CN108046381B - 一种用于工业废水处理的电催化渗透墙反应装置 - Google Patents
一种用于工业废水处理的电催化渗透墙反应装置 Download PDFInfo
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
Abstract
本发明涉及工业废水处理领域，特别涉及一种可用于工业废水处理的电催化渗透墙反应装置。通过氧化的方法在钛废料表面原位生成TiO2前驱体，通过热固化反应使得TiO2前驱体转化为具有特定晶型结构的TiO2，再利用还原剂石墨以及氢气在高温下将TiO2还原转化为具有催化活性的Ti4O7。通过机械将负载有催化剂的钛废料压制成疏松、多孔的反应墙体。当水体穿透反应墙体时显著强化污染物向催化层的传质，同时较大的反应面积也可促进污染物的氧化降解。
Description
技术领域
本发明涉及工业废水处理领域，特别涉及一种可用于工业废水处理的电催化渗透墙反应装置。
背景技术
随着现代工业的发展，各类生物难降解有机废水的排放越来越多，其中多数含有“致畸、致癌、致突变”等三致物质，传统的生化处理法已经不能满足目前越来越高的环保要求。因此针对生物难降解污染物，寻求有效的深度处理技术已迫在眉睫，也成为学术界和工业界关注的研究热点。
近年来，具有环境友好型特点的电化学(阳极)氧化法在废水处理领域受到广泛关注。该反应本质上是一种通过电子迁移反应引发的电催化过程，在阳极表面通过水分子的失电子反应生成强氧化性的·OH，进而将电极表面的污染物直接氧化而转化成毒性较低的物质或生物易降解物质，甚至无机化，从而达到削减污染物的目的。电化学氧化技术并被认为是一种极具工业化应用前景的新型高级氧化法。阳极材料是电化学氧化水处理体系的核心，其中掺杂锑的二氧化锡(Sb-SnO2)、二氧化铅(PbO2)以及掺硼金刚石(BDD)作为非活性阳极的典型材料，其对析氧副反应的抑制能力较强，对有机物的氧化效率高，因此在电化学氧化研究领域近些年来关于这些材料的研究与应用备受关注。以上三种电极之中，BDD电极氧化效率最优，但是大规模制备成本高，难以工业化应用，二氧化铅电化学氧化能力和环保性能相对较差，二氧化锡是三者之中最经济的阳极材料，但是却存在稳定性不足的短板。亚氧化钛材料是对一系列非化学计量式钛氧化物的统称，其通式为TinO2n-1(4≤n≤10)，其中Ti4O7具有导电率最高(1500S/cm)，高析氧点位(约为2V)、化学稳定性好、耐化学腐烛性强等优良性能。此外，研究发现Ti4O7作为阳极材料时可表现出类似非活性BDD阳极的特点，即在电极表面引发水的氧化反应从而生成强氧化性的·OH的生成，因此近几年来Ti4O7优越的电化学性能使其很适合作为电极材料用于电化学工艺处理难降解有机污染物。尽管在阳极催化剂的研发制备上已取得一定的成果，但是目前电催化技术的能耗还相对较高，其主要原因是电催化过程是异相反应，溶液中污染物向板式/网式电极传质效率较低。
发明内容
本发明要解决的技术问题是目前电催化技术的能耗还相对较高，其主要原因是电催化过程是异相反应，溶液中污染物向板式/网式电极传质效率较低。
为解决上述问题，本发明提供一种可用于工业废水处理的电催化渗透墙反应装置，提供了高传质效率的阳极构型，同时在钛基底表面原位生成新型Ti4O7催化层，可显著提升电催化反应效率，同时降低处理成本。
具体的技术方案为：
一种用于工业废水处理的电催化渗透墙反应装置，利用钛废料作为催化载体，依次通过氧化、热固化以及热还原工艺在其表面原位合成Ti4O7催化层，并通过机械成型工艺构建阳极可渗透墙，在电能驱动下实现对工业废水的连续式处理。
优选方案如下：
所述的钛废料，为钛颗粒、钛刨花、钛屑等中的一种或多种混合。
所述的催化剂载体钛废料的氧化剂选用过氧化氢、硫酸、硝酸等，使得钛基材料表面负载有为二氧化钛前驱体，采用氧化剂浓度为≤5mM。
所述的热固化处理工艺选用温度为300-700℃，使得氧化生成的二氧化钛前驱体转化为金红石或锐钛矿。
所述的热还原工艺选用温度为1000-1400℃，还原剂为氢气或者石墨，通过高温处理使得金红石或者锐钛矿转化为Ti4O7。
所述的阳极可渗透墙可通过机械将负载有Ti4O7的钛废料压制成为具有空隙发达、蓬松的墙体结构，其厚度≤500mm。强化污染物向催化层的传质，同时较大的反应面积也可促进污染物的氧化降解。
所述的连续式处理工艺是以可渗透反应墙为阳极，阴极为钛网或者铁网，通过连续式交叉排列，构建多级反应体系，阴阳两极间距为5-200mm。
发明的原理：
通过氧化的方法在钛废料表面原位生成TiO2前驱体，通过热固化反应使得TiO2前驱体转化为具有特定晶型结构的TiO2，再利用还原剂石墨以及氢气在高温下将TiO2还原转化为具有催化活性的Ti4O7。通过机械将负载有催化剂的钛废料压制成疏松、多孔的反应墙体。当水体穿透反应墙体时显著强化污染物向催化层的传质，同时较大的反应面积也可促进污染物的氧化降解。
本发明所具有的优点在于：
(1)采用钛废料为载体、利用液相氧化和热处理手段原位生成具有强氧化能力的Ti4O7。
(2)通过机械手段将钛废料压制成具有疏松多孔的结构，显著提升了传质效率和有效电催化面积。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，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，都属于本发明保护的范围。
实施例1：
一种用于工业废水处理的电催化渗透墙反应装置，利用100g钛刨花废料作为催化载体，将该载体在一定浓度的氢氧化钠溶液中去除油渍，再加入60℃、1mmol/L H2O2溶液中进行氧化反应5h；之后将载体在500℃下煅烧1h进行热固化反应；再在1000℃氢气氛围下还原2h；最后利用机械成型工艺将上述材料压制成具有一定2cm厚度的板体。以上述板体为阳极，阴极为钛网或者铁网，通过连续式交叉排列，构建多级反应体系，阴阳两极间距为10mm。
使用上述装置，在输入电流密度为5mA/cm2下，通过30min放电反应可实现初始COD为4500mg/L左右的垃圾渗滤液的处理效率达到70％，能量效率远远小于已有相关技术。
Claims (4)
1.一种用于工业废水处理的电催化渗透墙反应装置，其特征在于：具有阳极可渗透墙，对工业废水进行连续式处理；所述阳极可渗透墙以钛废料作为催化载体，钛废料为钛颗粒、钛刨花、钛屑中的一种或两种以上的混合物，将钛废料在氢氧化钠溶液中去除油渍，再加入氧化剂进行反应；之后将载体在300-700℃下煅烧进行热固化反应；然后再在1000-1400℃下由氢气或者石墨还原生成Ti4O7催化层；最后利用机械成型工艺将负载有Ti4O7的钛废料压制成孔隙发达、蓬松的墙体结构构成阳极可渗透墙，墙体厚度≤500mm。
2.根据权利要求1所述的一种用于工业废水处理的电催化渗透墙反应装置，其特征在于：所述的氧化剂为过氧化氢、硫酸、硝酸中的一种或两种以上的混合物，浓度为≤5mM。
3.根据权利要求1所述的一种用于工业废水处理的电催化渗透墙反应装置，其特征在于：所述的连续式处理为将阳极可渗透墙和阴极连续式交叉排列，构建多级反应体系，阴阳两极间距为5-200mm。
4.根据权利要求3所述的一种用于工业废水处理的电催化渗透墙反应装置，其特征在于：所述阴极为钛网或者铁网。
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