KR100735540B1 - Process for preparing polyalumium hydroxy chloro sulfate as a flocculant for treating water - Google Patents

Process for preparing polyalumium hydroxy chloro sulfate as a flocculant for treating water Download PDF

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KR100735540B1
KR100735540B1 KR1020050100060A KR20050100060A KR100735540B1 KR 100735540 B1 KR100735540 B1 KR 100735540B1 KR 1020050100060 A KR1020050100060 A KR 1020050100060A KR 20050100060 A KR20050100060 A KR 20050100060A KR 100735540 B1 KR100735540 B1 KR 100735540B1
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sulfate
polyaluminum
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권영준
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고도화학(주)
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron

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Abstract

본 발명은 기존의 상수처리용 제제로 상용되고 있는 황산알루미늄(Aluminum sulfate, AS)과 폴리염화알루미늄(Polyaluminum chloride, PAC)을 사용하여 기존의 응집제가 갖는 단분자와 저염기도의 단점을 보완하여, 높은 염기도로서 우수한 안정성, 반응성 및 응집활성을 갖는 수처리응집제인 폴리수산화염화황산알루미늄(Polyaluminum hydroxy chloro sulfate, PAHCS)을 제조하는 방법에 관한 것이다.The present invention uses aluminum sulfate (AS) and polyaluminum chloride (PAC), which are commonly used as preparations for water treatment, to compensate for the shortcomings of monomolecules and low bases of the existing flocculant. The present invention relates to a method for producing polyaluminum hydroxy chloro sulfate (PAHCS), which is a water treatment coagulant having high stability and reactivity and coagulation activity.

먼저 황산알루미늄을 알카리와 반응시켜 폴리황산알루미늄으로 되는 반응식은 다음과 같고,First, a reaction scheme in which aluminum sulfate is reacted with alkali to form polyaluminum sulfate is

Figure 112006040872405-pat00001
Figure 112006040872405-pat00001

상기에서 얻어진 폴리황산알루미늄의 일반식은 The general formula of the aluminum polysulfate obtained above

[Al2(OH)n(SO4)3-n/2]m 으로 표시되며,Represented by [Al 2 (OH) n (SO 4 ) 3-n / 2 ] m ,

여기에서 n은 1≤n≥5 이며 m은 m<10이다.Where n is 1 ≦ n ≧ 5 and m is m <10.

다음에 상기에서 얻어진 폴리황산알루미늄과 폴리염화알루미늄의 반응에 의해 폴리수산화염화황산알루미늄이 되는 반응식은 다음과 같으며,Next, a reaction formula for producing polyaluminum hydroxide sulfate by the reaction of polyaluminum sulfate and polyaluminum chloride obtained above is as follows.

Figure 112006040872405-pat00006
Figure 112006040872405-pat00006

일반식은 [Al2(OH)aClb(SO4)c]m이며 m이며 m은 m<10이다.The general formula is [Al 2 (OH) a Cl b (SO 4 ) c ] m , where m is m <10.

Description

수처리용 응집제인 폴리수산화염화황산알루미늄의 제조방법 {Process for preparing polyalumium hydroxy chloro sulfate as a flocculant for treating water}Process for preparing polyalumium hydroxy chloro sulfate as a flocculant for treating water

도 1 내지 도 3은 응집활성을 비교한 것으로 본 발명 실시예 2에서 얻은 제품(PAMCS)을 AS, PAC 등과 비교한 그래프1 to 3 is a graph comparing the activity of the product (PAMCS) obtained in Example 2 of the present invention to compare the aggregation activity, AS, PAC, etc.

본 발명은 기존의 수처리 응집제로서 널리 사용 있는 단분자 응집제인 황산알루미늄(Aluminum sulfate, AS)과 저염기도의 폴리염화알루미늄(Polyaluminum chloride, PAC)을 일정비율의 알카리제로 중합 및 숙성시켜, 높은 염기도와 고분자의 특성을 가지면서 안정성이 우수하고 반응성과 응집성능도 탁월한 폴리수산화염화황산알루미늄(Polyaluminum hydroxy chloro sulfate, PAHCS)을 제조하는 방법에 관한 것이다.The present invention polymerizes and matures a monomolecular flocculant (Aluminum sulfate, AS), which is widely used as a conventional water treatment flocculant, and a polybasic chloride (PAC) having a low basic degree, with a certain ratio of an alkaline agent, thereby achieving high basicity. The present invention relates to a method of preparing polyaluminum hydroxy chloro sulfate (PAHCS) having excellent polymer properties and excellent stability and excellent reactivity and cohesive performance.

본 발명에서 사용되는 원료중 하나인 황산알루미늄(Aluminum sulfate; Al2(SO4)3 xH2O)은 Alum 또는 황산반토라고도 불리는 것으로서, 우수한 응집특성을 가지면서 저렴하고 무독성이며 거의 모든 혼탁 수중에 적용되면서 취급도 용이하여 오늘날까지 가장 광범위하게 사용되고 있는 응집제이다.Aluminum sulfate (Al 2 (SO 4 ) 3 x H 2 O), which is one of the raw materials used in the present invention, is also called Alum or alumina sulfate, and has excellent cohesive properties, is inexpensive, non-toxic, and in almost all turbid water. It is a coagulant that is widely used to this day because it is easy to handle while being applied.

이와 같은 황산알루미늄은 최근 알루미늄공업의 발달에 따라 값싼 수산화알루미늄을 얻을 수 있기 때문에 그 수산화알루미늄을 주원료로 아래 반응식과 같이 황산과 반응시켜 불순물을 함유하지 않은 순도 높은 제품을 얻을 수가 있다.Such aluminum sulfate can be obtained cheap aluminum hydroxide in accordance with the recent development of the aluminum industry, it is possible to obtain a high-purity product containing no impurities by reacting the aluminum hydroxide with sulfuric acid as the following reaction formula.

2Al2(OH)3 + 3H2SO4 → 2Al2(SO4)3 + 6H2O2Al 2 (OH) 3 + 3H 2 SO 4 → 2Al 2 (SO 4 ) 3 + 6H 2 O

황산알루미늄은 고상과 액상이 있으며 고상은 알루미나고형분(Al2O3)로서 14~15%이고 액상은 알루미나고형분(Al2O3)로서 8%인 것이 일반적이다.Aluminum sulfate has a solid phase and a liquid phase. The solid phase is generally 14-15% as alumina solids (Al 2 O 3 ) and the liquid phase is generally 8% as alumina solids (Al 2 O 3 ).

황산알루미늄의 결정석출점은 8.3%일때 -14℃로 가장 낮으며 농도가 증가하면 결정석출온도가 급격히 높아져 상온에서도 결정이 석출되어 보관 및 주입설비를 폐쇄하게 되므로 사용할 수가 없게 된다.The crystal precipitation point of aluminum sulfate is the lowest at -14 ℃ when 8.3%, and as the concentration increases, the crystal precipitation temperature increases rapidly, and crystals precipitate at room temperature and thus cannot be used because the storage and injection facilities are closed.

또한 황산알루미늄 1㎎/ℓ의 주입에 따른 수중의 알카리 소모율은 탄산칼슘(CaCO3)을 기준으로 0.45㎎/ℓ이다.In addition, the alkali consumption in water according to the injection of aluminum sulfate 1mg / l is 0.45mg / l based on calcium carbonate (CaCO 3 ).

알카리 소모율 = 1㎎/ℓ× {(3×CaCO3)/Al2(SO4)3 xH2O} = 0.45㎎/ℓAlkaline Consumption Rate = 1 mg / l × {(3 × CaCO 3 ) / Al 2 (SO 4 ) 3 xH 2 O} = 0.45 mg / l

그리고 본 발명에서 사용하고자 하는 또하나의 원료인 폴리염화알루미늄(Polyaluminum chloride ; [Al2(OH)nCl6-n]m,PAC)은 황산알루미늄 이후 새로 나온 응집제로서 응집성능이 탁월하여 현재는 정수처리장에서 황산알루미늄 대용으로 가장 많이 사용되고 있는 것이다.In addition, polyaluminum chloride ([Al 2 (OH) n Cl 6-n ] m , PAC), which is another raw material to be used in the present invention, is a new coagulant since aluminum sulfate, and has excellent cohesive performance. It is the most used substitute of aluminum sulfate in water treatment plant.

상수도용 폴리염화알루미늄은 무색 내지 담황색의 투명한 액체로 Al2O3(알루미나분)로서 10~17%인 제품이 일반적으로 사용되고 있다.Water-soluble polyaluminum chloride is a colorless to pale yellow transparent liquid, and a product having 10 to 17% as Al 2 O 3 (alumina powder) is generally used.

PAC의 염기도는 조성, 구조, 이화학적 성질, 응집효과, 저장의 안정성등과 매우 밀접한 관계가 있는 중요한 성질이며 PAC중의 Al의 당량과 Al에 결합되어 있는 OH기 당량의 백분율을 말한다.The basicity of PAC is an important property that is closely related to composition, structure, physicochemical properties, coagulation effect, storage stability, etc. It is the percentage of the equivalent of Al in PAC and the equivalent of OH group bound to Al.

PAC의 조성이 Al2(OH)3Cl3인 경우 염기도는 아래와 같이 산출한다.When the composition of PAC is Al 2 (OH) 3 Cl 3 The basicity is calculated as follows.

(3×OH-)/(2×Al3 +) ×100 = (3/6) ×100 = 50% (3 × OH -) / ( 2 × Al 3 +) × 100 = (3/6) × 100 = 50%

즉, 염기도가 증가하면 안정성이 증가하여 중합도가 증가하고 교질성이 증가되어 응집성도 크게 된다. That is, as the basicity is increased, the stability is increased, the degree of polymerization is increased, the colloid is increased, and the cohesiveness is also increased.

보통 수도용 PAC의 분자량은 238.4이며 Al백분율은 22.7%이다.Usually the molecular weight of PAC for water is 238.4 and Al percentage is 22.7%.

보통 상수도용 폴리염화알루미늄의 염기도는 안정성 때문에 36~60%로 규정하고 있으나, 이론적으로는 염기도가 높을수록 응집성능이 증가되므로 염기도 60%이상에서도 안정성을 가지는 응집제가 가장 이상적인 응집제라 할 수 있다.Generally, the basicity of polyaluminum chloride for water supply is defined as 36 to 60% due to stability. However, in theory, the higher the basicity, the higher the cohesiveness.

폴리수산화염화황산알루미늄은 환경부고시 187호(2002. 12. 9 고시)에서 수처리제로 고시된 조성물이나 지금까지의 제조방법들은 기초 원료인 수산화알루미늄에 염산, 황산을 고온 또는 고압반응시켜 제조하는 것으로, 복잡한 제조과정으로 긴 반응시간 및 숙성시간이 필요하며, 반응조건의 변화에 따라 응집제의 성능이 좌우되므로 응집제로서의 성능이 매우 불안정하며, 원료물질의 순도와 반응조건에 따 라 미 반응물들이 발생하게 되고 따라서 여과공정을 거쳐야 하므로 폐기물이 발생하고 특히 반응시설 등에서 많은 량의 대기오염물질들이 배출 되므로 대형의 방지시설들을 필요로 하지만 본 발명은 검증된 제품들을 원료로 사용하고 상온 상압의 중합방법을 사용함으로서 대기오염물질의 발생이 거의 없으므로 공해 방지시설을 크게 줄일 수 있다. Polyhydroxyaluminum hydrochloride is a composition disclosed as a water treatment agent in the Environmental Declaration No. 187 (Notice of Dec. 9, 2002), but the manufacturing methods so far are produced by high temperature or high pressure reaction of hydrochloric acid and sulfuric acid to the basic raw material aluminum hydroxide, Due to the complicated manufacturing process, long reaction time and aging time are required, and the performance of the coagulant is very unstable because the performance of the coagulant depends on the change of reaction conditions, and the reactants are generated depending on the purity and reaction conditions of the raw materials. Therefore, the wastewater is generated and a large amount of air pollutants are discharged from the reaction facilities, so large prevention facilities are required. However, the present invention uses proven products as raw materials and by using a normal temperature and pressure polymerization method. Since there is little generation of air pollutants, pollution prevention facilities can be greatly reduced.

본 발명은 응집제로서 널리 사용되는 황산알루미늄(AS)과 폴리염화알루미늄(PAC)을 원료로 사용하며, 먼저 황산알루미늄(AS)의 단점인 단분자를 폴리황산알루미늄(PAS)으로 고분자화 시킨 후 일정비율의 폴리염화알루미늄과 알칼리를 투입하여 고염기도의 폴리수산화염화황산알루미늄(Polyaluminum hydroxy chloro sulfate, PAHCS)을 제조하는 것으로서, 원료인 황산알루미늄(AS)과 폴리염화알루미늄(PAC)은 직접 제조하여 사용해도 되지만 현재 국내에는 많은 수처리제 제조업체들이 시판하고 있으므로, 그 제품을 구입해 원료로 사용함으로서 제조설비의 중복 투자를 줄일 수 있으며, 제조공정을 단순화 시킬 수 있는 장점이 있다. In the present invention, aluminum sulfate (AS) and polyaluminum chloride (PAC), which are widely used as flocculants, are used as raw materials. First, a polymer having a disadvantage of aluminum sulfate (AS) is polymerized with polysulfate of aluminum (PAS). Poly Aluminum Chloride (PAHCS) is prepared by adding polyaluminum chloride and alkali in a ratio, and raw materials of Aluminum Sulfate (AS) and Poly Aluminum Chloride (PAC) are manufactured and used directly. Although many domestic water treatment agent manufacturers are currently on the market, the product can be purchased and used as a raw material, thereby reducing the overlapping investment of manufacturing facilities and simplifying the manufacturing process.

또한 이와 같은 방법으로 제조한 응집제는 안정성과 더불어 기존의 응집제에 비하여 빠른 반응성과 부유물제거에 탁월한 응집성능을 발휘하게 된다.In addition, the flocculant prepared in this manner exhibits excellent reactivity and excellent flocculation performance in the removal of suspended solids as well as stability of the existing flocculant.

특히 반응은 상온에서도 가능하므로 보일러 등의 열원공급이 전혀 필요 없다.In particular, since the reaction is possible at room temperature, no heat source supply such as a boiler is required.

본 발명은 상술한 바와 같은 황산알루미늄(AS)과 폴리염화알루미늄(PAC)의 각각의 단점인 단분자 및 낮은 염기도의 문제점을 해결함으로서, 높은 염기도에서도 고분자의 특성을 가지면서, 제품의 안정성을 유지하는 폴리수산화염화황산알루미늄(Polyaluminum hydroxy chloro sulfate, PAHCS)을 제조하는 방법을 제공하고져 하는 것으로서 이를 실시예를 들어 상세히 설명하면 다음과 같다.The present invention solves the problems of monomolecules and low basicity, which are the disadvantages of aluminum sulfate (AS) and polyaluminum chloride (PAC) as described above, thereby maintaining the stability of the product while maintaining the properties of the polymer even at high basicity. To provide a method for producing polyhydroxyaluminum sulphate (Polyaluminum hydroxy chloro sulfate, PAHCS) to be described in detail for the embodiment as follows.

본 발명은 일반식The present invention is a general formula

[Al2(OH)aClb(SO4)c]m[Al 2 (OH) a Cl b (SO 4 ) c ] m

으로 표시되는Indicated by

(상기에서 a+b+2c=6, 3≤a≤5, 0.9≤b≤2.9, 0.05≤c≤0.5, m<10)(A + b + 2c = 6, 3 ≦ a ≦ 5, 0.9 ≦ b ≦ 2.9, 0.05 ≦ c ≦ 0.5, m <10)

통상의 수처리 응집제인 폴리수산화염화황산알루미늄에 있어서, In polyaluminum hydrochloride sulfate which is a common water treatment flocculant,

Al2O3 고형분7~17%의 황산알루미늄 5wt%~20wt% 또는 Al2O3 고형분5~10%의 폴리황산알루미늄(PAS) 5wt%~20wt% 중에서 선택된 어느하나와 Al2O3 고형분11~18%인 폴리염화알루미늄(PAC) 50wt%~85wt% 를 15~50%의 알카리수용액 9wt%~30wt%의 존재하에서 30~60℃ 를 유지하면서 반응시켜 폴리수산화염화황산알루미늄을 제조하는 것에 특징이 있다.Al 2 O 3 solid content of 7-17% of aluminum sulfate 5wt% ~ 20wt% or Al 2 O 3 solid content: 5% to 10% of poly aluminum sulphate (PAS) 5wt% ~ 20wt% at least one selected from the Al 2 O 3 solid content 11 50% to 85% by weight of polyaluminum chloride (PAC) of 18% is reacted while maintaining 30 to 60 ° C in the presence of 15% to 50% of an alkaline aqueous solution of 9% to 30% by weight. There is this.

상기에서 폴리황산알루미늄(PAS)은 In the above polyaluminum sulfate (PAS) is

일반식General formula

[Al2(OH)n(SO4)3-n/2]m으로 표시되는 것으로서Represented by [Al 2 (OH) n (SO 4 ) 3-n / 2 ] m

(상기에서 n은 1≤n≤5이며 m은 m＜10임)(Where n is 1 ≦ n ≦ 5 and m is m <10)

Al2O3의 고형분이 7~17%인 황산알루미늄(AS) 5wt%~20wt%과 15~30%의 알카리수용액 9wt%~30wt%을 반응온도 30~60℃ 에서 30~60분 동안 반응시켜 제조한다.5 wt% to 20 wt% of aluminum sulfate (AS) having a solid content of Al 2 O 3 and 9 wt% to 30 wt% of an aqueous alkaline solution of 15 to 30% are reacted at a reaction temperature of 30 to 60 ° C. for 30 to 60 minutes. Manufacture.

상기에서 알카리수용액은 탄산나트륨(Na2CO3), 수산화나트륨(NaOH) 또는 수산화마그네슘(Mg(OH)2)중에서 선택된 어느 한가지를 사용 한다. In the alkaline aqueous solution, any one selected from sodium carbonate (Na 2 CO 3 ), sodium hydroxide (NaOH) or magnesium hydroxide (Mg (OH) 2 ) is used.

폴리황산알루미늄(PAS)은 염기도 및 중합도가 높을수록 물리화학적 영향을 받기 쉬우며, 특히 열역학적으로 불안정하게 되므로 고염기성 용액으로 만들기가 어렵다. Polyaluminum sulfate (PAS) is more susceptible to physicochemical effects as the basicity and degree of polymerization are higher, and in particular, it is difficult to make a highly basic solution because it becomes thermodynamically unstable.

폴리황산알루미늄(PAS)의 응집특성은 염기도가 50%정도의 용액이 가장 좋으며 응집제의 응집성능, 제탁효과, 알카리조제의 절감효과, 적정주입율의 범위, 응집PH범위 등이 폴리염화알루미늄(PAC)과 유사하다.The best cohesive property of polyaluminum sulfate (PAS) is the solution with basicity of about 50%, and the coagulant performance of the coagulant, the elution effect, the saving effect of alkali preparation, the range of proper injection rate, the coagulation PH range, etc. Similar to).

PAS는 원래 성분 중에 다가음이온인 SO4 2-를 다량으로 함유하고 있기 때문에 염기도의 상승에 따른 폴리알루미늄이온의 증가에 의하여 복잡한 상호작용이 생기므로 PAC 등의 1가의 염기를 성분으로 하는 폴리알루미늄염과는 다른 거동을 나타내며 PH, 동결점, 안정성 등에 현저한 차이를 나타낸다.Since PAS contains a large amount of polyanion SO 4 2- in its original components, a complex interaction occurs due to an increase in the polyaluminum ion due to an increase in basicity, so that a polyaluminum salt containing monovalent base such as PAC Are different from each other and show a significant difference in pH, freezing point, stability, and the like.

즉, 폴리황산알루미늄(PAS)은 염기도 및 중합도가 높을수록 물리화학적 영향을 받기 쉬우며 특히 열역학적으로 불안정하게 되므로 높은 염기도의 제품을 만들기 어려우며 제조조건에 따라 약간의 차이를 나타낸다.That is, polyaluminum sulfate (PAS) is more susceptible to physicochemical effects as the basicity and polymerization degree are high, and particularly thermodynamically unstable, making it difficult to produce a high basicity product and exhibits slight differences depending on manufacturing conditions.

본 발명에서 제조되는 고염기도의 폴리수산화염화황산알루미늄(Polyaluminum hydroxy chloro sulfate, PAHCS)은 염기도 50~80%까지 제조할 수 있으며, 황산알루미늄(AS), 폴리염화알루미늄(PAC)등과 비교시 적은 투입량에도 빠른 반응성과 부유물의 응집성능에 탁월한 효과를 나타냈다.The polybasic aluminum hydroxy chloro sulfate (PAHCS) of the high basic degree prepared in the present invention can be prepared up to 50-80% basicity, and a small amount compared to aluminum sulfate (AS), poly aluminum chloride (PAC), etc. Edo showed excellent effect on fast reactivity and flocculation performance.

실시예1Example 1

Al2O3 고형분8%를 갖는 황산알루미늄 720g을 반응기에 넣고 교반하면서 탄산나트륨수용액(탄산나트륨 60g과 물254g)을 천천히 반응기내로 투입하되, 이때 투입시간은 30분간 천천히 투입하고, 반응온도는 60℃ 이하로 유지하며, 탄산나트륨용액 투입이 완료되면 약30분간 동안 교반을 계속하면서 숙성시켜 1000g의 폴리황산알루미늄(PAS)을 얻었다.720 g of aluminum sulfate having 8% Al 2 O 3 solid content was added to the reactor and slowly added an aqueous sodium carbonate solution (60 g of sodium carbonate and 254 g of water) into the reactor. At this time, the input time was slowly added for 30 minutes, and the reaction temperature was 60 ° C. Maintaining below, when the sodium carbonate solution was added, it was aged while continuing stirring for about 30 minutes to obtain 1000 g of aluminum sulfate (PAS).

상기 예에서 얻어진 응집제는 Al2O3 고형분5.8%, 염기도 23%의 폴리황산알루미늄으로서 폴리수산화염화황산알루미늄을 제조하는데 사용하였다.The flocculant obtained in the above example was used to prepare polyaluminum hydroxide sulfate as polyaluminum sulfate having 5.8% Al 2 O 3 solid content and 23% basicity.

실시예2Example 2

실시예1에서 제조된 폴리황산알루미늄 160g과 Al2O3 17%이고 염기도 38%인 폴리염화알루미늄 560g을 반응기에 순서대로 넣고 10분간 교반 후 탄산나트륨용액(탄산나트륨 60g과 물254g)을 천천히 반응기내로 투입한다. 160 g of polyaluminum sulfate prepared in Example 1 and 560 g of polyaluminum chloride having a basicity of 38% and 38% of Al 2 O 3 were sequentially added to the reactor, followed by stirring for 10 minutes. Input.

이때 투입시간은 약30분간으로 하여 천천히 투입하고, 반응온도는 60℃ 이하로 유지하면서, 탄산나트륨용액 투입이 완료되면 약1시간동안 교반을 계속하면서 숙성시켜 1000g의 폴리수산화염화황산알루미늄(PAHCS)을 얻었다.At this time, the input time is about 30 minutes and slowly added, the reaction temperature is maintained at 60 ℃ or less, and when the sodium carbonate solution is added, the stirring is continued for about 1 hour to aging 1000g of polyaluminum hydroxide hydrochloride (PAHCS). Got it.

상기 예에서 얻어진 응집제 PAHCS는 Al2O3 고형분 10%, 염기도 60%였다.The flocculant PAHCS obtained in the above example was 10% Al 2 O 3 solid content and 60% basicity.

실시예3Example 3

Al2O3 고형분8%의 농도를 갖는 황산알루미늄 120g과 Al2O3 농도17%이고 염기도 38%인 폴리염화알루미늄 560g을 반응기에 순서대로 넣고 10분간 교반 후 탄산나트륨용액(탄산나트륨 100g과 물277g)을 천천히 반응기내로 투입하되, 이때 투입시간은 30분간 천천히 투입하고, 반응온도는 60℃ 이하로 유지하며, 탄산나트륨용액 투입이 완료되면 약1시간동안 교반을 계속하면서 숙성시켜 1000g의 폴리수산화염화황산알루미늄(PAHCS)을 얻었다.120 g of aluminum sulfate having an Al 2 O 3 solid content of 8% and 560 g of poly aluminum chloride having an Al 2 O 3 concentration of 17% and a basicity of 38% were sequentially added to the reactor, followed by stirring for 10 minutes. Sodium carbonate solution (100 g of sodium carbonate and 277 g of water) Slowly into the reactor, at which time the input time is slowly added for 30 minutes, the reaction temperature is maintained at 60 ℃ or less, and after the completion of the sodium carbonate solution to continue stirring for about 1 hour to aging 1000g of polyhydroxide hydrochloric acid Aluminum (PAHCS) was obtained.

상기 예에서 얻어진 응집제 PAHCS는 Al2O3 농도 10%, 염기도 70%였다.The flocculant PAHCS obtained in the above example had an Al 2 O 3 concentration of 10% and a basicity of 70%.

실시예4Example 4

Al2O3 8%의 농도를 가지는 황산알루미늄 120g과 Al2O3 농도17%이고, 염기도 40%인 폴리염화알루미늄 560g을 반응기에 순서대로 넣고 10분간 교반 후 탄산나트륨 50g과 수산화나트륨 38g 및 물 260g을 천천히 반응기내로 투입하되, 이때 투입시간은 30분간으로하여 천천히 투입하고, 반응온도는 60℃ 이하로 유지하며, 탄산나트륨용액 투입이 완료되면 약1시간동안 교반을 계속하면서 숙성시켜 1000g의 폴리수산화염화황산알루미늄(PAHCS)을 얻었다.Al 2 O 3 8% concentration with aluminum sulfate 120g and Al 2 O 3 concentration of 17%, a basicity of 40% of poly aluminum chloride 560g and then were placed in the reactor in order stirring for 10 minutes sodium carbonate, 50g of sodium hydroxide, 38g and water 260g Slowly into the reactor, at which time the input time is 30 minutes and slowly added, the reaction temperature is maintained at 60 ℃ or less, and when the completion of the sodium carbonate solution is stirred for about 1 hour while aging while stirring for 1000g of polyhydroxide Aluminum chloride (PAHCS) was obtained.

상기에서 얻어진 응집제 PAHSC는 Al2O3 농도10%, 염기도 68%였다.The flocculant PAHSC obtained above was 10% Al 2 O 3 concentration and 68% basicity.

첨부한 도1 내지 도3은 응집활성을 비교한 것으로 본 발명 실시예2에서 얻은 제품(PAHCS)을 AS, PAC 등과 비교한 그래프로서1 to 3 are graphs comparing the aggregation activity of the product (PAHCS) obtained in Example 2 of the present invention, such as AS, PAC, etc.

도1은 pH 6.49, 탁도 31NTU의 원수를 사용하여 150rpm의 급속교반으로 1분간, 50rpm의 완속교반으로 5분간 교반후, 5분간 정치하였다가 탁도를 비교한 그래프이다. FIG. 1 is a graph comparing turbidity after stirring for 1 minute with rapid stirring at 150 rpm using a raw water having a pH of 6.49 and a turbidity of 31 NTU, and stirring for 5 minutes at a slow stirring of 50 rpm.

도2는 pH 6.49, 탁도 31NTU의 원수를 사용하여 150rpm의 급속교반으로 1분간, 50rpm의 완속교반으로 15분간 교반후, 15분간 정치하였다가 탁도를 비교한 그래프이다. FIG. 2 is a graph comparing turbidity after 1 minute of stirring at 150 rpm using a raw water having a pH of 6.49 and a turbidity of 31 NTU, for 15 minutes at 50 rpm of slow stirring.

도3은 pH 6.49, 탁도 31NTU의 원수를 사용하여 응집시 주입량에 따른 pH 변화를 비교한 그래프이다. Figure 3 is a graph comparing the pH change according to the injection amount during aggregation using raw water of pH 6.49, turbidity 31NTU.

상기한 바와 같은 본 발명에 의해 제조된 수처리 응집제인 폴리수산화염화황산알루미늄(Polyaluminum hydroxy chloro sulfate, PAHCS)은 그것을 제조하는 원료인 황산알루미늄(AS)과 폴리염화알루미늄(PAC)을 직접 제조하여 사용해도 되지만 이 물질들은 현재 국내에서 많은 수처리제 제조업체들이 시판하고 있으므로, 그 제품을 구입해 원료로 사용하게되면 제조설비의 중복 투자를 줄일 수 있으면서, 제조공정을 단순화시킬 수 있어서 원가절감 효과가 있고, 더구나 본 발명 제조방법은 상온에서 반응을 시키므로써 가열 열원이 필요 없고, 반응시간이 짧아 저렴한 생산원가로 높은 효율의 제품을 얻을 수 있는 효과가 있으며, 상기와 같은 방법으로 제조한 본 발명 응집제는 황산알루미늄(AS)과 폴리염화알루미늄(PAC)의 각각의 단점 인 단분자 및 낮은 염기도의 문제점을 해결하여 높은 염기도로서 고분자의 특성을 가지며, 안정성과 빠른 반응성 및 부유물제거에 탁월한 응집성능을 갖는 효과를 얻을 수 있다.Polyaluminum hydroxy chloro sulfate (PAHCS), which is a water treatment flocculant prepared by the present invention as described above, may be used by directly preparing aluminum sulfate (AS) and polyaluminum chloride (PAC), which are raw materials for producing the same. However, since these materials are currently marketed by many water treatment agent manufacturers in Korea, purchasing the product and using it as a raw material can reduce the overlapping investment of manufacturing facilities and simplify the manufacturing process, thereby reducing the cost, and further, the present invention. The production method does not require a heating heat source by reacting at room temperature, the reaction time is short, the effect of obtaining a high efficiency product at a low production cost, the coagulant of the present invention prepared by the method described above aluminum sulfate (AS ) And the problems of low basicity, which are the disadvantages of polyaluminum chloride (PAC), respectively The solution to have the characteristics of the polymer as a high basicity, effects can be obtained having excellent flocculation performance, the stability and fast reactivity and the suspension removal.

Claims (3)

일반식General formula [Al2(OH)aClb(SO4)c]m[Al 2 (OH) a Cl b (SO 4 ) c ] m 으로 표시되는Indicated by (상기에서 a+b+2c=6, 3≤a≤5, 0.9≤b≤2.9, 0.05≤c≤0.5, m<10)(A + b + 2c = 6, 3 ≦ a ≦ 5, 0.9 ≦ b ≦ 2.9, 0.05 ≦ c ≦ 0.5, m <10) 통상의 수처리 응집제인 폴리수산화염화황산알루미늄(PAHCS)에 있어서, In polyaluminum hydrochloride sulfate (PAHCS) which is a common water treatment flocculant, Al2O3 고형분7~17%인 황산알루미늄 5wt%~20wt% 또는 Al2O3 고형분5~10%인 폴리황산알루미늄(PAS) 5wt%~20wt% 중에서 선택된 어느하나와 Al2O3 고형분11~18%인 폴리염화알루미늄(PAC) 50wt%~85wt% 를 15~50%의 알카리수용액 9wt%~30wt%의 존재하에서 30~60℃ 를 유지하면서 반응시킴을 특징으로하는 수처리용 응집제인 폴리수산화염화황산알루미늄(Polyaluminum hydroxy chloro sulfate, PAHCS)의 제조방법.Al 2 O 3 solid content of 7-17% of aluminum sulfate 5wt% ~ 20wt% or Al 2 O 3 solid content of 5 to 10% of poly aluminum sulphate (PAS) 5wt% ~ 20wt% one and Al 2 O 3 solid content of 11 selected from Polyhydric acid, a coagulant for water treatment, characterized by reacting 50 wt% to 85 wt% of ~ 18% polyaluminum chloride (PAC) at 30 to 60 ° C. in the presence of 15 wt% to 50 wt% of an aqueous alkaline solution of 9 wt% to 30 wt%. Method for preparing aluminum chloride (Polyaluminum hydroxy chloro sulfate, PAHCS). 제1항에 있어서, 폴리황산알루미늄(PAS)은The method of claim 1, wherein the aluminum polysulfate (PAS) is 일반식General formula [Al2(OH)n(SO4)3-n/2]m으로서As [Al 2 (OH) n (SO 4 ) 3-n / 2 ] m (상기에서 n은 1≤n≤5이며 m은 m＜10임)(Where n is 1 ≦ n ≦ 5 and m is m <10) Al2O3의 고형분이 7~17%인 황산알루미늄(AS)과 15~50%의 탄산나트륨(Na2CO3)수용액 9wt%~30wt%를 반응온도 30~60℃ 에서 30~60분 동안 반응시켜 제조함을 특징으로하는 수처리용 응집제인 폴리수산화염화황산알루미늄(Polyaluminum hydroxy chloro sulfate, PAHCS)의 제조방법.Reaction of aluminum sulfate (AS) with 7 ~ 17% solid content of Al 2 O 3 and 9wt% ~ 30wt% of 15-50% sodium carbonate (Na 2 CO 3 ) solution for 30 ~ 60 minutes at reaction temperature 30 ~ 60 ℃ A method for producing polyaluminum hydroxy chloro sulfate (PAHCS), which is a flocculant for water treatment, characterized in that the preparation is carried out. 제1항에 있어서, 알카리 수용액은 탄산나트륨(Na2CO3), 수산화나트륨(NaOH) 또는 수산화마그네슘(Mg(OH)2)중에서 선택된 어느 한가지를 사용 함을 특징으로하는 수처리용 응집제인 폴리수산화염화황산알루미늄(Polyaluminum hydroxy chloro sulfate, PAHCS)의 제조방법.According to claim 1, Alkali aqueous solution is polyhydraulic chloride which is a flocculant for water treatment, characterized in that any one selected from sodium carbonate (Na 2 CO 3 ), sodium hydroxide (NaOH) or magnesium hydroxide (Mg (OH) 2 ). Method for manufacturing aluminum sulfate (Polyaluminum hydroxy chloro sulfate, PAHCS).
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