CN102115287B - 一种焦化污水深度处理零排放工艺 - Google Patents
一种焦化污水深度处理零排放工艺 Download PDFInfo
- Publication number
- CN102115287B CN102115287B CN2011100067578A CN201110006757A CN102115287B CN 102115287 B CN102115287 B CN 102115287B CN 2011100067578 A CN2011100067578 A CN 2011100067578A CN 201110006757 A CN201110006757 A CN 201110006757A CN 102115287 B CN102115287 B CN 102115287B
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- Prior art keywords
- water
- ammonia nitrogen
- waste water
- reverse osmosis
- treatment
- Prior art date
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- 239000002351 wastewater Substances 0.000 title claims abstract description 23
- 238000000034 methods Methods 0.000 title claims abstract description 14
- 238000004939 coking Methods 0.000 title abstract description 7
- 239000011901 water Substances 0.000 claims abstract description 54
- 238000007254 oxidation reactions Methods 0.000 claims abstract description 30
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 24
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound 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[N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 241000276438 Gadus morhua Species 0.000 claims abstract description 17
- 239000011651 chromium Substances 0.000 claims abstract description 17
- 235000019516 cod Nutrition 0.000 claims abstract description 17
- 230000003197 catalytic Effects 0.000 claims abstract description 15
- 239000000919 ceramics Substances 0.000 claims abstract description 14
- 238000007667 floating Methods 0.000 claims abstract description 9
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 7
- 239000003921 oils Substances 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound 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OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000011780 sodium chloride Substances 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound 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C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011892 benzene Substances 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 28
- 239000010865 sewage Substances 0.000 claims description 13
- 238000006243 chemical reactions Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 230000002829 reduced Effects 0.000 claims description 7
- 239000002253 acids Substances 0.000 claims description 6
- 230000037250 Clearance Effects 0.000 claims description 5
- 230000035512 clearance Effects 0.000 claims description 5
- 239000000084 colloidal systems Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000012267 brine Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 230000004059 degradation Effects 0.000 claims description 3
- 238000006731 degradation reactions Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- DZBUGLKDJFMEHC-UHFFFAOYSA-N Acridine Chemical compound 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C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930013066 Indole Natural products 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 230000033558 biomineral tissue development Effects 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound 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C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
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- GLUUGHFHXGJENI-UHFFFAOYSA-N piperazine Chemical compound 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C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound 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C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000008091 pyridine Substances 0.000 claims description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound 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- 231100000614 Poisons Toxicity 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[N] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 description 1
- 230000003000 nontoxic Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010525 oxidative degradation reactions Methods 0.000 description 1
- 239000002245 particles Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound 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- 238000003860 storage Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound 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[S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agents Toxicity 0.000 description 1
- 238000005429 turbidity Methods 0.000 description 1
- 239000002699 waste materials Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
Description
一种焦化污水深度处理零排放工艺
技术领域
[0001] 本发明属于焦化污水处理及回用技术领域,特别涉及一种焦化污水处理零排放工艺。
背景技术
[0002] 我国是世界焦炭第一生产大国和出口大 国,产量占世界焦炭产量的45%以上。规模庞大的焦炭行业在促进经济增长、社会发展的同时带来了巨大的污染,严重地危害了自然环境、生态平衡和身体健康。1989年以前,国家环保政策对焦化污水的排放标准相对较为宽松;90年代以后,《污水综合排放标准》及《钢铁工业水污染排放标准》中提出了氨氮和CODcr的排放要求。随着国民经济的飞速发展和人民生活水平不断提高,可利用水资源的匮乏已经成为制约我国经济可持续性发展的瓶颈;水资源节约、综合利用、污水深度处理、循环使用势在必行,迫在眉睫。2006年以后,国家把节能减排提到了一个全新的高度,出台了一系列严格控制污染物排放与消减、污染行业新建与扩建、淘汰高耗能高污染工艺、鼓励与扶持污水处理回用等相关政策。目前我国焦化行业已进入到关键时期,焦化污水的深度处理回用将成为企业低碳环保、节能减排、可持续发展的关键保障和重要体现。
[0003] 焦化污水是在生产焦炭、煤气、及焦化产品深加工过程中产生的污水,含有多种污染物质。其中有机物以酚类化合物为主,占总有机物的一半以上;有机物中包括大量的多环芳香族化合物和含氮、氧、硫的杂环化合物等;处理难度很大,属于难降解的高浓度有机工业污水。
[0004] 目前国内多数焦化企业的生产污水采用A/0等工艺生化处理后,再用物化法处理后;处理后水质指标波动剧烈,难以达标排放。如果在传统处理工艺后采用适当的技术进行深度处理并回用,使焦化污水的资源化,节约了水资源,实现焦化污水零排放。
发明内容
[0005] 本发明的目的在于提供一种焦化污水处理零排放工艺,可广泛用于国内焦化行业污水深度处理,实现焦化污水的零排放。
[0006] 本发明采用“电气浮+电催化氧化+陶瓷超滤膜+反渗透膜”处理工艺。
[0007] 本发明的原水为焦化污水处理厂生化处理后出水,其水质为:C0D& = 150〜400mg/L,氨氮=25 〜120mg/L,SS = 70 〜100mg/L,pH = 6 〜9,电导率=5000 〜9000 y s/cm,油=5 〜10mg/L。
[0008] 本发明所述的电气浮可以有效去除水中的溶解性胶体和悬浮态污染物,产生的新生态的[0]和[Cl]等强氧化剂可对污水中有机物和氨氮进行氧化,通过气浮和氧化双重功效来去除污水中的0©&和氨氮,C0D&去除率可达50%以上,氨氮的去除率16. 7%以上。
[0009] 本发明所述的电催化氧化可完全将焦化污水中含有酚、喹啉、吡啶、吲哚、呋喃、哌嗪、吖啶、咪唑、长链烷烃、环烷烃、苯、联苯、卤代烷烃及少量的醇、酸、酯等难以生物降解有机物矿化,反应生成物为C02、H2O和N2,对芳香族物质的开环表现出高反应活性;出水C0D&平均值小于50mg/L,氨氮平均值小于5mg/L,CODcr去除率高达75%,氨氮去除率为95%。
[0010] 本发明所述的闭式冷却塔主要是将电催化氧化后的水温从55°C降至35°C以下,同时添加还原剂以降低产水的氧化性。
[0011] 本发明所述的陶瓷超滤膜作为反渗透膜的预处理,采用错流过滤方式,能够把悬浮固体、胶体、大分子有机物几乎全部被截留,出水SDI15 ( 3。陶瓷膜具有超强的化学稳定性,抗氧化能力强,耐强酸、强碱,耐高温,PH值适用范围1-14,机械强度高,清洗再生容易,过滤精度高的物理和化学性能,陶瓷膜使用寿命是有机膜的2-3倍。
[0012] 本发明所述的反渗透膜主要脱除污水中绝大 部分的盐份及大分子有机物,反渗透膜采用进口超低压抗污染反渗透膜,系统脱盐率> 95 %,回收率为70 %,其产水水质为CODcr ^ 10mg/L,氨氮< 5mg/L,SS ^ lmg/L,pH = 7 〜8,电导率< 450 y s/cm,油< 0. 05mg/L,可回用于工业循环冷却水的补充水;反渗透膜的浓盐水可通过固化处理。
[0013] 本发明具有节约水资源、系统出水水质稳定,运行管理方便等特点,可广泛用于国内焦化行业污水深度处理,实现焦化污水的零排放。
附图说明
[0014] 图I为本发明具体实施方式的焦化污水深度处理零排放工艺流程图。
具体实施方式
[0015] 焦化污水深度处理零排放工艺的具体实施方式如下:
[0016] 原水为焦化污水处理厂生化处理后出水,原水首先通过电气浮进行处理,电气浮的原理是通过电解水产生大量的致密气泡,微小气泡携带污水中的胶体微粒、油污共同上浮,达到分离净化的目的,在阳极上同时还发生电氧化反应,可部分去除污水中的C0D&、氨氮、酚、氰,CODtt去除率可达50%以上,氨氮的去除率16. 7%以上。浮渣通过刮渣机刮至贮渣池,通过泵提升至原污水处理厂污泥处理系统。电气浮的出水进入电气浮产水池,在电气浮产水池内投加NaOH,将污水的pH值调整到9〜10,有利于在电催化氧化过程中将氨氮去除。
[0017] 电气浮产水池的水经提升后进入电催化氧化进行反应,将污水中难以生物降解的有机物及有毒、有害物质分解成CO2和水。电催化氧化是电化学阳极发生氧化的过程,也可分为两种:一种是直接氧化即污染物直接在阳极失去电子而发生氧化,有机物的直接电催化氧化转化分两类进行。(I)是电化学转换,即把有毒物质转变为无毒物质,或把非生物相容的有机物转化为生物相容的物质(如芳香物开环氧化为脂肪酸),以便进一步实施生物处理;(2)是电化学“燃烧”,即直接将有机物深度氧化为C02。另一种是间接氧化即通过阳极反应生成具有强氧化作用的中间产物或发生阳极反应之外的中间反应,氧化被处理污染物,最终达到氧化降解污染物的目的。电催化氧化的出水进入电催化氧化产水池,在水池内停留时间I. 5h以上,由于水中含有大量的氧化剂,为充分利用水中的氧化剂对电氧化出水中的有机物和NH3-N进一步氧化,降低运行能耗。
[0018] 电催化氧化产水池的水经提升后进入闭式冷却塔进行降温,将水温从55°C降至35°C以下,同时添加还原剂以降低产水的氧化性,冷却后的水进入冷却水池。
[0019] 冷却水池内的水经提升后进入陶瓷超滤膜,可以进一步降低水中的悬浮物、浊度、胶体含量,降低水中部分COD&,陶瓷超滤膜采用错流过滤方式,出水SDI15 ( 3,满足反渗透膜的进水要求,系统回收率为90%。陶瓷膜具有超强的化学稳定性,抗氧化能力强,耐强酸、强碱,耐高温,PH值适用范围1-14,机械强度高,易清洗,过滤精度高的物理和化学性能,陶瓷膜使用寿命是有机膜的2-3倍。陶瓷超滤膜的出水进入超滤产水池。
[0020] 超滤产水池内的水经提升后进入5 U m的保安过滤器,再由高压泵加压送至反渗透膜。反渗透膜主要是将溶剂和溶剂中离子范围的溶质分开,只允许水、溶剂通过,可脱除水中绝大部分的悬浮物、胶体、有机物及盐份。反渗透膜采用进口超低压抗污染反渗透膜,系统脱盐率> 95%,回收率为70%。反渗透膜 入口投加阻垢剂和还原剂,以防止反渗透膜结垢和被氧化。反渗透膜的产水进入反渗透产水池,再泵送入厂区除盐水管网,可回用于工业循环冷却水的补充水;反渗透膜的浓盐水进入反渗透浓水池,可通过固化处理,实现焦化污水的零排放。
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