CN101665311A - 高浓度难降解有机废水的催化微电解组合工艺 - Google Patents
高浓度难降解有机废水的催化微电解组合工艺 Download PDFInfo
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- CN101665311A CN101665311A CN200910307667A CN200910307667A CN101665311A CN 101665311 A CN101665311 A CN 101665311A CN 200910307667 A CN200910307667 A CN 200910307667A CN 200910307667 A CN200910307667 A CN 200910307667A CN 101665311 A CN101665311 A CN 101665311A
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- iron
- charcoal
- water
- catalysis
- electrolysis
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 61
- 239000002351 wastewater Substances 0.000 title claims abstract description 41
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 31
- 238000005516 engineering process Methods 0.000 title claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,PD94bWwgdmVyc2lvbj0nMS4wJyBlbmNvZGluZz0naXNvLTg4NTktMSc/Pgo8c3ZnIHZlcnNpb249JzEuMScgYmFzZVByb2ZpbGU9J2Z1bGwnCiAgICAgICAgICAgICAgeG1sbnM9J2h0dHA6Ly93d3cudzMub3JnLzIwMDAvc3ZnJwogICAgICAgICAgICAgICAgICAgICAgeG1sbnM6cmRraXQ9J2h0dHA6Ly93d3cucmRraXQub3JnL3htbCcKICAgICAgICAgICAgICAgICAgICAgIHhtbG5zOnhsaW5rPSdodHRwOi8vd3d3LnczLm9yZy8xOTk5L3hsaW5rJwogICAgICAgICAgICAgICAgICB4bWw6c3BhY2U9J3ByZXNlcnZlJwp3aWR0aD0nODVweCcgaGVpZ2h0PSc4NXB4JyB2aWV3Qm94PScwIDAgODUgODUnPgo8IS0tIEVORCBPRiBIRUFERVIgLS0+CjxyZWN0IHN0eWxlPSdvcGFjaXR5OjEuMDtmaWxsOiNGRkZGRkY7c3Ryb2tlOm5vbmUnIHdpZHRoPSc4NS4wJyBoZWlnaHQ9Jzg1LjAnIHg9JzAuMCcgeT0nMC4wJz4gPC9yZWN0Pgo8dGV4dCB4PSczNS4wJyB5PSc1My42JyBjbGFzcz0nYXRvbS0wJyBzdHlsZT0nZm9udC1zaXplOjIzcHg7Zm9udC1zdHlsZTpub3JtYWw7Zm9udC13ZWlnaHQ6bm9ybWFsO2ZpbGwtb3BhY2l0eToxO3N0cm9rZTpub25lO2ZvbnQtZmFtaWx5OnNhbnMtc2VyaWY7dGV4dC1hbmNob3I6c3RhcnQ7ZmlsbDojM0I0MTQzJyA+RjwvdGV4dD4KPHRleHQgeD0nNTEuMCcgeT0nNTMuNicgY2xhc3M9J2F0b20tMCcgc3R5bGU9J2ZvbnQtc2l6ZToyM3B4O2ZvbnQtc3R5bGU6bm9ybWFsO2ZvbnQtd2VpZ2h0Om5vcm1hbDtmaWxsLW9wYWNpdHk6MTtzdHJva2U6bm9uZTtmb250LWZhbWlseTpzYW5zLXNlcmlmO3RleHQtYW5jaG9yOnN0YXJ0O2ZpbGw6IzNCNDE0MycgPmU8L3RleHQ+Cjwvc3ZnPgo= [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 117
- 229910052742 iron Inorganic materials 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances data:image/svg+xml;base64,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 data:image/svg+xml;base64,PD94bWwgdmVyc2lvbj0nMS4wJyBlbmNvZGluZz0naXNvLTg4NTktMSc/Pgo8c3ZnIHZlcnNpb249JzEuMScgYmFzZVByb2ZpbGU9J2Z1bGwnCiAgICAgICAgICAgICAgeG1sbnM9J2h0dHA6Ly93d3cudzMub3JnLzIwMDAvc3ZnJwogICAgICAgICAgICAgICAgICAgICAgeG1sbnM6cmRraXQ9J2h0dHA6Ly93d3cucmRraXQub3JnL3htbCcKICAgICAgICAgICAgICAgICAgICAgIHhtbG5zOnhsaW5rPSdodHRwOi8vd3d3LnczLm9yZy8xOTk5L3hsaW5rJwogICAgICAgICAgICAgICAgICB4bWw6c3BhY2U9J3ByZXNlcnZlJwp3aWR0aD0nODVweCcgaGVpZ2h0PSc4NXB4JyB2aWV3Qm94PScwIDAgODUgODUnPgo8IS0tIEVORCBPRiBIRUFERVIgLS0+CjxyZWN0IHN0eWxlPSdvcGFjaXR5OjEuMDtmaWxsOiNGRkZGRkY7c3Ryb2tlOm5vbmUnIHdpZHRoPSc4NS4wJyBoZWlnaHQ9Jzg1LjAnIHg9JzAuMCcgeT0nMC4wJz4gPC9yZWN0Pgo8dGV4dCB4PScxMy4zJyB5PSc1My42JyBjbGFzcz0nYXRvbS0wJyBzdHlsZT0nZm9udC1zaXplOjIzcHg7Zm9udC1zdHlsZTpub3JtYWw7Zm9udC13ZWlnaHQ6bm9ybWFsO2ZpbGwtb3BhY2l0eToxO3N0cm9rZTpub25lO2ZvbnQtZmFtaWx5OnNhbnMtc2VyaWY7dGV4dC1hbmNob3I6c3RhcnQ7ZmlsbDojRTg0MjM1JyA+SDwvdGV4dD4KPHRleHQgeD0nMjguMicgeT0nNjIuOScgY2xhc3M9J2F0b20tMCcgc3R5bGU9J2ZvbnQtc2l6ZToxNXB4O2ZvbnQtc3R5bGU6bm9ybWFsO2ZvbnQtd2VpZ2h0Om5vcm1hbDtmaWxsLW9wYWNpdHk6MTtzdHJva2U6bm9uZTtmb250LWZhbWlseTpzYW5zLXNlcmlmO3RleHQtYW5jaG9yOnN0YXJ0O2ZpbGw6I0U4NDIzNScgPjI8L3RleHQ+Cjx0ZXh0IHg9JzM1LjAnIHk9JzUzLjYnIGNsYXNzPSdhdG9tLTAnIHN0eWxlPSdmb250LXNpemU6MjNweDtmb250LXN0eWxlOm5vcm1hbDtmb250LXdlaWdodDpub3JtYWw7ZmlsbC1vcGFjaXR5OjE7c3Ryb2tlOm5vbmU7Zm9udC1mYW1pbHk6c2Fucy1zZXJpZjt0ZXh0LWFuY2hvcjpzdGFydDtmaWxsOiNFODQyMzUnID5PPC90ZXh0Pgo8L3N2Zz4K O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound 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[N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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- 230000015556 catabolic process Effects 0.000 claims description 12
- 230000004059 degradation Effects 0.000 claims description 12
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- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class 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[O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000000247 postprecipitation Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 15
- -1 iron-carbon Chemical compound 0.000 abstract description 6
- 238000003487 electrochemical reaction Methods 0.000 abstract description 5
- 230000000593 degrading Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 2
- 230000003197 catalytic Effects 0.000 abstract 2
- 238000010979 pH adjustment Methods 0.000 abstract 2
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Chemical compound 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O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 230000003851 biochemical process Effects 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound 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CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound 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[OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound 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OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 238000011068 load Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006213 oxygenation reaction Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound 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OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
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- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound 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Abstract
高浓度难降解有机废水的催化微电解组合工艺,有机废水收集至调节池,经水量与水质调3节,进入到气浮池气浮处理去除部分有机物,浮渣收集处理或回收,废水经pH调节后,进入催化铁炭微电解单元提高可生化性,出水经pH调节后进入沉淀池,沉淀池出水采用缺氧-好氧生化处理,去除有机物及氨氮后达标排放;催化铁炭微电解单元的填料包括铁、炭及催化剂,其中,填料质量比为铁∶炭∶催化剂=1∶(0.3-1.5)∶(0.01-0.5)。本发明可有效提高微电解电化学反应效率及对有机物降解能力,并同时,降低废水处理成本,工艺操作方便。
Description
解组合工艺
技术领域
本发明属环境工程技术领域,具体涉及高浓度难降解有机废水处理组合工艺。 背景技术
随着工业的发展,生产过程中排放的各类有机废水日益增多,尤其是高浓度难降解有机 废水,其处理方法一直是困扰环境治理的难题,寻求技术可行、经济合理的处理方法具有较 强的现实意义。电化学法处理废水起始于1940年代,近年来,随着电力工业的发展,电化 学法才被真正应用于废水处理过程,包括垃圾渗滤液、制革废水、印染废水、石油和化工废 水等。电化学方法是"环境友好"工艺,具有多种其它方法所不能比拟的优势与特点:①不
需另外添加氧化还原剂,电子转移只在电极及溶液间进行,避免了二次污染。②反应器设备 及其操作简单,便于实施自动控制。通过改变电流密度来改变产生气泡的量,对特定的分离 对象,可通过选择合适的电极表面,调节溶液的化学状况来获取最佳的处理效果。③反应条 件温和,在常温常压下就可进行。④既可以作为单独处理,又可以与其他处理相结合。©设 备占地面积小。
电化学废水处理包括电解法(电氧化和电还原)、电絮凝、电气浮、电渗析、微(内) 电解等多种方法,其中,以废铁屑为原料的铁炭微电解因不消耗电力资源、处理效果好、使 用寿命长及成本低廉等优点而广泛应用。铁炭微电解是在酸性条件下,以铁和炭作为填料, 铁为阳极,碳为阴极,通过铁与炭之间形成的无数个微电流反应器产生微电流,使废水中的
有机物在微电流的作用下被氧化还原,实现对废水的净化处理,提高废水的B/C比值。其净 化作用包括氧化还原作用、铁离子的絮凝作用、铁盐沉淀等多重作用。如微电解时,有机物 参与阴极的还原反应,使官能团发生变化,改变原有机物的性质、降低色度,改善了B/C比 值;阳极生成的氢气具有还原性,能将部分化合物还原成低毒、易降解的化合物;少量无机 物、胶体粒子和微小分散污染物受电场作用,产生电泳现象,向相反电荷的电极移动,并聚 集在电极上使水澄清;阳极新生态的铁离子经石灰中和生成氢氧化物沉淀,具有极强的吸附 能力,使废水得以净化。
铁炭微电解具有诸多优点,但也需要看到其不足之处。普通铁炭微电解的电极电位较低 、电化学反应效率及有机物降解能力较差,同时,铁炭微电解体系的传质效率不高、铁屑易 于发生钝化。有研究者在Fenton试剂的启发下,向铁炭微电解体系中加入双氧水,以达到提高处理效率的目的(刘汝鹏,曲莹,王全勇.强化微电解去除中段废水中TOC和色度的研究. 工业废水处理,2008, 28(10).),但双氧水利用率低,大量双氧水的加入较大地提高了废 水处理成本。其次,由于有机废水的复杂性,采用单一的铁炭微电解方法处理复杂废水的成 本高、可操作性差。例如,电化学方法可以很好地降解苯酚污染物,但是酚完全矿化为水和 C02需要24个电子,因此,完全采用电化学方法降解苯酚成本高。又如印染废水,其水量大 、色度深、碱度高、水质复杂多变,且含有PVA浆料、新型助剂等难生物降解有机物,可生 化性很差。对此,传统的生物处理技术只能有限度地去除印染废水的COD和色度,电化学法 有较大优势,但印染废水中高浓度的悬浮物和胶质固体会阻碍电化学反应。 发明内容
本发明的目的在于,针对石油化工等高浓度难降解有机废水的特点,提供一种组合工艺 ,可有效提高微电解电化学反应效率及对有机物降解能力,并同时,降低废水处理成本,工 艺操作方便,有利于工程实际应用及对已有石油化工废水处理流程的技术改造。
本发明的目的是通过下述方式实现的:
本发明方案为:有机废水收集至调节池,经水量与水质调节,进入到气浮池气浮预处理 去除部分有机物,浮渣收集处理或回收,废水经pH调节后,进入催化铁炭微电解单元,出水 经pH调节后进入沉淀池沉淀去除有机物与大部分胶体及微粒,最后进入生化处理,通过缺氧 -好氧相结合的方式,去除有机物及氨氮后,达标排放;催化铁炭微电解单元的填料包括铁 、炭及催化剂,其中,填料质量比为铁:炭:催化剂=1: (0.3-1.5): (0.01-0.5)。
发明人通过气浮处理去除分散油及绝大部分乳化油,降低催化微电解处理负荷;在微电 解单元中添加可提高电极电位的催化剂,进一步提高微电解的处理能力与效率,提高难降解 有机废水的可生化性、降低废水的COD浓度,并通过充氧(空气)强化对有机物的氧化,保持 填料活性;最后生化工艺采用缺氧-好氧工艺,以达到高浓度难降解有机废水中COD与氨氮同 时高效处理、达标排放。本组合工艺中将气浮与催化微电解作为缺氧-好氧生化工艺的前置 处理单元,可以降低废水处理成本17%,同时由于气浮与催化微电解的设施设备简单,更有 利于工程实际应用及对已有石油化工废水处理流程的技术改造。
废水进入催化铁炭微电解前,需经pH调节,pH值范围1.5-10.5,最优选pH值范围 1. 8-4. 5,以使固态铁在酸性环境中溶解变成铁离子。
铁采用粒径为0.5-50mm铁屑、抱花铁或铸铁中的一种或几种;炭可以是活性碳、焦碳、 竹碳或木炭中的一种或几种,粒径l-50mm。
催化剂用以提高微电解电位,进而提高微电解氧化还原效率,最优选铁锰氧化物、铜、阳离子改性沸石或阳离子交换树脂等。
催化铁炭微电解通过充入氧或空气强化微电解单元中有机物降解能力、减弱铁的钝化过程。
催化铁炭微电解填料通过采用定期或不定期反冲洗,以保持铁炭微电解填料的高活性, (可通过填料底部设置的冲洗管道进行反冲洗,这样设置即简单,又操作方便),反冲洗可 采用高压水冲洗、气冲洗及气-水联合反冲洗的方式。
气浮池可采用溶气、散气的平流池或竖流池,也可以采用电解气浮方式,根据水中有机 物特性,特别是油类的含量与种类,必要时可在气浮池前增加隔油池或只用隔油池。
沉淀池可采用平流式或辐流式;沉淀池进水需进行pH调节,pH值范围6.5-10.5;沉淀池 的沉渣可通过板框压滤机进行浓縮,或采用其他浓縮手段处理。当废水中污染物浓度低于 1500mg/L时,可不设沉淀池。
生化处理:采用缺氧-好氧相结合的工艺流程(A/0),高效去除有机物及氨氮。其中, 缺氧与好氧段根据水质进行调整,缺氧A段可采用预酸化、水解酸化(HAT)、 A、 A2、升流式 厌氧污泥床(UASB)等及其组合方式,好氧O段包括各类生化好氧处理方法,可采用O、 02、曝 气生物滤池(BAF)等方式;生化处理出水经二次沉淀池沉淀后出水,或通过滤膜过滤的方式 直接出水,以提高生化工艺中活性污泥浓度;生化处理的剩余污泥通过浓縮池、板框压滤机 等进行浓縮。
过滤膜是有机聚合物膜或无机陶瓷膜,膜孔平均孔径为O. 01-1 y m。 本发明所需难降解有机废水来源于某石化企业的己内酰胺生产废水,废水中COD浓度高 、色度大、氨氮含量高,且含苯、甲苯等苯系物而难于生物降解,单一的生化处理难以实现 达标排放目的,本发明采用气浮拊呋 5.缃鉬生化处理组合工艺。虽已有采用微电解与生化 方法组合的工艺实现对高浓度有机废水的处理(刘俊新,曲久辉,雷鹏举.处理染料废水的 生物-电化学组合系统及其操作方法.CN101024534A;黄斌,邓建利,张方银等.活性污泥法 -微电解法处理工业废水.CN1429779A),但其铁炭微电解未添加催化剂,电极电位较低、 电化学反应效率及有机物降解能力不强,同时,所采用生化工艺的氨氮去除效果较差;此外 ,已公开的微电解与缺氧/好氧的组合工艺专利(贾金平,徐新燕,吕洲等.缺氧/好氧两段 式内电解处理有机废水.CN1935681A)将微电解单元放置于生化缺氧单元内部,相对于前述 专利,该专利縮短了组合工艺流程、氨氮处理效率较高,但受装置构造限制,其铁炭微电解 体系处理能力有限、传质效率不高,难以实现对水质波动大的石油化工废水的处理,将微电 解内置于缺氧单元内部也增大了系统装配与维修难度。本发明相对于以上技术及现有技术的优点在于:微电解前置气浮处理,有效降低微电 解处理负荷。微电解单元添加催化剂,通过该单元铁、炭、催化剂的有效配比,实现催化微 电解,提高微电解电位差进而提高微电解对有机物的氧化还原效率;通过充氧(空气)、反 清洗等进一步提高催化微电解的处理能力与效率。此外,本发明针大多数石化废水中氨氮浓 度较高的特点,后置生化处理采用缺氧-好氧工艺,在有效去除COD的同时,确保氨氮达标排 放。
综上所述,本发明的一种含催化微电解的废水处理组合工艺,在铁微电解中添加一定量 催化剂以提高微电解电位差及氧化还原效率,通过充氧(空气)、反清洗等进一步提高电化 学处理能力与效率,提高难降解有机废水的可生化性、降低废水的COD浓度。催化铁炭微电 解前置气浮预处理,以降低催化铁炭微电解处理负荷,催化铁炭微电解后置缺氧-好氧生化 处理,实现高浓度难降解有机废水中COD与氨氮的同时高效处理、达标排放。
本发明的气浮拊呋 5.缃鉬生化处理组合工艺反应器设备及其操作简单,便于实施自动 控制,反应在常温常压下进行,设备占地面积小。
附图说明
图l为本发明废水处理组合工艺的具体流程图。 具体实施方式
以下实施例旨在说明本发明而不是对本发明的进一步限定。 实施例l
某石化企业己内酰胺生产高浓度有机废水处理实施步骤。
① 调节池中原水用微量泵按5L/h流量进入散气气浮池进行气浮处理,气浮池设计停留时 间18min。
② 气浮池出水采用5。/。的硫酸溶液调节废水pb3.0,用铁:炭:催化剂比为2: 1: 0.02的 催化铁炭微电解柱处理,废水停留时间1. 5h,水与填料体积比2 :3 ,催化铁炭微电解柱反冲 洗方式为气-水联合反冲洗,反冲洗时间间隔8h。
③ 催化铁炭微电解柱出水采用10y。的石灰乳调节pH为8. O后进入平流式沉淀池,沉淀池停 留时间取1.5h。
④ 沉淀池出水进入生化处理系统,生化系统采用缺氧-好氧(A/0)工艺。A段内有潜水搅 拌器,停留时间10h; O段设有曝气装置,保证水中溶解氧含量大于4mg/L,停留时间30h。生 化处理系统污泥回流比取l.O。经A/0处理后的废水最后进入二次沉淀池,停留时间3h。
实施例2某化工企业有机废水处理实施步骤。
① 调节池中原水用泵按5L/h流量进入气浮处理系统,气浮采用溶气、平流浮池方式,溶 气水压力取0.3MPa,停留时间15mim。
② 气浮池出水采用10。/。的硫酸溶液调节废水pH4.8,用铁、炭及催化剂比为3: 2: 0. l的 催化铁炭微电解柱处理,废水停留时间1.5h,水与填料体积比l:l,反冲洗方式为高压水反 冲洗。
③ 催化铁炭微电解柱出水采用10y。的石灰乳调节pH为7. 5后进入平流式沉淀池,沉淀池停 留时间取1.5h。
④ 沉淀池出水进入生化处理系统,生化系统采用缺氧-好氧(A/0)工艺。A段内有潜水搅 拌器,停留时间8h; O段设有曝气装置,保证水中溶解氧含量大于4mg/L,停留时间35h。生 化处理系统污泥回流比取l. 0。出水采用浸没式PVC膜过滤的方式,膜孔O. 1 y m。
实施例3
含甲苯废水模拟液处理实施步骤。
① 调节池中原水用泵按3L/h流量进入散气气浮池气浮处理,气浮时间16min。
② 气浮池出水采用5。/。的硫酸溶液调节废水pb2. 5,用铁、炭及催化剂比为2: 1: 0.2的 催化铁炭微电解柱处理,废水停留时间1.5h,水与填料体积比l:l,反冲洗方式为气-水联合 反冲洗。
③ 催化铁炭微电解柱出水采用10。/。的石灰乳调节pH为7. 5后进入生化处理系统,生化系统 采用水解酸化-好氧曝气(HAT/0)工艺。HAT段内置YDT弹性立体填料,停留时间8h; O段设 有曝气装置,保证水中溶解氧含量大于4mg/L,停留时间35h,生化处理系统污泥回流比取 0.75。 A/0剩余污染进入二沉池,停留时间3h。
表1为实施例1〜3废水处理测试结果。
表l废水处理分析结果 mg/L
项目 原水 微电解出水 : ,出水
CODCr B0D5 NH3-N CODCr B0D5 NH3-N CODCr B0D5 NH3-N
实施例l 7410 283 1390 3620 450 1100 52. 0 18. 1<table>table see original document page 9</column></row>
<table>
Claims (10)
1.高浓度难降解有机废水的催化微电解组合工艺,其特征在于,有机废水收集至调节池,经水量与水质调节,进入到气浮池气浮处理去除部分有机物,浮渣收集处理或回收,废水经pH调节后,进入催化铁炭微电解单元提高可生化性,出水经pH调节后进入沉淀池,沉淀池出水采用缺氧好氧生化处理,去除有机物及氨氮后达标排放;催化铁炭微电解单元的填料包括铁、炭及催化剂,其中,填料质量比为铁∶炭∶催化剂=1∶(0.3-1.5)∶(0.01-0.5)。
2 根据权利要求l所述的方法,其特征在于:废水进入催化铁炭微电 解前,需经pH调节,pH值范围1.5-10. 5。
3 根据权利要求2所述的方法,其特征在于:废水进入催化铁炭微电 解前,pH值范围1.8-4. 5。
4 根据权利要求l所述的方法,其特征在于:铁采用粒径为 0.5-50mm铁屑、抱花铁或铸铁中的一种或几种;炭是活性碳、焦碳、竹碳或木炭中的一种或 几种。
5 根据权利要求l所述的方法,其特征在于:催化剂为铁锰氧化物、 铜、阳离子改性沸石或阳离子交换树脂。
6 根据权利要求1或5所述的方法,其特征在于:催化铁炭微电解通过充入氧或空气强化微电解单元中有机物降解能力、减弱铁的钝化过程。
7 根据权利要求l-5任一项所述的方法,其特征在于:催化铁炭微电解填料通过采用定期或不定期反冲洗,以保持铁炭微电解填料的高活性,反冲洗采用高压水 冲洗、气冲洗或气-水联合反冲洗的方式。
8 根据权利要求l所述的方法,其特征在于:气浮池采用溶气、散气 的平流池或竖流池,或者是采用电解气浮池;根据水中有机物特性,包括油类的含量与种类 ,在气浮池前增加隔油池或只用隔油池。
9 根据权利要求l所述的方法,其特征在于:沉淀池采用平流式或辐 流式;沉淀池进水需进行pH调节,pH值范围6. 5-10. 5;沉淀池的沉渣通过板框压滤机进行浓 縮,或采用其他浓縮手段处理;当废水中污染物浓度低于1500mg/L时,不设沉淀池。
10 根据权利要求l所述的方法,其特征在于:生化处理采用缺氧-好 氧即A/0相结合方式,高效去除有机物及氨氮;其中,缺氧与好氧段根据水质进行调整,缺 氧A段采用预酸化、水解酸化、A、 A2、升流式厌氧污染床中的一种或几种组合方式,好氧O 段采用O、 02、曝气生物滤池方式;生化处理出水通过二次沉淀池沉淀后排放,或通过滤膜 过滤的方式直接出水;生化处理的剩余污泥通过浓縮池或板框压滤机进行浓縮;过滤膜是有 机聚合物膜或无机陶瓷膜,膜孔平均孔径为O. 01-1 y m。
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