KR20030046557A - Method for carbon source of biological denitrification using distillery wastewater - Google Patents
Method for carbon source of biological denitrification using distillery wastewater Download PDFInfo
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- KR20030046557A KR20030046557A KR1020010076406A KR20010076406A KR20030046557A KR 20030046557 A KR20030046557 A KR 20030046557A KR 1020010076406 A KR1020010076406 A KR 1020010076406A KR 20010076406 A KR20010076406 A KR 20010076406A KR 20030046557 A KR20030046557 A KR 20030046557A
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
Description
본 발명은 주정 폐액을 생물학적 탈질용 탄소원으로 이용하는 방법에 관한 것으로, 더욱 상세하게는 주정폐액을 탈수하여 얻어지는 케이크는 사료 및 퇴비로 이용하고, 그 탈리액은 가용성을 높이기 위한 전처리를 거쳐 메탄올을 대체할 수 있는 생물학적 탈질용 탄소원으로 이용하는 방법에 관한 것이다.The present invention relates to a method of using alcoholic waste liquor as a carbon source for biological denitrification, and more particularly, a cake obtained by dehydration of alcoholic waste liquor is used as feed and compost, and the desorption liquid is replaced with methanol after pretreatment to increase solubility. The present invention relates to a method for using as a carbon source for biological denitrification.
일반적으로 주정(酒精)은 소주 등과 같은 주류를 제조하기 위한 에틸 알코올(Ethyl Alcohol)을 말하며, 이러한 주정은 원료처리공정, 발효공정, 증류공정 등을 거쳐 생산된다. 이때 상기 증류공정에서 발생된 고농도의 유기질 폐수를 주정폐액이라 한다. 한편, 주정을 제조하기 위한 주정원료는 크게 당질, 전분질 및섬유질로 대별되고, 당질 원료로는 당밀, 사탕수수 등이 널리 사용되며, 전분질 원료로는 서류인 고구마, 감자, 타피오카(고구마의 일종)와 곡류인 보리, 옥수수 등이 사용되고 있다. 특히 우리나라는 타피오카, 쌀보리, 겉보리, 절간고구마, 옥수수 등을 주정 원료로 많이 사용하고 있다.In general, alcohol (酒精) refers to ethyl alcohol (Ethyl Alcohol) for the production of liquor, such as shochu, such alcohol is produced through a raw material processing process, fermentation process, distillation process. At this time, the high concentration of organic wastewater generated in the distillation process is referred to as spirit waste. Meanwhile, alcohol raw materials for the manufacture of alcohol are largely divided into sugar, starch and fiber, and molasses and sugar cane are widely used as sugar raw materials, and sweet potatoes, potatoes, and tapioca, which are documents, are used as starch raw materials. And grains such as barley and corn are used. In particular, Korea uses tapioca, rice barley, crushed barley, sweet potato, corn, etc. as alcoholic raw materials.
따라서 이러한 주정원료를 적당한 입도로 분쇄한 다음 발효공정에서 물을 혼합하고 효소와 효모를 이용하여 알콜이 되도록 발효시킨다. 이어 증류공정에서는 발효된 알콜을 증류하여 불순물이 제거된 95%의 알콜을 생산하게 된다. 그리고 이러한 증류공정에서 남은 주정폐액은 탈수공정에서 케이크와 탈리액으로 분리되고 분리된 탈리액은 2차 증류시설을 거친 후 농축액은 부산물로 활용하거나 폐기하며 그 나머지 폐수는 혐기성 발효조에서 정화된 후 방류된다.Therefore, these alcohol raw materials are ground to an appropriate particle size and then mixed with water in a fermentation process and fermented to an alcohol using enzymes and yeasts. Subsequently, the distillation process distills the fermented alcohol to produce 95% of alcohol free of impurities. The alcoholic liquor remaining in the distillation process is separated into cake and desorption liquid in the dehydration process, and the separated desorption liquid passes through the secondary distillation facility, and then the concentrate is used or discarded as a by-product and the remaining waste water is purified after anaerobic fermentation.
이와 같이, 주정공정에서 발생되는 주정폐액은 높은 온도로 배출되기 때문에 고온 혐기성 발효법으로 처리되는 것이 일반적이며, 주정폐액을 혐기성 발효법으로 처리하는 것은 메탄을 생산할 수 있는 장점을 가지고 있다. 그러나 주정원료가 쌀보리, 대현맥과 같은 곡류의 경우에는 혐기성 발효법의 처리효율의 크게 저하함은 물론 심할 경우 발효조가 단순히 저류조의 역할밖에 할 수 없을 정도로 운영상의 많은 문제점이 야기되고 있다.As described above, the liquor waste liquid generated in the liquor process is discharged at a high temperature, so it is generally treated by high temperature anaerobic fermentation. The liquor waste liquor treatment has an advantage of producing methane. However, in the case of grains such as rice barley and daehyun, the processing efficiency of the anaerobic fermentation method is greatly reduced, and in severe cases, the fermentation tank can only serve as a storage tank, causing a lot of operational problems.
아울러 종래에는 발효산물인 주정폐액을 단순히 폐기되어야 할 오염물질로만 취급하였기 때문에 주정폐액의 처리비용을 기업체가 부담할 수밖에 없었다. 반면 최근에는 하수처리장으로 유입되는 하수의 오염농도가 크게 낮아 빈부하(貧負荷)현상으로 인한 시설의 유지관리에 어려움이 초래되고 있을 뿐만 아니라 고도처리시무산소조의 탈질율을 높이기 위해 외부에서 유기탄소원을 공급해야 하는 경제적인 문제점에 직면하고 있다. 또한 방류수질 기준강화로 산업폐수 중 산세정 공정에서 발생되는 질소화합물을 처리하기 위해 외부탄소원으로 메탄올을 공급해야 하는 어려움이 있다. 따라서 고가의 메탄올 구입비용은 고도처리공정의 운전비용에 상당한 부담을 줌으로써 하·폐수의 고도처리를 더욱 어렵게 하는 요인이 되고 있다.In addition, since the liquor waste, which is a fermentation product, was treated only as a pollutant to be disposed of in the past, the company had to bear the cost of treating the liquor waste. On the other hand, in recent years, the pollution concentration of sewage flowing into sewage treatment plants is so low that it is difficult to maintain the facilities due to the poor load phenomenon, and to increase the denitrification rate of anoxic tank during advanced treatment, You face economic problems to supply. In addition, there is a difficulty in supplying methanol as an external carbon source to treat nitrogen compounds generated in an acid washing process in industrial wastewater due to enhanced discharge water quality standards. Therefore, the expensive methanol purchase cost has a significant burden on the operation cost of the advanced treatment process, which makes the advanced treatment of sewage and wastewater more difficult.
즉, 폐수 중의 질소가 처리되지 않고 호소, 하천, 바다 등과 같은 수계에 배출되면 많은 악영향을 미치게 된다. 특히 암모니아성 질소는 수생생물에 독성을 주며, 질산염으로 산화되는 과정에서 물에 녹아 있는 용존산소를 고갈시킨다. 따라서 위와 같은 수계의 수질악화 방지와 수자원을 보호하기 위하여 하·폐수로부터 질소제거가 필수적이다.That is, if the nitrogen in the waste water is not treated and discharged to water systems such as lakes, rivers, seas, etc., many adverse effects are caused. Ammonia nitrogen, in particular, is toxic to aquatic organisms and depletes dissolved oxygen in water during oxidation to nitrates. Therefore, it is essential to remove nitrogen from sewage and wastewater in order to prevent water deterioration and protect water resources.
그리고, 생물학적 탈질의 원리는 호기성 상태에서 질산화균에 의해 암모니아성 질소를 산화하여 질산염으로 전환시킨다. 이를 다시 무산소 상태에서 질산염형태의 결합산소가 용존산소 대용으로 이용하게 되어 질소(N2)가스로 전환시켜 제거되며 이때 전자공여체로서 유기물이 소요된다.In addition, the principle of biological denitrification converts ammonia nitrogen into nitric acid by nitrifying bacteria in an aerobic state. In the anoxic state, the combined oxygen in the form of nitrate is used as a substitute for dissolved oxygen, and is converted to nitrogen (N 2 ) gas to be removed. In this case, organic matter is required as an electron donor.
일반적으로 하·폐수 내에 포함된 질소처리를 목적으로 사용되는 외부탄소원으로는 메탄올이 주로 사용되고 있다. 그러나 메탄올은 운전비용을 크게 증대시킬 뿐만 아니라 휘발성 및 인체 유해성 등으로 인한 취급·보관이 어렵고 미생물에 대한 독성으로 인한 미생물 활성을 감소시키는 문제점이 있다.In general, methanol is mainly used as an external carbon source used for nitrogen treatment contained in sewage and wastewater. However, methanol not only greatly increases the operating cost but also has a problem in that it is difficult to handle and store due to volatility and human hazards and to reduce microbial activity due to toxicity to microorganisms.
따라서 본 발명자는 이러한 문제점에 대한 해결방안의 일환으로 탈질공정에주정폐액을 생물학적 탈질용 외부탄소원으로 대체함으로써 메탄올 구입비용을 절감함은 물론 주정폐수의 처리에 드는 비용도 절감할 수 있다는 사실에 착안하여 본 발명을 완성하기에 이르렀다. 그러나 주정공정에서 발생되는 주정폐액은 부유물질의 함량이 높고, 상당량의 인 및 질소성분이 포함되어 있으며 메탄올에 비해 용해성 물질의 비율이 낮으므로 탈질효율이 떨어지는 문제가 있다.Therefore, the present inventors focus on the fact that, as part of the solution to this problem, by replacing the liquor waste liquor with an external carbon source for biological denitrification in the denitrification process, it is possible not only to reduce the cost of methanol purchase but also to reduce the cost of treating the liquor wastewater. Thus, the present invention has been completed. However, the liquor waste liquor generated in the liquor process has a high content of suspended solids, contains a large amount of phosphorus and nitrogen components, and has a low denitrification efficiency because the ratio of soluble substances is lower than that of methanol.
본 발명은 상술한 문제점을 해결하기 위해 이루어진 것으로, 본 발명의 주된 목적은 주정공정에서 발생된 주정폐액에 포함되어 있는 고형물질, 인 성분 및 질소성분 등을 제거하고 탈질에 필요한 탄소성분의 용해성을 좋게 하도록 전처리함으로써 생물학적 탈질용 외부탄소원으로 재활용하기 위한 방법을 제공하는 것이다.The present invention has been made to solve the above-mentioned problems, the main object of the present invention is to remove the solids, phosphorus and nitrogen components, etc. contained in the liquor waste generated in the brewing process and solubility of the carbon component required for denitrification It provides a method for recycling to an external carbon source for biological denitrification by pretreatment for good.
본 발명은 또한 주정공정에서 발생되는 주정폐액을 음식물쓰레기, 하수슬러지, 분뇨 및 축산폐수 등 유기성 폐수에 혼합하여 유기성 폐수의 가수분해 및 산발효를 증진시킴으로써 메탄올을 대체할 수 있는 생물학적 탈질용 외부탄소원으로 이용하는 방법을 제공하는 것이다.The present invention also mixes the alcoholic liquor generated in the alcoholic process with organic wastewater such as food waste, sewage sludge, manure and livestock wastewater to promote the hydrolysis and acid fermentation of organic wastewater, which can replace methanol for biological denitrification. It is to provide a method to use.
도1은 종래 기술에 따른 주정폐액의 처리 과정을 보여주는 개략적인 공정도이고,1 is a schematic process chart showing a process of treating alcoholic liquor according to the prior art,
도2는 본 발명에 따른 주정폐액의 전처리 공정을 보여주는 개략적인 공정도이다.2 is a schematic process chart showing a pretreatment process of alcoholic liquor according to the present invention.
상술한 본 발명의 목적은 주정공정에서 발생되는 주정폐액을 탈수하여 얻어지는 케이크는 사료화 및 퇴비화 시설에 공급하고 그 탈리액은 물리화학적 및 생물학적으로 전처리를 거쳐 용해성을 높인 다음 생물학적 탈질용 탄소원으로 사용하는 방법에 의해 달성된다.The object of the present invention described above is to obtain a cake obtained by dehydrating the liquor waste liquid generated in the alcoholic process to feed and composting facilities, the desorbent is subjected to physicochemical and biological pretreatment to increase the solubility and then used as a carbon source for biological denitrification Is achieved by.
본 발명에 따른 주정폐액의 전처리 방법은 물화학적 방법과 생물학적 방법이모두 가능하며 생물화학적 전처리 방법은 탈수공정을 거친 탈리액에 알칼리를 투여하여 pH를 조정하는 pH조정단계와, 상기 pH조정단계에서 pH가 조정된 탈리액을 화학적으로 가수분해 시키는 가수분해단계와 생물학적으로 발효시키는 산발효단계를 포함하여 이루어진다.The pretreatment method of alcoholic liquor according to the present invention may be both a water chemical method and a biological method. The biochemical pretreatment method may include a pH adjustment step of adjusting pH by administering alkali to a desorption solution that has undergone a dehydration step, and a pH adjustment step. It comprises a hydrolysis step of chemically hydrolyzing the adjusted stripping solution and an acid fermentation step of biological fermentation.
또한 본 발명에 따른 물리화학적 전처리 방법은 상기 탈수공정을 거친 탈리액에 알칼리를 투여하여 pH를 조정하는 pH조정단계와, 상기 pH조정단계에서 pH가 조정된 탈리액을 초음파 처리하여 분해시키는 초음파 분해단계를 포함하여 이루어진다.In addition, the physicochemical pretreatment method according to the present invention includes a pH adjustment step of adjusting the pH by administering alkali to the desorption solution that has undergone the dehydration process, and an ultrasonic decomposition step of decomposing the desorption solution whose pH has been adjusted in the pH adjustment step by sonication. It is made to include.
본 발명은 또한 상기 탈수공정을 거친 탈리액을 유기성 폐수에 첨가하여 유기성 폐수의 가수분해 및 산발효를 증진시켜 메탄올을 대체할 수 있는 생물학적 탈질용 외부탄소원으로 사용하는 것을 특징으로 한다.The present invention is also characterized in that the desorption liquid, which has undergone the dehydration process, is added to the organic wastewater to promote hydrolysis and acid fermentation of the organic wastewater and used as an external carbon source for biological denitrification that can replace methanol.
즉, 주정폐액은 당과 함께 미생물의 영양성분이 되는 유기물질이 다량 함유되어 있으므로 효모의 배양기질로 이용될 수 있으나 배양말기에는 균체농도가 낮기 때문에 부족한 영양성분을 첨가하여 균체농도를 높이면 가용화 효과를 증진시킬 수 있게 된다. 따라서 음식물쓰레기, 하수슬러지, 분뇨 및 축산폐수 등과 같은 유기성 폐수에 주정폐액의 탈리액을 첨가함으로써 가수분해 및 산발효 효율을 증대시킬 수 있다.In other words, alcoholic liquor can be used as a culture substrate of yeast because it contains a large amount of organic substances that are nutrients of microorganisms with sugar, but at the end of the culture, the cell concentration is low. It can be promoted. Therefore, by adding a desorption solution of alcoholic liquor to organic wastewater, such as food waste, sewage sludge, manure and livestock wastewater, hydrolysis and acid fermentation efficiency can be increased.
이하 상기한 바와 같은 목적을 달성하고 종래의 결점을 해소하기 위해서, 폐기처분되는 주정폐액을 생물학적 탈질용 탄소원으로 이용하기 위한 전처리 방법을 단계별로 상세히 설명한다.In order to achieve the object as described above and to solve the conventional drawbacks, a pre-treatment method for using the waste liquor disposed of as a carbon source for biological denitrification will be described in detail step by step.
<실시예1> 주정폐액의 탈수단계Example 1 Dehydration Step of Alcohol Waste
발효조를 거친 주정액 중 증류 후 남아있는 주정폐액은 총부유물질(TSS)이 23,280mg/ℓ이고 BOD/T-N 및 COD/T-N은 각각 28과 44이며, BOD/T-P 및 COD/T-P는 177과 281로 나타났다. 이와 같이 주정폐액 자체는 고형물질, 질소 및 인 성분이 다량으로 포함되어 있으므로 탈질용 탄소원으로 사용하기 적합하지 않다. 즉, 고형물질과 질소 및 인이 다량으로 포함된 주정폐액을 탈질용 탄소원으로 사용하게 되면 다량의 인과 질소가 투입되어 탈질효율이 크게 떨어지고 고형물질이 처리수에 포함되어 수질이 악화되는 문제가 있다.The alcoholic liquor remaining after distillation in the fermented liquor was 23,280 mg / l of total suspended solids (TSS), 28 and 44 for BOD / TN and COD / TN, and 177 and 281 for BOD / TP and COD / TP, respectively. Appeared. As such, the liquor waste liquor itself is not suitable for use as a carbon source for denitrification because it contains a large amount of solids, nitrogen and phosphorus. In other words, when a liquor waste liquid containing a large amount of solid material and nitrogen and phosphorus is used as a carbon source for denitrification, a large amount of phosphorus and nitrogen is introduced, so the denitrification efficiency is greatly decreased, and the solid material is included in the treated water, thereby deteriorating water quality. .
<표1> 주정폐액의 성상 (단위 : mg/ℓ)<Table 1> Characteristics of alcoholic liquor (Unit: mg / ℓ)
그러나 <표1>에서 보듯이 본 발명에 따른 탈수공정을 거침으로써 TSS 91%, T-N 87%, NH4-N 68%, T-P 37%가 제거되었으며, BOD/T-N 및 COD/T-N은 각각 132와 220이었고, BOD/T-P 및 COD/T-P는 178과 295이었다. 본 실시예에서는 기계식 압착 탈수기를 사용하였으나 기타 다른 탈수기를 사용하여도 동일한 효과가 있을 것이다. 이러한 탈수공정에서 얻어진 케이크는 사료화 및 퇴비화로 재활용이 가능하며, 또한 주정폐액은 탈수성이 좋기 때문에 별도의 약품 첨가가 필요하지 않다.However, as shown in Table 1, the TSS 91%, TN 87%, NH 4 -N 68%, TP 37% were removed by the dehydration process according to the present invention, BOD / TN and COD / TN is 132 and 220 and BOD / TP and COD / TP were 178 and 295. In this embodiment, a mechanical crimping dehydrator is used, but other dehydrators may be used. The cake obtained in this dehydration process can be recycled by feed and composting, and the liquor waste is dehydrated so that no additional chemicals are required.
<실시예2> 주정폐액의 pH조정과 가수분해 및 산발효단계<Example 2> pH adjustment, hydrolysis and acid fermentation of alcoholic liquor
전처리Ⅰ은 주정폐액을 탈수한 여액의 초기 pH가 3.6이고 COD와 TS가 각각 31,230mg/ℓ 및 24,600mg/ℓ인 시료를 사용하였으며, 전처리Ⅱ는 NaOH용액으로 여액의 초기 pH를 7.0으로 조정한 후 COD와 TS가 각각 24,400mg/ℓ 및 27,890mg/ℓ인 시료를 사용하였다. 즉, 전처리Ⅰ은 pH조정단계를 거치지 않고 바로 가수분해 및 산발효 시키는 것이고 전처리Ⅱ는 pH조정단계를 거친 후에 가수분해 및 산발효 시키는 것이다.In pretreatment I, the initial pH of the filtrate dehydrated alcoholic liquor was 3.6, and the samples with COD and TS of 31,230 mg / l and 24,600 mg / l, respectively.Pretreatment II was NaOH solution and adjusted the initial pH of the filtrate to 7.0. Post COD and TS samples of 24,400 mg / l and 27,890 mg / l, respectively, were used. That is, pretreatment I is hydrolysis and acid fermentation without going through the pH adjustment step, and pretreatment II is hydrolysis and acid fermentation after going through the pH adjustment step.
이어 상기 탈리액을 가수분해 시키기 위해 0∼0.15gNaOH/gTS를 단계별로 주입한 후 온도 36∼37℃이고 교반강도 120rpm인 진탕배양기에서 48시간 동안 액성변화와 가용화 효과에 대해 분석하였으며 그 결과는 <표2>와 같다.Subsequently, 0 ~ 0.15gNaOH / gTS was injected step by step to hydrolyze the desorption solution, and then the change in liquidity and solubilization effect were analyzed for 48 hours in a shaking incubator with a temperature of 36 ~ 37 ℃ and a stirring strength of 120rpm. 2>
전처리 방법별 주정여액의 SCOD/COD의 변화는 반응시간 24hr에서 전처리Ⅰ인 pH를 조정하지 않은 주정여액과 전처리Ⅱ인 pH를 조정한 주정여액의 경우 각각 85∼89% 및 89∼93%로 전처리Ⅱ에서 NaOH투여량이 증가할수록 용존성 물질이 증가되었다. 즉, 탈질용 탄소원의 가용성은 용해성 물질(SCOD)의 농도와 비례하므로 용해성 물질의 농도가 높은 전처리Ⅱ, 즉, pH조정단계를 거친 후에 가수분해 및 산발효 시키는 방법이 바람직하다.The change of SCOD / COD of the alcoholic filtrate by pretreatment method was 85 ~ 89% and 89-93% for the alcoholic filtrate without pH adjusted as pretreatment I and the alcoholic acid with pH adjusted as pretreatment II at 24hr reaction time, respectively. As the amount of NaOH increased in II, dissolved substances increased. That is, since the solubility of the denitrification carbon source is proportional to the concentration of the soluble substance (SCOD), the method of pretreatment II having a high concentration of the soluble substance, ie, a pH adjustment step, followed by hydrolysis and acid fermentation is preferable.
또한 입상COD의 가용화 효과(Ps)의 경우 반응시간 24hr에서 전처리Ⅰ과 전처리Ⅱ의 경우 각각 45∼60% 및 53∼62%로 전처리Ⅱ에서 다소 높은 효율을 보였다.The solubilization effect (Ps) of the granular COD was 45 ~ 60% and 53 ~ 62% in pretreatment I and pretreatment II at 24hr reaction time, respectively.
<실시예3> 초음파 분해단계Example 3 Ultrasonic Decomposition
전처리Ⅲ은 주정폐액을 탈수한 여액의 초기 pH가 3.5이고 COD가 25,700mg/ℓ인 시료를 pH를 조정하지 않고 사용하였으며, 전처리Ⅳ는 NaOH용액으로 초기 pH를 7.0으로 조정한 후 COD가 25,100mg/ℓ인 시료를 사용하였다.In the pretreatment III, a sample having an initial pH of 3.5 and a COD of 25,700 mg / l was used without adjusting the pH. The pretreatment IV was adjusted with an NaOH solution to 7.0, after which the COD was 25,100 mg. A sample of / l was used.
각 시료를 초음파 항온조 온도 20℃에서 6시간동안 35kHz로 처리한 후 액성변화와 가용화 효과에 대해 분석한 결과는 <표3>과 같다.Each sample was treated at 35 kHz for 6 hours at 20 ° C ultrasonic bath temperature, and the results of liquid change and solubilization were analyzed as shown in <Table 3>.
초음파 분해는 초음파를 동력으로 이용한 것으로서 액체 중에 초음파를 발사시키면 초당 25,000-35,000회 정도 진동이 생성되어 액체 중에 포함되어 있는 물질을 빠르게 진동시켜 물리적으로 분쇄시킬 뿐만 아니라 이러한 진동에 의해 수반되는 화학적, 열적 작용으로 탈리액 중의 물질을 분해시키게 된다. 따라서 고형물질과 비용해성 물질이 포함된 탈리액에 초음파를 발사하면 고형물질은 침전되어 분리되고 비용해성 물질은 분해되어 용해성 물질로 전환되게 된다. 아울러 탈리액에 포함되어 있는 미생물이 물리화학적으로 분해되어 사멸되게 된다.Ultrasonic decomposition is an ultrasonic power source. When ultrasonic waves are fired in a liquid, vibrations are generated about 25,000-35,000 times per second, and the material contained in the liquid is rapidly vibrated to physically pulverize, and chemical and thermal Action to decompose the material in the desorption solution. Therefore, when the ultrasonic wave is emitted to the stripping solution containing the solid material and the insoluble material, the solid material is precipitated and separated, and the insoluble material is decomposed and converted into the soluble material. In addition, the microorganisms contained in the desorption liquid are physically decomposed and killed.
한편, 전처리 방법별 주정여액을 초음파 처리한 후의 SCOD/COD변화는 전처리Ⅲ인 pH를 조정하지 않은 주정여액과 전처리Ⅳ인 pH를 조정한 후 초음파 처리를 한 경우 각각 79∼86% 및 75∼94%로 나타나 전처리Ⅳ의 반응시간 4hr이후에서 가장 높은 효율을 보였다. 따라서 pH조정단계를 거친 탈리액을 4시간이상 초음파로 분해하는 것이 용해성 물질(SCOD)의 비율을 높이는 데 가장 바람직하였다.On the other hand, the SCOD / COD change after sonication of the alcoholic liquor by pretreatment method was 79-86% and 75-94 when sonication was performed after adjusting the pH of the liquor filtrate without pretreatment III and the pH of pretreatment IV, respectively. The highest efficiency was obtained after 4hr of pretreatment IV. Therefore, it was most preferable to increase the ratio of soluble substance (SCOD) by dissolving the desorption solution after the pH adjustment step by ultrasonic wave for more than 4 hours.
<실시예4> 각 전처리방법별 생분해Example 4 Biodegradation for Each Pretreatment Method
전처리Ⅴ는 전처리Ⅲ과 같이 주정폐액을 탈수한 여액을 시료로 사용하였으며, 전처리Ⅵ은 전처리Ⅳ와 같이 pH를 7.0으로 조정한 시료에 0.025gNaOH/gTS를 주입한 후 온도 36∼37℃이고 교반강도 120rpm인 진탕배양기에서 24시간 동안 가수분해 및 산발효한 시료를 사용하였다. 수온이 20℃이고 MLSS농도가 약 3000mg/ℓ인 호기성 조건에서 생분해한 결과를 토대로 기질제거 속도상수와 비기질 소모율을 산출한 결과는 <표4>와 같다.Pretreatment V used the filtrate dehydrated alcoholic waste liquid as the pretreatment III, and in the pretreatment VI, after injecting 0.025gNaOH / gTS into the sample whose pH was adjusted to 7.0 as in pretreatment IV, the temperature was 36-37 ℃ and the stirring strength was Hydrolyzed and acid fermented samples were used for 24 hours in a shaker at 120 rpm. Based on the results of biodegradation under aerobic conditions with a water temperature of 20 ° C and an MLSS concentration of about 3000 mg / ℓ, the results of calculating the substrate removal rate constant and non-substrate consumption are shown in <Table 4>.
실험결과, 메탄올을 기준하여 전처리Ⅴ 및 전처리Ⅵ의 탈리액에 대한 기질제거 속도상수를 상대 비교한 결과 0.86과 0.91로 미생물에 의한 기질제거능이 우수하였다. 한편 비기질 소모율을 토대로 반응시간별 비기질 소모속도상수를 산출하여 메탄올과 탈리액에 대해 상대 비교한 결과 0.96∼0.97로 상당히 우수한 비기질 소모율을 보였다.As a result, the substrate removal rate constants of the pretreatment V and the pretreatment VI based on methanol were 0.86 and 0.91. On the other hand, the relative substrate consumption rate constant was calculated based on the specific substrate consumption rate, and the relative comparison with methanol and leachate showed 0.96 to 0.97.
<실시예5> 각 전처리방법별 탈질Example 5 Denitrification by Pretreatment Method
제 3 단계에서 사용한 동일한 시료를 수온 20℃이고 MLSS농도가 3000mg/ℓ인 무산소조에서 탈질 실험한 결과를 토대로 질소제거속도상수(kDN)와 탈질율 그리고 탈질에 따른 유기물 소모율을 산출한 결과는 <표5>와 같다.Based on the results of the denitrification experiment in the anoxic tank with the same sample used in the third step, the water temperature is 20 ℃ and the MLSS concentration is 3000mg / L, the nitrogen removal rate constant (k DN ), the denitrification rate, and the organic consumption rate according to denitrification are calculated. 5>.
메탄올을 기준하여 전처리Ⅴ 및 전처리Ⅵ의 질소제거속도상수와 탈질율을 상대 비교한 결과 0.85 및 0.84로서 탈질효과가 우수하였으며, 유기물 소모율의 경우 메탄올에 비해 약 8∼10% 더 소모되었다.As a result of comparing the nitrogen removal rate constant and denitrification rate of pretreatment V and pretreatment VI based on methanol, the denitrification effect was excellent as 0.85 and 0.84, and organic consumption was about 8-10% higher than methanol.
<실시예6> 유기성 폐수와 혼합Example 6 Mixing with Organic Wastewater
주정폐액은 당과 함께 미생물의 영양성분인 유기물질을 함유하고 있으므로 효모의 배양기질로 이용될 수 있으나 배양말기의 주정폐액은 영양성분의 부족으로 균체의 농도가 낮다. 따라서 주정폐액의 탈리액을 음식물쓰레기, 하수슬러지, 분뇨 및 축산폐수 등의 유기성 폐수에 첨가하여 균체의 농도를 높이면 음식물쓰레기 등의 유기성 폐수가 가수분해 및 산발효되어 가용성이 증진되게 된다.Alcoholic liquor can be used as a culture substrate of yeast because it contains organic substances, which are nutrients of microorganisms, but alcohol concentration at the end of the culture is low due to lack of nutrients. Therefore, if the desorption liquid of alcoholic liquor is added to organic wastewater such as food waste, sewage sludge, manure and livestock wastewater, and the concentration of the cells is increased, organic wastewater such as food waste is hydrolyzed and acid fermented to improve solubility.
즉, 음식물쓰레기의 유기성 폐수에 대해 10중량%의 주정폐액의 탈리액을 첨가하였을 때, 유기성 폐수의 가수분해 및 산발효가 크게 증대되었다. 따라서 탈리액이 첨가된 유기성 폐수를 생물학적 탈질용 외부탄소원으로 사용하는 경우 질소제거 효율을 크게 향상시킬 수 있게 된다.That is, hydrolyzation and acid fermentation of organic wastewater were greatly increased when 10% by weight of liquor liquor was added to the organic wastewater of food waste. Therefore, when the organic wastewater to which the desorbing liquid is added is used as an external carbon source for biological denitrification, nitrogen removal efficiency can be greatly improved.
이상에서 설명한 바와 같이, 본 발명에 따른 주정폐액 전처리 방법은 주정폐액에 포함되어 있는 고형물질과 인 및 질소성분을 제거하여 생물학적 탈질공정에서 메탄올을 대체할 수 있는 탈질용 외부탄소원으로 가공함으로써 탈질용 탄소원의 구입비용을 획기적으로 절감시킬 뿐만 아니라 주정폐수를 저렴한 비용으로 처리할 수 있는 효과가 있다.As described above, the liquor waste pretreatment method according to the present invention removes solid matter, phosphorus and nitrogen contained in the liquor waste liquor and processes it as an external carbon source for denitrification to replace methanol in a biological denitrification process. Not only will it dramatically reduce the cost of purchasing carbon sources, but it will also have the effect of treating alcoholic waste water at low cost.
또한 본 발명에 따라 주정폐액을 초음파 분해시킴으로써 용해성 물질의 농도를 높여 가용성을 증진시킬 뿐만 아니라 주정폐액에 포함되어 있는 미생물이 사멸되어 탈질용 탄소원의 장기 보관이 가능하게 되는 효과가 있다.In addition, by ultrasonically decomposing the alcoholic liquor according to the present invention to increase the concentration of the soluble substance to enhance the solubility, the microorganisms contained in the alcoholic liquor is killed and the long-term storage of the denitrification carbon source is possible.
본 발명은 또한 주정폐액에서 분리된 탈리액을 음식물쓰레기, 하수슬러지, 분뇨 및 축산폐수 등 유기성 폐수에 첨가함으로써 탈리액에 포함되어 있는 미생물을 이용하여 유기성 폐수를 가수분해 및 산발효시켜 우수한 탈질용 탄소원으로 사용할 수 있는 효과가 있다.The present invention is also added to the organic wastewater, such as food waste, sewage sludge, manure and livestock waste, by separating the liquor from the alcoholic waste liquor, using the microorganisms contained in the leachate to hydrolyze and acid ferment the organic wastewater as an excellent carbon source for denitrification There is an effect that can be used.
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| KR101126702B1 (en) * | 2011-06-08 | 2012-03-29 | 주식회사 이앤비 | Microorganism activator composition for nitrogen and phosphorus removal from wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0299199A (en) * | 1988-10-06 | 1990-04-11 | Fujita Corp | Organic sludge treatment |
| JP3572199B2 (en) * | 1998-06-23 | 2004-09-29 | 三菱重工業株式会社 | Organic solid matter methane recovery method |
| KR100354968B1 (en) * | 1999-11-15 | 2002-10-05 | 주식회사 제오텍 | Annexation disposal method of food waste and sewage |
| KR100334496B1 (en) * | 2000-01-12 | 2002-05-08 | 박종웅 | Method for preliminary treatment of food waste |
| KR200199315Y1 (en) * | 2000-04-18 | 2000-10-02 | 주식회사제오텍 | Annexation disposal system of food waste and sewage |
| KR100370244B1 (en) * | 2001-01-22 | 2003-02-05 | 효성에바라환경엔지니어링 주식회사 | Food waste treatment and recycling mathod and device |
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2001
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| KR100478937B1 (en) * | 2002-10-28 | 2005-03-28 | 박종웅 | Manufacturing method of acid fermentation for biological denitrification using food waste |
| KR100783785B1 (en) * | 2005-11-29 | 2007-12-10 | 주식회사 포스코건설 | Carbon source preparing method for advanced biological treatment of sewage and wastewater |
| KR100845195B1 (en) * | 2007-06-13 | 2008-07-10 | 한국과학기술원 | Treating method of slaughterhouse wastewater using sequencing batch bioreactor |
| KR101101843B1 (en) * | 2011-07-04 | 2012-01-05 | (주) 청연 | Biological reactor for removing tn and tp in winter time, and controlling method thereof |
| CN113072178A (en) * | 2021-04-01 | 2021-07-06 | 宜宾五粮液股份有限公司 | Method for improving denitrification performance of anaerobic ammonium oxidation bacteria by adopting brewing wastewater |
| CN113072178B (en) * | 2021-04-01 | 2023-01-03 | 宜宾五粮液股份有限公司 | Method for improving denitrification performance of anaerobic ammonium oxidation bacteria by adopting brewing wastewater |
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| KR100417761B1 (en) | 2004-02-14 |
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