KR0149124B1 - Cohesive agent composition - Google Patents
Cohesive agent compositionInfo
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- KR0149124B1 KR0149124B1 KR1019950020163A KR19950020163A KR0149124B1 KR 0149124 B1 KR0149124 B1 KR 0149124B1 KR 1019950020163 A KR1019950020163 A KR 1019950020163A KR 19950020163 A KR19950020163 A KR 19950020163A KR 0149124 B1 KR0149124 B1 KR 0149124B1
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Abstract
본 발명은 수처리과정(상수, 하수, 폐수)에서 오염물질인 유기물, 부유입자를 효율적으로 제거하고 처리후 잔류알루미늄 농도를 최소화하는데 유용한 신규응집제 조성물에 관한 것이다. 구체적으로 응집력이 강한 Al계 무기고분자와 침강성이 강한 Fe계 응집제를 일정한 비율로 혼합한 조성물에 관한 것이다.The present invention relates to a novel coagulant composition useful for efficiently removing contaminants, suspended solids, and minimizing residual aluminum concentrations during water treatment (water, sewage, wastewater). Specifically, the present invention relates to a composition in which a cohesive Al-based inorganic polymer and a precipitated Fe coagulant are mixed at a constant ratio.
종래에 염기도가 영인 황산알루미늄(Al2O38%)이나 염기도가 45~50인 폴리염화알루미늄(Al2O310%)에 단분자 응집제인 철응집제를 적절한 비율로 혼합하여 제조한 것이 있으나 응집능력이나 침전속도, 유기물의 제거율, 처리후 잔류알루미늄에 있어서 불리하다.Conventionally, an aluminum sulfate (Al 2 O 3 8%) having basicity or polyaluminum chloride (Al 2 O 3 10%) having a basicity of 45-50 is mixed with an iron coagulant as a single molecule in an appropriate ratio. It is disadvantageous in terms of flocculation capacity, settling rate, removal rate of organic matter and residual aluminum after treatment.
본 발명의 응집제 조성물을 시험해본 결과 기존의 응집제보다 탁도 및 유기물제거, 잔류알루미늄의 감소효과가 월등히 개선되었다. 본 발명에서 Al-Fe계 응집제는 무기고분자인 Al계 응집제와 Fe계 응집제를 일정 비율로 혼합하여 사용할 수 있는 신규 응집제로 사용형태가 액상 및 고체상 모두 될 수 있다.As a result of testing the flocculant composition of the present invention, turbidity, organic matter removal, and reduction of residual aluminum were much improved than the existing flocculant. In the present invention, the Al-Fe-based flocculant is a novel flocculant that can be mixed with an inorganic polymer Al-based flocculant and a Fe-based flocculant in a predetermined ratio and can be used in both liquid and solid phase.
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Description
본 발명은 상수의 원수, 하수 및 폐수 등의 정수과정에서 오염물질인 유기물, 부유입자를 효율적으로 제거하고 정수 처리후 잔류알루미늄 농도를 최소화하는데 유용한 신규응집제 조성물에 관한 것이다. 구체적으로는 응집력이 강한 알루미늄(AI)계 무기고분자 물질과 침강성이 강한 철(Fe)계 무기고분자 물질을 일정한 비율로 혼합 조성한 무기계 고분자 정수용 응집제 조성물에 관한 것이다. 기존에 사용되고 있는 단분자 AI계 및 Fe계 응집제로서는 황산알루미늄(AI2(SO4)3), 염화제1철(FeCI2), 염화제2철(FeCI3), 황산제2철(Fe2(SO4)3), 황산제1철(FeSO4) 등이 사용되고 있으며, 무기고분자응집제로는 폴리염화알루미늄(polyaluminium chloride :PAC), 폴리황산규산알루미늄(polyaluminium sulfate-silicate : PASS), 폴리수산화염화규산알루미늄(polyaluminium hydrxide-chloride-silicate : PAHCS) 등이 사용되고 있다.The present invention relates to a novel coagulant composition useful for efficiently removing contaminants, suspended solids, and minimizing residual aluminum concentration after purified water in the purification process of raw water, sewage and wastewater. More specifically, the present invention relates to a coagulant composition for inorganic polymer water purification comprising a composition of a cohesive aluminum (AI) inorganic high molecular material and a strong sedimentable iron (Fe) inorganic high molecular material in a fixed ratio. Conventional monomolecular AI and Fe-based flocculants include aluminum sulfate (AI 2 (SO 4 ) 3 ), ferrous chloride (FeCI 2 ), ferric chloride (FeCI 3 ), and ferric sulfate (Fe 2). (SO 4 ) 3 ), ferrous sulfate (FeSO 4 ), and the like, and inorganic inorganic coagulants include polyaluminium chloride (PAC), polyaluminum sulfate-silicate (PASS), and polyhydroxide. Aluminum chloride (polyaluminium hydrxide-chloride-silicate (PAHCS)) is used.
그러나 산업의 발달과 인구의 증가로 하수처리량의 증가 및 하천수의 오염도가가증됨에 따라 현재의 정수처리시스템으로 양질의 정수처리를 하기에는 한계에 이른 실정이다. 단분자 응집제들은 응집능력, 플럭(floc)의 성장속도, 침강속도, 유기물의 제거능력이 낮을 뿐 아니라, 처리후 처리 수중 금속 성분의 잔류율이 높아 정수처리시의 문제점으로 지적되고 있다. 특히 잔류 알루미늄의 농도를 우리나라에서는 0.2㎎/ℓ 이하로 규제하고 있는 실정이기 때문에 새로운 응집제의 개발이 요구되고 있는 실정이다.However, with the development of the industry and the increase of population, the increase of sewage treatment capacity and the pollution degree of river water are increasing, which is the limit of the current water treatment system. The monomolecular flocculants have a low flocculation capacity, floc growth rate, sedimentation rate and organic matter removal ability, as well as a high residual ratio of metal components in the treated water after treatment. In particular, since the concentration of residual aluminum is regulated to 0.2 mg / l or less in Korea, the development of a new flocculant is required.
이러한 문제점을 개선하기 위한 방법으로는 염기도가 0(zero)인 황산알루미늄(Al2O38중량%의 것)이나 염기도가 45~50인 폴리염화알루미늄(Al2O310중량%인 것)에 단분자 철계 응집제를 일정한 비율로 혼합하여 제조한 것이 있으나 이러한 응집제는 응집능력이나 침전속도, 유기물의 제거율이 저조하다는 문제가 있다. (대한민국 특허공고, 공고번호 제94-1798 호) 일반적으로 단분자 응집제는 분자량이 1000이하인 것으로 응집과정에서 수화반응을 통하여 분자량이 증가, 응집상승효과를 유발하기는 하지만 알칼리도(pH)가 높을 경우에는 국부적으로 분산될 우려가 있기 때문에 투입량의 증대가 요구되며, 심하면 과량의 수산화알루미늄(Al(OH)3)에 의한 백탁현상을 초래하여 양질의 정수처리를 할 수 없게 된다. 백탁현상이 나타나면 잔류알루미늄의 농도가 증가하기 때문에 알츠하이머병을 유발할 수도 있어 상당한 주의를 요하게 된다. 분자량이 낮으면 생성되는 플럭의 크기가 무기고분자 응집제보다 작게되며, 뿐만 아니라 미세플럭들이 여과지로 월류하여 여과세척주기가 짧아져 경제적인 손실도 따른다. 또한 정수처리시에는 정수처리후 배수되는 물의 pH가 7∼7.5정도의 중성을 유지하여야 하는바, 단분자 응집제는 응집처리후 아래식과 같이 pH를 저하시키기 때문에 처리후 소석회나 가성소다로 pH를 다시 조정해야 하므로 경제적으로 손실이 따를 뿐 아니라 수처리 공정이 상당히 번거롭게 된다는 단점을 수반하게 된다.To solve this problem, aluminum sulfate having a basicity of 0 (zero) (Al 2 O 3 8% by weight) or polybasic aluminum chloride having a basicity of 45 to 50 (Al 2 O 3 10% by weight) Although the monomolecular iron-based coagulant is prepared by mixing in a fixed ratio, such a coagulant has a problem of low coagulation capacity, precipitation rate, and removal rate of organic matter. (Korean Patent Publication, Publication No. 94-1798) In general, a monomolecular flocculant has a molecular weight of 1000 or less, which increases the molecular weight through the hydration reaction during the aggregation process and causes a synergistic effect, but has a high alkalinity (pH). There is a possibility that it may be dispersed locally, the increase of the input amount is required, and if it is severe, it will cause the turbidity caused by the excess aluminum hydroxide (Al (OH) 3 ), it is impossible to perform a good water purification treatment. When clouding occurs, the concentration of residual aluminum increases, which can lead to Alzheimer's disease. If the molecular weight is low, the size of the generated floes is smaller than that of the inorganic polymer flocculant. In addition, the microfluids flow over the filter paper, which shortens the filtration washing cycle, resulting in economic losses. In addition, during the water treatment, the pH of the water drained after the water treatment should be maintained at a neutral value of about 7 to 7.5. Since the monomolecular flocculant lowers the pH after the coagulation treatment as shown in the following equation, the pH is again changed with calcined lime or caustic soda. The adjustment has to be economically costly and has the disadvantage of making the water treatment process quite cumbersome.
※ 상기식에서 Al+3또는 Fe+3는 황산염 또는 염화물 형태에서 발생된 것이며 염화알루미늄 무기 고분자 물질은 일반적으로 다음과 같은 구조식을 갖는다.In the above formula, Al +3 or Fe +3 is generated in the form of sulfate or chloride, and the inorganic aluminum chloride inorganic polymer generally has the following structural formula.
일반적으로 이분야에서 염기도는 다음과 같이 나타낸다.In general, the basicity in this field is represented as follows.
단분자 Al 또는 Fe는 단분자 1몰(mole)당 3몰의 수소이온을 발생시키기 때문에 투입량이 증가할수록 pH 저하가 증가한다. 그러나 무기고분자의 경우는 상기식 2에서 처럼 단분자인 황산알루미늄보다 수소이온의 발생량이 적다. 특히 홍수시 원수의 탁도가 증가할 경우 평상시보다 응집제의 투입량이 2배이상 되어야 하므로 단분자의 경우 pH저하는 심화 된다. 그러나 무기 고분자 응집제는 같은 알루미늄계 또는 철계라 하더라도 염기도가 높아 pH저하가 상대적으로 낮아지는 잇점이 있다.Since monomolecular Al or Fe generates 3 moles of hydrogen ions per mole of monomolecules, the pH decreases as the input amount increases. However, in the case of the inorganic polymer, hydrogen ions are generated less than the monomolecular aluminum sulfate as in Equation 2. In particular, when the turbidity of raw water increases during flooding, the input of flocculant should be more than twice as usual, so the pH decreases in the case of single molecules. However, even when the inorganic polymer flocculant is the same aluminum-based or iron-based, there is an advantage that the pH decreases relatively high due to high basicity.
본 발명자들은 단분자 무기응집제가 갖고 있는 문제점들을 개선하고자 수년간 실험을 통하여 정수처리능력을 비교해본 결과 기존의 응집제보다 탁도 및 유기물제거, 침전속도 등이 월등히 개선되는 것이 확인되어 본 발명을 완성하게 되었다. 본 발명은 염기도가 10~50 범위이면서 평균분자량이 100,000 이상인 폴리황산규산알루미늄(PASS-Al2O38 중량%)과 염기도가 20~80이면서 평균분자량이 300,000 이상인 폴리수산화염화규산알루미늄(PAHCS-Al2O316~18중량%)인 무기고분자와 3가 철을 중심으로한 폴리황산철(PIS-poly Iron sulfate)과 단분자 황산철(FeSO4)응집제를 혼합하여서 된 정수용 응집제 조성물에 관한 것이다.The present inventors have compared the water treatment capacity through experiments for several years to improve the problems of the monomolecular inorganic coagulant, and it was confirmed that the turbidity, organic matter removal, precipitation rate, etc. are significantly improved than the existing coagulant to complete the present invention. . The present invention has a polybasic acid silicate (PASS-Al 2 O 3 8 wt%) having a basicity of 10 to 50 and an average molecular weight of 100,000 or more and a polyaluminum hydrochloride silicate (PAHCS- having a basicity of 20 to 80 and an average molecular weight of 300,000 or more. Regarding the coagulant composition for water purification, a mixture of inorganic polymer (Al 2 O 3 16-18% by weight)) and PIS-poly Iron sulfate based on trivalent iron and a monomolecular iron sulfate (FeSO 4 ) will be.
본 발명에서 사용할 수 있는 수용성 무기 고분자 응집제는 염기도가 5~80범위에 있는 Al계 응집제로서, 모두 중합물질의 형태다. 본 발명에서 염기도는 N / 3M × 100(%)로 정의되며 M은 3가 금속(Fe 혹은 Al)을 표시하며 N은 OH수를 나타낸다. 또한 본 발명에서 사용할 수 있는 철응집제는 2가 및 3가철을 중심으로 하는 수용성 무기화합물로 음이온이 황산이온 및 염소이온으로 되어 있는 화합물이다.The water-soluble inorganic polymer flocculant that can be used in the present invention is an Al-based flocculant having a basicity in the range of 5 to 80, all in the form of a polymer. In the present invention, the basicity is defined as N / 3M × 100 (%), M represents a trivalent metal (Fe or Al) and N represents the number of OH. In addition, the iron coagulant which can be used in the present invention is a water-soluble inorganic compound based on divalent and trivalent iron, and anion is a compound in which sulfate ions and chlorine ions are used.
본 발명에서 Al-Fe계 응집제는 무기고분자인 Al계 응집제와 Fe계 응집제를 일정비율로 혼합하여 사용할 수 있는 신규 응집제로 사용형태가 액상 또는 고체상 어느것으로도 될 수 있다. 두 무기고분자화합물의 혼합시 조성물의 Al/Fe 몰(mole)비는 처리 대상원수의 성상에 따라 다르게 된다. 상수처리시에는 응집력이 우수한 Al함량을 높게 하는 것이 유리하나, 조류(藻類-Algae) 발생시에는 Fe 함량을 높게 하는 것이 더욱 바람직하다.In the present invention, the Al-Fe-based flocculant is a novel flocculant that can be used by mixing the Al-based flocculant and the Fe-based flocculant, which are inorganic polymers, at a predetermined ratio, and can be used in either liquid or solid phase. When mixing two inorganic polymer compounds, the Al / Fe mole ratio of the composition varies depending on the nature of the raw water to be treated. In the water treatment, it is advantageous to increase the Al content, which is excellent in cohesion, but it is more preferable to increase the Fe content in the case of algae.
반면 폐수처리시 유기물의 함량이 높을 경우에는 산화력이 우수한 3가철의 함량을 증가시키는 것이 유리하다. 또한 원수의 pH가 8이상 올라갈 경우에는 응집범위가 더 넓은 Fe계 응집제 함량을 증가시키는 것이 유리하다. 하수의 경우도 유기물이 다량 포함되어 있으므로 유기물의 분해를 촉진시킬 수 있는 3가 Fe를 증가시키는 것이 바람직하다. 그러나 어떤 경우에도 Fe계통의 응집제는 침전능력이나 산화능력은 우수하지만 Al응집제에 비하여 응집능력이 상대적으로 낮으므로 두응집제로부터 신규 조성물의 응집제는 한계영역의 Al/Fe비가 존재한다.On the other hand, when the organic matter content is high during the wastewater treatment, it is advantageous to increase the content of trivalent iron having excellent oxidation power. In addition, when the pH of the raw water rises more than 8, it is advantageous to increase the content of Fe-based coagulant having a wider aggregation range. In the case of sewage, since a large amount of organic matter is contained, it is preferable to increase trivalent Fe which can promote decomposition of organic matter. In any case, however, the Fe-based coagulant has excellent precipitation and oxidizing ability, but the coagulant is relatively lower than that of the Al coagulant. Therefore, the coagulant of the novel composition from the coagulant has an Al / Fe ratio in the limit region.
본 발명에서 신규응집제 조성물은 용액상태로 사용하는 것이 보다 편리하며, 대상폐수에 따라서 고상으로 하여 분말로 사용할 수도 있고, 물에 용해하여 사용할 수도 있다.In the present invention, the new coagulant composition is more convenient to use in a solution state, and may be used as a powder as a solid phase depending on the target wastewater, or may be used by dissolving in water.
가장 적절한 혼합조성비는 처리 대상원수에 따라 달리 제조하는 것이 이상적이다. 본 발명에서 Al-Fe계 혼합응집제를 제조하는데 있어서 폴리황산규산알루미늄(PASS)과 폴리황산철(PIS)을 원료로 사용할 때 용액중의 Al + Fe의 총 농도는 4~20% 범위가 적당하며, 단분자 응집제 형태인 황산철을 사용할 경우에는 Al + Fe의 총 농도는 4~18%가 적당하다. 무기고분자로 폴리수산화염화규산알루미늄(PAHCS)을 사용할 경우, Fe성분으로 폴리염화철(PIC) 혹은 염화철(2가철, 3가철)일 경우 Fe + Al 총 농도가 4~20%, 단분자인 황산철(2가, 3가철)일 경우는 4~18% 범위가 적당하다.The most suitable mixing ratio is ideally prepared differently depending on the raw water to be treated. In the present invention, the total concentration of Al + Fe in the solution is appropriate in the range of 4-20% when using polyaluminum silicate (PASS) and iron polysulfate (PIS) as raw materials in the preparation of the Al-Fe-based coagulant. In case of using iron sulfate in the form of a monomolecular flocculant, the total concentration of Al + Fe is 4-18%. In case of using polyhydroxyaluminum silicate (PAHCS) as an inorganic polymer, the total Fe + Al concentration is 4 ~ 20% in the case of poly iron chloride (PIC) or iron chloride (ferric iron, trivalent iron) as Fe component, and iron sulfate In the case of (bivalent, trivalent), the 4-18% range is appropriate.
이하 실시예를 들어 본 발명을 구체적으로 설명한다.The present invention will be described in detail with reference to the following Examples.
[실시예 1]Example 1
폴리황산규산알루미늄(PASS, Al 4.5중량%)과 폴리황산철(PIS, 12.1%Fe)을 Fe/Al 몰비가 0.10, 0.15, 0.20 되도록 각각 제조하였다. 제조된 시료로 기존의 응집제와 응집성능비교를 위하여 처리대상원수에 대하여 쟈-테스트를 수행하였다. 실험은 교반속도를 자동조절 가능한 테스터(mini-jar tester)를 사용하였으며, 교반조건은 급속 120 rpm에서 1분, 60rpm에서 5분, 0 rpm에서 10분으로 각각 테스트하였다. 그 결과를 3회 평균하여 표 1에 나타내었다. 표 1에서 보는 것처럼 폴리황산규산알루미늄(PASS)에 폴리황산철(PIS)가 혼합되었을 때 침강 및 유기물의 제거능력이 우수하게 나타났다.Poly (aluminum silicate) (PASS, 4.5 wt% Al) and iron polysulfate (PIS, 12.1% Fe) were prepared so that the Fe / Al molar ratio was 0.10, 0.15, and 0.20, respectively. In order to compare the coagulant performance with the existing coagulant, the prepared sample was subjected to JA-test. In the experiment, a tester (mini-jar tester) capable of automatically adjusting the stirring speed was used, and the stirring conditions were tested at a rapid 120 rpm for 1 minute, at 60 rpm for 5 minutes, and at 0 rpm for 10 minutes, respectively. The results are averaged three times and shown in Table 1. As shown in Table 1, the ability of sedimentation and organic matter removal was excellent when polysulfate of aluminum (PASS) was mixed with polysulfate of iron (PIS).
[실시예 2]Example 2
폴리수산화염화규산알루미늄(PAHCS, Al 9%)과 폴리염화철(PIS, Fe³12.1%)을 혼합하여 Fe/ Al몰비가 0.30, 0.40, 0.50인 용액을 제조하였다. 제조된 시료로 기존의 응집제와 응집성능비교를 위하여 처리대상 원수에 대하여 쟈-테스트를 수행하였다. 그 결과를 3회 평균하여 표 2에 나타내었다. 탁도제거율에서 특히 우수하였다.Polyhydric aluminum chloride silicate (PAHCS, Al 9%) and polyiron chloride (PIS, Fe 32.1%) were mixed to prepare a solution having a Fe / Al molar ratio of 0.30, 0.40, and 0.50. In order to compare the coagulant performance with the existing coagulant, the prepared sample was subjected to a jar test. The results are averaged three times and are shown in Table 2. Particularly excellent in turbidity removal rate.
[실시예 3]Example 3
폴리수산화염화규산알루미늄(PAHCS, Al 9%)과 폴리염화철(PIS,12.1%)을 혼합하여 Fe/Al 몰비가 각각 0.10, 0.15, 0.20인 용액을 제조하였다. 고탁도, 고유기물 원수처리에서 응지선능을 비교한 결과를 표 3에 나타내었다. 표 4에서는 조류제거효과를 비교하였다.Polyaluminum hydrochloride silicate (PAHCS, Al 9%) and polyiron chloride (PIS, 12.1%) were mixed to prepare solutions having a Fe / Al molar ratio of 0.10, 0.15, and 0.20, respectively. Table 3 shows the results of comparing the coagulation ability in the high turbidity and natural water treatment. Table 4 compares the algae removal effect.
[실시예 4]Example 4
폴리수산화염화규산알루미늄(PAHCS,Al 9%)과 폴리염화철(PIS, Fe 12.1%)율)과 염화제1철(Fe 4.2%)혼합, Fe/ Al 몰비가 각각 0.10, 0.15되도록 제조하였다. 이 응집제로 각 샘플에 대하여 처리후 잔류알루미늄을 측정하였다(잔류알루미늄측정기기 ICP, SPECTRO-P Model). 표 5에서 보여준 바와같이 잔류알루미늄은 철함량이 높을수록 감소하였고, 2가 철보다는 3가철인 경우가 더 감소하였다. 또한 단분자 철을 혼합하는 것보다는 중합된 무기고분자로 혼합하는 것이 효율적이었다Polyaluminum hydrochloride silicate (PAHCS, Al 9%) and polyiron chloride (PIS, Fe 12.1%) ratio) and ferrous chloride (Fe 4.2%) mixture, Fe / Al molar ratio was prepared so that 0.10, 0.15, respectively. Residual aluminum was measured after treatment with each coagulant for each sample (residual aluminum measuring instrument ICP, SPECTRO-P Model). As shown in Table 5, the residual aluminum decreased with higher iron content, and decreased more with trivalent iron than with divalent iron. It was also more efficient to mix polymerized inorganic polymers than to mix monomolecular iron.
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| KR20010107799A (en) * | 2001-09-17 | 2001-12-07 | 신호상 | New Coagulant mixture for the Chlorine Dioxide By-product Control |
| KR20030065733A (en) * | 2002-01-30 | 2003-08-09 | 서왕식 | The product composition of a solution and a solid material for purification and activation of utility water. |
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