KR100905487B1 - Biological treatment of paper mill wastewater - Google Patents

Biological treatment of paper mill wastewater Download PDF

Info

Publication number
KR100905487B1
KR100905487B1 KR1020070076720A KR20070076720A KR100905487B1 KR 100905487 B1 KR100905487 B1 KR 100905487B1 KR 1020070076720 A KR1020070076720 A KR 1020070076720A KR 20070076720 A KR20070076720 A KR 20070076720A KR 100905487 B1 KR100905487 B1 KR 100905487B1
Authority
KR
South Korea
Prior art keywords
wastewater
species
treatment
nix
burkholderia
Prior art date
Application number
KR1020070076720A
Other languages
Korean (ko)
Other versions
KR20090012688A (en
Inventor
이상열
이상섭
윤민우
Original Assignee
주식회사 닉시안
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 닉시안 filed Critical 주식회사 닉시안
Priority to KR1020070076720A priority Critical patent/KR100905487B1/en
Publication of KR20090012688A publication Critical patent/KR20090012688A/en
Application granted granted Critical
Publication of KR100905487B1 publication Critical patent/KR100905487B1/en

Links

Images

Classifications

    • 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
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/341Consortia of bacteria
    • 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
    • C02F3/02Aerobic processes
    • C02F3/04Aerobic processes using trickle filters
    • 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
    • C02F3/28Anaerobic digestion processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/10Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/22O2

Abstract

본 발명은 제지 폐수 처리 활성을 가지는 혼합 균주 Nix-37을 이용하여 제지 폐수를 처리하는 방법에 관한 것이다. 본 발명의 혼합 균주 Nix-37을 이용한 제지 폐수의 생물학적 처리는 처리 효율이 높을 뿐만 아니라 기존의 화학적 처리 및 물리학적 처리 방법에 비하여 안전하고 경제적이라는 장점을 가진다.The present invention relates to a method for treating paper wastewater using a mixed strain Nix-37 having paper wastewater treatment activity. Biological treatment of paper wastewater using the mixed strain Nix-37 of the present invention has not only high treatment efficiency but also safety and economical advantages over conventional chemical and physical treatment methods.

제지 폐수, 생물학적 처리 Paper wastewater, biological treatment

Description

제지 폐수의 생물학적 처리법{Biological treatment of paper mill wastewater}Biological treatment of paper mill wastewater

본 발명은 제지 폐수 처리 활성을 가지는 혼합 균주를 이용하여 제지 폐수를 처리하는 방법에 관한 것이다.The present invention relates to a method for treating paper wastewater using a mixed strain having paper wastewater treatment activity.

펄프 및 제지공정은 다른 제조업에 비해 물을 다량으로 사용하는 업종이다. 세계적으로 볼 때 담수의 사용량에서 일차 금속 산업 및 화학 산업에 이어 펄프 및 제지공업이 세 번째를 차지한다. 현대의 효율적인 운영기술을 사용하여도 종이 1톤당 60m2의 물을 사용하게 된다 [G. Thompson, J. Swain, M.Kay, and C.F. Forster, The treatment of pulp and paper mill effluent, Bioresource Technology, 77, 275∼286 (2001)]. 이렇게 사용된 물의 재활용이 효율적이지만, 완전히 정화되지 않은 물의 재사용은 생산 공정 및 기계시설에 여러 가지 문제를 야기시킨다 [Robertson, L.R., Schwingel, W.R., Effect of water reuse on paper machine microbiology. In:Proceedings of the 1997 Environmental Conference, vol.1. TAPPI press, Norcross, GA, pp.87~93 (1997)].Pulp and paper making industry uses more water than other manufacturing industries. In the world, pulp and paper industry account for the third largest use of fresh water after the primary metal and chemical industries. Even modern efficient operating techniques use 60 m 2 of water per tonne of paper [G. Thompson, J. Swain, M. Kay, and CF Forster, The treatment of pulp and paper mill effluent, Bioresource Technology, 77, 275-286 (2001). Recycling of this used water is efficient, but reuse of water that is not completely purified leads to problems for production processes and machinery [Robertson, LR, Schwingel, WR, Effect of water reuse on paper machine microbiology. In: Proceedings of the 1997 Environmental Conference, vol. TAPPI press, Norcross, GA, pp. 87-93 (1997)].

또한, 제지 폐수내에 포함되어 있는 PCBs, PAHs, 그리고 디옥신 (dioxin) 등은 널리 알려진 독성물질로서 인체에 직·간접적으로 인간에게 해를 줄 수 있다 [Tanu Rana, Shashank Gupta, Dhiraj Kumar, Sharad Sharma, Manish Rana, Vikram S. Rathore, Ben M.J.Pereira, Toxic effects if pulp and paper-mill effluents on male reproductive organs and some systemic parameters in rats]. 이러한 제지 폐수의 처리에는 현재 생물학적 처리와 화학적 처리 두 가지가 병행되고 있으며, 기존의 방법은 비용면에서 경제적이지 않고 비용에 비해 처리효율 또한 만족스럽지 못하였다.  In addition, PCBs, PAHs, and dioxin, which are contained in paper wastewater, are widely known toxic substances that can harm humans directly or indirectly [Tanu Rana, Shashank Gupta, Dhiraj Kumar, Sharad Sharma]. , Manish Rana, Vikram S. Rathore, Ben MJPereira, Toxic effects if pulp and paper-mill effluents on male reproductive organs and some systemic parameters in rats]. The treatment of paper wastewater is currently carried out in parallel with biological treatment and chemical treatment, and the conventional method is not economical in terms of cost and unsatisfactory in terms of treatment efficiency.

이에, 제지 폐수를 재활용하는 방법이나 배출량을 감소시키는 방안들이 다각도로 연구되고 있으며, 그 중에서도 우수한 기질 분해 능력을 갖는 미생물 균주를 이용하는 생물학적 처리 방법으로 폐수를 처리하는 것이 보다 경제적이고 효율적이며, 이에 따라 새로운 미생물 균주를 분리해내고 이를 이용한 공정 조건을 최적화하는 것이 필요하다.Accordingly, methods for recycling paper wastewater and reducing emissions have been studied in various ways. Among them, it is more economical and efficient to treat wastewater by a biological treatment method using a microbial strain having excellent substrate decomposition ability. It is necessary to isolate new microbial strains and optimize process conditions using them.

이에, 본 발명자는 제지 폐수로부터 폐수의 처리활성이 우수한 슈도모나스 종 Nix-37 혼합 균주를 분리한 뒤 분리된 균주를 제지 폐수의 생물학적 처리에 유용하게 사용할 수 있다는 것을 확인하고 본 발명을 완성하기에 이르렀다.Accordingly, the present inventors have isolated the Pseudomonas species Nix-37 mixed strain having excellent wastewater treatment activity from paper wastewater and confirmed that the isolated strain can be usefully used for biological treatment of paper wastewater. .

따라서, 본 발명의 하나의 목적은 제지 폐수 처리 활성을 가지는 혼합 균주 Nix-37를 사용하여 제지 폐수를 처리하는 방법을 제공하는 것이다.Accordingly, one object of the present invention is to provide a method for treating paper wastewater using a mixed strain Nix-37 having paper wastewater treatment activity.

본 발명의 또 다른 목적은 혼합 균주 Nix-37을 포함하는 제지 폐수 처리용 조성물을 제공하는 것이다. Still another object of the present invention is to provide a composition for treating paper wastewater, including mixed strain Nix-37.

하나의 양태로서, 본 발명은 제지 폐수를 처리하기 위한 수탁번호 KACC 91259P로 기탁된 혼합 균주 Nix-37과, 상기 혼합 균주 Nix-37을 포함하는 제지 폐수 처리 조성물에 관한 것이다.In one aspect, the present invention relates to a mixed strain Nix-37 deposited with accession number KACC 91259P for treating paper wastewater and a papermaking wastewater treatment composition comprising the mixed strain Nix-37.

본 발명에 따라 제지 폐수의 생물학적 처리에 사용되는 "혼합 균주 Nix-37"은 경기도 소재의 한 제지공장의 폐수 시료로부터 높은 제지 폐수 처리 활성을 가지는 미생물을 분리하는 과정에서 최종 선별된 균주들로서, 이들은 총 4개의 균주에 대한 혼합이며, 이들은 각각은 API kit 20NE를 이용하여 생리·생화학적 동정결과 부르크홀데리아 (Burkholderia) 2종, 크리소모나스 (Chryseomonas) 1종 및 에어 로모나스 (Aeromonas) 1종으로 이루어지며, KACC에 수탁번호 KACC 91259P로 기탁되어 있다.The "mixed strain Nix-37" used for the biological treatment of paper wastewater according to the present invention is the strains finally selected in the process of separating microorganisms having high paper wastewater treatment activity from wastewater samples of a paper mill in Gyeonggi-do. and mixed for a total of four strains, each of which is Freiburg to physiological and biochemical identification results using the API 20NE kit RIA holde (Burkholderia) 2 species, Cree consumption eggplant (Chryseomonas) 1 species and air our Nasu ( Aeromonas ) It consists of one species and has been deposited with KACC under accession number KACC 91259P.

본 발명에서 사용된 용어, "생물학적 처리"란 미생물을 증식시켜 이들의 대 사 작용을 이용하여 폐수 내의 난분해성 물질을 포함하는 유기물질을 제거하는 공정을 의미한다. 본 발명의 혼합 균주 Nix-37의 제지 폐수에 대한 생물학적 처리 효율을, 유입수와 유출수에서 CODMn를 측정하여 유기물질이 제거된 정도로 살펴본 결과, 90% 이상의 유기물질 제거 효율을 가지는 것을 확인할 수 있었다.As used herein, the term "biological treatment" refers to a process of removing organic substances including hardly decomposable substances in wastewater by multiplying microorganisms and utilizing their metabolism. The biological treatment efficiency of the papermaking wastewater of the mixed strain Nix-37 of the present invention was determined by measuring COD Mn in the influent and the effluent to the extent that the organic material was removed, and it was confirmed that the organic material removal efficiency was greater than 90%.

특히, 본 발명의 혼합 균주는 다양한 폐수 환경에 대하여 혼합 균주 내 각 균주가 상호 보완적으로 작용하므로 환경 조건에 따라 적합하게 상승적 처리 효과를 나타낸다는 장점을 가진다. In particular, the mixed strain of the present invention has the advantage that each of the strains in the mixed strain complementary to the various wastewater environment exhibits a synergistic treatment effect appropriately according to the environmental conditions.

본 발명의 조성물은 (ⅰ) 혼합 균주 Nix-37 단독; 또는 (ⅱ) 혼합 균주 Nix-37 외에 제지 폐수 처리활성을 가지는 다른 미생물을 추가로 혼합하여 사용할 수 있다.The composition of the present invention comprises (i) mixed strain Nix-37 alone; Or (ii) in addition to the mixed strain Nix-37, other microorganisms having papermaking wastewater treatment activity may be further mixed.

또한, 본 발명의 조성물은 상기 미생물 외에 보존성을 높이는 제제, 재활성화를 촉진하는 제제, 부형제 등의 다양한 첨가제를 추가로 첨가할 수 있으며, 액체 또는 분말 등의 다양한 제형으로 제조 가능하다.In addition, the composition of the present invention may further add a variety of additives such as preparations to increase the preservation, agents to promote reactivation, excipients, etc., in addition to the microorganism, it can be prepared in a variety of formulations, such as liquid or powder.

또 다른 양태로서, 본 발명은 혼합 균주 Nix-37을 이용하는 것을 특징으로 하는 제지 폐수 처리 방법에 관한 것이다.As another aspect, the present invention relates to a papermaking wastewater treatment method using a mixed strain Nix-37.

본 발명의 혼합 균주 Nix-37을 이용하여 폐수 처리 방법은 특별히 제한되지 않으며, 당업자에게 알려진 모든 방법에 사용될 수 있다. 활성 슬러지법 (activated sludge treatment process), 상향류식 혐기성 슬러지 블랭킷 (upflow anaerobic sludge blanket: USAB), AOP (advanced oxygen process)공법, 생물여과 (biological aerated filter: BAF), 살수여상법 (trickling filter process), 산화지법 (oxidation pond), 회전원판법 (rotating biological contactor) 등의 생물학적 처리 방법을 그 구체적인 예로 들 수 있으며, 그 중에서 활성 슬러지법이 바람직하다. The wastewater treatment method using the mixed strain Nix-37 of the present invention is not particularly limited and may be used in all methods known to those skilled in the art. Activated sludge treatment process, upflow anaerobic sludge blanket (USAB), advanced oxygen process (AOP), biological aerated filter (BAF), trickling filter process Specific examples include biological treatment methods such as oxidation pond and rotating biological contactor, and activated sludge method is preferable.

본 발명의 혼합 균주 Nix-37을 활성 슬러지법에 적용 시 균주의 투여 방법, 투여 시기, 투여 조건 등은 당업자에 의해 적의 선택할 수 있다. 예를 들어, 본 발명의 혼합 균주 Nix-37을 폐수 처리시, 폐수에 부유 현탁한 상태로 처리하는 부유현탁법으로 처리하거나 균주를 지지체에 고정시킨 고착 형태로 처리할 수 있다.When the mixed strain Nix-37 of the present invention is applied to the activated sludge method, the administration method, administration time, administration conditions, etc. of the strain can be appropriately selected by those skilled in the art. For example, the mixed strain Nix-37 of the present invention may be treated by a suspension method in which the mixed strain Nix-37 is suspended in the wastewater, or treated in a fixed form in which the strain is fixed to a support.

본 발명의 혼합 균주를 활성 슬러지법에 적용 시 혼합 균주 Nix-37가 높은 활성을 나타내도록, 2 내지 3 mg/L의 DO (Dissolved Oxygen), 3,000 내지 4,000 mg/L의 MLSS (Mixed Liquor Suspended Solid), 24 내지 48 시간의 HRT (Hydraulic Retention Time), 20 내지 30일의 SRT (Solids Retention Time)를 유지하는 것이 바람직하다.When the mixed strain of the present invention is applied to the activated sludge method, the mixed strain Nix-37 exhibits high activity so that 2 to 3 mg / L of DO (Dissolved Oxygen) and 3,000 to 4,000 mg / L of MLSS (Mixed Liquor Suspended Solid) ), 24 to 48 hours of HRT (Hydraulic Retention Time), 20 to 30 days of SRT (Solids Retention Time).

구체적으로, 본 발명의 혼합 균주 Nix-37은 도 1과 같은 모식도를 가지는 바이오리액터에서 제1 및 제2 포기조의 DO를 2 mg/L와 3 mg/L로 유지하고, MLSS를 4000, HRT를 48시간, SRT를 30일로 유지할 때 최고 93.1%의 CODMn 제거 효율을 보였으며, 이 때 유출수의 CODMn는 최저 33.5 mg/L를 나타내었다.Specifically, the mixed strain Nix-37 of the present invention maintains DO of the first and second aeration tanks at 2 mg / L and 3 mg / L in the bioreactor having the schematic diagram as shown in FIG. 48 hours, when maintained for 30 SRT days showed the highest 93.1% Mn COD removal efficiency, COD Mn of this time, the effluent exhibited the lowest 33.5 mg / L.

상기 유출수의 CODMn 수치는 방류수 수질 기준인 CODMn 40 mg/L보다 휠씬 낮은 수치로, 제지 폐수를 본 발명의 혼합 균주 Nix-37를 이용하여 처리할 경우, 방류수 기준에 적합한 CODMn 수치를 만족시키는 유출수로 최종 처리할 수 있다는 것을 의미한다.COD Mn of the effluent The value is much lower than 40 mg / L of COD Mn , the effluent water quality standard, and when papermaking wastewater is treated with the mixed strain Nix-37 of the present invention, the final treatment is performed with effluent that satisfies the COD Mn value suitable for the effluent standard. It means you can do it.

본 발명에 따라 혼합 균주 Nix-37를 사용하여 제지 폐수를 생물학적 처리함으로써, 기존의 화학적 처리와 물리학적 처리 방법보다 독성을 가진 2차 오염 물질의 발생 없이 보다 안전하고 경제적으로 수행할 수 있다.By biologically treating the paper wastewater using the mixed strain Nix-37 according to the present invention, it can be performed more safely and economically without the generation of toxic secondary pollutants than conventional chemical and physical treatment methods.

이하 본 발명을 실시예에 의해 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

하기 실시예들은 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 실시예에 의해 한정되는 것은 아니다.The following examples are merely illustrative of the present invention, but the content of the present invention is not limited by the examples.

실시예Example 1  One

(1) 실험장치 및 반응조 운전 (1) Experiment and Reactor Operation

본 발명에 사용한 제지 폐수는 경기도 소재의 제지공장의 부상조로부터 수득한 것이었다. 현장에서는 생산되는 지종에 따라 배출되는 폐수의 성상이 변하기 때문에 본 발명에서는 이점을 고려해 지종에 따라 시료를 얻어 반응기에 유입수로 이용하였다. 본 실험실 규모의 반응기는 아크릴 재질로 제작되었고, 유입수조, 제 1 포기조, 제 2 포기조, 침전조로 구성되었다. 제 1 포기조와 제 2 포기조의 용적 은 각각 15L, 20L로 제작하였다 (도 1). The paper wastewater used in the present invention was obtained from the flotation tank of a paper mill in Gyeonggi-do. In the present invention, since the properties of the wastewater discharged vary according to the type of paper produced, in the present invention, samples were taken according to the type of paper and used as influent in the reactor in consideration of advantages. The laboratory scale reactor was made of acrylic material and consisted of influent tank, first aeration tank, second aeration tank, and sedimentation tank. The volumes of the first and second aeration tanks were made of 15L and 20L, respectively (Fig. 1).

포기조의 온도는 23 내지 25℃를 유지하였다. 유입수조와 침전조는 원통형으로 혼합이 가능하도록 교반 장치를 설치하여 유입수질이 균등하였으며, 포기조에서는 0 내지 200rpm으로 지정이 가능한 교반 장치를 설치하여 슬러지의 혼합이 원활하도록 하였다. 원형 침전조에는 1rmp인 교반장치를 설치하여 슬러지의 침강유도와 원활한 슬러지 수집이 이루어지도록 유도하였다. 유입폐수는 펌프에 의해서 제 1 포기조, 제 2 포기조 순으로 이동하고, 침전조로부터 제 1 포기조로의 반송 슬러지는 유입수 유량 대비 1Q로 조정하였다.The temperature of the aeration tank was maintained at 23 to 25 ° C. The inflow water tank and the settling tank were installed in the mixing device so that the mixing was possible in a cylindrical shape, and the inflow water quality was equal, and in the aeration tank, the agitation device that could be designated from 0 to 200rpm was installed to facilitate the mixing of the sludge. In the circular sedimentation tank, a 1-rpm stirrer was installed to induce sludge settling and smooth sludge collection. The influent wastewater was moved to the first aeration tank and the second aeration tank by a pump, and the return sludge from the sedimentation tank to the first aeration tank was adjusted to 1Q relative to the influent flow rate.

(2) 분석방법(2) Analysis method

유기물질 농도는 CODMn으로 측정하였으며, DO의 측정은 2시간 간격으로 YSI model 58을 이용하여 측정하였다. pH의 측정은 유기물 측정을 위해 얻었던 샘플을 이용해 매일 Radiometer 사의 PHM 92로 측정하였다. MLSS와 MLVSS 측정은 표준법 (예시적인 문헌을 기재하는 것이 바람직합니다)에 따라 매일 실시하였다. Organic matter concentration was measured by COD Mn , and DO was measured by YSI model 58 at 2 hour intervals. The pH was measured every day using PHM 92 by Radiometer, using the sample obtained for organic matter measurement. MLSS and MLVSS measurements were performed daily according to standard methods (preferably documenting exemplary literature).

(3) 고효율 균주의 분리 (3) Isolation of Highly Efficient Strains

유기물질의 제거능이 뛰어난 혼합균주 Nix-37은 제지 폐수에서 분리하였다.The mixed strain Nix-37, which has excellent ability of removing organic substances, was isolated from paper wastewater.

(3-1) 증식 배양과 균주 분리(3-1) Proliferation Culture and Strain Separation

500 ml 바틀에 100 ml 영양 브로쓰 (Difco,U.S.A.)를 넣고 온도 121℃에서 15분 동안 습윤 멸균한 후, 제지폐수 원액을 10ml넣고 48시간동안 증식 배양하였다. 증식배양된 배양액을 스트리크 플레이트 방법을 이용하여 균주를 단일균주로 분리한 후, 그램 염색을 통하여 순수분리 여부를 확인하였다.100 ml nutrient broth (Difco, U.S.A.) was put into a 500 ml bottle and wet sterilized at a temperature of 121 ° C. for 15 minutes, and 10 ml of the papermaking wastewater was added and cultured for 48 hours. After culturing the cultured culture medium using a streak plate method to isolate the strain into a single strain, it was confirmed whether the pure separation through gram staining.

(3-2) 스크리닝 시험(3-2) Screening Test

스크리닝 시험은 순수분리된 미생물 각각의 유기물 제거능을 알아보기 위하여 실시하였다. 이때 미생물의 성장을 위하여 제지폐수의 원액을 사용하여 실험하였다. 미생물의 접종 농도는 1.0 g/L (습윤 중량)이였으며, 폐수의 양은 100 ml였다. 유기물 제거능을 확인하여기 위하여 CODMn은 0h과 48h에 2번 측정하였다.Screening tests were conducted to determine the organic matter removal ability of each purely isolated microorganism. At this time, the experiment was performed using the stock solution of paper wastewater for the growth of microorganisms. The inoculation concentration of the microorganisms was 1.0 g / L (wet weight) and the amount of wastewater was 100 ml. COD Mn was measured twice at 0h and 48h to confirm the organic removal ability.

0h0h 48h48h Rem.(%)Rem. (%) 0h0h 48h48h Rem.(%)Rem. (%) BlankBlank 567.8567.8 556.4556.4 2.0 2.0 D13D13 567.8567.8 241.3241.3 57.5 57.5 D4D4 567.8567.8 395.1395.1 30.4 30.4 D15D15 567.8567.8 247.0247.0 56.5 56.5 D14D14 567.8567.8 428.6428.6 24.5 24.5 D2D2 567.8567.8 254.7254.7 55.1 55.1 D19D19 567.8567.8 429.5429.5 24.4 24.4 D20D20 567.8567.8 272.8272.8 52.0 52.0 D5D5 567.8567.8 447.2447.2 21.2 21.2 D6D6 567.8567.8 314.7314.7 44.6 44.6 D8D8 567.8567.8 475.7475.7 16.2 16.2 D11D11 567.8567.8 344.8344.8 39.3 39.3 D1D1 567.8567.8 485.2485.2 14.5 14.5 D9D9 567.8567.8 348.4348.4 38.6 38.6 D10D10 567.8567.8 495.7495.7 12.7 12.7 D16D16 567.8567.8 355.5355.5 37.4 37.4 D7D7 567.8567.8 521.9521.9 8.1 8.1 D17D17 567.8567.8 356.9356.9 37.1 37.1 D3D3 567.8567.8 528.4528.4 6.9 6.9 D12D12 567.8567.8 365.9365.9 35.6 35.6 D18D18 567.8567.8 547.7547.7 3.5 3.5

제지폐수에서 총 24개의 미생물이 분리되어 이들 각각에 대해서 스크린 테스트를 거쳐 고효율 균주 4개체를 선별하였다. 선별된 4개체는 D13, D15, D02, D20는 API Kit 20NE로 생리·생화학적 동정한 결과, D13와 D15는 부크홀데리아 종으로 동정되었다. D02는 크리세오모나스 종으로 동정되었고, D15는 아에로모나스 종으로 동정되었다. 이들 4종의 미생물들을 혼합하여 제작된 혼합균주 Nix-37가 반응기 연구에 사용되었다. A total of 24 microorganisms were isolated from the papermaking wastewater, and each of them was screened and four highly efficient strains were selected. D13, D15, D02, and D20 were identified as API Kit 20NE by physiological and biochemical identification. D02 has been identified as a Cryeomonas species and D15 has been identified as an Aeromonas species. Mixed strain Nix-37 prepared by mixing these four microorganisms was used in the reactor study.

D13D13 D15D15 D2D2 D20D20 ShapeShape rodrod rodrod rodrod rodrod GramGram -- -- -- -- SizeSize 0.5-0.7x1.0-1.50.5-0.7x1.0-1.5 0.5-0.7x1.0-1.50.5-0.7x1.0-1.5 0.5x1.0-1.50.5x1.0-1.5 0.5x1.0-1.50.5x1.0-1.5 CatalaseCatalase ++ ++ ++ ++ OxidaseOxidase -- -- -- -- NO3NO3 ++ ++ ++ ++ INDIND -- -- ++ ++ ADHADH ++ -- ++ -- UREURE -- -- -- -- ESCESC -- -- ++ ++ GELGEL -- -- ++ -- PNPGPNPG ++ ++ ++ ++ GLUGLU ++ ++ -- ++ ARAARA ++ ++ -- ++ MNEMNE ++ ++ -- ++ MANMAN ++ ++ -- ++ NAGNAG ++ ++ -- ++ MALMAL ++ ++ -- ++ GNTGNT ++ ++ -- ++ CAPCAP ++ ++ -- -- ADIADI -- -- -- -- MLTMLT ++ ++ -- ++ CITCIT ++ ++ -- -- PACPAC ++ ++ -- ++ Burkholderia sp. Burkholderia sp. Burkholderia sp. Burkholderia sp. Chryseomonas sp. Chryseomonas sp. Aeromonas sp. Aeromonas sp.

Abbreviation: NO3, nitrate reduction; IND, indole production; ADH, arginine dihydrolase; URE, urease; ESC, hydrolysis esculin; GEL, hydrolysis gelatin; PNPG, β-galactosidase; GLU, D-glucose; ARA, L-arabinose; MNE, D-mannose; MAN, D-mannitol; NAG, N-acetyl-glucosamine; MAL, D-maltose; GNT, potassium gluconate; CAP, capric acid; ADI, adipic acid; MLT, malic acid; CIT, trisodium citrate; PAC, phenylacetic acid Abbreviation: NO 3, nitrate reduction; IND, indole production; ADH, arginine dihydrolase; URE, urease; ESC, hydrolysis esculin; GEL, hydrolysis gelatin; PNPG, β-galactosidase; GLU, D-glucose; ARA, L-arabinose; MNE, D-mannose; MAN, D-mannitol; NAG, N-acetyl-glucosamine; MAL, D-maltose; GNT, potassium gluconate; CAP, capric acid; ADI, adipic acid; MLT, malic acid; CIT, trisodium citrate; PAC, phenylacetic acid

본 발명에서 분리한 제지 폐수에 대하여 높은 처리 효율을 가지는 혼합 균주 Nix-37를, 경기도 수원시 권선구 서둔동 225에 소재하는 한국농업미생물자원센터 (Korean Agricultural Culture Collection: KACC)에 2006년 8월 1일자로 기탁번호 KACC 91259P로 기탁되었다. As of August 1, 2006, the mixed strain Nix-37 having high treatment efficiency with respect to the paper wastewater isolated in the present invention was obtained from the Korea Agricultural Culture Collection (KACC) located at 225, Seodun-dong, Gwon-gu, Suwon-si, Gyeonggi-do. Deposited under accession number KACC 91259P.

상기 균주의 배양을 위하여 배지는 영양 브로쓰 (Difco)을 이용하였다. 24 내지 48시간 배양된 혼합균주는 5 g/L (w/w)로 주기적으로 7일 내지 10일 간격으로 제 1 포기조에 주입시켰다. For culturing the strain, nutrient broth (Difco) was used as a medium. Mixed strains cultured for 24 to 48 hours were injected into the first aeration tank at intervals of 7 to 10 days at 5 g / L (w / w).

(4) 반응기 조건 (4) reactor conditions

반응기가 안정화된 3주후부터 용존산소 (Dissolved Oxygen: DO), 폭기조내 혼합액 부유물질량 (Mixed Liquor Suspended Solids: MLSS), 수리학적 체류 시간 (Hydraulic Retention Time: HRT), 고형물 체류 시간 (Solids Retention Time: SRT) 4가지 인자들의 다양한 변화를 통해 반응기의 제지 폐수 처리 효율을 관찰하였다. Dissolved Oxygen (DO), Mixed Liquor Suspended Solids (MLSS), Hydraulic Retention Time (HRT), and Solids Retention Time: SRT) The efficiency of paper wastewater treatment in the reactor was observed through various changes of four factors.

DO의 변화는 제 1포기조의 DO를 0.5 mg/L와 2 mg/L 차이를 주었고, 이 외의 조건은 MLSS 4000, HRT 24시간, SRT 20일 유지하였다. The change in DO gave 0.5 mg / L and 2 mg / L of DO in the first aeration vessel, and the other conditions were maintained for MLSS 4000, HRT 24 hours, and SRT 20 days.

MLSS의 변화의 경우, MLSS 3000과 MLSS 4000으로 처리효율을 확인하였고, 이 외의 조건은 HRT 24시간, SRT 20일, DO는 제 1,2 포기조 각각 2 mg/L, 3 mg/L로 유지하였다. In the case of the change of MLSS, treatment efficiency was confirmed by MLSS 3000 and MLSS 4000, and other conditions were maintained at HRT 24 hours, SRT 20 days, and DO at 2 mg / L and 3 mg / L, respectively. .

HRT는 24시간, 48시간 두 가지로 실험을 진행하였으며 다른 조건은 SRT 20일, MLSS 4000, DO는 제 1,2 포기조 각각 2 mg/L, 3 mg/L로 조정하였다. 모든 조건의 온도는 23 내지 25℃를 유지하였다.HRT was conducted in 24 hours and 48 hours, and the other conditions were adjusted to 20 mg of SRT, MLSS 4000, and DO to 2 mg / L and 3 mg / L, respectively. The temperature of all conditions was maintained at 23 to 25 ° C.

(5) 유입수 성상(5) Influent Properties

유입수의 화학적 산소 요구량 (CODMn)은 생산되는 종이의 종류에 따라 다양하였으며, 대표적인 유입수 지종과 CODMn은 표 3과 같이 나타났다. The chemical oxygen demand (COD Mn ) of the influent varied according to the type of paper produced. The representative influent species and COD Mn are shown in Table 3.

지종에 따른 유입수의 특징 (단위: mg/L) Characteristics of influent by region (Unit: mg / L) 지종 Kind CODMn COD Mn 지 종Species CODMn COD Mn 지 종Species CODMn COD Mn 지 종Species CODMn COD Mn C300,SKPC300, SKP 524.0524.0 CB,KAYCB, KAY 507.6507.6 CB,DCB, D 596.7596.7 K2K2 457.4457.4 K2,CAK2, CA 650.0650.0 C,CBC, CB 887.7887.7 CB400,DCB400, D 612.7612.7 CA,DCA, D 628.9628.9 CA,KARCA, KAR 495.0495.0 CB,KARCB, KAR 633.4633.4 YKYK 727.3727.3 SKP,DSKP, D 678.5678.5 CB,SKPCB, SKP 619.0619.0 CB,KAYCB, KAY 636.1636.1 KAY,DKAY, D 721.1721.1 CA,KAYCA, KAY 600.0600.0 CA.D250CA.D250 553.0553.0 CA,DCA, D 631.8631.8 CA,DCA, D 715.8715.8 SKP,CBSKP, CB 444.6444.6

실시예Example 2  2

(1) DO 변화에 따른 처리 효율(1) Treatment efficiency according to DO change

MLSS 4000mg/L, HRT24h, SRT 20일 유지하면서, 제 1포기조의 DO를 변화에 따른 처리 효율의 분석결과, DO를 0.5 mg/L로 유지한 결과, 유입수의 유기물질의 농도는 326.6 내지 625.8 mg/L로 평균 468.0 mg/LCODMn로써, 처리효율이 72.5 내지 85.9%로 평균 79.9%였다 (도 1a). 또한, 제 1 포기조의 DO를 2 mg/L로 유지한 결과, 유입수의 유기물질 농도는 348.5 내지 772.2 mg/L로 평균 농도는 535.2 mg/L였고, 처리효율은 80.7 내지 91.5%로 평균 처리효율 85.3%를 나타내었다 도 1b). As a result of analysis of treatment efficiency according to the change of DO in the first aeration vessel while maintaining MLSS 4000 mg / L, HRT24h, and SRT for 20 days, the concentration of organic matter in the influent was 326.6 to 625.8 mg as a result of maintaining DO at 0.5 mg / L. The average of 468.0 mg / LCOD Mn / L, the treatment efficiency was 72.5-85.9%, 79.9% of the average (Fig. 1a). In addition, as a result of maintaining DO of the first aeration tank at 2 mg / L, the organic matter concentration of the influent was 348.5 to 772.2 mg / L, the average concentration was 535.2 mg / L, and the treatment efficiency was 80.7 to 91.5%. 85.3%. Figure 1b).

2) MLSS 변화에 따른 처리 효율2) Treatment efficiency according to MLSS change

HRT 24h , SRT 20일, D.O.는 제 1포기조 2mg/L, 제 2포기조 3mg/L로 유지하면서, MLSS 3000의 경우, 유입수 농도 CODMn)는 418.0 내지 663.3 mg/L으로 평균534.4 mg/L였고, 처리효율의 분석 결과 평균 73.4%였으며, 최저 64.0 % 에서 최고 89.6%를 나타냈다. 이 경우 처리 효율은 유입수의 농도에 따라서 불안정하게 변화되는 것을 나타내고 있다 도 2a). 반면, MLSS 4000의 경우, 유입수의 농도는 316.4 내지 820.6 mg/L로 평균 농도는 554.7 mg/L였다. 처리효율은 77.5 내지 91.7%로 평균 처리효율은 83.1%로 나타났다. MLSS 4000이 MLSS 3000 보다 더 안정적이고, 뛰어난 효율을 나타내었다 도 2b). For HSS 24h, SRT 20 days, DO was maintained at 2 mg / L of the first aeration basin and 3 mg / L of the second aeration basin, for the MLSS 3000, the influent concentration COD Mn ) was 418.0 to 663.3 mg / L, averaging 534.4 mg / L. The result of analysis of the treatment efficiency was 73.4% on average, and the lowest was 64.0% and the highest was 89.6%. In this case, the treatment efficiency is unstable depending on the concentration of the influent water. On the other hand, for the MLSS 4000, the concentration of influent was 316.4 to 820.6 mg / L with an average concentration of 554.7 mg / L. The treatment efficiency was 77.5 to 91.7%, and the average treatment efficiency was 83.1%. MLSS 4000 is more stable and shows better efficiency than MLSS 3000 (FIG. 2B).

3) HRT변화에 따른 처리효율3) Treatment efficiency according to HRT change

SRT 20일, MLSS 4000mg/L, D.O.는 제 1포기조 2mg/L, 제 2포기조 3mg/L로 유지, 유기물질에 대한 처리 효율은 HRT 24시간일 때, 유입수 농도는 316.4 내지 820.6 mg/L CODMn였으며, 평균 554.7 mg/L CODmn으로 나타났으며, 처리효율은 77.5 내지 91.7%이고 평균 처리효율은 83.1%였다 도 3a.). HRT 36시간의 경우, 유입수 농도는 412.8 내지 635.9mg/L CODMn였으며, 평균 507.9 mg/L로 나타났다. 처리효율은 81.4 내지 91.5%로 평균 86.5%의 처리율을 나타내었다 도 3b). SRT 20 days, MLSS 4000mg / L, DO is maintained at 1mg of 1st basin and 2mg of 2nd basin, 3mg / L of 2nd basin, influent concentration of 316.4 to 820.6mg / L when the treatment efficiency for organic matter is 24 hours of HRT Mn , the average was 554.7 mg / L CODmn, the treatment efficiency was 77.5 to 91.7% and the average treatment efficiency was 83.1% Figure 3a.). For 36 h of HRT, the influent concentrations ranged from 412.8 to 635.9 mg / L COD Mn , with an average of 507.9 mg / L. Treatment efficiency ranged from 81.4 to 91.5% with an average rate of 86.5%.

HRT 48시간의 경우, 유입수 농도는 368.1 내지 655.9 mg/L CODMn로 평균 498.4 mg/L였다. 처리효율은 88.2 내지 93.4%로 평균 제거효율은 90.3%로 나타났다, HRT 48시간은 농도에 상관없이 안정적으로 평균 90.3% TCODMn 제거율을 보였다. HRT 48시간으로의 변화는 보다 안정적인 제거율을 나타내었다 도 3c).For 48 hours of HRT, the influent concentrations ranged from 368.1 to 655.9 mg / L COD Mn with an average of 498.4 mg / L. The treatment efficiency ranged from 88.2 to 93.4% with an average removal efficiency of 90.3%. HRT 48 hrs showed a stable 90.3% TCOD Mn removal rate regardless of the concentration. Changes to 48 hours of HRT showed a more stable removal rate (FIG. 3C).

4) SRT 변화에 따른 처리효율4) Processing efficiency due to SRT change

MLSS를 4000mg/L, HRT를 48시간, D.O.를 제1포기조 2mg/L, 제2포기조 3mg/L를 유지하며, SRT를 20일 경우, 도 4a에서와 같이 유입수 농도는 368.1 내지 655.9 mg/L CODMn로 평균 498.4 mg/L였다. 처리효율은 88.2 내지 93.4%로 평균 제거효율은 90.3%로 나타났다. SRT 30일의 경우 유입수의 농도는 401.6 내지 539.7 mg/L CODMn으로 나타났으며, 유입수 평균 농도는 444.3 mg/L였다. 처리효율은 90.1 내지 93.1%로 평균 91.7%의 제거효율을 나타내었다. SRT 20일과 30일은 모두 좋은 효율을 보여주고 있지만, SRT 30이 조금 더 안정적이고 높은 제거율을 나타내었다 도 4b).Maintain MLSS 4000mg / L, HRT 48 hours, DO 1st aeration tank 2mg / L, 2nd aeration tank 3mg / L, and SRT 20, the influent concentration is 368.1 to 655.9 mg / L as shown in Fig. 4a. The mean COD Mn was 498.4 mg / L. The treatment efficiency was 88.2 to 93.4%, and the average removal efficiency was 90.3%. For 30 days of SRT, the concentration of influent was 401.6 to 539.7 mg / L COD Mn , and the average influent was 444.3 mg / L. Treatment efficiency ranged from 90.1 to 93.1%, representing an average removal efficiency of 91.7%. Both SRT 20 and 30 showed good efficiency, but SRT 30 showed a little more stable and high removal rate (FIG. 4B).

5) 최적조건5) Optimum condition

제지 폐수 처리에 있어서 최적 조건은 도 4에서 나타내는 것과 같이 HRT를 48시간, MLSS를 4000, SRT를 30일 및 DO는 제 1,2 포기조 각각 2 mg/L와 3 mg/L이며, 이 때, 최고 93.1%의 제거효율을 보이고 방류수의 최저값이 33.5 mg/L CODmn으로 나타났다. As shown in Fig. 4, the optimum conditions for paper wastewater treatment are HRT for 48 hours, MLSS for 4000, SRT for 30 days, and DO for 2nd and 2nd aeration tanks, respectively, 2 mg / L and 3 mg / L. The maximum removal efficiency was 93.1% and the lowest value of effluent was 33.5 mg / L CODmn.

도 1은 제지 폐수를 생물학적 처리하기 위한 바이오리액터의 모식도를 나타낸다. 1 shows a schematic of a bioreactor for biological treatment of papermaking wastewater.

도 2는 유입수와 유출수 사이의 TCODMn를 (a) 제1 포기조에서 DO가 0.5mg/L (b) 제1 포기조에서 DO가 2 mg/L인 조건에서 살펴본 결과이고 (◆ : 유입수, ■ : 유출수, ▲ : 제거효율), 화살표는 종균제 투입을 의미한다.2 shows the TCOD Mn between the influent and the effluent in (a) 0.5 mg / L of DO in the first aeration tank and (b) in a condition of DO of 2 mg / L in the first aeration tank (◆: influent, ■: Runoff, ▲: removal efficiency), arrow means seed input.

도 3은 유입수와 유출수 사이에 TCODMn를 (a) HRT 24시간, (b) HRT 36시간, (c) HRT 48시간인 조건에서 각 살펴본 결과이고 (◆ : 유입수, ■ : 유출수, ▲ : 제거효율), 화살표는 종균제 투입을 의미한다.Figure 3 shows the results of the TCOD Mn between the influent and the effluent under (a) HRT 24 hours, (b) HRT 36 hours, (c) HRT 48 hours and (◆: influent, ■: effluent, ▲: removal Efficiency), arrow means seed input.

도 4는 SRT를 30일로 유지하였을 때, 유입수와 유출수 사이의 TCODmn (◆ : 유입수, ■ : 유출수, ▲ : 제거효율)를 살펴본 결과이고, 화살표는 종균제 투입을 의미한다. 4 is a result of examining the TCODmn (◆: influent, ■: effluent, ▲: removal efficiency) between the influent and the effluent when the SRT is maintained for 30 days, and the arrow indicates the seed agent input.

Claims (4)

제지 폐수를 처리하기 위한 수탁번호 KACC 91259P로 기탁된 부르크홀데리아 (Burkholderia) 2종, 크리소모나스 (Chryseomonas) 1종 및 에어로모나스 (Aeromonas) 1종으로 이루어지는 혼합 균주 Nix-37.The Burkholderia deposited as accession No. 91259P KACC for processing paper wastewater Liao (Burkholderia) 2 species, Cree consumption eggplant (Chryseomonas) 1 species and Pseudomonas aero (Aeromonas) Mixed strain Nix-37 consisting of one species. 활성 슬러지법 (activated sludge treatment process), 상향류식 혐기성 슬러지 블랭킷 (upflow anaerobic sludge blanket: USAB), AOP (advanced oxygen process)공법, 생물여과 (biological aerated filter: BAF), 살수여상법 (trickling filter process), 산화지법 (oxidation pond), 회전원판법 (rotating biological contactor)과 같은 생물학적 처리 방법을 사용하여 제지 폐수를 처리하는 방법에 있어서, Activated sludge treatment process, upflow anaerobic sludge blanket (USAB), advanced oxygen process (AOP), biological aerated filter (BAF), trickling filter process In the process of treating paper wastewater using biological treatment methods such as oxidation pond, rotating biological contactor, 상기 생물학적 처리 방법은 수탁번호 KACC 91259P로 기탁된 부르크홀데리아 (Burkholderia) 2종, 크리소모나스 (Chryseomonas) 1종 및 에어로모나스 (Aeromonas) 1종으로 이루어지는 혼합 균주 Nix-37을 사용하는 것을 특징으로 하는 제지 폐수 처리 방법.The biological treatment method is deposited as accession No. 91259P KACC Burkholderia (Burkholderia) 2 species, Cree consumption eggplant (Chryseomonas) 1 species and Pseudomonas aero (Aeromonas) The papermaking wastewater treatment method characterized by using the mixed strain Nix-37 which consists of 1 type. 제2항에 있어서, 활성 슬러지법을 이용하는 것을 특징으로 하는 방법.The method according to claim 2, wherein the activated sludge method is used. 제3항에 있어서, DO Dissolved Oxygen)를 2 내지 3 mg/L, MLSS Mixed Liquor Suspended Solid)를 3,000 내지 4,000 mg/L, HRT Hydraulic Retention Time)를 24 내지 48 시간, SRT Solids Retention Time)를 20 내지 30일 동안 유지함을 특징으로 하는 방법.According to claim 3, DO Dissolved Oxygen) 2 to 3 mg / L, MLSS Mixed Liquor Suspended Solid) 3,000 to 4,000 mg / L, HRT Hydraulic Retention Time (24 to 48 hours), SRT Solids Retention Time (20) Retaining for 30 to 30 days.
KR1020070076720A 2007-07-31 2007-07-31 Biological treatment of paper mill wastewater KR100905487B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020070076720A KR100905487B1 (en) 2007-07-31 2007-07-31 Biological treatment of paper mill wastewater

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020070076720A KR100905487B1 (en) 2007-07-31 2007-07-31 Biological treatment of paper mill wastewater

Publications (2)

Publication Number Publication Date
KR20090012688A KR20090012688A (en) 2009-02-04
KR100905487B1 true KR100905487B1 (en) 2009-07-01

Family

ID=40683417

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020070076720A KR100905487B1 (en) 2007-07-31 2007-07-31 Biological treatment of paper mill wastewater

Country Status (1)

Country Link
KR (1) KR100905487B1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000028528A (en) * 1998-10-31 2000-05-25 손경식 Biological treatment method of organic wastewater
KR20000028524A (en) * 1998-10-31 2000-05-25 손경식 Biological treatment method of wastewater including cellulose
KR20000063394A (en) * 2000-07-05 2000-11-06 구영환 Bacillus sp., poly saccharide producing therefrom and wastewater treatment method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000028528A (en) * 1998-10-31 2000-05-25 손경식 Biological treatment method of organic wastewater
KR20000028524A (en) * 1998-10-31 2000-05-25 손경식 Biological treatment method of wastewater including cellulose
KR20000063394A (en) * 2000-07-05 2000-11-06 구영환 Bacillus sp., poly saccharide producing therefrom and wastewater treatment method

Also Published As

Publication number Publication date
KR20090012688A (en) 2009-02-04

Similar Documents

Publication Publication Date Title
CA2682864C (en) The treatment of wastewater with fungi
Tsang et al. Optimization of biological treatment of paper mill effluent in a sequencing batch reactor
Tondee et al. Decolorization of molasses wastewater by yeast strain, Issatchenkia orientalis No. SF9-246
Nielsen et al. Control of Microthrix parvicella in activated sludge plants by dosage of polyaluminium salts: possible mechanisms
Cillie et al. Anaerobic digestion—IV. The application of the process in waste purification
US6780317B1 (en) Method of purifying water, suitable bacteria for the method and use thereof
CN109502745A (en) A method of quickly taming the microorganism of degradable 2,4,6- trichlorophenol
JP3836338B2 (en) Novel microorganisms and oil-containing wastewater treatment equipment using the same
KR20190023073A (en) Preparation of liner board and treatment of cellulosic waste water sludge for cellulose ethanol production
US20210380452A1 (en) Method for treatment and resource utilization of acidic organic wastewater
Khelifi et al. Enhancement of textile wastewater decolourization and biodegradation by isolated bacterial and fungal strains
KR100905487B1 (en) Biological treatment of paper mill wastewater
CN114538711A (en) Microbial degradation treatment method for Maotai-flavor liquor wastewater
JP3816357B2 (en) Novel microorganisms and organic wastewater treatment equipment using the same
Jain et al. Isolation, screening and identification of bacterial strains for degradation of predigested distillery wastewater
CN111977893A (en) Biochemical treatment method for wastewater generated in production of hydrogen peroxide by anthraquinone process based on composite microbial inoculum
CN1098070A (en) Method with photosynthetic bacterial treatment paper waste
JPH10165983A (en) Treatment of waste water
CN101830605B (en) Biochemical pharmaceutical wastewater treatment process
JP3691102B2 (en) Wastewater treatment method
JP3062121B2 (en) Formaldehyde decomposition method
CN115108629B (en) Advanced sewage treatment method and system
CN112813004B (en) Ultraviolet-resistant and antioxidant immobile bacterium and application thereof
JPH06106186A (en) Treatment of waste liquid produced by shochu distilling
JP4142410B2 (en) Wastewater treatment method

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20120525

Year of fee payment: 4

FPAY Annual fee payment

Payment date: 20130611

Year of fee payment: 5

LAPS Lapse due to unpaid annual fee