CN1239414C - 一种利用微生物处理焦化废水的方法 - Google Patents
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
本发明公开了一种利用微生物处理焦化废水的方法。采用了O-A-O的生化工艺，由预曝阶段先去除大部分影响微生物活性的COD和大量有机物，并在二段生化阶段添加微生物菌群及其载体，使得焦化废水中的氨氮控制在15mg/L以下，COD控制在100mg/L以下，其他指标也可以达到国家一级排放标准。
Description
技术领域
本发明属于工业污水处理领域，特别是涉及一种利用微生物处理焦化废水的方法。
背景技术
焦化废水是由原煤在高温干燥、煤气净化和化工产品精制过程中产生的工业废水，特别是煤气在冷却、洗涤、净化过程中，产生大量成分复杂、浓度高的废水，是一种含有大量有毒有害物质的有机废水，包括钢铁焦化废水、煤气焦化废水等练焦工艺产生的废水。核磁共振色谱图中显示，焦化废水中含有数十种无机和有机化合物。其中无机化合物主要是大量氮盐、硫氰化物、硫化物、氰化物等，有机化合物除酚类外，还有单环及多环的芳香族化合物，含氮、硫、氧的杂环化合物等。从水质上看，焦化废水一般COD含量高，多在2000-10000mg/L，并且含有大量对生物有抑制作用的有机污染物。
目前对焦化废水的处理一般需经过多段处理，常用的预处理技术是厌氧酸化法，二级处理方法很多，有生物化学法、物理法、化学法以及物理化学法等。目前应用比较多的主要有普通活性污泥法、催化湿式演化法、缺氧-好氧-接触法等，其中最多最有效的是普通活性污泥法，但处理效果很难达到国家规定的排放标准。根据现行《污水综合排放标准》(GB8978-96)，对焦化废水新改扩建项目要求：NH3-N≤15mg/L，COD≤100mg/L，目前企业很难达到处理要求，分析后认为主要存在以下几个原因：1.焦化废水中难降解的CODcr值高，同时含有一定的有毒有害物质，使得传统生化法难以去除部分杂质；2.传统活性污泥法存在自身的缺陷，如耐冲击负荷差，剩余污泥多，泥龄短，造成细菌种类不全、数量不足，对难降解物无去除效果：3.传统工艺对NH3-N的去除重视不够，无法完成对NH3-N的去除。
目前国内治理焦化废水也提出了一些新的工艺，如中国专利98121488.6公开了一种废水处理方法，它是在将废水经过吸附吸收有机物之后，再经过一个厌氧反硝化-有氧硝化-厌氧反硝化-有氧硝化的处理过程，即A-O-A-O，O代表曝气状态，A代表厌氧或兼氧状态。其他A-O、A-A-O等方法在实际中也多有应用，这些方法在实际运行中克服了常规活性污泥法的诸多弊病，但也存在微生物生存环境要求较高，总停留时间较长，占地面积较大，投资费用高，运行管理复杂，运行费用高的毛病，因此没有得到广泛应用和推广。
发明内容
本发明要解决的是焦化废水处理效果不好的技术问题，提供一种能有效脱除焦化废水中各种杂质，使出水符合国家排放标准的，利用微生物处理焦化废水的方法。
为此，本发明采用的技术方案如下：
一种利用微生物处理焦化废水的方法，其特征在于废水在经过二段生化系统进行硝化反硝化作用之前先经过一个好氧的预曝池，由预曝池去除COD和大量有机物，二段生化系统包括厌氧或兼氧池和好氧池，厌氧或兼氧池进行反硝化脱氮，好氧池进行硝化作用，即为O-A-O工艺，且在预曝池和厌氧或兼氧池中预先各直接加入各自体积1.5％～4.0％的微生物茵群和各自体积1.0％～2.5％的微生物载体。
即使整个工艺过程中没有外加碳源，用本发明所公开的方法也可以实现同样的处理效果，而且可以大大降低处理成本。
在工艺上还可以有如下优化：即在预曝池后还有一个一沉池，与预曝池组成预曝系统，二段生化系统中的好氧池可以分成多段，在好氧池后还有一个二沉池。在实践中可根据需要将好氧池分为若干段，以提高硝化作用的效能。
预曝系统中由微生物菌群和微生物载体组成的活性污泥采用独立循环方式由一沉池回流至预曝池，回流比1∶1～1∶2，在二段生化系统中既有污泥回流又有硝化液回流，其中好氧池回流至兼氧池的回流比为1∶1～1∶4，二沉池的活性污泥和硝化液既可以回流至好氧池，也可以回流至厌氧或兼氧池，或者同时回流至好氧池和厌氧或兼氧池，回流比为1∶1～l∶2。
添加的微生物载体可以为粉末活性炭。
在预曝池和厌氧池或兼氧池中直接加入的微生物菌群(以下简称为HSBTMBM制剂)可以是包含有以下来自47个属的105种微生物。
Acetobacter aceti 醋酸醋杆菌
Acetobacter liquefaciens 液化醋杆菌
Acetobacter xylinum 木醋杆茵
Achromobacter xerosis 干燥无色菌
Aeromonans hydrophila 嗜水气单胞菌
Aeromonas media 中间气单胞菌
Aeromonans sobria 温和气单胞菌
Bacillus alvei 分支芽孢杆菌
Bacillus coagulans 凝结芽孢杆菌
Bacillus subtilis 枯草芽孢杆菌
Bacillus leutis 迟缓芽孢杆菌
Bacillus firmus 坚强芽孢杆菌
Bacillus mycoides 状芽孢杆菌
Bacillus megaterium 巨大芽孢杆菌
Bacillus alcalophilus 嗜碱芽孢杆菌
Bacillus cereus 蜡样芽孢杆菌
Bacillus licheniformis 地衣芽孢杆菌
Bacillus pumilus 短小芽孢杆菌
Bacillus spaericus 球形芽孢杆菌
Bacillus marinus 海洋芽孢杆菌
Alcaligenes denitrificans 反硝化亚种
Alcaligenes faecalis 粪产碱菌
Alcaligenes xylosoxydans 木糖氧化产碱菌
Brevibacterium acetylicum 乙炔短杆菌
Brevibacterium ammoniagenes 解氨短杆菌
Brevibacterium casei 乳酪短杆菌
Brevibacillus brevis 短短芽孢杆菌
Enterobacter cloacae 阴沟肠杆菌
Enterobacter aerogenes 产气肠杆菌
Enterobacter agglomerans 成团肠杆菌
Thiobacillus novellas
Thiobacillus thioparus
Thiobacillus denitrificans 反硝化硫杆菌
Thiobacillus thiooxidans 氧化硫杆菌
Thiorhodococcus minus 硫红球菌
Rhodopseudomonas palustris 沼泽红假单胞茵
Rhodopseudomonas acidphia 嗜酸红假单胞菌
Gluconobacter aibidus 浅井氏葡糖杆菌
Gluconobacte oxydans 葡糖氧化杆菌
Lactobacilius fermentum 发酵乳杆菌
Lactobacillus plantarum 植物乳杆菌
Lactobacillus alimentarius 消化乳杆菌
Lactobacillus amylophillus 食淀粉乳杆菌
Lactobacillus ruminis 瘤胃乳杆菌
Lactobacillus bervis 短乳杆菌
Micrococcus leutus 藤黄微球菌
Micrococcus halobius 喜盐微球菌
Pseudomonas alcaligenes 产碱假单胞菌
Pseudomonas aureofaciens 致黄色假单胞菌
Pseudomonas chlororaphis 绿针假单胞菌
Pseudomonas nitroreducens 硝化假单胞菌
Pseudomonas riboflavina 核黄素假单胞菌
Pseudomonas putina 恶臭假单胞菌
Pseudomonas facilis 敏捷假单胞菌
paenibacillus gluconolyticus 解葡聚糖类芽孢杆菌
paenibacillus thiaminlyticus 解硫胺素类芽孢杆菌
Saccharomyces telluris
Beggiatoa alba
Nitrobacter winogradskyi 硝化杆菌
Nitrosomonas europaea 亚硝化单胞菌
Nitrosococcus nitrosus
Photobacterium angustum 狭小发光杆菌
Photobacterium phosphoreum 明亮发光杆菌
Photobacterium leiognathi 鳆发光杆菌
Haloferax denitrificans 反硝化盐富饶菌
Haloferax mediterranei 地中海盐富饶菌
Methanobacterium bryantii 布氏甲烷杆菌
Methanobacterium paluster 沼泽甲烷杆菌
Methanobacterium uliginosum 泥沼甲烷杆菌
Cellulomonas biazotes 双氮纤维单胞菌
Cellulomonas fimi 粪肥纤维单胞茵
Kurthia zopfii 佐氏库特氏菌
Thiosphaera pantotropha
Alcaligenes sp
Chlorobium limicola 泥生绿菌
Erythrobacter longus 长赤细菌
Erothromonas ursincola 红单胞菌
Azomonas macrocytogenes 巨胞氮单胞菌
Xanthobacter flavus 黄黄色杆菌
Methylcoccus capsulatus 荚膜甲基球菌
Alteromonas denitrificans 反硝化交替单胞菌
Alteromonas nigrifaciens 产黑交替单胞菌
Telluria mxita 混合地神菌
Bacteroides cellulosovens 溶纤维素拟杆菌
Bacteroides stercoris 粪便拟杆菌
Ilyobacter ploytropus 多营养泥杆菌
Pseudobutyrivibrio ruminis 瘤胃假丁酸弧菌
Syntrophomonas wolfei 澳氏互营养单胞菌
Pimelobacter simplex 简单脂肪杆菌
Pimelobacter tumescens 肿胀脂肪杆菌
Brachybacterium faecium 粪短状杆菌
Jonesia denitrificans 反硝化琼斯氏菌
Rarobacter faecitabidus 渣腐稀有杆菌
Eubacterium formicigenerans 产甲酸真杆菌
Eubacterium nitritogenes 产亚硝酸真杆菌
Eubacterium xylanophilum 嗜聚木糖真杆菌
Exiguobacterium aurantiacum 金橙黄微小杆菌
Synteophobacter wolinii 沃氏互营养杆菌
Synteophobacter pnnigii 芬氏互营养杆菌
Pelobacter acetylenicus 乙炔居泥杆菌
Pelobacter propionicus 产丙酸居泥杆菌
Thiodictyon elegans 美网硫菌
Thiocystis violacea 紫囊硫菌
Anaerovibrio glycerini 甘油厌氧弧菌
Anaerovibrio lipolytica 解脂厌氧弧菌
另外，还可以对以上步骤进行如下优化，即在焦化废水进入预爆池之前还经过气浮池出水，经一沉池处理后的废水先由集水池收集后再用泵送入兼氧池或厌氧池。
焦化废水含有COD、NH3-N和挥发酚、硫氰酸盐及其他多种有机污染物，其中挥发酚对大多数微生物具有毒害作用，同时挥发酚也是可分解利用的，并且是一种速效碳源，在一定浓度下可很快被微生物分解利用，它对硝化作用有很强的抑制作用，本发明将挥发酚的去除设定在预曝系统完成，这是本发明能够成功脱氮的关键。
氰化物的存在会抑制菌种的正常代谢反应，特别是生物硝化和反硝化脱氮，本发明通过预曝系统的短时间曝气就可以把硫氰酸盐降低到足够低的程度。
由于硝化反硝化脱氮对碳源、溶解氧、抑制物浓度等因素的影响比较敏感，合理的工艺结合，有助于为脱氮提供一个稳定的条件，对氨氮的去除有很好的促进效果。
焦化废水中的大量有机污染物中有很大一部分对生物有抑制作用，很难被生物降解，但通过使用本发明中所公开的微生物菌群，可以提高对各种有机污染物的降解效能且污泥产量少。
经本发明利用微生物处理焦化废水的方法处理后，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焦化废水的方法，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
图l为本发明利用微生物处理焦化废水的工艺流程图。
具体实施方式
下面结合附图对本发明所公开的利用微生物处理焦化废水的方法进行详细阐述。
如图1所示，含有COD、NH3-N和挥发酚、硫氰酸盐和其他有机污染物的焦化废水先经过气浮池出水，除去油和悬浮物(及渣)，然后将焦化废水送入预曝系统进行预处理，废水先进入预先添加有预曝池体积1.5％～4.0％的HSBTMBM制剂和预曝池体积1.0％～2.5％的活性炭粉末的预曝池，控制温度在15～40℃，pH值6.5～9.0，溶解氧0.6～3.2mg/L，污泥沉降比SV30为10％～25％，停留时间12～28小时，进水COD指标1500～3500mg/L，出水COD指标400～650mg/L，COD降解效率40％～75％，出水时各种对硝化和反硝化有影响的各种指标不超过50mg/L；从预曝池出来的废水再经一沉池沉淀，污泥回流至预曝池，污泥回流比例1∶l～1∶2。
集水池收集经预曝处理后的出水，再用泵打到二段生化系统中的兼氧池进行反硝化脱氮，控制温度在20～35℃，pH值6.5～7.5，溶解氧0.5mg/L以下，污泥沉降比SV30为15％～30％，停留时间16～24小时，进水COD指标400～650mg/L，出水COD指标150～300mg/L，进水亚硝酸盐和硝酸盐含量为150～400mg/L。
经兼氧池处理后的废水再进入预先添加有好氧池体积1.5％～4.0％的HSBTMBM制剂和好氧池体积1.0％～2.5％的活性炭粉末的好氧池中进行硝化作用和进一步降解COD，控制温度在20～38℃，加碱控制pH值6.8～9.0，溶解氧1.5～4.2mg/L，污泥沉降比SV30为15％～30％，停留时间24～48小时，出水COD指标为60～150mg/L；好氧池中的污泥和硝化液回流至兼氧池或厌氧池，回流比1∶1～1∶4，出好氧池的废水经再经二沉池收集污泥和回流后放流，以维持系统中污泥的稳定。二沉池中的活性污泥和硝化液既可以回流至好氧池，也可以回流至厌氧或兼氧池，或者同时回流至好氧池和厌氧或兼氧池，回流比为1∶1～1∶2。
各工艺参数及HSBTMBM制剂添加量与COD及氨氮的去除率的相关关系如下表所示。
| 组别 | 微生物菌群添加量 | 活性炭添加量 | 温度℃ | pH | SV30％ | 溶解氧mg/l | 预曝停留时间h | 二段停留时间h | 总停留时间 | COD去除率％ | 氨氮去除率％ | 污泥回流比 |
| 实施例1 | 1.5％ | 2.5％ | 27 | 7.5 | 24 | 4.2 | 16 | 40 | 60 | 96 | 95.7 | 1∶1 |
| 实施例2 | 1.8％ | 2.4％ | 25 | 7.8 | 21 | 3.3 | 9 | 48 | 61 | 92 | 96.5 | 1∶1.2 |
| 实施例3 | 2.1％ | 2.2％ | 20 | 8.2 | 30 | ＜0.5 | 12 | 50 | 66 | 95 | 94. | 1∶2.1 |
| 实施例4 | 2.4％ | 2.0％ | 15 | 8.5 | 27 | 0.8 | 10 | 42 | 56 | 93 | 94.4 | 1∶2.5 |
| 实施例5 | 2.7％ | 1.8％ | 10 | 9.0 | 18 | 1.5 | 8 | 30 | 42 | 95.5 | 98.2 | 1∶3 |
| 实施例6 | 3.0％ | 1.6％ | 42 | 5.0 | 22 | 2.2 | 14 | 36 | 54 | 94 | 98 | 1∶3.5 |
| 实施例7 | 3.3％ | 1.4％ | 35 | 5.5 | 20 | 2.5 | 18 | 24 | 46 | 94.5 | 97.6 | 1∶3.8 |
| 实施例8 | 3.6％ | 1.2％ | 33 | 7.0 | 12 | 3.0 | 11 | 27 | 42 | 93.8 | 96 | 1∶4 |
| 实施例9 | 4.0％ | 1.0％ | 30 | 6.5 | 15 | 3.5 | 17 | 45 | 66 | 92.7 | 95 | 1∶5.5 |
Claims (6)
1.一种利用微生物处理焦化废水的方法，其特征在于废水在经过二段生化系统进行硝化反硝化作用之前先经过一个好氧的预曝池，由预曝池去除COD和大量有机物，二段生化系统包括厌氧或兼氧池和好氧池，厌氧或兼氧池进行反硝化脱氮，好氧池进行硝化作用，即为O-A-O工艺，且在预曝池中预先直接加入体积1.5％~4.0％的微生物菌群和体积1.0％~2.5％的微生物载体。
2.如权利要求1所述的一种利用微生物处理焦化废水的方法，其特征在于整个工艺过程中没有外加碳源。
3.如权利要求1或2所述的一种利用微生物处理焦化废水的方法，其特征在于预曝池后还有一个一沉池，与预曝池组成预曝系统，二段生化系统中的好氧池可以分成多段，在好氧池后还有一个二沉池。
4.如权利要求3所述的一种利用微生物处理焦化废水的方法，其特征在于预曝系统中由微生物菌群和微生物载体组成的活性污泥采用独立循环方式由一沉池回流至预曝池，回流比1∶1~1∶2，在二段生化系统中既有污泥回流又有硝化液回流，其中好氧池回流至厌氧或兼氧池的回流比为1∶1~1∶4，二沉池的活性污泥和硝化液既可以回流至好氧池，也可以回流至厌氧或兼氧池，或者同时回流至好氧池和厌氧或兼氧池，回流比为1∶1~1∶2。
5.如权利要求1或2所述的一种利用微生物处理焦化废水的方法，其特征在于添加的微生物载体为粉末活性炭。
6.如权利要求1或2所述的一种利用微生物处理焦化废水的方法，其特征在于在预曝池中直接加入的微生物菌群包含有以下来自47个属的105种微生物：
Acetobacter aceti 醋酸醋杆菌
Acetobacter liquefaciens 液化醋杆菌
Acetobacter xylinum 木醋杆菌
Achromobacter xerosis 干燥无色菌
Aeromonans hydrophila 嗜水气单胞菌
Aeromonas media 中间气单胞菌
Aeromonans sobria 温和气单胞菌
Bacillus alvei 分支芽孢杆菌
Bacillus coagulans 凝结芽孢杆菌
Bacillus subtilis 枯草芽孢杆菌
Bacillus leutis 迟缓芽孢杆菌
Bacillus firmus 坚强芽孢杆菌
Bacillus mycoides 状芽孢杆菌
Bacillus megaterium 巨大芽孢杆菌
Bacillus alcalophilus 嗜碱芽孢杆菌
Bacillus cereus 蜡样芽孢杆菌
Bacillus licheniformis 地衣芽孢杆菌
Bacillus pumilus 短小芽孢杆菌
Bacillus spaericus 球形芽孢杆菌
Bacillus marinus 海洋芽孢杆菌
Alcaligenes denitrificans 反硝化亚种
Alcaligenes faecalis 粪产碱菌
Alcaligenes xylosoxydans 木糖氧化产碱菌
Brevibacterium acetylicum 乙炔短杆菌
Brevibacterium ammoniagenes 解氨短杆菌
Brevibacterium casei 乳酪短杆菌
Brevibacillus brevis 短短芽孢杆菌
Enterobacter cloacae 阴沟肠杆菌
Enterobacter aerogenes 产气肠杆菌
Enterobacter agglomerans 成团肠杆菌
Thiobacillus novellas
Thiobacillus thioparus
Thiobacillus denitrificans 反硝化硫杆菌
Thiobacillus thiooxidans 氧化硫杆菌
Thiorhodococcus minus 硫红球菌
Rhodopseudomonas palustris 沼泽红假单胞菌
Rhodopseudomonas acidphia 嗜酸红假单胞菌
Gluconobacter albidus 浅井氏葡糖杆菌
Gluconobacte oxydans 葡糖氧化杆菌
Lactobacillus fermentum 发酵乳杆菌
Lactobacillus plantarum 植物乳杆菌
Lactobacillus alimentarius 消化乳杆菌
Lactobacillus amylophillus 食淀粉乳杆菌
Lactobacillus ruminis 瘤胃乳杆菌
Lactobacillus bervis 短乳杆菌
Micrococcus leutus 藤黄微球菌
Micrococcus halobius 喜盐微球菌
Pseudomonas alcaligenes 产碱假单胞菌
Pseudomonas aureofaciens 致黄色假单胞菌
Pseudomonas chlororaphis 绿针假单胞菌
Pseudomonas nitroreducens 硝化假单胞菌
Pseudomonas riboflavina 核黄素假单胞菌
Pseudomonas put ina 恶臭假单胞菌
Pseudomonas facilis 敏捷假单胞菌
paenibacillus gluconolyticus 解葡聚糖类芽孢杆菌
paenibacillus thiaminlyticus 解硫胺素类芽抱杆菌
Saccharomyces telluris
Beggiatoa alba
Nitrobacter winogradskyi 硝化杆菌
Nitrosomonas europaea 亚硝化单胞菌
Nitrosococcus nitrosus
Photobacterium angustum 狭小发光杆菌
Photobacterium phosphoreum 明亮发光杆菌
Photobacterium leiognathi 鳆发光杆菌
Haloferax denitrificans 反硝化盐富饶菌
Haloferax mediterranei 地中海盐富饶菌
Methanobacterium bryantii 布氏甲烷杆菌
Methanobacterium paluster 沼泽甲烷杆菌
Methanobacterium uliginosum 泥沼甲烷杆菌
Cellulomonas biazotes 双氮纤维单胞菌
Cellulomonas fimi 粪肥纤维单胞菌
Kurthia zopfii 佐氏库特氏菌
Thiosphaera pantotropha
Alcaligenes sp
Chlorobium limicola 泥生绿菌
Erythrobacter longus 长赤细菌
Erothromonas ursincola 红单胞菌
Azomonas macrocytogenes 巨胞氮单胞菌
Xanthobacter flavus 黄黄色杆菌
Methylcoccus capsulatus 荚膜甲基球菌
Alteromonas denitrificans 反硝化交替单胞菌
Alteromonas nigrifaciens 产黑交替单胞菌
Telluria mxita 混合地神菌
Bacteroides cellulosovens 溶纤维素拟杆菌
Bacteroides stercoris 粪便拟杆菌
Ilyobacter ploytropus 多营养泥杆菌
Pseudobutyrivibrio ruminis 瘤胃假丁酸弧菌
Syntrophomonas wolfei 澳氏互营养单胞菌
Pimelobacter simplex 简单脂肪杆菌
Pimelobacter tumescens 肿胀脂肪杆菌
Brachybacterium faecium 粪短状杆菌
Jonesia denitrificans 反硝化琼斯氏菌
Rarobacter faecitabidus 渣腐稀有杆菌
Eubacterium formicigenerans 产甲酸真杆菌
Eubacterium nitritogenes 产亚硝酸真杆菌
Eubacterium xylanophilum 嗜聚木糖真杆菌
Exiguobacterium aurantiacum 金橙黄微小杆菌
Synteophobacter wolinii 沃氏互营养杆菌
Synteophobacter pnnigii 芬氏互营养杆菌
Pelobacter acetylenicus 乙炔居泥杆菌
Pelobacter propionicus 产丙酸居泥杆菌
Thiodictyon elegans 美网硫菌
Thiocystis violacea 紫囊硫菌
Anaerovibrio glycerini 甘油厌氧弧菌
Anaerovibrio lipolytica 解脂厌氧弧菌。
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| CN100503485C (zh) * | 2007-06-27 | 2009-06-24 | 同济大学 | 一种抗冲击的倍增组合式焦化废水处理工艺 |
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| CN100503485C (zh) * | 2007-06-27 | 2009-06-24 | 同济大学 | 一种抗冲击的倍增组合式焦化废水处理工艺 |
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