KR960002271B1 - Dyeing water treatment method - Google Patents

Dyeing water treatment method Download PDF

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KR960002271B1
KR960002271B1 KR1019930013890A KR930013890A KR960002271B1 KR 960002271 B1 KR960002271 B1 KR 960002271B1 KR 1019930013890 A KR1019930013890 A KR 1019930013890A KR 930013890 A KR930013890 A KR 930013890A KR 960002271 B1 KR960002271 B1 KR 960002271B1
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treatment
ferrous chloride
wastewater
alkali
cod
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KR950003191A (en
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김형이
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김형이
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage

Abstract

The treatment of waste water from dyeing is conducted by (A) adjusting the pH of waste water at weak alkali or neutral value, (B) treating waste water biologically, and (C) treating it chemically with ferrous chloride and equivalent alkali to effectively remove BOD, COD and color sources. The amount of ferrous chloride used is 0.1-0.2 vol% with respect to waste water, whereas ferrous chloride being a mixture of 2-3wt% FeCl2 and 15-18wt% HCl. As alkali is used sodium hydroxide or calcium hydroxide.

Description

염색폐수의 처리방법Treatment method of dye wastewater

본 발명은 염색폐수의 처리방법에 관한 것이다.The present invention relates to a method for treating dyed wastewater.

특히, 본 발명 염색폐수를 먼저 생물학적처리를 행한 후에 염화제일철액 및 당량의 알칼리로 화학처리를 행하여 BOD, COD원은 물론 색도원의 제거에 특히 효율이 좋은 염색폐수의 처리방법에 관한 것이다.In particular, the present invention relates to a method for treating dyed wastewater, which is particularly efficient in removing BOD, COD sources, as well as chromatic sources by subjecting the dyeing wastewater to a biological treatment first followed by chemical treatment with ferrous chloride solution and an equivalent alkali.

염색폐수는 통상 BOD, COD 및 색도가 대단히 높아 이의 처리가 큰 문제점으로 대두되고 있다. 염색폐수처리공정과 사용약품은 각 배출업소의 여건에 따라서 다양하지만, 통상의 처리공정은 1차 화학처리, 2차 생물학적처리(활성오니처리)를 행하는 것이 보통이다. 지금까지 통상의 처리법은 다음과 같다.Dyeing wastewater is usually very high BOD, COD and chromaticity, the treatment is emerging as a big problem. The dyeing wastewater treatment process and the chemicals used vary depending on the conditions of each discharger. However, in the general treatment process, primary chemical treatment and secondary biological treatment (active sludge treatment) are usually performed. The conventional treatment method is as follows.

1) 공정도 :1) Process Chart:

2) 처리방법 :2) How to Treat:

1차 처리는 통상으로 산, 알카리약제로 중화공정을 거치고 각종 유기 및 뮤기의응집제를 사용하여 인위적으로 뜬찌끼(Scum)를 형성시켜서 폐수중의 BOD, COD 및 색도원인 물질과 기타 중금속물질 등을 흡착침전(부상)으로 제거한다. 이때에 산으로는 황산이 주로 사용되며, 알카리제로서는 가성소다 및 소석회가 사용된다.The first treatment is usually neutralized with acid and alkali chemicals, and artificially formed scum using various organic and muco flocculants to remove BOD, COD, and other heavy metals from wastewater. Removed by adsorption precipitation (injury). At this time, sulfuric acid is mainly used as an acid, and caustic soda and slaked lime are used as an alkaline agent.

무기응집제로서는 염화제이철(FeCl3), 황산제이철(Fe2(SO4)3), 폴리황산제이철(Poly-Fe2(SO4)3) 등의 제이철염을 주제로 한 것과 액체 유산반도(LAS : 1-Al2(SO4)3), PAC(Poly-Aluminium Chloride : [Al2(OH)nCl6-n]m, PAS(Poly-Aluminium Sulfate : [Al2(OH)n(SO4)3-n/2]m 등의 알루미늄을 주제로한 것 등의 다양한 종류가 산업현장에서 선택 사용되고 있다.Inorganic coagulants include ferric salts such as ferric chloride (FeCl 3 ), ferric sulfate (Fe 2 (SO 4 ) 3 ), and ferric polysulfate (Poly-Fe 2 (SO 4 ) 3 ) and liquid lactose peninsula (LAS). : 1-Al 2 (SO 4 ) 3 ), PAC (Poly-Aluminium Chloride: [Al 2 (OH) n Cl 6-n ] m, PAS (Poly-Aluminium Sulfate: [Al 2 (OH) n (SO 4) ) Various types such as aluminum themes such as 3-n / 2 ] m are selected and used in industrial sites.

통상으로 1차 화학처리에서 BOD, COD 및 색도의 제거효율은 30% 정도이며, 다음의 공정인 생물학적처리(활성오니처리)에서 수질환경보전법상의 배출허용기준 수준으로 처리한다.Generally, the removal efficiency of BOD, COD and chromaticity is about 30% in the primary chemical treatment, and the biological treatment (active sludge treatment), which is the next process, is treated to the emission limit standard of the Water Conservation Act.

생물학적처리기술은 다양하게 개발되어 있으며, 이는 통상의 방법으로 본 발명에서는 그 설명을 생략한다. 다만 생물학적처리후에도 배출허용기준을 준수하기 어려운 경우에는 생물학적처리공정을 반복하거나 또는 2차 화학처리를 행하여야만 한다. 그러나, 상기의 처리방법으로도 원폐수의 오염도가 심한 경우에는 대단위의 설비투자없이는 배출허용기준치인 BOD(50-150ppm), COD(50-150ppm) 및 SS(50-150ppm)(허용기준치는 폐수배출량 및 방류수역에 따라서 다름)을 준수하기가 대단히 어렵다.Various biological treatment techniques have been developed, and the description thereof is omitted in the present invention by conventional methods. However, in the event that it is difficult to comply with the emission limit even after biological treatment, the biological treatment process must be repeated or secondary chemical treatment must be performed. However, even in the case of the above treatment method, if the pollution level of raw waste water is severe, BOD (50-150ppm), COD (50-150ppm) and SS (50-150ppm) (allowable wastewater) are the allowable emission standards without major facility investment. Very dependent on emissions and discharges).

본 발명자는 다년간 다음의 공정도에서와 같은 기존방법으로 면직물염색폐수, 폴리에스테르 섬유염색폐수, 나염폐수 등 혼합폐수를 처리한 수질은 다음의 표 1과 같다.The inventors of the present invention treated the mixed wastewater, such as cotton textile dyeing wastewater, polyester fiber dyeing wastewater, and printing wastewater by the conventional method as in the following process chart for many years are shown in Table 1 below.

[표 1]TABLE 1

현장 실제운전결과 평균수치Average value of actual field operation results

상기와 같은 현장운전 결과에서 확인되는 바와 같이 통상의 처리방법으로는 배출허용기준의 준수가 대단히 어렵고 특히 색도제거가 대단히 어려운 과제로 대두된다.As can be seen from the field operation results as described above, it is very difficult to comply with the emission allowance standard, and in particular, the color removal is very difficult as a conventional treatment method.

본 발명자는 특히 염색폐수처리에 있어서 이러한 BOD, COD 및 색도원의 제거에 대하여 오랜동안 연구를 행하여 왔다. 그 결과 원폐수를 산, 바람직하게는 황산으로 중화시켜서 pH를 약알칼리 내지 중성으로 조절한 다음 생물학적처리를 행하고 그 다음에 염화제일철(FeCl2)액 및 당량의 알칼리로 화학처리를 행하면 BOD, COD가 기준치 이하로 감소함은 물론 색도가 크게 저하되는 놀라운 사실을 발견하여 본 발명을 완성하였다.The present inventors have long studied the removal of such BOD, COD and chromatic source, especially in dyeing wastewater treatment. As a result, the raw wastewater is neutralized with acid, preferably sulfuric acid, the pH is adjusted from weak alkali to neutral, followed by biological treatment, followed by chemical treatment with ferrous chloride (FeCl 2 ) solution and equivalent alkali. The present invention was completed by discovering the surprising fact that the color decreases below the reference value and the color is greatly reduced.

따라서, 본 발명의 목적은 염색폐수의 처리에 있어서, 원폐수를 산으로 pH를 약알칼리 내지 중성으로 조절한 다음 생물학적처리를 먼저 행하고, 침전조에서 침전시킨 다음 염화제일철 및 알칼리로 화학처리를 행한 후 고분자응집제로 응집 침강시켜서 BOD, COD 및 색도를 현저하게 낮추는 방법을 제공하는 것이다.Accordingly, an object of the present invention, in the treatment of dye wastewater, the pH of the raw wastewater is adjusted to weak alkali to neutral with acid and then subjected to biological treatment first, and then precipitated in the precipitation tank and then chemical treatment with ferrous chloride and alkali It is to provide a method of significantly lowering the BOD, COD and chromaticity by flocculation sedimentation with a polymer coagulant.

본 발명을 공정도로 표시하면 다음과 같다.The present invention is represented by a process diagram as follows.

다음에 본 발명을 실시예로써 상세히 설명한다.Next, the present invention will be described in detail by way of examples.

[실시예]EXAMPLE

염색폐수(pH 11.5-12.0 ; BOD 900-1000 ; COD 850-950 ; 색도 1,000)를 사용한다.Dye wastewater (pH 11.5-12.0; BOD 900-1000; COD 850-950; chromaticity 1,000) is used.

가) 염색폐수를 황산으로 pH 7.2-7.5로 조절하여 후공정인 생물학적처리에 지장을 주지 않도록 한다.A) Adjust the dyeing wastewater to pH 7.2-7.5 with sulfuric acid so that it does not interfere with the biological treatment, which is a post-process.

나) 1차 생물학적처리는 24시간 폭기처리하고 침전후 후공정에 투입한다.B) The first biological treatment is aerated for 24 hours, and after precipitation, it is put into the post-process.

다) 2차 생물학적처리는 12시간 폭기로서 침전한 후 처리한다.C) Secondary biological treatment is treated after precipitation as a 12-hour aeration.

라) 염화제일철 2-3%(중량) 및 염산(15-18%중량)을 함유하도록 염화제일철과 염산으로 조제하여 사용하거나 또는 제철 및 제선제조공정에서 부산물로 나오는 염화제일철을 함유한 폐염산을 사용하여 농도를 조절하여 염화제일철액을 제조한다.D) Waste hydrochloric acid containing ferrous chloride which is prepared by using ferric chloride and hydrochloric acid to contain 2-3% by weight of ferrous chloride and hydrochloric acid (15-18% by weight) or as a by-product from iron and steel making processes. To adjust the concentration to prepare a ferric chloride solution.

마) 염화제일철액을 원수대비 0.1% 내지 0.2%(용량) 정도의 량을 투입하고 가성소다를 동시에 투입한다.E) Add 0.1% to 0.2% (capacity) of ferrous chloride to raw water and caustic soda at the same time.

바) 고분자응집제를 적량 투입하고 응집 및 침강시킨다.F) A proper amount of polymer coagulant is added and coagulated and settled.

이렇게 처리한 방류액의 pH, BOD, COD 및 색도는 다음 표 2와 같다.The pH, BOD, COD and chromaticity of the treated effluent are shown in Table 2 below.

[표 2]TABLE 2

현장 실제운전 결과On-site actual operation result

상기의 표 2와 표 1의 대비에서와 같이, 본 발명의 방법으로 처리한 염색폐수의 방류액은 BOD, COD 및 색도에 있어서 그 정화정도가 월등히 개선됨을 알 수 있다.As in the contrast of Table 2 and Table 1, it can be seen that the effluent of the dyeing wastewater treated by the method of the present invention is significantly improved in the degree of purification in BOD, COD and chromaticity.

염화제일철은 가성소다나 또는 수산화칼슘과 같은 알칼리와 반응하면 다음의 반응식에 따라 수산화제일철이 생성된다.(가성소다를 사용한 경우의 예)When ferric chloride reacts with an alkali such as caustic soda or calcium hydroxide, ferrous hydroxide is produced according to the following reaction formula. (Example of using caustic soda)

이렇게 생성된 수산화제일철은 용해도 큰 물질이며 공기중에서 자연산화되어 수산화제이철(Fe(OH)2)로 산화되며 이 수산화제이철은 적황색을 띠우며 따라서 색조에 문제가 있을 것으로 예단(豫斷)하여 염색폐수의 정화에는 지금까지 이를 직접적으로 사용하지는 않아왔다.The ferrous hydroxide thus produced is a highly soluble material and is naturally oxidized in air to be oxidized to ferric hydroxide (Fe (OH) 2 ), which is reddish yellow and therefore, it is expected that there will be a problem in coloration. It has not been used directly until now.

그러나, 본 발명자는 오랜 연구를 행한 결과 염화제일철을 사용하여도 상기와 같은 문재점은 나타나지 않을 뿐만 아니라, 오히려 그 색도에 있어서도 거의 완벽하게 제거되는 놀라운 사실을 발견하였다.However, the present inventors have found a surprising fact that the use of ferrous chloride does not exhibit such a problem, but rather almost completely eliminates the chromaticity.

이상에서 상세히 설명한 바와 같이, 염색폐수를 처리함에 있어서 종래의 방법인 선화학처리를 행하고 다음에 생물학적처리를 행하는 방법과는 달리, 먼저 생물학적처리를 행하고 다음에 염화제일철액 및 당량의 알칼리를 사용하여 화학처리를 행하여 그 처리효율을 대단히 높일 수 있는 것이다.As described in detail above, in the treatment of the dye wastewater, unlike the conventional method of performing the chemical treatment and then the biological treatment, first biological treatment and then using the ferric chloride and the equivalent alkali By chemical treatment, the processing efficiency can be greatly increased.

본 발명에서는 염화제일철을 사용할 수도 있고, 또는 제철 및 제선공장에서 부산물로 나오는 폐염산을 그대로 사용할 수도 있고 또는 농도를 조절하여 사용할 수도 있다.In the present invention, ferrous chloride may be used, or waste hydrochloric acid as a by-product from iron and steel mills may be used as it is or may be used by adjusting the concentration.

본 발명의 효과를 나타내면 다음과 같다.The effects of the present invention are as follows.

첫째 : 염색페수처리의 가장 큰 난제인 색도원을 효과적으로 제거할 수 있어 방류수질을 대폭 개선할 수 있다.First, it is possible to effectively remove the chromatic source, which is the biggest challenge of dyeing water treatment, which can greatly improve the quality of discharged water.

둘째 : BOD 및 COD 원 제거에도 대단히 효과적이다.Secondly, it is very effective for removing BOD and COD sources.

셋째 : 고가의 약품(무기응집제,제색제)를 사용하지 않고도 제철공장의 부산물인 염화제일철액을 이용함으로써 그 원자를 대폭 절감할 수 있다.Third: By using ferrous chloride, a by-product of the steel mill, without using expensive chemicals (inorganic coagulants, colorants), the atom can be greatly reduced.

Claims (5)

염색폐수의 처리에 있어서, 폐수를 pH 약알칼리 내지 중성으로 조절한 다음 생물학적처리를 먼저 행하고 다음에 염화제일철액 및 당량의 알칼리로 화학처리를 행하여 BOD, COD 및 색도원을 효과적으로 제거하는 방법.In the treatment of dye wastewater, the wastewater is adjusted to pH alkaline or neutral and then subjected to biological treatment first and then chemically treated with ferrous chloride solution and equivalent alkali to effectively remove BOD, COD and chromatic source. 제1항에 있어서, 염화제일철액을 폐수대비 0.1-0.2%(용량)의 량을 사용하는 방법.The method according to claim 1, wherein the ferrous chloride solution is used in an amount of 0.1-0.2% (volume) relative to the wastewater. 제1항에 있어서, 염화제일철액으로 FeCL22-3%(중량) 및 염산 15-18%(중량)의 혼합액을 사용하는 방법.The method according to claim 1, wherein a mixed solution of 2-3% by weight of FeCL 2 and 15-18% by weight of hydrochloric acid is used as the ferric chloride solution. 제1항에 있어서, 알칼리로 수산화나트륨 또는 수산화칼슘을 사용하는 방법.The method of claim 1 wherein sodium hydroxide or calcium hydroxide is used as the alkali. 제1항에 있어서, 염화제일철액으로 제철 및 제선공장에서 배출되는 염산폐액을 그대로 사용하거나 또는 농도를 조절하여 사용하는 방법.The method according to claim 1, wherein the hydrochloric acid waste liquid discharged from the steelmaking and steel mills is used as ferrous chloride solution or the concentration is adjusted.
KR1019930013890A 1993-07-22 1993-07-22 Dyeing water treatment method KR960002271B1 (en)

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CN110759511A (en) * 2018-07-27 2020-02-07 广州超邦化工有限公司 Treatment method of gun black tin-nickel alloy electroplating wastewater

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