은 제조방법에서는 염기도를 올리기 위해서 탄산나트륨(Na2CO3)을 폴리염화알루미늄(PAC)에 첨가하게 되는데, 통상적으로 탄산나트륨을 폴리염화알루미늄에 첨가하게 되면 탄산가스(CO2)에 의해 폴리염화알루미늄의 구조가 취약하게 되고 외부온도가 상온보다 낮거나 높은 경우 폴리염화알루미늄의 구조가 변형되어 수산화알루미늄(Al(OH)3)의 침전물이 발생하여 물의 정제능력이 떨어질 뿐 아니라 침전물을 자주 청소해야 하는 문제가 있다.However, in the production method as described above to raise the basicity of sodium carbonate (Na 2 CO 3) poly aluminum chloride (PAC) there is the added to, typically when the addition of sodium carbonate in a poly aluminum chloride acid gas Poly by (CO 2) If the structure of aluminum chloride is weakened and the external temperature is lower than or higher than room temperature, the structure of poly (aluminum chloride) is deformed and precipitates of aluminum hydroxide (Al (OH) 3 ) are generated to deteriorate water refining ability. There is a problem to be done.
한편, 본 발명에서는 고염기도 폴리염화알루미늄의 제조공정에 있어 미반응물의 증가에 따르는 응집능력 저하 또는 침전물 발생 등 제품의 안정성이 불안하게 되는 수처리 응집제의 문제점을 해결하기 위해 노력한 결과, 저염기성 폴리염화알루미늄과 알루민산소다(NaAl(OH)4)와 더불어 황산나트륨(Na2SO4, 망초)으로 구성되는 알칼리성분을 반응시킴에 의해 원수의 pH를 높이고 정제능력을 향상시키며, 또한 저염기성 폴리염화알루미늄(LBPAC)의 축 중합 반응시 저농도의 염산(HCl) 수용액을 첨가함으로써 제품의 저장 안정성을 향상시키는 효과가 있음을 발견하여 본 발명을 완성하게 되었다.In the meantime, the present invention has been made to solve the problems of a water-treatment coagulant which is unstable in the stability of products such as a decrease in cohesion ability or an occurrence of precipitates due to an increase in unreacted materials in the process of producing highly salt- Alkaline components composed of aluminum and sodium aluminate (NaAl (OH) 4 ) as well as sodium sulfate (Na 2 SO 4 , mangochi) are reacted to enhance the pH of the raw water and improve the refining ability. (HCl) aqueous solution during the polycondensation reaction of LBPAC, thereby improving the storage stability of the product. Thus, the present invention has been completed.
본 발명의 목적은 응집제를 이용하여 정수처리 시 높은 염기도로 조절되어 유기물질과 부유물질 제거율이 우수하고 탁도 및 농도 안정성이 개선되어 응집제 사용량을 절감할 수 있으며, 또한 잔류알루미늄이 감소될 뿐만 아니라 침전물의 빈번한 청소와 같은 부담을 획기적으로 개선할 수 있는 고염기성 폴리염화알루미늄 응집제의 제조방법을 제공하고자 하는 것이다.An object of the present invention is to provide a method for treating a flocculant by using a flocculant, which is adjusted to a high basicity in the treatment of a water purification, so that the removal rate of organic substances and suspended matters is excellent and turbidity and concentration stability are improved, The present invention is to provide a method for producing a highly basic polychlorinated aluminum flocculant which can dramatically improve the burden of frequent cleaning of the aluminum chloride flocculant.
상기와 같은 과제를 해결하기 위한 본 발명의 고염기성 폴리염화알루미늄 응집제의 제조방법은, 수산화알루미늄(Al(OH)3) 100중량부를 기준으로 하여 10 ∼ 35중량％ 농도의 염산(HCl) 수용액 200 ∼ 300중량부를 140 ∼ 160℃의 온도 및 2 ∼ 5kgf/㎠의 압력 하에서 4 ∼ 9시간 동안 반응시키면서 숙성시켜 산화알루미늄(Al2O3) 함량이 15 ∼ 18중량％이고 염기도가 30 ∼ 40％인 저염기성 폴리염화알루미늄(LBPAC)을 제조하는 제1단계; 상기 반응이 완료된 저염기성 폴리염화알루미늄(PAC)을 20 ∼ 50℃의 온도로 냉각시킨 다음, 농도 조절을 위해 물을 800 ∼ 1200중량부 정도로 첨가하여 저염기성 폴리염화알루미늄(LBPAC) 수용액을 제조하는 제2단계; 상기 제2단계에서 제조된 저염기성 폴리염화알루미늄(LBPAC) 수용액 1000g을 기준으로 알루민산소다(NaAl(OH)4) 400g, 황산나트륨(Na2SO4) 60g 및 2중량％ 농도의 염산(HCl) 수용액 340g을 혼합하고 40 ∼ 70℃의 온도에서 8시간 동안 반응시켜 고염기성 폴리염화알루미늄(HBPAC)을 제조하는 제3단계로 이루어지는 것을 특징으로 한다.Production process of the high basicity polyaluminum chloride flocculant of the present invention to solve the problems described above, the aluminum hydroxide (Al (OH) 3) 100 parts by weight in the 10 to hydrochloric acid of 35% concentration (HCl) aqueous solution of 200 standard (Al 2 O 3 ) content of 15 to 18% by weight and a basicity of 30 to 40% by weight under aged condition at a temperature of 140 to 160 ° C. and a pressure of 2 to 5 kgf / (LBPAC), which is the first step of the present invention; After the completion of the reaction, the low-basic poly (aluminum chloride) (PAC) is cooled to a temperature of 20 to 50 ° C, and water is added in an amount of about 800 to 1200 parts by weight for controlling the concentration to prepare an aqueous solution of low basicity polychlorinated aluminum (LBPAC) A second step; 400 g of sodium aluminate (NaAl (OH) 4 ), 60 g of sodium sulfate (Na 2 SO 4 ) and 60 g of hydrochloric acid (HCl) at a concentration of 2% by weight were added to 1000 g of the aqueous low-basic polychlorinated aluminum (LBPAC) And 340 g of an aqueous solution are mixed and reacted at a temperature of 40 to 70 DEG C for 8 hours to produce high basic poly (aluminum chloride) (HBPAC).
또한, 상기 제3단계 공정에서의 알루민산소다(NaAl(OH)4)는 산화알루미늄(Al2O3) 함량 4 ∼ 10중량％이고, Na2O 함량 3 ∼ 7중량％이고, 그리고 제3단계 공정 중에 발생되는 플록(floc)은 2000 ∼ 4000rpm의 고속교반기를 이용하여 50 ∼ 100㎛ 크기로 균일하게 파쇄하며, 그로부터 제조되는 고염기성 폴리염화알루미늄(HBPAC)은 염기도 60 ∼ 75％, 산화알루미늄(Al2O3) 함량 10 ∼ 15중량％인 것을 특징으로 하고 있다.In the third step, sodium aluminate (NaAl (OH) 4 ) has a content of aluminum oxide (Al 2 O 3 ) of 4 to 10 wt%, an Na 2 O content of 3 to 7 wt% The floc generated during the step process is homogeneously crushed to a size of 50 to 100 μm using a high-speed stirrer at 2000 to 4000 rpm, and the high basic polychlorinated aluminum (HBPAC) produced therefrom has a basicity of 60 to 75% (Al 2 O 3 ) content of 10 to 15% by weight.
본 발명의 제조방법으로 제조되는 고염기성 폴리염화알루미늄 응집제는 염기도가 60 ∼ 75％이고 산화알루미늄(Al2O3) 함량이 10 ∼ 15중량％로 조절되어 우수한 응집력과 pH조절 성능이 유지되며, 장기간 동안 고체상의 침전물이 석출되지 않는 등 우수한 저장 안정성을 나타낸다.The high basicity polychlorinated aluminum flocculant prepared by the production method of the present invention has a basicity of 60 to 75% and an aluminum oxide (Al 2 O 3 ) content of 10 to 15% by weight, And exhibits excellent storage stability such as precipitation of solid phase precipitates for a long period of time.
또한, 본 발명에 따라 제조된 고염기성 폴리염화알루미늄 응집제는 반응성과 응집능력이 우수하여 정수처리 과정에서 발생되는 슬러지의 부피와 응집제 사용량을 감소시키며, 이로 인하여 원수에 대한 잔류알루미늄의 감소와 탁도 개선 및 유기물과 부유물질 제거율 향상에 탁월한 효과가 있다.In addition, the highly basic polychlorinated aluminum flocculant prepared according to the present invention has excellent reactivity and cohesion ability, thereby reducing the volume of the sludge and the amount of flocculant used in the water treatment process, thereby reducing residual aluminum and improving turbidity And an improvement in removal efficiency of organic substances and suspended matters.
본 발명의 고염기성 폴리염화알루미늄 응집제의 제조방법은, 수산화알루미늄(Al(OH)3) 100중량부를 기준으로 하여 10 ∼ 35중량％ 농도의 염산(HCl) 수용액 200 ∼ 300중량부를 140 ∼ 160℃의 온도 및 2 ∼ 5kgf/㎠의 압력 하에서 4 ∼ 9시간 동안 반응시키면서 숙성시켜 산화알루미늄(Al2O3) 함량이 15 ∼ 18 중량％이고 염기도가 30 ∼ 40％인 저염기성 폴리염화알루미늄(LBPAC)을 제조하는 제1단계; 상기 반응이 완료된 저염기성 폴리염화알루미늄(PAC)을 20 ∼ 50℃의 온도로 냉각시킨 다음, 농도 조절을 위해 물을 800 ∼ 1200중량부 정도로 첨가하여 저염기성 폴리염화알루미늄(LBPAC) 수용액을 제조하는 제2단계; 상기 제2단계에서 제조된 저염기성 폴리염화알루미늄(LBPAC) 수용액 1000g을 기준으로 알루민산소다(NaAl(OH)4) 400g, 황산나트륨(Na2SO4) 60g 및 2중량％ 농도의 염산(HCl) 수용액 340g을 혼합하고 40 ∼ 70℃의 온도에서 8시간 동안 반응시켜 고염기성 폴리염화알루미늄(HBPAC)을 제조하는 제3단계로 이루어진다.The method for producing a highly basic polychlorinated aluminum flocculant of the present invention comprises 200-300 parts by weight of an aqueous solution of hydrochloric acid (HCl) at a concentration of 10-35% by weight based on 100 parts by weight of aluminum hydroxide (Al (OH) 3 ) (Al 2 O 3 ) in an amount of 15 to 18% by weight and a basicity of 30 to 40% by weight while being reacted under a pressure of 2 to 5 kgf / ); After the completion of the reaction, the low-basic poly (aluminum chloride) (PAC) is cooled to a temperature of 20 to 50 ° C, and water is added in an amount of about 800 to 1200 parts by weight for controlling the concentration to prepare an aqueous solution of low basicity polychlorinated aluminum (LBPAC) A second step; 400 g of sodium aluminate (NaAl (OH) 4 ), 60 g of sodium sulfate (Na 2 SO 4 ) and 60 g of hydrochloric acid (HCl) at a concentration of 2% by weight were added to 1000 g of the aqueous low-basic polychlorinated aluminum (LBPAC) And 340 g of an aqueous solution are mixed and reacted at a temperature of 40 to 70 DEG C for 8 hours to produce high basic poly (aluminum chloride) (HBPAC).
이하에서는 본 발명에 의한 고염기성 폴리염화알루미늄 응집제의 제조방법에 대하여 설명하기로 하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 예시하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Hereinafter, a method for producing a high-basic poly (aluminum chloride) flocculant according to the present invention will be described. However, it is to be understood that the present invention is not limited thereto, And this does not mean that the technical idea and scope of the present invention are limited.
본 발명에 있어 제1단계 공정은 수산화알루미늄(Al(OH)3) 100중량부를 기준으로 하여 10 ∼ 35중량％ 농도의 염산(HCl) 수용액 200 ∼ 300중량부를 140 ∼ 160℃의 온도 및 2 ∼ 5kgf/㎠의 압력 하에서 4 ∼ 9시간 동안 반응시키면서 숙성시켜 산화알루미늄(Al2O3) 함량이 15 ∼ 18중량％이고 염기도가 30 ∼ 40％인 저염기성 폴리염화알루미늄(LBPAC)을 제조하는 과정이다.In the first step of the present invention, 200-300 parts by weight of a hydrochloric acid (HCl) aqueous solution having a concentration of 10-35% by weight based on 100 parts by weight of aluminum hydroxide (Al (OH) 3 ) (LBPAC) having an aluminum oxide (Al 2 O 3 ) content of 15 to 18% by weight and a basicity of 30 to 40% while being reacted under a pressure of 5 kgf / cm 2 for 4 to 9 hours to be.
상기 저염기성 폴리염화알루미늄을 제조하기 위하여, 수산화알루미늄과 염산(HCl) 수용액을 140 ∼ 160℃의 온도에서 4 ∼ 9시간 동안 반응시키는데, 이때, 염산은 10 ∼ 35％ 농도로 유지하는 것이 반응율이 가장 좋은 것으로 연구되었다. 그리고 반응온도가 140℃ 미만이면 미반응물이 발생하는 문제가 있을 수 있고, 160℃ 초과 시에는 반응압력이 높아져 위험하므로 상기 범위 내의 온도에서 반응시키는 것이 바람직하며, 반응시간은 설정된 범위 내에서 반응온도에 따라 유동적으로 정해진다.In order to produce the low-basic poly (aluminum chloride), an aqueous solution of aluminum hydroxide and hydrochloric acid (HCl) is reacted at a temperature of 140 to 160 ° C. for 4 to 9 hours, It was studied as the best. If the reaction temperature is less than 140 ° C, there may be a problem that unreacted materials are generated. When the reaction temperature exceeds 160 ° C, the reaction pressure is increased and dangerous. Therefore, the reaction is preferably performed at the temperature within the above range. . ≪ / RTI >
상기 제1단계 공정에서의 반응물인 수산화알루미늄(Al(OH)3)은 산화알루미늄(Al2O3) 함량 45 ∼ 60중량％ 정도로서, 염산(HCl)과 반응하여 산화알루미늄(Al2O3) 함량이 15 ∼ 18중량％ 정도인 저염기성 폴리염화알루미늄(LBPAC)을 제조하게 되며, 이때 저염기성 폴리염화알루미늄은 염기도가 30 ∼ 40％ 정도로 생성되어 응집성능이 우수하게 되는 반면, 장기간 저장될 경우 고체상의 침전물이 석출되는 등 안정성이 낮은 상태에 있게 된다.Wherein the reaction product of aluminum hydroxide (Al (OH) 3) in a first step the aluminum (Al 2 O 3) content of 45 to the degree of 60% by weight, and hydrochloric acid (HCl) aluminum oxide reacts with the oxide (Al 2 O 3) (LBPAC) having a content of about 15 to 18% by weight, wherein the basicity of the low-poly aluminum chloride is about 30 to 40% and the coagulation performance is excellent. On the other hand, The stability is low, such as precipitation of solid phase precipitate.
이로 인하여, 제2단계 공정은 상기 반응이 완료된 저염기성 폴리염화알루미늄(LBPAC)을 20 ∼ 50℃의 온도로 냉각시킨 다음, 농도 조절을 위해 물을 첨가하는데, 그 사용량은 상기 수산화알루미늄 100중량부 및 염산(HCl) 수용액 200 ∼ 300중량부를 기준으로 할 때, 800 ∼ 1200중량부 정도의 물을 첨가하고 희석시킴에 의해 저염기성 폴리염화알루미늄(LBPAC) 수용액을 제조하는 과정으로서, 상기 제2단계는 차후에 저염기성 폴리염화알루미늄 수용액이 산-알칼리 발열반응을 통하여 고염기도 폴리염화알루미늄(HBPAC)으로 제조되기 위한 적합한 농도의 상태로 준비된다.Accordingly, in the second step, the low-basic polychlorinated aluminum (LBPAC) having undergone the reaction is cooled to a temperature of 20 to 50 ° C, and water is added to adjust the concentration. The amount of the low- (LBPAC) aqueous solution by adding water in an amount of about 800 to 1200 parts by weight based on 200 to 300 parts by weight of an aqueous solution of hydrochloric acid (HCl) and diluting the aqueous solution, Is prepared in a state of suitable concentration so that a low-basic poly (aluminum chloride) aqueous solution can be subsequently prepared through an acid-alkali exothermic reaction with highly salt-resistant polychlorinated aluminum (HBPAC).
제3단계 공정은 상기 저염기성 폴리염화알루미늄(LBPAC) 수용액 1000g을 기준으로 알루민산소다(NaAl(OH)4) 400g, 황산나트륨(Na2SO4) 60g 및 2중량％ 농도의 염산(HCl) 수용액 340g을 혼합하고 40 ∼ 70℃의 온도에서 8시간 동안 반응시켜 고염기성 폴리염화알루미늄(HBPAC)을 제조하는 과정이다.In the third step, 400 g of sodium aluminate (NaAl (OH) 4 ), 60 g of sodium sulfate (Na 2 SO 4 ) and a 2% by weight aqueous hydrochloric acid (HCl) solution (HBPAC) is prepared by mixing and reacting the mixture at a temperature of 40 to 70 ° C. for 8 hours.
이에 대하여 앞서본 종래기술에서는 저염기도 폴리염화알루미늄계 응집제와 규산염 등과 혼합하는 과정을 거친 다음, 알칼리성인 알루민산소다(NaAl(OH)4, Sodium aluminate, SA)를 반응시키거나, 또는 저염기도 폴리염화알루미늄계 응집제를 직접 수산화알루미늄과 가성소다로 반응시켜 만든 알루민산소다를 이용하여 고염기도 응집제를 제조하는 등과 같은 방법으로 고염기성 폴리염화알루미늄을 제조하였다.In contrast to this, in the prior art as described above, after mixing with a low-salt polychlorinated aluminum chloride coagulant and a silicate, the mixture is reacted with alkaline sodium aluminate (NaAl (OH) 4 , sodium aluminate, SA) Highly basic poly (aluminum chloride) was prepared by the same method as the preparation of high salt antifoaming coagulant by using sodium aluminate soda made by reacting aluminum chloride coagulant with aluminum hydroxide and caustic soda directly.
그러나 본 발명은 상기와 같은 종래기술과 달리, 탄산나트륨(Na2CO3)을 첨가하지 않기 때문에 수산화알루미늄(Al(OH)3)의 침전물이 거의 발생되지 않으며, 그 대신 본 발명에서는 추가적인 응집보조제를 이용하여 저염기성 폴리염화알루미늄(LBPAC) 수용액과 알루민산소다(NaAl(OH)4)의 산-알칼리 반응을 촉진시키기 위해 알칼리성분인 황산나트륨(Na2SO4, 망초)을 적정량 포함시킴으로써, 제품의 응집력을 더욱 향상시키게 될 뿐만 아니라 산성인 저염기성 폴리염화알루미늄 화합물과 알칼리성인 알루민산소다(NaAl(OH)4)에 대한 반응율을 더욱 높이게 되어 고분자량의 고염기도 폴리염화알루미늄(HBPAC)을 효과적으로 제조할 수 있게 된다.However, unlike the conventional art as described above, since no sodium carbonate (Na 2 CO 3 ) is added, precipitates of aluminum hydroxide (Al (OH) 3 ) hardly occur and instead, (Na 2 SO 4 , manganese) in order to promote the acid-alkali reaction of low-basicity polyaluminum chloride (LBPAC) aqueous solution and sodium aluminate (NaAl (OH) 4 ) The cohesion is further improved and the reaction rate to the acidic low-basic polychlorinated aluminum compound and the alkaline sodium aluminate (NaAl (OH) 4 ) is further increased to effectively manufacture high molecular weight high-salt polychlorinated aluminum (HBPAC) .
또한, 본 발명에서는 2중량％ 농도의 염산(HCl) 수용액을 첨가하고 혼합시킴에 의해 미반응 수산화알루미늄(Al(OH)3)의 반응율을 증가시켜 고농도의 폴리염화알루미늄을 효율적으로 제조함으로써 제품의 안정성 문제를 더욱 향상시킬 수 있게 된다. 그리고 본 발명에서 사용되는 알루민산소다(NaAl(OH)4)는 산화알루미늄(Al2O3) 함량이 4 ∼ 10중량％이고 Na2O 함량이 3 ∼ 7중량％ 정도로 희석하여 균질화 반응기에서 저염기성 폴리염화알루미늄과 반응시킴에 의해 수산화알루미늄(Al(OH)3)의 침전물 발생을 최대한 방지하게 된다. 이때, 반응기의 온도는 40 ∼ 70℃로 유지하여 발열반응에 의해 발산되는 열을 적정 온도로 냉각시키는 것이 안전하며, 반응시간은 4시간 이상 8시간 이내로 설정하면 본 발명의 효과를 구현하는데 충분한 것으로 조사되었다.In addition, in the present invention, the reaction rate of unreacted aluminum hydroxide (Al (OH) 3 ) is increased by adding and mixing an aqueous hydrochloric acid (HCl) solution at a concentration of 2 wt% The stability problem can be further improved. Sodium aluminate (NaAl (OH) 4 ) used in the present invention may be prepared by diluting aluminum oxide (Al 2 O 3 ) content to 4 to 10 wt% and Na 2 O content to 3 to 7 wt% By reacting with basic poly (aluminum chloride), the generation of precipitates of aluminum hydroxide (Al (OH) 3 ) is prevented as much as possible. At this time, it is safe to keep the temperature of the reactor at 40 to 70 ° C and to cool the heat emitted by the exothermic reaction to an appropriate temperature, and if the reaction time is set within 4 hours to 8 hours, it is sufficient to realize the effect of the present invention .
그리고 제3단계 공정 중에 발생되는 플록(floc)은 약 2,000 ∼ 4,000rpm의 고속교반기를 이용하여 50 ∼ 100㎛ 크기로 파쇄시킴에 의해 제품이 균질화되는 과정에서 단시간 동안 백탁이 발생되지만, 이후 교반을 멈추고 일정한 시간이 경과됨에 따라 제조되는 고염기도 폴리염화알루미늄(HBPAC)은 미황색을 띠는 투명한 현탁액으로서 염기도 60 ∼ 75％, 산화알루미늄(Al2O3) 함량 10 ∼ 15중량％의 제품으로 제조되는 것이다. 아울러 본 발명에 의한 제품은 이를 건조하여 백색 분말로 제조할 수도 있으며, 어떠한 물리적 상태에서도 물에 대한 용해성이 우수하므로 사용상의 편리함도 탁월하다.Floc generated during the third step process is crushed to a size of 50 to 100 탆 by using a high-speed stirrer of about 2,000 to 4,000 rpm to cause clouding during a short period of time in the process of homogenizing the product, (HBPAC) is a light yellowish transparent suspension prepared as a product having a basicity of 60 to 75% and an aluminum oxide (Al 2 O 3 ) content of 10 to 15% by weight will be. In addition, the product of the present invention can be dried to produce a white powder, and since it has excellent solubility in water even in any physical state, its convenience in use is also excellent.
위와 같이 제조된 고염기도 폴리염화알루미늄(HBPAC) 응집제는 축합반응에 의한 수용성 활성 다핵 착이온을 고농도로 형성하고 있기 때문에 더욱 향상된 응집성능을 발휘하는데, 기존의 황산알루미늄이나 폴리염화알루미늄 응집제에 비해서 흡착활성도가 높고 플록의 형성시간 및 침강속도가 빠르며, 비교적 무겁고 큰 플록을 형성하여 교반, 혼화, 체류, 침전 등의 처리시간이 단축된다.The high-salt-free polychlorinated aluminum (HBPAC) coagulant prepared as described above exhibits improved flocculation performance due to the high concentration of water-soluble polynuclear ion generated by the condensation reaction. As compared with conventional aluminum sulfate or polychlorinated aluminum flocculant, The activity is high and the floc formation time and sedimentation rate are fast and relatively heavy and large flocs are formed and the treatment time such as stirring, mixing, retention, precipitation is shortened.
이상에서 살펴본 바와 같이 본 발명은 수많은 실험을 거쳐 완성되었으나, 이하에서는 당 업자가 용이하게 이해하고 실시할 수 있을 정도의 바람직한 실시예를 통하여 본 발명을 설명한다.As described above, the present invention has been completed through a number of experiments. However, the present invention will be described below with reference to preferred embodiments which the present invention can easily understand and implement.
저염기성 폴리염화알루미늄(LBPAC) 수용액 제조Manufacture of aqueous solution of low basic polychlorinated aluminum (LBPAC)
산화알루미늄(Al2O3) 함량이 60중량％인 수산화알루미늄(Al(OH)3) 100g, 35중량％ 농도의 염산(HCl) 수용액 220g을 140 ∼ 160℃의 온도 및 2 ∼ 5kgf/㎠의 압력 하에서 8시간 동안 반응시켜서 산화알루미늄(Al2O3) 함량이 17중량％이고 염기도가 40％인 저염기성 폴리염화알루미늄을 제조하였다. 상기 반응이 완료된 저염기성 폴리염화알루미늄을 약 40℃의 온도로 자연 냉각시킨 다음 물을 680g 정도로 첨가하여 저염기성 폴리염화알루미늄 수용액을 제조하였다.100 g of aluminum hydroxide (Al (OH) 3 ) having an aluminum oxide (Al 2 O 3 ) content of 60% by weight and 220 g of an aqueous solution of hydrochloric acid (HCl) at a concentration of 35% by weight were mixed at a temperature of 140 to 160 ° C and a temperature of 2 to 5 kgf / The reaction was conducted under pressure for 8 hours to prepare a low-basic polychlorinated aluminum having an aluminum oxide (Al 2 O 3 ) content of 17% by weight and a basicity of 40%. After completion of the reaction, the low-basic poly (aluminum chloride) was naturally cooled at a temperature of about 40 ° C, and water was added to about 680 g to prepare a low-basic poly (aluminum chloride) aqueous solution.
고염기도 폴리염화알루미늄(HBPAC) 응집제 제조Manufacture of highly salt-resistant polychlorinated aluminum (HBPAC) flocculants
상기 저염기성 폴리염화알루미늄 수용액 500g, 알루민산소다(NaAl(OH)4) 200g, 황산나트륨(Na2SO4) 30g, 2중량％ 농도의 염산(HCl) 수용액 170g을 혼합하고 40 ∼ 70℃의 온도에서 2,000 ∼ 4,000rpm으로 속도로 교반하면서 약 8시간동안 반응시켜 고염기도 폴리염화알루미늄을 제조하였다. 반응이 완료된 고염기도 폴리염화알루미늄은 100㎛이하의 크기로 균일하게 파쇄되어 미황색을 띠는 투명한 현탁액을 얻었는데, 상기와 같이 제조된 고염기성 폴리염화알루미늄 응집제는 염기도가 65％이고 산화알루미늄(Al2O3) 함량은 12중량％로 분석되었다.Wherein the low basic poly aluminum chloride aqueous solution 500g, aluminate soda (NaAl (OH) 4) 200g , sodium sulfate (Na 2 SO 4) 30g, 2 wt% of hydrochloric acid (HCl) aqueous solution of 170g of mixture and the temperature of 40 ~ 70 ℃ At a rate of 2,000 ~ 4,000 rpm for about 8 hours with stirring at a rate of 2,000 ~ 4,000 rpm to prepare high salt polychlorinated aluminum. The highly basic polychlorinated aluminum flocculant thus prepared was found to have a basicity of 65% and aluminum oxide (Al (Al)) was obtained. 2 O 3 ) content was analyzed to be 12 wt%.
＜비교예 1＞≪ Comparative Example 1 &
상기 실시예 1에서 제조된 저염기성 폴리염화알루미늄 수용액을 이용하여 고염기성 폴리염화알루미늄 응집제를 제조하되, 황산나트륨(Na2SO4), 그리고 2중량％ 농도의 염산(HCl) 수용액을 첨가하지 않은 것을 제외하고는 실시예 1와 동일한 방법으로 저염기성 폴리염화알루미늄 수용액 제조하였다.A high basicity polychlorinated aluminum flocculant was prepared using the aqueous low-poly aluminum chloride solution prepared in Example 1, except that sodium sulfate (Na 2 SO 4 ) and no aqueous solution of hydrochloric acid (HCl) at a concentration of 2 wt% , A low-basicity polyaluminum chloride aqueous solution was prepared in the same manner as in Example 1.
＜실험예 1＞<Experimental Example 1>
안정성 시험Stability test
상기 실시예 2와 비교예 1에서 각각 제조한 고염기성 폴리염화알루미늄 응집제에 대한 안정성 비교를 위하여 영하 20℃ 및 영상 20℃ 에서 6개월 동안의 장기간 저장에 따른 침전물 발생, 동결 발생 여부 등을 측정하여 제품의 안정성에 대한 평가를 한 결과를 아래 [표 1]에 나타내었다.In order to compare the stability of the highly basic polychlorinated aluminum flocculants prepared in Example 2 and Comparative Example 1, sediment generation and freezing occurrence during long-term storage at -20 ° C and 20 ° C for 6 months were measured The results of evaluating the stability of the product are shown in [Table 1] below.
＜실험예 2＞<Experimental Example 2>
응집처리 시험Coagulation treatment test
상기 실시예 2 및 비교예 1에서 제조한 응집제를 각각 15ppm이 되도록 원수에 투입하여, 20℃의 온도에서 원수의 탁도 개선효과 및 유기물 제거율 등을 수회 측정한 결과의 평균값을 아래 [표 2]에 나타내었다.The average value of the turbidity improvement effect and the organic matter removal rate of the raw water several times measured at a temperature of 20 캜 by charging the coagulant prepared in Example 2 and Comparative Example 1 to 15 ppm respectively is shown in Table 2 below Respectively.
상기 표 2와 같이, 실시예 2와 비교예 1로 각각 제조된 응집제를 동일한 조건에서 비교한 결과를 보면, 본 발명의 제조방법으로 제조된 염기성 폴리염화알루미늄 응집제는 기존의 방법에 의해 제조된 비교예 1에 비해 탁도, pH, 총유기물 제거율, 원수에 잔류하는 알루미늄 농도 등 모든 시험항목에서 매우 우수한 품질을 발휘하게 되므로, 본 발명은 그 기술적 사상을 벗어나지 않는 범위 내에서 당업자에 의해 여러 가지로 치환, 변형 및 변경이 가능하여 다양한 용도와 형태로 사용되어 질 수 있다.As shown in Table 2, when the coagulants prepared in Example 2 and Comparative Example 1 were compared under the same conditions, the basic polychlorinated aluminum flocculant prepared by the production method of the present invention showed a comparative Compared to Example 1, the present invention exhibits excellent quality in all test items such as turbidity, pH, total organic matter removal rate, and aluminum concentration remaining in raw water. Therefore, the present invention can be variously substituted by a person skilled in the art And can be used in various applications and forms.
Claims (4)
(b) 반응이 완료된 저염기성 폴리염화알루미늄을 40℃의 온도로 냉각시킨 다음 물을 680g 첨가하여 저염기성 폴리염화알루미늄 수용액을 제조하는 제2단계; 및
(c) 제조된 저염기성 폴리염화알루미늄(LBPAC) 수용액 1000g을 기준으로 알루민산소다(NaAl(OH)4) 400g, 황산나트륨(Na2SO4) 60g 및 2중량％ 농도의 염산(HCl) 수용액 340g을 혼합하고 40 ~ 70℃의 온도에서 8시간 동안 반응시켜 고염기성 폴리염화알루미늄(HBPAC)을 제조하는 제3단계;
를 포함하며,
상기 제3단계에서의 알루민산소다(NaAl(OH)4)는 산화알루미늄(Al2O3) 함량 4 ~ 10중량％이고, Na2O 함량 3 ~ 7중량％이고,
상기 제3단계 중에 발생되는 플록(floc)은 2,000 ~ 4,000rpm의 고속교반기를 이용하여 50 ~ 100㎛ 크기로 균일하게 파쇄하며,
상기 제3단계에서 제조되는 고염기도 폴리염화알루미늄(HBPAC)은 염기도 60 ~ 75％, 산화알루미늄(Al2O3) 함량 10 ~ 15중량％인 것을 특징으로 하는 고염기성 폴리염화알루미늄 응집제의 제조방법.(a) 220 g of an aqueous solution of hydrochloric acid (HCl) at a concentration of 35% by weight based on 100 g of aluminum hydroxide (Al (OH) 3 ) were mixed and reacted at a temperature of 140 to 160 ° C and a pressure of 2 to 5 kgf / cm 2 for 8 hours (LBPAC) having a content of aluminum oxide (Al 2 O 3 ) of 17% by weight and a basicity of 40%;
(b) a second step of cooling the low-basic poly (aluminum chloride) having completed the reaction to a temperature of 40 캜 and then adding 680 g of water to prepare a low-basic poly (aluminum chloride) aqueous solution; And
(c) 400 g of sodium aluminate (NaAl (OH) 4 ), 60 g of sodium sulfate (Na 2 SO 4 ) and 340 g of a hydrochloric acid (HCl) aqueous solution having a concentration of 2% by weight, based on 1000 g of the aqueous low- And then reacting the mixture at a temperature of 40 to 70 DEG C for 8 hours to prepare high basic polyaluminum chloride (HBPAC);
/ RTI >
In the third step, sodium aluminate (NaAl (OH) 4 ) has an aluminum oxide (Al 2 O 3 ) content of 4 to 10 wt% and an Na 2 O content of 3 to 7 wt%
The floc generated in the third step is uniformly crushed to a size of 50 to 100 탆 using a high-speed stirrer at 2,000 to 4,000 rpm,
Wherein the high salt polychlorinated aluminum (HBPAC) produced in the third step has a basicity of 60 to 75% and an aluminum oxide (Al 2 O 3 ) content of 10 to 15% by weight .
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