WO2014012201A1 - Method for removing total nitrogen during treatment of coking wastewater by using microorganisms - Google Patents

Method for removing total nitrogen during treatment of coking wastewater by using microorganisms Download PDF

Info

Publication number
WO2014012201A1
WO2014012201A1 PCT/CN2012/078665 CN2012078665W WO2014012201A1 WO 2014012201 A1 WO2014012201 A1 WO 2014012201A1 CN 2012078665 W CN2012078665 W CN 2012078665W WO 2014012201 A1 WO2014012201 A1 WO 2014012201A1
Authority
WO
WIPO (PCT)
Prior art keywords
phi phi
tank
pool
bacillus
aerobic
Prior art date
Application number
PCT/CN2012/078665
Other languages
French (fr)
Chinese (zh)
Inventor
凌亮
Original Assignee
Ling Liang
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 Ling Liang filed Critical Ling Liang
Priority to PCT/CN2012/078665 priority Critical patent/WO2014012201A1/en
Publication of WO2014012201A1 publication Critical patent/WO2014012201A1/en

Links

Classifications

    • 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
    • C02F3/28—Anaerobic digestion processes
    • C02F3/2806—Anaerobic processes using solid supports for microorganisms
    • 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
    • C02F3/30—Aerobic and anaerobic processes
    • 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
    • C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds

Definitions

  • the present invention relates to the field of biochemical environmental protection technology, and mainly relates to a method for treating dehydrogenation of coking wastewater by using microorganisms.
  • Coking wastewater is produced in the process of high-temperature coking, gas purification and chemical product refining of coal, and its composition and properties are closely related to the raw coal quality, carbonization temperature, production process and chemical product recovery methods.
  • the water quality of the steamed ammonia wastewater in the general coking plant is as follows: COD Cr 2000 7000 mg/L, phenol 100-900 mg/L, cyanide 10 ⁇ 50 mg/L, oil 50-200 mg/L, ammonia nitrogen 100-700 mg/L.
  • the coking wastewater mainly comes from the residual ammonia water waste liquid produced by high temperature cracking of coal and cooling of waste gas.
  • the water quality is complex, the variety of components is various, and the concentration of pollutants is high.
  • the remaining ammonia water accounts for 10 ⁇ 14% of the coking coal content (combined with coal water 8-10%, combined water 2-4%), and the remaining ammonia water is the main source of phenol wastewater in small coking plants.
  • Phenolic compounds are prototype poisons that are toxic to all organisms. It can chemically react through human skin and mucous membrane contact to form insoluble proteins, which can make cells lose vitality. The high concentration of phenol solution can also coagulate proteins; phenol can also damage and necrosis of deep tissues until systemic poisoning. Drinking phenol-contaminated water for a long time can cause dizziness, anemia, and various neurological disorders. Water bodies are contaminated with phenol-containing sewage and have serious adverse consequences. Because the oxygen consumption of phenol wastewater is high, the balance of oxygen in the water is destroyed. When the water contains phenol 0.0002 ⁇ 0.015mg/L, chlorination will produce phenol odor and cannot be used as drinking water. The water contains phenol l ⁇ 0.2mg.
  • Nitrogen mainly includes organic nitrogen, ammonia nitrogen, nitrite nitrogen and nitrate nitrogen.
  • Organic nitrogen is an indicator of the total amount of nitrogen-containing organic matter such as protein, amino acids and urea in water.
  • the hazards of nitrogen in water bodies are mainly caused by the eutrophication of water bodies, the difficulty of treatment of water supply, the consumption of oxygen in water bodies, and the toxic effects on humans and organisms, including direct factors and predisposing factors.
  • Cyanide can enter the human body through the skin, respiratory tract or digestive tract, and then quickly decomposes free cyanine by binding to metal ions such as iron, copper and molybdenum in various intracellular respiratory enzymes, resulting in inactivation of the enzyme, resulting in cells not being able to
  • the use of oxygen, resulting in intracellular asphyxia, causing coma or severe respiratory depression may be sudden death.
  • the pollution control of coking wastewater at this stage has always been a major problem in the control of industrial wastewater pollution.
  • the biological treatment method is still the main wastewater treatment method adopted by most coking plants.
  • the main methods are the traditional A/0 (anoxic/aerobic) process as shown in Figure 1 and the A 2 /0 (analogous) shown in Figure 2.
  • Oxygen/anoxic/aerobic process For the A 2 /0 process, its biggest feature is the introduction of anaerobic pretreatment, the use of anaerobic hydrolysis acidification to change the composition and biodegradability of organic matter in coking wastewater, and the conversion of biodegradable organic matter in coking wastewater into Some organic matter that is easily biodegradable, which improves the processing capacity and efficiency of the entire system.
  • the main problem faced by the coking plant currently treating the coking wastewater with the A 2 /0 activated sludge process is that the activated sludge itself is difficult to adapt to the large changes in the quality of the coking wastewater, and the ability to withstand shock loads is poor; Because the biooxidation of microorganisms in the aerobic section and the biological nitrification are difficult to play their respective roles, the concentration of COD and H 3 -N in the effluent is difficult to reach the standard at the same time.
  • the object of the present invention is to provide a method for treating dehydrogenation of coking wastewater by using microorganisms, so as to solve the technical problem that the concentration of COD and H 3 -N in the effluent is difficult to reach the standard at the same time.
  • a method for treating dehydrogenation of coking wastewater by using microorganisms wherein the wastewater sequentially enters a regulating tank, a hydrolysis acidification tank, a first aerobic tank, a primary sedimentation tank, a facultative oxygen tank, a second aerobic tank and a secondary settling tank, and finally reaches the standard discharge
  • the characteristics are: the hydrolysis acidification tank, the first aerobic pool, the primary sedimentation tank constitute the first stage A/0 system; the facultative oxygen tank, the second aerobic tank and the second settling tank constitute the second stage A/0 system, two
  • the segment A/0 system constitutes two independent sludge systems; and in each of the hydrolysis acidification tank, the first aerobic tank, the anaerobic tank, and the second aerobic tank, microbial carriers each having a volume of 1.0% to 2.5% are added and 1.5 % ⁇ 4.0% of environmental microbial preparations.
  • the pH of the hydrolysis acidification tank is controlled by 7 ⁇ 9, DO (dissolved oxygen) ⁇ 0.2mg/L, MLVSS (effective sludge concentration) is 3 ⁇ 6g/L; the first aerobic pool water temperature is controlled at 25 ⁇ 35 ° C, pH control 6.8 ⁇ 7.2, DO ⁇ 2 ⁇ 4mg / L.
  • the water temperature of the anaerobic pool is controlled at 25 to 35 ° C
  • the pH is controlled by 6 to 9
  • the water temperature of the second aerobic pool is controlled at 25 to 35 ° C
  • the pH is controlled by 6.8 to 7.2. , DO ⁇ 2 ⁇ 4mg/L.
  • the primary settling tank is provided with a sludge return pipe to the hydrolysis acidification tank
  • the second settling tank is provided with a sludge return pipe to the anaerobic tank, and the reflux ratio is 1:1 ⁇ 2
  • the first aerobic tank outlet is provided with nitrification liquid reflux
  • the pipeline is connected to the water inlet of the hydrolysis acidification tank
  • the outlet of the second aerobic tank is provided with a nitrification liquid return pipe to the inlet of the anaerobic tank, and the reflux ratio is 1:2-8.
  • the microbial carrier is a powdered activated carbon.
  • the environmental microbial preparation is composed of the following 89 microorganisms:
  • Bacillus algalophilus Bacillus alcalophilus
  • Bacillus sp. Brevibscillus brevis Bacillus sp. Brevibscillus brevis
  • Lactobacillus bervis Lactobacillus bervis
  • Micrococcus lentus Micrococcus lentus
  • Paenibacillus gluconolyticus genus Bacillus, Paenibacillus thiaminlyticus, Nitrobacter winogradskyi
  • Bacteroides cellulosovens Bacteroides stercoris
  • Ilyobacter ploytropus rumen Pseudobutyrivibrio mminis Syntrophomonas wolgei simple famelobacter simplex feimelobacter simplex famelobacter tumescens Brachybacterium faecium Jones Jonesia denitrificans Raubacter faecitabidus
  • Rhodobacter xylanophilus Rhodobacter xylanophilus Rarobacter xylanophilum.
  • the invention provides a two-stage A/O system.
  • a first aerobic tank is arranged after the hydrolysis acidification tank, and the aerobic nitrification reaction of the first aerobic tank converts the ammonia nitrogen in the wastewater into Nitro nitrogen.
  • a primary sedimentation tank is set, and the sludge of the primary sedimentation tank is returned to the water inlet of the hydrolysis acidification tank, and the outlet of the first aerobic tank is provided with a nitrification return pipe to the water inlet of the hydrolysis acidification tank, and the first aerobic tank is The produced nitro nitrogen is brought to the hydrolysis acidification tank, and the nitro nitrogen is subjected to denitrification reaction in the hydrolysis acidification tank.
  • the nitro nitrogen brought back and the ammonia nitrogen in the wastewater undergo anaerobic ammonium oxidation reaction, and the nitro nitrogen and ammonia nitrogen are directly reacted to complete the denitrification.
  • the treated wastewater is sent to the second section of the A/0 system for further biochemical treatment of the pollutants in the wastewater.
  • the anaerobic tank continues to denitrify the total nitrogen remaining in the effluent from the first stage A/0 system, further removing total nitrogen, and achieving efficient removal of nitrogen in the system, Nitrification requires a large amount of carbon source. In order to ensure sufficient supply of carbon in the reaction, there will be some carbon source excess at this stage. Therefore, the aeration unit is added at the end of the system to remove excess COD, and finally achieve the compliance of pollutants such as C0D and total nitrogen. emission. At this stage, the denitrification reaction is used to greatly reduce the sludge reflux ratio, thereby reducing the energy consumption of the system.
  • the entire system of the present invention is shared by the two sections of sludge before and after, and the operating efficiency and the risk resistance coefficient of the overall system are improved.
  • the two-stage A/0 treatment system can significantly reduce the energy consumption of removing total nitrogen, and the double sludge process is more resistant to impact.
  • the first stage A/0 system bears the main load, and the second stage A/0 system has less influence on the nitrogen-removing microorganisms, so that the whole system will not be thrown off and cause an accident; on the other hand,
  • the dual sludge system also allows microorganisms to perform their maximum contaminant degradation in their respective environments.
  • the microbial carrier added in the present invention is a powdery activated carbon, which has the characteristics of stable property, fast mass transfer, large specific area, easy acquisition and high strength.
  • the environmental treatment microbial preparation used in the invention has an efficient treatment effect on high COD and high ammonia nitrogen wastewater under the two-stage A/0 process.
  • the microbial preparation group has a complete decomposition chain, the substrate is completely decomposed, and the sludge production is only one tenth of the conventional activated sludge, so that the sludge production and sludge disposal cost can be greatly reduced.
  • the microbial preparation combined with the special microbial carrier is a one-time dosing, has the characteristics of strong adaptability, and can be operated for a long time without additional addition.
  • the invention has simple process flow, adopts two-stage A/0 process and environmental treatment microbial technology, and is applicable to a wide range of water quality, reduces construction cost, improves processing capacity, and does not directly add dilution water during the whole process, and directly performs raw water. Treatment, reducing water consumption and total emissions.
  • the wastewater treatment process of the treatment of total nitrogen in coking wastewater by the combination of two A/0 and environmental treatment microbial technology is better than the existing A/0 and A 2 /0 processes.
  • the ammonia nitrogen of the coking wastewater can be controlled below 15 mg/L
  • the COD can be controlled below 100 mg/L
  • other indicators can also reach the national first-class discharge standard.
  • the method for treating high-concentration nitrogen wastewater by using microorganisms disclosed in the invention is also applicable to refractory production wastewater such as pharmaceutical wastewater, fermentation wastewater, food enterprise wastewater, and can also be used for treatment of municipal wastewater and domestic sewage. . BRIEF DESCRIPTION OF THE DRAWINGS Embodiments of the invention are described in detail below with reference to the drawings.
  • Figure 1 is a schematic diagram of a conventional A/0 water treatment process.
  • Figure 2 is a schematic diagram of a conventional A70 water treatment process.
  • FIG. 3 is a schematic diagram of a process flow according to an embodiment of the present invention.
  • A Waste water
  • B sludge return
  • C nitration reflux
  • D HL-003 environmental microbial preparation and activated carbon.
  • the water treatment system of the present embodiment is spatially composed of eight main units: a gas floating pool, a regulating tank, a hydrolysis acidification tank, a first aerobic tank, a primary settling tank, a facultative oxygen tank, a second aerobic tank and a secondary settling tank.
  • the primary settling tank is provided with a sludge return pipe to the hydrolysis acidification tank
  • the first aerobic tank outlet is provided with a nitrifying liquid return pipe to the water inlet of the hydrolysis acidification tank
  • the second settling tank is provided with a sludge return pipe to the anaerobic tank
  • the second aerobic The tank outlet is provided with a nitrifying liquid return line to the hydration tank inlet.
  • the effluent is sent to the hydrolysis acidification tank, and 1.0% ⁇ 2.5% (by volume) of activated carbon and 1.5% ⁇ 4.0% (volume%) of HL-003 environmental microbial preparation are combined in the effluent by micro-stirring.
  • nitrate nitrogen degrades some harmful substances in sewage and improves the biodegradability of sewage.
  • the parameters of the hydrolysis acidification tank are controlled to pH control 7 ⁇ 9, DO (dissolved oxygen) ⁇ 0.2mg/L, MLVSS (effective sludge concentration) is 3 ⁇ 6g/L, and the sewage in the pool is stirred and mixed by mixing equipment to prevent Suspended solids in the water are deposited at the bottom of the pool.
  • DO dissolved oxygen
  • MLVSS effective sludge concentration
  • the effluent from the hydrolysis acidification tank enters the first aerobic tank for nitrification reaction.
  • the water temperature of the first aerobic tank is controlled at 25-35 °C, the pH is controlled by 6.8 ⁇ 7.2, and DO ⁇ 2 ⁇ 4mg/L.
  • the first aerobic tank effluent enters the primary sedimentation tank for sludge water separation, and the sludge is returned to the hydrolysis acidification tank, and the sludge reflux ratio is 1:1 ⁇ 2; the upper layer water is nitrification liquid, and is refluxed to the hydrolysis acidification tank, and the nitrification liquid reflux ratio is 1: 2 ⁇ 8.
  • the effluent from the first stage A/0 biochemical system flows to the anaerobic tank.
  • the parameters of the facultative tank are controlled by water temperature of 25-35 °C, pH control of 6 ⁇ 9, DO ⁇ 0.5mg/L.
  • the organic matter in the influent is used as the carbon source and energy for denitrification (to ensure the sufficient carbon source, supplement the carbon source), and the nitrate nitrogen in the nitrifying reflux liquid is used as the denitrifying nitrogen source, and 1.0 is added in the pool.
  • the denitrification and denitrification reaction is carried out under the action of the above reaction sources, so that the pollutants such as H 3 -N in the wastewater are removed and degraded, and the treated effluent flows into the second aerobic Pool.
  • the excess COD in the anaerobic tank is completely removed and degraded by aeration.
  • the water temperature of the second aerobic tank is controlled at 25 ⁇ 35 °C, the pH is controlled by 6.8 ⁇ 7.2, DO ⁇ 2 ⁇ 4mg/L. .
  • the treated effluent flows into the secondary settling tank.
  • the second settling tank completes the separation of the muddy water, and most of the sludge is returned to the anaerobic tank through the sludge returning pipeline as needed, and the surplus sludge is discharged according to the needs and actual operating conditions, and the upper layer of water is discharged to the standard.
  • the effluent quality after treatment in this example is significantly better than the conventional A/0, A 2 /0 process, and the effluent water quality index meets or exceeds the national standard.

Abstract

A method for removing total nitrogen during treatment of coking wastewater by using microorganisms. Wastewater (A) enters a regulation pool, a hydrolysis acidification pool, a first aerobic pool, a preliminary sedimentation pool, a facultative pool, a second aerobic pool and a secondary sedimentation pool, and is finally discharged after meeting standard requirements. The hydrolysis acidification pool, the first aerobic pool and the preliminary sedimentation pool form a first-stage A/O system. The facultative pool, the second aerobic pool and the secondary sedimentation pool form a second-stage A/O system. The first-stage and second-stage A/O systems form two independent sludge systems. In addition, the hydrolysis acidification pool, the first aerobic pool, the facultative pool and the second aerobic pool are respectively added with 1.0% to 2.5% of microbial carriers and 1.5% to 4.0% of environmental microorganism preparations based on their respective volumes.

Description

一种利用微生物处理焦化废水脱总氮的方法 技术领域 本发明属于生化环保技术领域， 主要是涉及了一种利用微生物处理焦化废水 脱总氮的方法。 背景技术 焦化废水是在煤的高温干熘、煤气净化及化工产品精制过程中产生的，其组 成和性质与原煤煤质、 碳化温度、 生产工艺以及化工产品回收方法等密切相关。 一般焦化厂的蒸氨废水水质如下： CODCr 2000 7000 mg/L、 酚 100~900mg/L、 氰 10~50mg/L、 油 50~200mg/L、 氨氮 100~700mg/L左右。 焦化废水的主要来源于 煤高温裂解和荒煤气冷却产生的剩余氨水废液， 其水质复杂， 组分种类繁多， 且 污染物浓度较高。有炼焦配合煤水分及炼焦生成的化合水， 以及焦炉上升管， 集 气管喷射的蒸汽和冷凝工段清扫管道的蒸汽所组成。一般情况下，剩余氨水占炼 焦配合煤量的 10~14% (配合煤水分 8~10%， 化合水 2~4% )， 剩余氨水是小型 焦化厂含酚废水的主要来源。 FIELD OF THE INVENTION The present invention relates to the field of biochemical environmental protection technology, and mainly relates to a method for treating dehydrogenation of coking wastewater by using microorganisms. BACKGROUND OF THE INVENTION Coking wastewater is produced in the process of high-temperature coking, gas purification and chemical product refining of coal, and its composition and properties are closely related to the raw coal quality, carbonization temperature, production process and chemical product recovery methods. The water quality of the steamed ammonia wastewater in the general coking plant is as follows: COD Cr 2000 7000 mg/L, phenol 100-900 mg/L, cyanide 10~50 mg/L, oil 50-200 mg/L, ammonia nitrogen 100-700 mg/L. The coking wastewater mainly comes from the residual ammonia water waste liquid produced by high temperature cracking of coal and cooling of waste gas. The water quality is complex, the variety of components is various, and the concentration of pollutants is high. There is coking coal with coal moisture and coking, and coke oven riser, steam from the gas collection pipe and steam from the condensation section. Under normal circumstances, the remaining ammonia water accounts for 10~14% of the coking coal content (combined with coal water 8-10%, combined water 2-4%), and the remaining ammonia water is the main source of phenol wastewater in small coking plants.
酚类化合物是原型毒物， 对一切生物都有毒害作用。 其可以通过人的皮肤、 粘膜接触发生化学反应， 形成不溶性的蛋白质， 而使细胞失去活力； 质量浓度高 的酚溶液还会使蛋白质凝固； 酚还能使深部组织损伤、 坏死， 直至全身中毒。 长 期饮用被酚污染过的水会引起头暈、贫血以及各种神经系统病症。水体受含酚污 水污染后会产生严重的不良后果。因为酚废水耗氧量高，水体中氧的平衡被破坏， 水中含酚 0.0002~0.015mg/L时，加氯消毒就会产生氯酚恶臭，不能作为饮用水； 水体中含酚 l~0.2mg/L 时， 鱼类有酚味， 浓度高时引起鱼类大量死亡。 废水中 的氨氮消耗收纳水体中的氧，氧化 lg H3-N需要耗氧 4.57g，致使水中的溶解氧 急剧下降， 出现亏氧， 使水质变差， 造成恶臭。 用未经处理的含酚废水 ( 100~75mg/L) 直接灌溉农田， 会使农作物减产甚至枯死。 氮类主要包括有机 氮、 氨氮、 亚硝酸氮和硝酸氮。 有机氮是反映水中蛋白质、 氨基酸、 尿素等含氮 有机物总量的一个指标。氮素在水体中的危害， 主要表现在造成水体的富营养化 现象， 增加给水处理的困难， 消耗水体的氧气， 对人及生物具有毒害作用， 其中 包括直接因素和诱发因素。氰化物可以通过皮肤、 呼吸道或消化道进入人体， 然 后迅速的分解出游离的氰通过与各种细胞内呼吸酶中的铁、铜、钼等金属离子结 合， 导致该酶失活， 致使细胞不能利用氧， 从而产生细胞内窒息， 使人昏迷或呼 吸抑制严重者可能骤死。 现阶段焦化废水的污染控制一直是工业废水污染控制的重大难题。生物处理 法目前仍是大多数焦化厂采用的主要的废水处理方法，主要方法有如图 1所示的 传统 A/0(缺氧 /好氧)工艺以及图 2所示的 A2/0(厌氧 /缺氧 /好氧)工艺。对于 A2/0 工艺而言，其最大的特点是引进了厌氧预处理，利用厌氧水解酸化改变焦化废水 中的有机物的组成和可生化性，将焦化废水中难以生物降解的有机物转化为一些 易于生物降解的有机物， 从而提高了整个系统的处理能力和效率。 但目前采用 A2/0 活性污泥法工艺处理焦化废水的焦化厂面临的主要问题是通常的活性污泥 本身难以适应焦化废水水质变化大的特点， 耐受冲击负荷能力差； 另一方面也是 因为好氧段中微生物的生物氧化作用与生物硝化作用难于同时发挥各自的作用， 导致出水 COD和 H3-N浓度很难同时达标。 发明内容 本发明的目的是提供一种利用微生物处理焦化废水脱总氮的方法，以解决出 水 COD和 H3-N浓度很难同时达标的技术难题。 为此， 本发明所采用的技术方案如下： 一种利用微生物处理焦化废水脱总氮的方法， 废水依次进入调节池、水解酸 化池、 第一好氧池、 初沉池、 兼氧池、 第二好氧池和二沉池， 最终达标排出； 其 特征在于： 水解酸化池、第一好氧池、初沉池组成第一阶段 A/0系统； 兼氧池、 第二好氧池和二沉池组成第二阶段 A/0系统， 两段 A/0系统构成两个独立的污 泥系统； 并且分别于水解酸化池、 第一好氧池、 兼氧池、 第二好氧池中加入各自 体积 1.0%~2.5%的微生物载体以及 1.5%~4.0%的环境微生物制剂。 Phenolic compounds are prototype poisons that are toxic to all organisms. It can chemically react through human skin and mucous membrane contact to form insoluble proteins, which can make cells lose vitality. The high concentration of phenol solution can also coagulate proteins; phenol can also damage and necrosis of deep tissues until systemic poisoning. Drinking phenol-contaminated water for a long time can cause dizziness, anemia, and various neurological disorders. Water bodies are contaminated with phenol-containing sewage and have serious adverse consequences. Because the oxygen consumption of phenol wastewater is high, the balance of oxygen in the water is destroyed. When the water contains phenol 0.0002~0.015mg/L, chlorination will produce phenol odor and cannot be used as drinking water. The water contains phenol l~0.2mg. At /L, fish have a phenolic taste, causing a large number of fish to die when the concentration is high. Waste water The ammonia nitrogen consumption stores oxygen in the water body, and oxidizing lg H 3 -N requires oxygen consumption of 4.57 g, causing the dissolved oxygen in the water to drop sharply, causing oxygen deficiency, which deteriorates the water quality and causes foul odor. Direct irrigation of farmland with untreated phenol-containing wastewater (100-75 mg/L) will result in reduced or even dead crops. Nitrogen mainly includes organic nitrogen, ammonia nitrogen, nitrite nitrogen and nitrate nitrogen. Organic nitrogen is an indicator of the total amount of nitrogen-containing organic matter such as protein, amino acids and urea in water. The hazards of nitrogen in water bodies are mainly caused by the eutrophication of water bodies, the difficulty of treatment of water supply, the consumption of oxygen in water bodies, and the toxic effects on humans and organisms, including direct factors and predisposing factors. Cyanide can enter the human body through the skin, respiratory tract or digestive tract, and then quickly decomposes free cyanine by binding to metal ions such as iron, copper and molybdenum in various intracellular respiratory enzymes, resulting in inactivation of the enzyme, resulting in cells not being able to The use of oxygen, resulting in intracellular asphyxia, causing coma or severe respiratory depression may be sudden death. The pollution control of coking wastewater at this stage has always been a major problem in the control of industrial wastewater pollution. The biological treatment method is still the main wastewater treatment method adopted by most coking plants. The main methods are the traditional A/0 (anoxic/aerobic) process as shown in Figure 1 and the A 2 /0 (analogous) shown in Figure 2. Oxygen/anoxic/aerobic process. For the A 2 /0 process, its biggest feature is the introduction of anaerobic pretreatment, the use of anaerobic hydrolysis acidification to change the composition and biodegradability of organic matter in coking wastewater, and the conversion of biodegradable organic matter in coking wastewater into Some organic matter that is easily biodegradable, which improves the processing capacity and efficiency of the entire system. However, the main problem faced by the coking plant currently treating the coking wastewater with the A 2 /0 activated sludge process is that the activated sludge itself is difficult to adapt to the large changes in the quality of the coking wastewater, and the ability to withstand shock loads is poor; Because the biooxidation of microorganisms in the aerobic section and the biological nitrification are difficult to play their respective roles, the concentration of COD and H 3 -N in the effluent is difficult to reach the standard at the same time. SUMMARY OF THE INVENTION The object of the present invention is to provide a method for treating dehydrogenation of coking wastewater by using microorganisms, so as to solve the technical problem that the concentration of COD and H 3 -N in the effluent is difficult to reach the standard at the same time. To this end, the technical solutions adopted by the present invention are as follows: A method for treating dehydrogenation of coking wastewater by using microorganisms, wherein the wastewater sequentially enters a regulating tank, a hydrolysis acidification tank, a first aerobic tank, a primary sedimentation tank, a facultative oxygen tank, a second aerobic tank and a secondary settling tank, and finally reaches the standard discharge The characteristics are: the hydrolysis acidification tank, the first aerobic pool, the primary sedimentation tank constitute the first stage A/0 system; the facultative oxygen tank, the second aerobic tank and the second settling tank constitute the second stage A/0 system, two The segment A/0 system constitutes two independent sludge systems; and in each of the hydrolysis acidification tank, the first aerobic tank, the anaerobic tank, and the second aerobic tank, microbial carriers each having a volume of 1.0% to 2.5% are added and 1.5 %~4.0% of environmental microbial preparations.
更进一步地，所述水解酸化池 pH控制 7~9， DO (溶解氧） <0.2mg/L， MLVSS (有效污泥浓度）在 3~6g/L;第一好氧池水温控制在 25~35°C， pH控制 6.8~7.2， DO<2~4mg/L。  Further, the pH of the hydrolysis acidification tank is controlled by 7~9, DO (dissolved oxygen) <0.2mg/L, MLVSS (effective sludge concentration) is 3~6g/L; the first aerobic pool water temperature is controlled at 25~ 35 ° C, pH control 6.8 ~ 7.2, DO < 2 ~ 4mg / L.
更进一步地，所述兼氧池水温控制在 25~35°C， pH控制 6~9， DO<0.5mg/L; 第二好氧池水温控制在 25~35°C， pH控制 6.8~7.2， DO<2~4mg/L。 Further, the water temperature of the anaerobic pool is controlled at 25 to 35 ° C, the pH is controlled by 6 to 9, DO < 0.5 mg / L ; the water temperature of the second aerobic pool is controlled at 25 to 35 ° C, and the pH is controlled by 6.8 to 7.2. , DO<2~4mg/L.
更进一步地， 初沉池设置污泥回流管道至水解酸化池， 二沉池设置污泥回流 管道至兼氧池， 回流比为 1 : 1~2； 第一好氧池出水口设置硝化液回流管道至水解 酸化池进水口； 第二好氧池出水口设置硝化液回流管道至兼氧池进水口， 回流比 为 1 :2~8。  Further, the primary settling tank is provided with a sludge return pipe to the hydrolysis acidification tank, and the second settling tank is provided with a sludge return pipe to the anaerobic tank, and the reflux ratio is 1:1~2; the first aerobic tank outlet is provided with nitrification liquid reflux The pipeline is connected to the water inlet of the hydrolysis acidification tank; the outlet of the second aerobic tank is provided with a nitrification liquid return pipe to the inlet of the anaerobic tank, and the reflux ratio is 1:2-8.
更进一步地， 所述的微生物载体是粉末状活性炭。  Further, the microbial carrier is a powdered activated carbon.
更进一步地， 所述的环境微生物制剂由以下 89种微生物组成：  Further, the environmental microbial preparation is composed of the following 89 microorganisms:
醋酸醋杆菌 Acetobacter aceti  Acetobacter aceti
液化醋杆菌 Acetobacter Liquefaciens  Acetobacter Liquefaciens
木醋杆菌 Acetobacter xylinus  Acetobacter xylinus
干燥无色菌 Achromobacter xerosis  Dry colorless bacteria Achromobacter xerosis
嗜水气单胞菌 Aeromenans hydrophila  Aeromonas hydrophila
巾间气单胞菌 Aeromenans media  Aeromonas media
温禾口气单胞菌 Aeromenans sobria 分子芽孢杆菌 Bacillus alvei Aeromonas sobria Bacillus alcei
凝结芽孢杆菌 Bacillus coagulans Bacillus coagulans
枯草芽孢杆菌 Bacillus subtilis Bacillus subtilis
迟缓芽孢杆菌 Bacillus leutis Bacillus leutis
坚强芽孢杆菌 Bacillus firmus Bacillus firmus
状芽孢杆菌 Bacillus mycides Bacillus mycides
巨大芽孢杆菌 Bacillus megaterium Bacillus megaterium
嗜碱芽孢杆菌 Bacillus alcalophilus Bacillus algalophilus Bacillus alcalophilus
地衣芽孢杆菌 Bacillus licheniformis 球形芽孢杆菌 Bacillus spaericus Bacillus licheniformis Bacillus spaericus
海洋芽孢杆菌 Bacillus marinus Bacillus marinus
反石肖化亚种 Alcaligenes denitrigicans 粪产碱菌 Alcaligenes faecalis Anti-Stone Shark Alcaligenes denitrigicans Alcaligenes faecalis
木糖氧化产碱菌 Alcaligenes xylososydans 角牟氨短杆菌 Brevibacterium ammoniagenes 乳酸短杆菌 Brevibacterium casei Xylose oxidizing Alcaligenes Alcaligenes xylososydans Brevibacterium ammoniagenes Brevibacterium casei Brevibacterium casei
短短芽孢菌 Brevibscillus brevis Bacillus sp. Brevibscillus brevis
产气肠杆菌 Enterobacter aerogenes 成团肠杆菌 Thiobacillus agglomerans 反硝化硫杆菌 Thiobacillus denitrificans 氧化硫杆菌 Thiobacillus thiooxidans 硫红球菌 Thiorhodococcus minus Enterobacter aerogenes Enterobacter aerogenes Enterobacter aeruginosa Thiobacillus agglomerans Thiobacillus denitrificans Thiobacillus thiooxidans Thiorhodococcus Thiorhodococcus minus
沼泽红假单胞菌 Rhodopseudomonas palustris 嗜酸红假单胞菌 Rhodopseudomonas acidphia 浅井氏葡萄杆菌 Gluconobacter albidus Rhodopseudomonas palustris Rhodopseudomonas acidphia Gluconobacter albidus
葡萄氧化杆菌 Gluconobacter oxydans Gluconobacter oxydans
发酵乳杆菌 Lactobacillus fermentum Lactobacillus fermentum
植物乳杆菌 Lactobacillus plantarum Lactobacillus plantarum
石肖化乳杆菌 Lactobacillus alimentarius Lactobacillus alimentarius
食淀粉乳杆菌 Lactobacillus amylophillus 瘤胃乳杆菌 Lactobacillus ruminis Lactobacillus amylophilus Lactobacillus ruminis
短乳杆菌 Lactobacillus bervis Lactobacillus bervis
藤黄微球菌 Micrococcus lentus Micrococcus lentus Micrococcus lentus
喜盐微球菌 Micrococcus halobius Micrococcus halobius
产碱假单胞菌 Pseudomonas alcaligenes 致黄色假单胞菌 Pseudomonas aureofaciens 绿针假单胞菌 Pseudomonas chlororaphis 石肖化假单胞菌 Pseudomonas nitroreducens 核黄素假单胞菌 Pseudomonas riboflavina 恶臭假单胞菌 Pseudomonas putina Pseudomonas alcaligenes Pseudomonas aureofaciens Pseudomonas aureofaciens Pseudomonas chlororaphis Pseudomonas nitroreducens Pseudomonas riboflavina Pseudomonas putina Pseudomonas putina
敏捷假单胞菌 Pseudomonas facilis Pseudomonas facilis
角旱葡聚糖类芽孢杆菌 Paenibacillus gluconolyticus 角军硫胶素类芽孢杆菌 Paenibacillus thiaminlyticus 石肖化杆菌 Nitrobacter winogradskyi Paenibacillus gluconolyticus, genus Bacillus, Paenibacillus thiaminlyticus, Nitrobacter winogradskyi
亚石肖化单胞菌 Nitrosococcus europaea Nitrosococcus europaea
狹小发光杆菌 Photobacterium angustum 明亮发光杆菌 Photobacterium phosphoreum 反石肖化盐富饶菌 Halogerax denitrificans 地中海盐富饶菌 Halogerax mediterranei 布氏甲焼杆菌 Methanobacterium bryantii 沼泽甲焼杆菌 Methanobacterium paluster 泥沼甲烧杆菌 Methanobacterium uliginosum 双氮纤维单胞菌 Cellulomonas biazotes 粪肥纤维单胞菌 Cellulomonas fimi 佐氏库特氏菌 Kurthia zopfii Photobacterium angustum Photobacterium phosphoreum Photobacterium phosphoreum anti-stone ossified salt-rich bacteria Halogerax denitrificans Mediterranean salt-rich bacteria Halogerax mediterranei Methanobacterium bryantii Marshanobacterium paluster Methanobacterium paluster Methanobacterium uliginosum Cellulomonas biazotes Cellulomonas fimi Kurthia zopfii
长赤细菌 Eeythrobacter longus Erythrobacter longus
红单胞菌 Erothromonas ursincola Rhodopseudomonas Erothromonas ursincola
巨胞氮单胞菌 Azomonas macrocytogenes 黄黄色杆菌 Xathobacter flavus Azomonas macrocytogenes yellow bacillus Xathobacter flavus
荚膜甲基球菌 Methylcoccus capsulatus 反銷化交替单胞菌 Alteromonas dentitrificans 产黑交替单胞菌 Alteromonas nigrifaciens 混合地神菌 Telluria mxita M. capsulatus Methylcoccus capsulatus Alternaria alternata dentitrificans Alternaria alternata Alteromonas nigrifaciens Mixed dementia Telluria mxita
溶纤维素拟杆菌 Bacteroides cellulosovens 粪便拟杆菌 Bacteroides stercoris Bacteroides cellulosovens Bacteroides stercoris
多营养拟杆菌 Ilyobacter ploytropus 瘤胃假丁酸弧菌 Pseudobutyrivibrio mminis 傲氏互营养单胞菌 Syntrophomonas wolgei 简单月旨肪肝菌 pimelobacter simplex 月中胀月旨肪肝菌 pimelobacter tumescens 粪短状杆菌 Brachybacterium faecium 反銷化琼斯氏菌 Jonesia denitrificans 渔腐稀有杆菌 Rarobacter faecitabidus Ilyobacter ploytropus rumen Pseudobutyrivibrio mminis Syntrophomonas wolgei simple famelobacter simplex feimelobacter simplex famelobacter tumescens Brachybacterium faecium Jones Jonesia denitrificans Raubacter faecitabidus
产亚銷酸真杆菌 Rarobacter formicigenerans  Producing A. sinensis Rarobacter formicigenerans
嗜聚木糖真杆菌 Rarobacter xylanophilum。  Rhodobacter xylanophilus Rarobacter xylanophilum.
本发明设置了两段 A/O系统， 在第一段 A/0系统中， 在水解酸化池后设置 第一好氧池，第一好氧池发生好氧硝化反应将废水中的氨氮转化为硝基氮。第一 好氧池后设置初沉池，初沉池的污泥回流至水解酸化池进水口， 同时第一好氧池 出口设置硝化回流管至水解酸化池进水口，将第一好氧池中产生的硝基氮带至水 解酸化池，硝基氮在水解酸化池中完成反硝化反应。 同时带回的硝基氮与废水中 的氨氮发生厌氧氨氧化反应， 使硝基氮和氨氮直接反应完成脱氮。处理后的废水 送入第二段 A/0系统中， 对废水中的污染物做进一步生化处理。  The invention provides a two-stage A/O system. In the first stage A/0 system, a first aerobic tank is arranged after the hydrolysis acidification tank, and the aerobic nitrification reaction of the first aerobic tank converts the ammonia nitrogen in the wastewater into Nitro nitrogen. After the first aerobic tank, a primary sedimentation tank is set, and the sludge of the primary sedimentation tank is returned to the water inlet of the hydrolysis acidification tank, and the outlet of the first aerobic tank is provided with a nitrification return pipe to the water inlet of the hydrolysis acidification tank, and the first aerobic tank is The produced nitro nitrogen is brought to the hydrolysis acidification tank, and the nitro nitrogen is subjected to denitrification reaction in the hydrolysis acidification tank. At the same time, the nitro nitrogen brought back and the ammonia nitrogen in the wastewater undergo anaerobic ammonium oxidation reaction, and the nitro nitrogen and ammonia nitrogen are directly reacted to complete the denitrification. The treated wastewater is sent to the second section of the A/0 system for further biochemical treatment of the pollutants in the wastewater.
在第二段 A/0系统中， 兼氧池继续对第一段 A/0系统中出水中残留的总氮 进行反硝化反应， 进一步去除总氮， 实现系统中氮的高效去除， 同时由于反硝化 需要大量碳源， 为保证反应中碳源的充足供应， 此阶段会有部分碳源过量， 因此 在系统末端增加曝气单元， 去除多余的 COD, 最终实现 C0D、 总氮等污染物的 达标排放。该阶段利用反硝化反应， 大大减小了污泥回流比， 从而减少了系统的 能耗。  In the second stage A/0 system, the anaerobic tank continues to denitrify the total nitrogen remaining in the effluent from the first stage A/0 system, further removing total nitrogen, and achieving efficient removal of nitrogen in the system, Nitrification requires a large amount of carbon source. In order to ensure sufficient supply of carbon in the reaction, there will be some carbon source excess at this stage. Therefore, the aeration unit is added at the end of the system to remove excess COD, and finally achieve the compliance of pollutants such as C0D and total nitrogen. emission. At this stage, the denitrification reaction is used to greatly reduce the sludge reflux ratio, thereby reducing the energy consumption of the system.
本发明的整个系统由前后两段污泥共同承担负荷，提高了整体系统的运行效 率和抗冲击风险系数。 两段 A/0处理系统能够大幅减少脱除总氮的能耗， 同时 这种双污泥工艺抗冲击能力更强。 当冲击负荷高时， 第一段 A/0系统承担主要 负荷，而对第二段 A/0系统中脱氮微生物影响较小，从而不会使整个系统垮掉， 造成事故； 另一方面，双污泥系统还可以使微生物在各自的环境里发挥最大的污 染物降解功能。  The entire system of the present invention is shared by the two sections of sludge before and after, and the operating efficiency and the risk resistance coefficient of the overall system are improved. The two-stage A/0 treatment system can significantly reduce the energy consumption of removing total nitrogen, and the double sludge process is more resistant to impact. When the impact load is high, the first stage A/0 system bears the main load, and the second stage A/0 system has less influence on the nitrogen-removing microorganisms, so that the whole system will not be thrown off and cause an accident; on the other hand, The dual sludge system also allows microorganisms to perform their maximum contaminant degradation in their respective environments.
本发明中所投加的微生物载体为粉末状活性炭， 具有性质稳定、 传质快、 比 面积大、 容易获取和强度高等特点。 本发明使用的环境治理微生物制剂是在两段 A/0工艺下对高 COD、 高氨氮 的废水具有高效的处理效果。另外本微生物制剂菌群具有完整的分解链，底物分 解彻底，产泥量只及常规活性污泥的十分之一以下， 从而可以大幅度减少污泥的 产量和污泥处置费用。而且本微生物制剂与特殊微生物载体相结合， 是一次性投 加， 具有适应能力强的特点， 可长期运行， 无需补加。 The microbial carrier added in the present invention is a powdery activated carbon, which has the characteristics of stable property, fast mass transfer, large specific area, easy acquisition and high strength. The environmental treatment microbial preparation used in the invention has an efficient treatment effect on high COD and high ammonia nitrogen wastewater under the two-stage A/0 process. In addition, the microbial preparation group has a complete decomposition chain, the substrate is completely decomposed, and the sludge production is only one tenth of the conventional activated sludge, so that the sludge production and sludge disposal cost can be greatly reduced. Moreover, the microbial preparation combined with the special microbial carrier is a one-time dosing, has the characteristics of strong adaptability, and can be operated for a long time without additional addition.
本发明工艺流程简洁， 采取两段 A/0 工艺和环境治理微生物技术相结合， 适用水质范围广泛， 降低了建造成本， 提高了处理能力， 在整个处理过程中无外 加稀释水， 对原水进行直接处理， 减少了水资源消耗及排放总量。 两段 A/0与 环境治理微生物技术相结合的微生物处理焦化废水总氮的废水处理工艺，其脱总 氮效果明显优于现有的 A/0、 A2/0工艺。 The invention has simple process flow, adopts two-stage A/0 process and environmental treatment microbial technology, and is applicable to a wide range of water quality, reduces construction cost, improves processing capacity, and does not directly add dilution water during the whole process, and directly performs raw water. Treatment, reducing water consumption and total emissions. The wastewater treatment process of the treatment of total nitrogen in coking wastewater by the combination of two A/0 and environmental treatment microbial technology is better than the existing A/0 and A 2 /0 processes.
经本发明处理后,焦化废水氨氮可以控制在 15mg/L以下， COD可以控制在 100mg/L以下， 其他指标也可以达到国家一级排放标准。 除焦化废水外， 本发明 所公开的利用微生物处理高浓度氮废水的方法， 也适用于制药废水、 发酵废水、 食品企业废水等难降解的生产废水， 还可以用于市政废水、 生活污水的处理。 附图说明 下面结合附图详细描述本发明的实施方式。  After treatment by the present invention, the ammonia nitrogen of the coking wastewater can be controlled below 15 mg/L, the COD can be controlled below 100 mg/L, and other indicators can also reach the national first-class discharge standard. In addition to coking wastewater, the method for treating high-concentration nitrogen wastewater by using microorganisms disclosed in the invention is also applicable to refractory production wastewater such as pharmaceutical wastewater, fermentation wastewater, food enterprise wastewater, and can also be used for treatment of municipal wastewater and domestic sewage. . BRIEF DESCRIPTION OF THE DRAWINGS Embodiments of the invention are described in detail below with reference to the drawings.
图 1为常规 A/0水处理工艺示意图。  Figure 1 is a schematic diagram of a conventional A/0 water treatment process.
图 2为常规 A70水处理工艺示意图。  Figure 2 is a schematic diagram of a conventional A70 water treatment process.
图 3为本发明实施例工艺流程示意图。  FIG. 3 is a schematic diagram of a process flow according to an embodiment of the present invention.
注： A: 废水； B: 污泥回流； C: 硝化液回流； D: HL-003环境微生物制 剂及活性炭。 具体实施方式 以下实施例是本发明在某废水处理工程中所做的运行试验，该试验为封闭试 验， 非特定人群不能接触、 了解试验过程。 Note: A: Waste water; B: sludge return; C: nitration reflux; D: HL-003 environmental microbial preparation and activated carbon. BEST MODE FOR CARRYING OUT THE INVENTION The following examples are operational tests performed by the present invention in a wastewater treatment project, which is a closed test, which is not accessible to a specific population and understands the test process.
参见图 3。本实施例的水处理体系在空间上由气浮池、调节池、水解酸化池、 第一好氧池、 初沉池、 兼氧池、 第二好氧池和二沉池这 8个主体单元构成。 其中 初沉池设置污泥回流管道至水解酸化池，第一好氧池出水口设置硝化液回流管道 至水解酸化池进水口； 二沉池设置污泥回流管道至兼氧池，第二好氧池出水口设 置硝化液回流管道至兼氧池进水口。  See Figure 3. The water treatment system of the present embodiment is spatially composed of eight main units: a gas floating pool, a regulating tank, a hydrolysis acidification tank, a first aerobic tank, a primary settling tank, a facultative oxygen tank, a second aerobic tank and a secondary settling tank. . Wherein the primary settling tank is provided with a sludge return pipe to the hydrolysis acidification tank, the first aerobic tank outlet is provided with a nitrifying liquid return pipe to the water inlet of the hydrolysis acidification tank; the second settling tank is provided with a sludge return pipe to the anaerobic tank, the second aerobic The tank outlet is provided with a nitrifying liquid return line to the hydration tank inlet.
某焦化废水， 流量为 300m 3/h， 其 COD&5800mg/L， 总氮 350mg/L， 进入系 统前先经过气浮池， 经气浮池预处理除去油和悬浮物及渣后进入调节池。出水送 入水解酸化池， 在废水池中通过微量搅拌， 投入 1.0%~2.5% (体积百分比） 的活 性炭以及 1.5%~4.0% (体积百分比） 的 HL-003环境微生物制剂， 结合硝化液中 的硝态氮作为反硝化的氮源，降解污水中一部分有害物质，提高污水的可生化性。 A coking wastewater with a flow rate of 300m 3 /h, COD & 5800mg / L, total nitrogen 350mg / L, before entering the system through the air floatation tank, pretreated by the air floatation tank to remove oil and suspended solids and slag into the regulation tank. The effluent is sent to the hydrolysis acidification tank, and 1.0%~2.5% (by volume) of activated carbon and 1.5%~4.0% (volume%) of HL-003 environmental microbial preparation are combined in the effluent by micro-stirring. As a nitrogen source for denitrification, nitrate nitrogen degrades some harmful substances in sewage and improves the biodegradability of sewage.
水解酸化池参数控制为 pH控制 7~9， DO (溶解氧） <0.2mg/L， MLVSS (有 效污泥浓度） 在 3~6g/L， 通过搅拌设备对池中污水进行搅拌混匀， 防止水中悬 浮物在池底沉积。  The parameters of the hydrolysis acidification tank are controlled to pH control 7~9, DO (dissolved oxygen) <0.2mg/L, MLVSS (effective sludge concentration) is 3~6g/L, and the sewage in the pool is stirred and mixed by mixing equipment to prevent Suspended solids in the water are deposited at the bottom of the pool.
水解酸化池出水进入第一好氧池进行硝化反应， 第一好氧池水温控制在 25-35 °C , pH控制 6.8~7.2， DO<2~4mg/L。 第一好氧池出水进入初沉池进行泥 水分离， 污泥回流到水解酸化池， 污泥回流比例 1 : 1~2； 上层水为硝化液， 回流 至水解酸化池， 硝化液回流比例 1 :2~8。  The effluent from the hydrolysis acidification tank enters the first aerobic tank for nitrification reaction. The water temperature of the first aerobic tank is controlled at 25-35 °C, the pH is controlled by 6.8~7.2, and DO<2~4mg/L. The first aerobic tank effluent enters the primary sedimentation tank for sludge water separation, and the sludge is returned to the hydrolysis acidification tank, and the sludge reflux ratio is 1:1~2; the upper layer water is nitrification liquid, and is refluxed to the hydrolysis acidification tank, and the nitrification liquid reflux ratio is 1: 2~8.
经过第一段 A/0 生化系统的出水流到兼氧池。 兼氧池参数控制为水温 25-35 °C , pH控制 6~9， DO<0.5mg/L。 以进水中的有机物作为反硝化的碳源和 能源 （为保证碳源的充足， 补加碳源）， 以硝化回流液中的硝态氮作为反硝化的 氮源， 在池中投加 1.0%~2.5% (体积百分比） 的活性炭以及 1.5%~4.0% (体积百 分比） 的 HL-003环境微生物制剂， 在以上反应源共同作用下进行反硝化脱氮反 应， 使废水中的 H3-N等污染物质得以去除和降解， 处理后的出水流入第二好 氧池。 第二好氧池中通过曝气对兼氧池中多余的 COD进行彻底去除和降解， 第 二好氧池水温控制在 25~35°C， pH控制 6.8~7.2， DO<2~4mg/L。 处理后的出水 流入二沉池。二沉池完成泥水分离，通过污泥回流管道根据需要将大部分污泥回 流至兼氧池， 根据需要和实际运行状况将富余污泥排放， 上层水达标排出。 The effluent from the first stage A/0 biochemical system flows to the anaerobic tank. The parameters of the facultative tank are controlled by water temperature of 25-35 °C, pH control of 6~9, DO<0.5mg/L. The organic matter in the influent is used as the carbon source and energy for denitrification (to ensure the sufficient carbon source, supplement the carbon source), and the nitrate nitrogen in the nitrifying reflux liquid is used as the denitrifying nitrogen source, and 1.0 is added in the pool. %~2.5% (by volume) of activated carbon and 1.5%~4.0% (volume In the HL-003 environmental microbial preparation, the denitrification and denitrification reaction is carried out under the action of the above reaction sources, so that the pollutants such as H 3 -N in the wastewater are removed and degraded, and the treated effluent flows into the second aerobic Pool. In the second aerobic tank, the excess COD in the anaerobic tank is completely removed and degraded by aeration. The water temperature of the second aerobic tank is controlled at 25~35 °C, the pH is controlled by 6.8~7.2, DO<2~4mg/L. . The treated effluent flows into the secondary settling tank. The second settling tank completes the separation of the muddy water, and most of the sludge is returned to the anaerobic tank through the sludge returning pipeline as needed, and the surplus sludge is discharged according to the needs and actual operating conditions, and the upper layer of water is discharged to the standard.
如表 1所示经本实施例处理后的出水水质,污水处理效果明显好于常规 A/0、 A2/0工艺， 出水水质指标达到或优于国家标准。 As shown in Table 1, the effluent quality after treatment in this example, the sewage treatment effect is significantly better than the conventional A/0, A 2 /0 process, and the effluent water quality index meets or exceeds the national standard.
表 1本发明与常规工艺对焦化废水处理比对  Table 1 Comparison of the present invention with conventional process coking wastewater treatment
Figure imgf000012_0001
Figure imgf000012_0001

Claims

权利要求书 Claim
1.一种利用微生物处理焦化废水脱总氮的方法， 废水依次进入调节池、 水解酸化 池、 第一好氧池、 初沉池、 兼氧池、 第二好氧池和二沉池， 最终达标排出； 其特 征在于： 水解酸化池、 第一好氧池、 初沉池组成第一阶段 A/0系统； 兼氧池、 第二好氧池和二沉池组成第二阶段 A/0系统， 两段 A/0系统构成两个独立的污 泥系统； 并且分别于水解酸化池、 第一好氧池、 兼氧池、 第二好氧池中加入各自 体积 1.0%~2.5%的微生物载体以及 1.5%~4.0%的环境微生物制剂。 1. A method for treating dehydrogenation of coking wastewater by using microorganisms, wherein the wastewater sequentially enters a regulating tank, a hydrolysis acidification tank, a first aerobic tank, a primary sedimentation tank, a facultative oxygen tank, a second aerobic tank, and a secondary settling tank, and finally The discharge is up to standard; the characteristics are: the hydrolysis acidification tank, the first aerobic tank, the primary sedimentation tank constitute the first stage A/0 system; the anaerobic tank, the second aerobic tank and the second settling tank constitute the second stage A/0 system The two-stage A/0 system constitutes two independent sludge systems; and the microbial carriers each having a volume of 1.0% to 2.5% are respectively added to the hydrolysis acidification tank, the first aerobic tank, the anaerobic tank, and the second aerobic tank. And 1.5% to 4.0% of environmental microbial preparations.
2.按照权利要求 1所述的一种利用微生物处理焦化废水脱总氮的方法， 其特征在 于： 所述水解酸化池 pH控制 7~9， DO (溶解氧） <0.2mg/L， MLVSS (有效污 泥浓度） 在 3~6g/L; 第一好氧池水温控制在 25~35°C， pH控制 6.8~7.2， DO<  2 . The method according to claim 1 , wherein the pH of the hydrolysis acidification tank is controlled by 7-9, DO (dissolved oxygen) <0.2 mg/L, MLVSS ( The effective sludge concentration is 3~6g/L; the first aerobic pool water temperature is controlled at 25~35°C, and the pH control is 6.8~7.2, DO<
3.按照权利要求 1所述的一种利用微生物处理焦化废水脱总氮的方法， 其特征在 于： 所述兼氧池水温控制在 25~35°C， pH控制 6~9， DO<0.5mg/L; 第二好氧池 水温控制在 25~35°C， pH控制 6.8~7.2， DO<2~4mg/L。 3 . The method according to claim 1 , wherein the water temperature of the anaerobic pool is controlled at 25 to 35° C., the pH is controlled by 6 to 9 , and the DO is less than 0.5 mg. /L ; The second aerobic pool water temperature is controlled at 25~35 °C, pH control is 6.8~7.2, DO<2~4mg/L.
4.按照权利要求 1所述的一种利用微生物处理焦化废水脱总氮的方法， 其特征在 于：初沉池设置污泥回流管道至水解酸化池，二沉池设置污泥回流管道至兼氧池， 回流比为 1 : 1~2； 第一好氧池出水口设置硝化液回流管道至水解酸化池进水口； 第二好氧池出水口设置硝化液回流管道至兼氧池进水口， 回流比为 1 :2~8。  4 . The method according to claim 1 , wherein the primary sedimentation tank is provided with a sludge return pipeline to the hydrolysis acidification tank, and the secondary sedimentation tank is provided with a sludge return pipeline to the anaerobic tank. Pool, reflux ratio is 1: 1~2; the first aerobic tank outlet is provided with a nitrifying liquid return pipe to the water inlet of the hydrolysis acidification tank; the second aerobic tank outlet is provided with a nitrifying liquid return pipe to the inlet of the anaerobic tank, reflux The ratio is 1:2~8.
5.按照权利要求 1所述的一种利用微生物处理焦化废水脱总氮的方法， 其特征在 于： 所述的微生物载体是粉末状活性炭。  A method for treating dehydrogenated coking wastewater by microorganisms according to claim 1, wherein: said microbial carrier is powdered activated carbon.
6.按照权利要求 1-5任一项所述的一种利用微生物处理焦化废水脱总氮的方法， 其特征在于： 所述的环境微生物制剂由以下 89种微生物组成：  A method for treating dehydrogenated coking wastewater by using a microorganism according to any one of claims 1 to 5, wherein: said environmental microbial preparation is composed of the following 89 microorganisms:
醋酸醋杆菌 Acetobacter aceti  Acetobacter aceti
液化醋杆菌 Acetobacter Liquefaciens  Acetobacter Liquefaciens
木醋杆菌 Acetobacter xylinus 干燥无色菌 Achromobacter xerosis 嗜水气单胞菌 Aeromenans hydrophila 中间气单胞菌 Aeromenans media 温禾口气单胞菌 Aeromenans sobria 分子芽孢杆菌 Bacillus alvei Acetobacter xylinus Dry Achromobacter xerosis Aeromonas hydrophila Aeromonas media Aeromonans sobria Bacillus alvei
凝结芽孢杆菌 Bacillus coagulans 枯草芽孢杆菌 Bacillus subtilis Bacillus coagulans Bacillus subtilis
迟缓芽孢杆菌 Bacillus leutis Bacillus leutis
坚强芽孢杆菌 Bacillus firmus Bacillus firmus
状芽孢杆菌 Bacillus mycides 巨大芽孢杆菌 Bacillus megaterium 嗜碱芽孢杆菌 Bacillus alcalophilus 地衣芽孢杆菌 Bacillus licheniformis 球形芽孢杆菌 Bacillus spaericus 海洋芽孢杆菌 Bacillus marinus 反石肖化亚禾中 Alcaligenes denitrigicans 粪产碱菌 Alcaligenes faecalis Bacillus mycides Bacillus megaterium Bacillus alcalophilus Bacillus licheniformis Bacillus cerevisiae Bacillus marinus Bacillus marinus Anti-Stone Physalis Alcaligenes denitrigicans Alcaligenes faecalis
木糖氧化产碱菌 Alcaligenes xylososydans 角旱氨短杆菌 Brevibacterium ammoniagenes 乳酸短杆菌 Brevibacterium casei 短短芽孢菌 Brevibscillus brevis 产气肠杆菌 Enterobacter aerogenes 成团肠杆菌 Thiobacillus agglomerans 反石肖化硫杆菌 Thiobacillus denitrificans 氧化硫杆菌 Thiobacillus thiooxidans Alcaligenes xylososydans, Brevibacterium ammoniagenes, Brevibacterium case, Brevibacterium casei, Brevibscillus brevis, Enterobacter aerogenes, Enterobacter aeruginans, Thiobacillus agglomerans, Thiobacillus denitrificans Thiobacillus thiooxidans
硫红球菌 Thiorhodococcus minus Rhodococcus erythromycin Thiorhodococcus minus
沼泽红假单胞菌 Rhodopseudomonas palustris 嗜酸红假单胞菌 Rhodopseudomonas acidphia 浅井氏葡萄杆菌 Gluconobacter albidus Rhodopseudomonas palustris Rhodopseudomonas rhodopseudomonas acidphia Gluconobacter albidus
葡萄氧化杆菌 Gluconobacter oxydans Gluconobacter oxydans
发酵乳杆菌 Lactobacillus fermentum Lactobacillus fermentum
植物乳杆菌 Lactobacillus plantarum Lactobacillus plantarum
石肖化乳杆菌 Lactobacillus alimentarius Lactobacillus alimentarius
食淀粉乳杆菌 Lactobacillus amylophillus 瘤胃乳杆菌 Lactobacillus niminis Lactobacillus amylophillus Lactobacillus niminis
短乳杆菌 Lactobacillus bervis Lactobacillus bervis
藤黄微球菌 Micrococcus lentus Micrococcus lentus Micrococcus lentus
喜盐微球菌 Micrococcus halobius Micrococcus halobius
产碱假单胞菌 Pseudomonas alcaligenes 至夂黄色假单胞菌 Pseudomonas aureofaciens 绿针假单胞菌 Pseudomonas chlororaphis 石肖化 'ί叚单胞菌 Pseudomonas nitroreducens 核黄素假单胞菌 Pseudomonas riboflavina 恶臭假单胞菌 Pseudomonas putina Pseudomonas alcaligenes to Pseudomonas aureofaciens Pseudomonas chlororaphis Stones of the genus Pseudomonas nitroreducens Pseudomonas riboflavina Pseudomonas putida Pseudomonas putina
敏捷假单胞菌 Pseudomonas facilis Pseudomonas facilis
解葡聚糖类芽孢杆菌 Paenibacillus gluconolyticus 角牟硫胶素类芽孢杆菌 Paenibacillus thiaminlyticus 確化杆菌 Nitrobacter winogradskyi 亚 ϊ肖化单胞菌 Nitrosococcus europaea 狭小发光杆菌 Photobacterium angustum 明亮发光杆菌 Photobacterium phosphoreum 反確化盐富饶菌 Halogerax denitrificans 地中海盐富饶菌 Halogerax mediterranei 布氏甲焼杆菌 Methanobacterium bryantii 沼泽甲焼杆菌 Methanobacterium paluster 泥沼甲院杆菌 Methanobacterium uliginosum 双氮纤维单胞菌 Cellulomonas biazotes 粪肥纤维单胞菌 Cellulomonas fimi 佐氏库特氏菌 Kurthia zopfii Paenibacillus gluconolyticus, Paenibacillus thiaminlyticus, Nitrobacter winogradskyi Photobacterium angustum Photobacterium angustum Photobacterium phosphoreum Photobacterium phosphoreum Degenerative salt-rich bacteria Halogerax denitrificans Halogerax mediterranei Methanobacterium bryantii Methanobacterium paluster Methanobacterium paluster Methanobacterium Uliginosum Cellulomonas biazotes Cellulomonas fimi Kurthia zopfii
长赤细菌 Eeythrobacter longus Erythrobacter longus
红单胞菌 Erothromonas ursincola Rhodopseudomonas Erothromonas ursincola
巨胞氮单胞菌 Azomonas macrocytogenes 黄黄色杆菌 Xathobacter flavus Azomonas macrocytogenes yellow bacillus Xathobacter flavus
荚膜甲基球菌 Methylcoccus capsulatus 反銷化交替单胞菌 Alteromonas dentitrificans 产黑交替单胞菌 Alteromonas nigrifaciens 混合地神菌 Telluria mxita M. capsulatus Methylcoccus capsulatus Alternaria alternata dentitrificans Alternaria alternata Alteromonas nigrifaciens Mixed dementia Telluria mxita
溶纤维素拟杆菌 Bacteroides cellulosovens 粪便拟杆菌 Bacteroides stercoris Bacteroides cellulosovens Bacteroides stercoris
多营养拟杆菌 Ilyobacter ploytropus 瘤胃假丁酸弧菌 Pseudobutyri vibrio ruminis 傲氏互营养单胞菌 Syntrophomonas wolgei 简单月旨肪肝菌 pimelobacter simplex 月中胀月旨肪肝菌 pimelobacter tumescens 粪短状杆菌 Brachybacterium faecium 反銷化琼斯氏菌 Jonesia denitrificans 渔腐稀有杆菌 Rarobacter faecitabidus 产亚硝酸真杆菌 Rarobacter formicigenerans 嗜聚木糖真杆菌 arobacter xylanophilum Ilyobacter ploytropus rumen Pseudobutyri vibrio ruminis Syntrophomonas wolgei 月 旨 pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi phi Bacillus arobacter xylanophilum
PCT/CN2012/078665 2012-07-14 2012-07-14 Method for removing total nitrogen during treatment of coking wastewater by using microorganisms WO2014012201A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2012/078665 WO2014012201A1 (en) 2012-07-14 2012-07-14 Method for removing total nitrogen during treatment of coking wastewater by using microorganisms

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2012/078665 WO2014012201A1 (en) 2012-07-14 2012-07-14 Method for removing total nitrogen during treatment of coking wastewater by using microorganisms

Publications (1)

Publication Number Publication Date
WO2014012201A1 true WO2014012201A1 (en) 2014-01-23

Family

ID=49948148

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2012/078665 WO2014012201A1 (en) 2012-07-14 2012-07-14 Method for removing total nitrogen during treatment of coking wastewater by using microorganisms

Country Status (1)

Country Link
WO (1) WO2014012201A1 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104016548A (en) * 2014-06-19 2014-09-03 中冶建筑研究总院有限公司 Biochemical treatment process of coking wastewater
CN105036458A (en) * 2015-06-19 2015-11-11 广州中科建禹环保有限公司 Wastewater treatment process adopting porous filler to fix dominant bacteria
CN105384311A (en) * 2015-12-09 2016-03-09 浦华环保股份有限公司 Method for processing high concentration comprehensive municipal sewage and apparatus thereof
CN105906151A (en) * 2016-06-08 2016-08-31 浙江省环境保护科学设计研究院 Sewage treatment device and method of high-density biochemical system in combination with activated carbon filtration system
CN107032495A (en) * 2017-05-22 2017-08-11 大连理工大学 A kind of biological treatment group technology of the high salinity pharmacy waste waters of high COD
CN107555588A (en) * 2017-09-26 2018-01-09 浙江元美环境科技有限公司 A kind of method that microbe carrier is added in MBR membrane bioreactors
CN107858311A (en) * 2017-12-07 2018-03-30 江西省农业科学院畜牧兽医研究所 A kind of Achromobacter xylosoxidans X10 and its application
CN108395051A (en) * 2017-02-08 2018-08-14 鞍钢股份有限公司 A kind of coking wastewater short-range nitration method of stability and high efficiency
CN109052827A (en) * 2018-08-21 2018-12-21 重庆中标环保集团有限公司 Food waste percolate enhanced processing method and system
CN109626743A (en) * 2019-01-09 2019-04-16 北京林业大学 A kind of coking waste water treatment method
CN109824220A (en) * 2019-04-04 2019-05-31 湖南湘奈环保科技有限责任公司 A kind of Biochemical Process for Treating Coke Plant Wastewater
CN110156262A (en) * 2019-05-27 2019-08-23 江西晏清环境科技有限公司 A kind of dispersant type domestic wastewater purification system
WO2022143243A1 (en) * 2020-12-30 2022-07-07 中冶焦耐(大连)工程技术有限公司 Coking wastewater treatment system and process for realizing gradient utilization of powdered activated carbon

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1562820A (en) * 2004-02-10 2005-01-12 凌亮 Method for treating wastewater of carbonization by using microbe
CN101514069A (en) * 2009-04-03 2009-08-26 北京首钢国际工程技术有限公司 Coking wastewater biological denitrificaion treatment process
KR20100131225A (en) * 2009-06-05 2010-12-15 대송환경개발(주) Device for filtering water
CN201746432U (en) * 2010-09-13 2011-02-16 李波 Apparatus for strengthening treatment of coking waste water
CN102417272A (en) * 2011-02-18 2012-04-18 江苏省纯江环保科技有限公司 Coking waste water treatment method and A / O technology apparatus

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1562820A (en) * 2004-02-10 2005-01-12 凌亮 Method for treating wastewater of carbonization by using microbe
CN101514069A (en) * 2009-04-03 2009-08-26 北京首钢国际工程技术有限公司 Coking wastewater biological denitrificaion treatment process
KR20100131225A (en) * 2009-06-05 2010-12-15 대송환경개발(주) Device for filtering water
CN201746432U (en) * 2010-09-13 2011-02-16 李波 Apparatus for strengthening treatment of coking waste water
CN102417272A (en) * 2011-02-18 2012-04-18 江苏省纯江环保科技有限公司 Coking waste water treatment method and A / O technology apparatus

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104016548B (en) * 2014-06-19 2016-04-06 中冶建筑研究总院有限公司 A kind of Biochemical Process for Treating Coke Plant Wastewater
CN104016548A (en) * 2014-06-19 2014-09-03 中冶建筑研究总院有限公司 Biochemical treatment process of coking wastewater
CN105036458A (en) * 2015-06-19 2015-11-11 广州中科建禹环保有限公司 Wastewater treatment process adopting porous filler to fix dominant bacteria
CN105384311A (en) * 2015-12-09 2016-03-09 浦华环保股份有限公司 Method for processing high concentration comprehensive municipal sewage and apparatus thereof
CN105906151A (en) * 2016-06-08 2016-08-31 浙江省环境保护科学设计研究院 Sewage treatment device and method of high-density biochemical system in combination with activated carbon filtration system
CN108395051A (en) * 2017-02-08 2018-08-14 鞍钢股份有限公司 A kind of coking wastewater short-range nitration method of stability and high efficiency
CN107032495A (en) * 2017-05-22 2017-08-11 大连理工大学 A kind of biological treatment group technology of the high salinity pharmacy waste waters of high COD
CN107555588A (en) * 2017-09-26 2018-01-09 浙江元美环境科技有限公司 A kind of method that microbe carrier is added in MBR membrane bioreactors
CN107858311A (en) * 2017-12-07 2018-03-30 江西省农业科学院畜牧兽医研究所 A kind of Achromobacter xylosoxidans X10 and its application
CN107858311B (en) * 2017-12-07 2020-11-24 江西省农业科学院畜牧兽医研究所 Achromobacter xylosoxidans X10 and application thereof
CN109052827A (en) * 2018-08-21 2018-12-21 重庆中标环保集团有限公司 Food waste percolate enhanced processing method and system
CN109626743A (en) * 2019-01-09 2019-04-16 北京林业大学 A kind of coking waste water treatment method
CN109824220A (en) * 2019-04-04 2019-05-31 湖南湘奈环保科技有限责任公司 A kind of Biochemical Process for Treating Coke Plant Wastewater
CN110156262A (en) * 2019-05-27 2019-08-23 江西晏清环境科技有限公司 A kind of dispersant type domestic wastewater purification system
WO2022143243A1 (en) * 2020-12-30 2022-07-07 中冶焦耐(大连)工程技术有限公司 Coking wastewater treatment system and process for realizing gradient utilization of powdered activated carbon

Similar Documents

Publication Publication Date Title
WO2014012201A1 (en) Method for removing total nitrogen during treatment of coking wastewater by using microorganisms
Zhang et al. Nitrogen removal by a metal‐resistant bacterium, Pseudomonas putida ZN1, capable of heterotrophic nitrification–aerobic denitrification
CN101259977B (en) Method for removing total nitrogen by using microorganism
Guimarães et al. Microbial pathways of nitrogen removal in aerobic granular sludge treating domestic wastewater
Zhu et al. Comparison of performance of two large-scale vertical-flow constructed wetlands treating wastewater treatment plant tail-water: Contaminants removal and associated microbial community
Lee et al. The effect of different carbon sources on respiratory denitrification in biological wastewater treatment
Corsino et al. Cultivation of granular sludge with hypersaline oily wastewater
CN101759329B (en) Method for processing organosilicon waste water
CN102071141B (en) Denitrified microbial agent as well as preparation method and application thereof
Zhao et al. Nitrogen removal and microbial community for the treatment of rural domestic sewage with low C/N ratio by A/O biofilter with Arundo donax as carbon source and filter media
CN101941762A (en) Method for treating wastewater by utilizing composite microbial preparation
Al-Dhabi et al. Removal of nitrogen from wastewater of date processing industries using a Saudi Arabian mesophilic bacterium, Stenotrophomonas maltophilia Al-Dhabi-17 in sequencing batch reactor
CN101259979A (en) Method and device for treating high concentration nitrogen-containing waste water by using microorganism
CN102249481A (en) Method for treating total nitrogen in coal chemical wastewater by using microbes
CN103466905A (en) Method for treating nitrobenzene and aniline in wastewater by using microorganisms
Meng et al. Nutrient removal from high ammonium swine wastewater in upflow microaerobic biofilm reactor suffered high hydraulic load
Li et al. Effects of Mn2+ and humic acid on microbial community structures, functional genes for nitrogen and phosphorus removal, and heavy metal resistance genes in wastewater treatment
Zainith et al. Microbes an ecofriendly tools for the treatment of industrial waste waters
CN101259980B (en) Method and device for treating high concentration nitrogen waste water by using microorganism
Choi et al. Development of a biological process for livestock wastewater treatment using a technique for predominant outgrowth of Bacillus species
Márquez et al. Activated sludge process versus rotating biological contactors in WWTPs: Evaluating the influence of operation and sludge bacterial content on their odor impact
CN102757127B (en) Method for treating coal water slurry gasification wastewater with microbes
Hamer Microbial consortia for multiple pollutant biodegradation
Chu et al. Effects of oxygen tension on the microbial community and functional gene expression of aerobic methane oxidation coupled to denitrification systems
WO2020097994A1 (en) Sphingobacterium having both heterotrophic nitrification and aerobic denitrification functions and application thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12881460

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12881460

Country of ref document: EP

Kind code of ref document: A1