KR920009840B1 - Fluorine removing method from the cokes waste water - Google Patents
Fluorine removing method from the cokes waste water Download PDFInfo
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Abstract
Description
제1도 본 발명을 실시하는데 필요한 장치의 개략도.1 is a schematic diagram of an apparatus required for practicing the present invention.
제2도 종래방법에 따라 NaOH로 pH를 조절할 후 염화제2철과 수산화칼슘의 첨가에 의한 불소이온 제거 효과를 나타내는 그래프.2 is a graph showing the effect of removing fluorine ions by the addition of ferric chloride and calcium hydroxide after adjusting the pH with NaOH according to the conventional method.
제3도 종래방법에 따라 수산화칼슘과 인산을 적당한 비율로 첨가에 의한 불소이온 제거효과를 나타내는 그래프.3 is a graph showing the effect of removing fluorine ions by adding calcium hydroxide and phosphoric acid in an appropriate ratio according to the conventional method.
제4도 종래방법에 따라 황산알루미늄 응집제의 첨가에 의한 불소이온 제거효과를 나타내는 그래프.4 is a graph showing the effect of removing fluorine ions by the addition of an aluminum sulfate flocculant according to the conventional method.
제5도 종래방법에 따라 염화제2철과 수산화 칼슘 첨가에 의한 불소이온 제거효과를 나타내는 그래프.5 is a graph showing the effect of removing fluorine ions by the addition of ferric chloride and calcium hydroxide according to the conventional method.
제6도 본 발명에 다르는 불소이온제거효과를 나타내는 그래프.6 is a graph showing the effect of removing fluorine ions according to the present invention.
제7도 본 발명의 실시에 따라 부수적으로 발생하는 복합폐수의 COD 제거효과를 나타내는 그래프.7 is a graph showing the effect of COD removal of the complex wastewater generated incidentally according to the practice of the present invention.
제8도 본 발명의 실시에 따라 부수적으로 발생하는 복합폐수의 CN-제거효과를 나타내는 그래프.8 is a graph showing the effect of CN − removal of complex wastewater incidentally according to the practice of the present invention.
* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for the main parts of the drawings
1 : 교반기 2 : pH측정기1: Stirrer 2: pH meter
본 발명은 코우크스(COKE)폐수중 불소이온제거 방법에 관한 것이며, 보다 상세하게는 코우크스 공장에서 발생되는 불소이온 뿐만아니라 페놀, 시안이온, 암모니움이온 및 유황화합물등 여러가지 유기물, 무기물이 함유된 복합폐수로부터 불소이온을 효과적으로 제거하는 처리방법에 관한 것이다. 종래의 폐수중의 불소 이온을 제거하는 방법으로서는 산화칼슘, 수산화칼슘 및 탄산칼슘등의 칼슘염을 첨가해서 불소이온을 칼슘염과 반응시켜 생성한 침전물을 분리제거하여 처리하는 방법 ; 황산알루미늄등의 응집첨가제에 의해 침전제거하는 방법 ; 칼슘염과 인산염의 적절한 투입에 의한 처리방법 ; 이온교환수지 및 활성알루미나에 의해 흡착제거하는 방법등이 주로 이용되어 왔다.The present invention relates to a method for removing fluorine ions from COKE wastewater, and more specifically, contains not only fluorine ions generated in a coke plant, but also various organic substances and inorganic substances such as phenol, cyan ions, ammonium ions and sulfur compounds. The present invention relates to a treatment method for effectively removing fluorine ions from mixed wastewater. As a conventional method for removing fluorine ions in wastewater, calcium salts such as calcium oxide, calcium hydroxide and calcium carbonate are added to remove and treat precipitates formed by reacting fluorine ions with calcium salts; Precipitation removal by coagulation additives, such as aluminum sulfate; Treatment method by appropriate addition of calcium salt and phosphate; Adsorption and removal by ion exchange resins and activated alumina have been mainly used.
그러나, 이러한 종래의 방법들은 폐수중에 불소이온 형태가 단순한 제철소의 산세공정이나 반도체회사에서와 같이 고농도의 불소이온이 함유된 폐수에서는 불소이온 제거효율이 좋으나, 코우크스공장에서 발생되는 폐수는 불소이온과 함께 페놀, 시안이온, 암모니움이온 및 유황화합물등이 함유되어 있는 복합성 폐수인 바, 상기 복합성 폐수중에는 50-80mg/l의 비교적 저농도의 불소이온이 함유되어 있어, 이같이 저농도의 불소이온이 함유된 폐수에 적용할시에는 20-40mg/l까지만 제거되는 문제점이 있다.However, these conventional methods have good fluorine ion removal efficiency in wastewater containing high concentrations of fluorine ions, such as pickling processes in steel mills with simple fluorine ions in wastewater or semiconductor companies. It is a complex wastewater containing phenol, cyan ion, ammonium ion, and sulfur compound. The complex wastewater contains 50-80 mg / l of relatively low concentration of fluorine ion, and thus contains low concentration of fluorine ion. When applied to the wastewater is a problem that only 20-40mg / l is removed.
또한, 이온교환수지나 활성알루미나를 이용한 흡착처리방법은 대량으로 발생되는 폐수에는 적합하지 않을 뿐만아니라 처리제를 재생하는데도 어려움이 있는 것이다.In addition, the adsorption treatment method using an ion exchange resin or activated alumina is not suitable for waste water generated in large quantities, and also has difficulty in regenerating the treatment agent.
이에, 본 발명의 목적은 염화제2철, 수산화칼슘 및 반응촉진제인 칼륨명반을 순차적으로 일정량 첨가하여 적절한 pH 범위로 조절함으로써 시안이온, 암모니움이온 및 유황화합물등이 다량 존재하는 코우크스 폐수중의 불소이온을 효과적으로 제거하는 방법을 제공하고자 하는 것이다.Accordingly, an object of the present invention is to add a predetermined amount of ferric chloride, calcium hydroxide and a reaction promoter potassium alum in order to adjust to an appropriate pH range in the coke wastewater containing a large amount of cyan ions, ammonia ions and sulfur compounds It is to provide a method for effectively removing fluorine ions.
본 발명은 불소이온을 함유한 코우크스(COKE)폐수를 상온에서 염화제2철을 투입시켜 pH를 3.5-4.5로 조절하여 1차 반응시킨후, 수산화 칼슘(Ca(OH)2)을 첨가해서 pH를 8-9로 조절하여 2차반응시킨 다음, 칼륨명반과 PAA(Poly Acryl Amide)를 첨가하여 pH를 5.0-8.5로 조절하여 불소이온을 침전시킨후 분리 제거하는 방법에 관한 것이다. 이하, 본 발명의 수치한정이유에 대하여 설명한다.In the present invention, COKE wastewater containing fluorine ions is first reacted by adding ferric chloride at room temperature to adjust pH to 3.5-4.5, and then calcium hydroxide (Ca (OH) 2 ) is added to Secondary reaction by adjusting the pH to 8-9, and then adding potassium alum and PAA (Poly Acryl Amide) to adjust the pH to 5.0-8.5 to precipitate and remove the fluorine ion after separation. The reason for numerical limitation of the present invention is explained below.
상기 1차반응시 pH가 3.5이하일때에는 제거효과에 비해 경제적인 문제가 대두되며, pH가 4.5이상일때에는 불소 및 시안제거효율이 떨어지기 때문에 1차 반응시 pH를 3.5-4.5로 조절하는 것이 바람직하다. 또한, 상기 2차반응시 pH가 8이하일때에는 Ca++이온의 부족으로 불소이온의 제거효율이 떨어지며, pH가 9 이상일때에는 제거효과의 상승에 비해 약품비용과다 및 슬러지 발생량의 과다로 비경제적이기 때문에 2차반응시의 pH를 8-9로 하는 것이 바람직하다. 또한, 마지막 반응시 pH가 5.0이하일때에는 제거효과에 비해 약품비용과다 및 침강슬러지의 플록형상이 좋지않아 비경제적이며 pH가 8.5이상일때에는 불소이온 제거효율이 현저히 떨어져 환경관리기준치인 15mg/l이하로 폐수중의 불소이온을 제거할 수 없기때문에 pH를 5.0-8.5로 하는 것이 바람직하다.When the pH of the first reaction is less than 3.5, an economical problem arises compared to the removal effect, and when the pH is 4.5 or more, it is preferable to adjust the pH to 3.5-4.5 during the first reaction because the efficiency of removing fluorine and cyanide decreases. . In addition, when the pH of the secondary reaction is 8 or less, the removal efficiency of fluorine ions is reduced due to the lack of Ca ++ ions, and when the pH is 9 or more, it is uneconomical due to excessive chemical cost and excessive sludge generation compared to the increase of the removal effect. It is preferable to make pH at the time of secondary reaction into 8-9. In addition, when the pH is lower than 5.0 at the last reaction, it is more economical than the removal effect and the floc shape of sedimented sludge is not economical.When the pH is higher than 8.5, the efficiency of removing fluorine ions is significantly lowered to 15 mg / l, which is the environmental management standard. Since fluorine ions in the wastewater cannot be removed, the pH is preferably 5.0-8.5.
본 발명에 있어서 코우크스공장에서 발생되는 복합성 폐수에 철이온의 공급원으로 염화제2철을 투입하여 상기와같이 pH를 3.5-4.5로 하면 반응식 (1)(2)에 따라 Fe4{Fe(CN)6}3가 형성되어 시안이온이 제거될 뿐만아니라, 잉여철이온은 암모니움이온과 불소이온의 착화합물 형태인(NH4)2FeF6등의 철염을 형성하여 수산화칼슘을 첨가시 반응식(3)에 의해 수산화철 및 수산화암모니움이 형성되어서 공침현상에 의해 수질이 향상된다.In the present invention, when ferric chloride is added as a source of iron ions to the complex wastewater generated in the coke plant and the pH is set to 3.5-4.5 as described above, Fe 4 {Fe (CN) according to Scheme (1) (2). ) scheme: 6} 3 is formed as well as a cyan ion removal, excess iron ions is added to the calcium hydroxide to form a ferrous salt such as ammonium ion and the complex form of the fluoride ion (NH 4) 2 FeF 6 ( 3) Iron hydroxide and ammonium hydroxide are formed by the co-precipitation to improve the water quality.
이때 반응촉진제인 칼륨명반을 투입하지 않으면(3)의 반응이 잘 일어나지 않아 불소이온처리가 잘되지 않으므로, 수산화칼슘을 pH 8-9가 되도록 조절하여 2차반응시킨 다음, 불소이온이 CaF2형태의 침전물로 잘 제거되도록 하기 위해 칼륨명반을 pH 5-8.5로 되도록 투입하고 플록을 잘 형성시키기 위해 고분자 응집촉진제인 PAA를 투입함으로서 종합폐수의 불소농도를 효과적으로 처리할 수가 있다.If it does not, put into a reaction promoter, potassium alum, the reaction (3) does not occur well well-fluoride treatment, in which the calcium hydroxide to adjust the pH to 8-9, and then 2-order reaction, the fluoride ions in the form of CaF 2 By adding potassium alum to pH 5-8.5 in order to remove the precipitate well and PAA, a polymer coagulant, to effectively form flocs, the fluorine concentration of the wastewater can be effectively treated.
본 발명의 방법을 실시하는데 필요한 장치는 제1도에 나타낸 바와같이 불소이온을 함유한 코우크스 폐수에 염화제2철용액을 투입하여 pH를 3.5-4.5로 조절하여 불소이온과 1차반응시키기 위한 제1반응조 ; 알칼리제인 수산화칼슘을 투입하여 pH를 8-9로 조절하여 칼슘이온과 반응시키기 위한 제2반응조 ; 폐수중의 불소화합물과 칼슘이온과의 반응을 촉진시키기 위한 반응촉진제인 칼륨명반과 응집촉진제인 PAA를 투입하여 pH를 5.0-8.5로 조절하여 불소이온을 제거하기 위한 제3반응조로 구성된다.The apparatus required for carrying out the method of the present invention, as shown in FIG. 1, is a method for primary reaction with fluorine ions by adjusting the pH to 3.5-4.5 by adding ferric chloride solution to coke wastewater containing fluorine ions. First reactor; A second reaction tank for reacting with calcium ions by adding calcium hydroxide as an alkaline agent to adjust the pH to 8-9; It consists of a third reactor to remove fluorine ions by adjusting the pH to 5.0-8.5 by adding potassium alum, which is a reaction promoter to promote the reaction between fluorine compounds and calcium ions in waste water, and PAA, which is an aggregation promoter.
상기 각 반응조에는 반응을 촉진하기 위한 교반기(1)와 pH측정기(2)가 설치되어 있다.Each said reaction tank is provided with the stirrer 1 and the
이하, 실시예를 통하여 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail through examples.
[실시예]EXAMPLE
제1도에 도시된 바와같이, 시험장치의 제1반응조에 불소이온이 50-80mg/l 함유된 pH 7전후의 코우크스 폐수를 넣고 상온에서 염화제2철을 투입하여 pH 4가 되도록 조절하여 5분간 1차반응시킨 다음 제2반응조에서 수산화칼슘을 첨가하여 pH 8-9가 되도록 조절하여 5분간 2차반응시킨후 제3반응조에서 칼륨명반과 고분자응집제를 투입하여 pH를 7.0-8.5로 조절하여 5분간 반응시킨후 30분간 유지시켜 응집처리를 하여 불소이온 제거실험을 행하였으며, 그 결과를 제6도에 나타내고, 이에따라 부수적으로 발생하는 제거효과를 제7도 및 제8도에 나타내었다.As shown in FIG. 1, coke wastewater containing pH 7 containing 50-80 mg / l of fluorine ion was added to the first reactor of the test apparatus, and ferric chloride was added at room temperature to adjust pH to 4 After the first reaction for 5 minutes, the pH was adjusted to pH 8-9 by adding calcium hydroxide in the second reactor, followed by secondary reaction for 5 minutes, and then the pH was adjusted to 7.0-8.5 by adding potassium alum and polymer coagulant in the third reactor. The reaction was carried out for 5 minutes, held for 30 minutes, and subjected to the flocculation treatment. The results were shown in FIG. 6, and the secondary effect was shown in FIG. 7 and FIG.
제6도에 나타난 바와같이 본 발명에 의한 응집촉진제인 칼륨명반을 투입함으로서 불소이온제거율이 80% 이상, 복합폐수중의 불소이온이 15mg/l 이하로 양호하게 처리됨을 알 수 있다.As shown in FIG. 6, it can be seen that by adding potassium alum, which is the flocculation promoter according to the present invention, the fluorine ion removal rate is 80% or more and the fluorine ion in the composite wastewater is treated well below 15 mg / l.
또한, 제7도로부터 100mg/l이상의 COD가 처리후 거의 60mg/l이하로 안정적으로 처리되었음을 알 수 있고, 제8도로부터 1.2mg/l의 시안이온농도가 0.7mg/l이하로 안정적으로 처리되었음을 알 수 있다.In addition, it can be seen from FIG. 7 that the COD of 100 mg / l or more was stably treated to less than 60 mg / l after the treatment, and that the cyan ion concentration of 1.2 mg / l was stable to 0.7 mg / l or less from FIG. It can be seen that.
[비교예 1]Comparative Example 1
실시예 1에서와 같이 불소이온을 함유한 폐수에 종래의 방법으로, NaOH로 pH를 조절한 후 염화제2철 150mg/l와 수산화칼슘 300mg/l를 투입하여 불소이온의 실험을 하였으며 그 결과를 제2도에 나타내었다. 제2도에 의하면 pH 9.5이상에서는 32mg/l 정도까지 불소이온이 제거되었음을 알 수 있다.As in Example 1, after adjusting the pH with NaOH in a conventional wastewater containing fluorine ions, 150 mg / l of ferric chloride and 300 mg / l of calcium hydroxide were added to test fluorine ions. It is shown in 2 degrees. According to Figure 2 it can be seen that the fluorine ion was removed to about 32mg / l above pH 9.5.
[비교예 2]Comparative Example 2
실시예 1에서와 같은 불소이온을 함유한 폐수에 종래의 방법으로 수산화칼슘과 인산을 5:3 비율, 즉 인산이온 90mg/l에 수산화칼슘 150mg/l를 투입하여 불소이온의 제거실험을 하였으며 그 결과를 제3도에 나타내었는 바, 이에 의하면 불소이온 제거효과가 거의 없음을 알 수 있다.In the wastewater containing fluorine ion as in Example 1, calcium hydroxide and phosphoric acid were added in a 5: 3 ratio, that is,
[비교예 3]Comparative Example 3
실시예 1에서와같은 불소이온을 함유한 폐수에 종래의 방법으로 황산알루미늄의 응집제를 투입하여 불소이온 제거실험을 행하였으며 그 결과로 제4도에 나타내었는 바, 이에 의하면 제거효율이 최고 27mg/l로서 칼슘염에 의한 처리방법에 비해 처리효율은 좋으나 폐수중의 불소이온을 15mg/l까지 제거하는 것은 불가능하였다.In the wastewater containing fluorine ions as in Example 1, a flocculant of aluminum sulfate was added by a conventional method, and the fluorine ion removal experiment was conducted. As a result, it is shown in FIG. The treatment efficiency was better than that of calcium salt, but it was not possible to remove fluoride ion up to 15mg / l.
[비교예 4][Comparative Example 4]
실시예 1에서와 같은 불소이온을 함유한 폐수에 종래방법으로 반응촉진제인 칼륨명반의 투입없이 단순히 염화제2철 100mg/l와 수산화칼슘만을 투입하여 불소이온 제거실험을 행하였으며 그 결과는 제5도에 나타난 바와같이 불소이온 제거효과가 좋지 않음을 알 수 있다.In the wastewater containing fluorine ions as in Example 1, fluoride ion removal experiment was conducted by simply adding 100 mg / l of ferric chloride and calcium hydroxide without adding potassium alum, which is a reaction promoter, according to a conventional method. As shown in Figure 1, the fluorine ion removal effect is not good.
상술한 바와같이 본 발명에 의한 방법에 의하면 코우크스공장에서 발생되는 복합폐수중에 저농도의 불소이온이 함유되더라도 종래의 방법에 비해, 훨씬 효율적으로 불소이온을 제거하는 효과가 있다.As described above, according to the method of the present invention, even if a low concentration of fluorine ions is contained in the complex wastewater generated in the coke plant, there is an effect of removing fluorine ions more efficiently than the conventional method.
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