CN104529019B - 一种适用于高盐度难降解废水的电催化组合处理方法 - Google Patents
一种适用于高盐度难降解废水的电催化组合处理方法 Download PDFInfo
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- CN104529019B CN104529019B CN201410837750.4A CN201410837750A CN104529019B CN 104529019 B CN104529019 B CN 104529019B CN 201410837750 A CN201410837750 A CN 201410837750A CN 104529019 B CN104529019 B CN 104529019B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 32
- 230000003197 catalytic Effects 0.000 title claims abstract 5
- 238000003672 processing method Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances data:image/svg+xml;base64,PD94bWwgdmVyc2lvbj0nMS4wJyBlbmNvZGluZz0naXNvLTg4NTktMSc/Pgo8c3ZnIHZlcnNpb249JzEuMScgYmFzZVByb2ZpbGU9J2Z1bGwnCiAgICAgICAgICAgICAgeG1sbnM9J2h0dHA6Ly93d3cudzMub3JnLzIwMDAvc3ZnJwogICAgICAgICAgICAgICAgICAgICAgeG1sbnM6cmRraXQ9J2h0dHA6Ly93d3cucmRraXQub3JnL3htbCcKICAgICAgICAgICAgICAgICAgICAgIHhtbG5zOnhsaW5rPSdodHRwOi8vd3d3LnczLm9yZy8xOTk5L3hsaW5rJwogICAgICAgICAgICAgICAgICB4bWw6c3BhY2U9J3ByZXNlcnZlJwp3aWR0aD0nMzAwcHgnIGhlaWdodD0nMzAwcHgnIHZpZXdCb3g9JzAgMCAzMDAgMzAwJz4KPCEtLSBFTkQgT0YgSEVBREVSIC0tPgo8cmVjdCBzdHlsZT0nb3BhY2l0eToxLjA7ZmlsbDojRkZGRkZGO3N0cm9rZTpub25lJyB3aWR0aD0nMzAwLjAnIGhlaWdodD0nMzAwLjAnIHg9JzAuMCcgeT0nMC4wJz4gPC9yZWN0Pgo8dGV4dCB4PScxMDAuNScgeT0nMTcwLjAnIGNsYXNzPSdhdG9tLTAnIHN0eWxlPSdmb250LXNpemU6NDBweDtmb250LXN0eWxlOm5vcm1hbDtmb250LXdlaWdodDpub3JtYWw7ZmlsbC1vcGFjaXR5OjE7c3Ryb2tlOm5vbmU7Zm9udC1mYW1pbHk6c2Fucy1zZXJpZjt0ZXh0LWFuY2hvcjpzdGFydDtmaWxsOiNFODQyMzUnID5IPC90ZXh0Pgo8dGV4dCB4PScxMjYuMScgeT0nMTg2LjAnIGNsYXNzPSdhdG9tLTAnIHN0eWxlPSdmb250LXNpemU6MjZweDtmb250LXN0eWxlOm5vcm1hbDtmb250LXdlaWdodDpub3JtYWw7ZmlsbC1vcGFjaXR5OjE7c3Ryb2tlOm5vbmU7Zm9udC1mYW1pbHk6c2Fucy1zZXJpZjt0ZXh0LWFuY2hvcjpzdGFydDtmaWxsOiNFODQyMzUnID4yPC90ZXh0Pgo8dGV4dCB4PScxMzguMCcgeT0nMTcwLjAnIGNsYXNzPSdhdG9tLTAnIHN0eWxlPSdmb250LXNpemU6NDBweDtmb250LXN0eWxlOm5vcm1hbDtmb250LXdlaWdodDpub3JtYWw7ZmlsbC1vcGFjaXR5OjE7c3Ryb2tlOm5vbmU7Zm9udC1mYW1pbHk6c2Fucy1zZXJpZjt0ZXh0LWFuY2hvcjpzdGFydDtmaWxsOiNFODQyMzUnID5PPC90ZXh0Pgo8L3N2Zz4K data:image/svg+xml;base64,PD94bWwgdmVyc2lvbj0nMS4wJyBlbmNvZGluZz0naXNvLTg4NTktMSc/Pgo8c3ZnIHZlcnNpb249JzEuMScgYmFzZVByb2ZpbGU9J2Z1bGwnCiAgICAgICAgICAgICAgeG1sbnM9J2h0dHA6Ly93d3cudzMub3JnLzIwMDAvc3ZnJwogICAgICAgICAgICAgICAgICAgICAgeG1sbnM6cmRraXQ9J2h0dHA6Ly93d3cucmRraXQub3JnL3htbCcKICAgICAgICAgICAgICAgICAgICAgIHhtbG5zOnhsaW5rPSdodHRwOi8vd3d3LnczLm9yZy8xOTk5L3hsaW5rJwogICAgICAgICAgICAgICAgICB4bWw6c3BhY2U9J3ByZXNlcnZlJwp3aWR0aD0nODVweCcgaGVpZ2h0PSc4NXB4JyB2aWV3Qm94PScwIDAgODUgODUnPgo8IS0tIEVORCBPRiBIRUFERVIgLS0+CjxyZWN0IHN0eWxlPSdvcGFjaXR5OjEuMDtmaWxsOiNGRkZGRkY7c3Ryb2tlOm5vbmUnIHdpZHRoPSc4NS4wJyBoZWlnaHQ9Jzg1LjAnIHg9JzAuMCcgeT0nMC4wJz4gPC9yZWN0Pgo8dGV4dCB4PScxMy4zJyB5PSc1My42JyBjbGFzcz0nYXRvbS0wJyBzdHlsZT0nZm9udC1zaXplOjIzcHg7Zm9udC1zdHlsZTpub3JtYWw7Zm9udC13ZWlnaHQ6bm9ybWFsO2ZpbGwtb3BhY2l0eToxO3N0cm9rZTpub25lO2ZvbnQtZmFtaWx5OnNhbnMtc2VyaWY7dGV4dC1hbmNob3I6c3RhcnQ7ZmlsbDojRTg0MjM1JyA+SDwvdGV4dD4KPHRleHQgeD0nMjguMicgeT0nNjIuOScgY2xhc3M9J2F0b20tMCcgc3R5bGU9J2ZvbnQtc2l6ZToxNXB4O2ZvbnQtc3R5bGU6bm9ybWFsO2ZvbnQtd2VpZ2h0Om5vcm1hbDtmaWxsLW9wYWNpdHk6MTtzdHJva2U6bm9uZTtmb250LWZhbWlseTpzYW5zLXNlcmlmO3RleHQtYW5jaG9yOnN0YXJ0O2ZpbGw6I0U4NDIzNScgPjI8L3RleHQ+Cjx0ZXh0IHg9JzM1LjAnIHk9JzUzLjYnIGNsYXNzPSdhdG9tLTAnIHN0eWxlPSdmb250LXNpemU6MjNweDtmb250LXN0eWxlOm5vcm1hbDtmb250LXdlaWdodDpub3JtYWw7ZmlsbC1vcGFjaXR5OjE7c3Ryb2tlOm5vbmU7Zm9udC1mYW1pbHk6c2Fucy1zZXJpZjt0ZXh0LWFuY2hvcjpzdGFydDtmaWxsOiNFODQyMzUnID5PPC90ZXh0Pgo8L3N2Zz4K O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 230000001112 coagulant Effects 0.000 claims abstract description 6
- 230000000593 degrading Effects 0.000 claims abstract description 3
- 238000006479 redox reaction Methods 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 29
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001465 metallisation Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 5
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials 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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
Abstract
本发明公开了一种适用于高盐度难降解废水的电催化组合处理方法,包括:将所处理高盐难降解废水进入沉沙池沉沙,沉沙后出水进入均质池均匀水质,同时向均质池中通入三维电催化反应器中产生的Cl2对废水进行预氧化,均质后出水进入电催化反应器停留进行电催化氧化还原反应,降解废水中的难降解有机物,电催化反应器的出水进入三级混凝池,通过投加的絮凝剂去除废水中的SS,使废水达到可生化性目标或排放目标。该方法通过将电催化氧化工艺与混凝工艺组成电催化组合工艺,解决了常规电化学氧化法运行费用高、电极材料制作要求高的问题,为高盐度难降解废水的处理提供一套运行费用省,操作、维护简单方便,处理效果高效稳定的电催化组合处理工艺。
Description
技术领域
[0001]本发明涉及废水处理领域,特别是涉及一种适用于高盐度难降解废水的电催化组合处理方法。
背景技术
[0002]近几十年来,科学技术飞跃进步,生产力迅猛发展,伴随着中国工业的大规模发展而来的一系列环境问题逐渐凸显,石油化工、印染、制药、精细化工等行业产生的一系列高盐、难降解废水亟待解决方法与处理工艺。由于高盐、难降解废水可生化性差,处理难度大,采用常规的生化处理方法,不仅运行困难,而且难以做到达标处理。20世纪80年代发展起来的高级氧化工艺(AOPs),通过反应产生氧化力极强的轻基自有基(.0H),能快速、高效的氧化降解污染物,从而受到广泛的重视。其中,电化学高级氧化工艺,以处理高效、操作简便、无二次污染、常温常压下即可运行等特点而受到广泛的研究。
[0003]根据电化学氧化法去除污染物的机理可将其分为:电化学还原法、电化学氧化法、电凝聚法、电浮选法、电渗析法。针对废水中污染物的组成、性质可选择相应的处理工艺,对于高盐度难降解废水,一般采用电化学氧化法较为有效。
[0004]电化学氧化法根据氧化有机物原理的不同可分为电-Fenton法、光电催化技术等。电-Fenton技术通过按照Fenton试剂中亚铁离子的来源,可分为牺牲阳极产生或Fe2+或外加Fe2+的方法,即以不锈钢或铁棒为阳极,经电化学氧化后,阳极失电子,产生Fenton试剂所需的Fe2+;根据双氧水的来源可分为阴极还原法和外加双氧水的方法,即在酸性条件下,对阴极进行曝气,经电化学氧化后,溶解氧被还原生成H2O2,电-Fenton技术为电化学氧化与Fenton技术的耦合,总体思路为减少Fenton试剂的投加量,降低运行费用,减少铁污泥的产量,因此研究中以阴极还原法见著较多,主要原因为阴极产生Fenton反应的同时,阳极还可氧化降解有机物,不仅提高了电流的利用效率,同时减少运行费用。但该方法常用金属及其氧化物、石墨等材料作为阴极材料,该类材料由于催化活性低,H2O2生成量少,Fe2+再生率不高,且PH适用范围窄等问题,应用推广较为困难。
[0005] 1972年日本的Fujishima发现光照半导体二氧化钛电极具有分解水的功能,使得纳米二氧化钛光电催化技术作为一种水处理的方法技术引起了广泛的重视。Ti02半导体光电催化技术是一种利用紫外光作激发光源,通过外加电压使光生电子和空穴得以有效分离,并分别与H2O或O2反应生成具有较强氧化能力的活性自由基来氧化降解有机物的一种氧化技术。通过将催化剂(如二氧化钛等)负载于某种基体表明,基体可作为电催化剂的载体,提供反应表面,增加强度、减小催化剂的用量、改变电极表面的结构与性能。从而很大程度上提高了羟基自由基的产量,氧化降解水中难降解有机化合物。基于反应原理,该方法无疑是非常先进的,但该方法在工程应用上却是极不成熟的,尚且不论催化电极制作的复杂程度及量产的难度,但就运行费用,由于污水的色度一般较高,紫外光光程短,照射幅度有限,为提高降解效率,只能提高激发光源的功率和增加灯管数量,增加了运行能耗,运行维修管理困难,导致很多光电催化技术在放大应用或工程应用中推广失败。
[0006]由此可以看出,电-Fenton法与光电催化氧化技术均能有效处理污水中的难降解性有机污染物,但由于电极材料制作困难,量产化难以实现、运行费用高等问题工程应用较少,推广较为困难。
发明内容
[0007]基于上述现有技术所存在的问题,本发明提供一种适用于高盐度难降解废水的电催化组合处理方法,电极材料制作要求低,占地面积小,处理效果稳定,运行费用省,能切实有效的解决高盐难降解废水的预处理问题。
[0008]为解决上述技术问题,本发明提供一种适用于高盐度难降解废水的电催化组合处理方法,包括:
[0009] 将所处理高盐难降解废水进入沉沙池进行沉沙,沉沙后出水进入均质池进行均匀水质,同时向均质池中通入电催化反应器中产生的Cl2对废水进行预氧化,均质后出水进入电催化反应器停留进行电催化氧化还原反应,降解废水中的难降解有机物,电催化反应器的出水进入三级混凝池,通过投加的絮凝剂进行混凝沉淀去除废水中的SS,使废水达到可生化性目标或排放目标。
[0010]上述处理方法中,电催化反应器的电催化氧化工艺采用三维电催化氧化工艺或二维电催化氧化工艺;
[0011 ]所述电催化反应器的电极采用钛基阳极;
[0012]所述电催化反应器内设有活性炭负载催化剂粒子和推流式搅拌装置。
[0013]上述处理方法中,钛基阳极采用PbO2钛基电极或RuO2钛基电极。
[0014] 上述处理方法中,电催化反应器中产生的Cl2通过气体压缩栗通入均质池。
[0015]本发明的有益效果为:通过将电催化氧化工艺与混凝工艺组成电催化组合工艺,解决了常规电化学氧化法运行费用高、电极材料制作要求高的问题,为高盐度难降解废水的处理提供一套运行费用省,操作、维护简单方便,处理效果高效稳定的电催化组合处理工
-H-
O
附图说明
[0016]为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域的普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他附图。
[0017]图1为本发明实施例提供的处理方法流程图。
具体实施方式
[0018]下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明的保护范围。
[0019]下面结合具体实施例对本发明作进一步说明。
[0020]本发明的电催化组合工艺流程如图1所示,高盐难降解废水由污水收集管汇集后经提升栗提升进入沉沙池,与市政污水不同,工业废水中大型悬浮物、漂浮物一般较少或没有,为防止后续处理工艺设备的运行磨损,设沉沙池去除其中细小的煤沙泥渣等;随后废水进入均质池,起到均匀水质,防止来水冲击,同时向均质池中通入电催化反应器中产生的Cl2将废水进行预氧化。随后废水进入三维电催化反应器,反应器采用的电极为DSA阳极(包含Pb02/Ru02等钛基电极),该类阳极具有价格低廉、导电性好、在酸性条件下稳定性高和使用寿命长等优点,特别是PbO2钛电极的析氯极化曲线的斜率小于析氧极化曲线的斜率,非常适合处理高盐分(含Cl—)废水。通过阳极氧化,阴极还原,废水中的难降解有机物同时被两种电化学作用所氧化降解:一种是在电极表面被直接氧化,一种是通过间接电化学反应生成的强氧化剂包括C12、C10—等与有机物发生氧化还原作用进行降解,而过量的Cl2由气体压缩栗送入均质池,对来水进行预氧化。为提高电流效率,电化学反应器中增加活性炭负载催化剂粒子,并采用推流式搅拌,防止发生浓差极化现象,降低电流效率。经过一定的停留时间,出水进入三级混凝池,通过投加PAC、PAM等絮凝剂去除废水中的SS,废水达到可生化性目标或排放目标,根据处理目标,废水可直接排放、回用或进入下一段生化处理工艺以进一步降低废水中有机物浓度达到排放要求。
[0021]该方法的特点在于对于高盐废水中的Cl—进行了有效利用,以均质池进行预氧化,以三维电极进行深度氧化提高生化性,以生化工艺进一步降低废水中有机物浓度,通过梯级氧化模式,合理分配不同氧化系统的处理效果,在保证出水达标的情况下,减少了运行费用及能耗。
[0022]本发明的电催化氧化组合处理方法适用于高盐难降解性工业废水的预处理,系统中沉沙池也可改为沉淀池或其他过滤工艺,均质池的预氧化工艺可采用其他工艺如微电解,Fenton氧化等。三维电催化工艺也可改为二维电催化工艺,后续的混凝沉淀工艺也可替换为其他过滤工艺技术。高盐难降解废水因生化性差,难以被氧化降解,但若因此而完全否定生化法的可行性则不可取。对于COD值在100〜300mg/L的废水来说,采用电催化氧化法将废水进行达标处理,较为可行;当废水COD值远大于300mg/L,则需要与生化工艺进行组合方能凸显其优势,采用本发明的处理方法可以提高提高C/N比,降低废水的对微生物的毒性使废水易于生化降解,最终达到降低运行费用的目的。本发明的处理方法处理效果稳定,设备占地面积小,基建费用少,运行费用低,运行管理维护方便。
[0023]以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书的保护范围为准。
Claims (3)
1.一种适用于高盐度难降解废水的电催化组合处理方法,其特征在于,包括: 将所处理高盐难降解废水进入沉沙池进行沉沙,沉沙后出水进入均质池进行均匀水质,同时向均质池中通入电催化反应器中产生的Cl2对废水进行预氧化,均质后出水进入电催化反应器停留进行电催化氧化还原反应,降解废水中的难降解有机物,电催化反应器的出水进入三级混凝池,通过投加的絮凝剂进行混凝沉淀去除废水中的SS,使废水达到可生化性目标或排放目标; 所述电催化反应器的电催化氧化工艺采用三维电催化氧化工艺或二维电催化氧化工-H-乙; 所述电催化反应器的电极采用钛基阳极; 所述电催化反应器内设有活性炭负载催化剂粒子和推流式搅拌装置。
2.根据权利要求1所述的一种适用于高盐度难降解废水的电催化组合处理方法,其特征在于,所述钛基阳极采用Pb02钛基电极或R11O2钛基电极。
3.根据权利要求1所述的一种适用于高盐度难降解废水的电催化组合处理方法,其特征在于,所述电催化反应器中产生的Cl2通过气体压缩栗通入均质池。
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