CN116514309A - 一种基于电化学的含铜含硅碱性废水的资源化处理方法 - Google Patents
一种基于电化学的含铜含硅碱性废水的资源化处理方法 Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 59
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 51
- 239000002351 wastewater Substances 0.000 title claims abstract description 51
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 50
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 48
- 239000010703 silicon Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004064 recycling Methods 0.000 title claims abstract description 17
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- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 7
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
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- 238000007599 discharging Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000010979 pH adjustment Methods 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 150000001804 chlorine Chemical class 0.000 claims description 2
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- 230000000593 degrading effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 229910004283 SiO 4 Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
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- 238000006731 degradation reaction Methods 0.000 description 3
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- 239000002244 precipitate Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 150000004699 copper complex Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000003825 pressing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 150000001879 copper Chemical class 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
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- 239000008394 flocculating agent Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/008—Leaching or slurrying with non-acid solutions containing salts of alkali or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/122—Lepidoic silicic acid
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- C01B33/20—Silicates
- C01B33/22—Magnesium silicates
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Abstract
本发明提出了一种基于电化学的含铜含硅碱性废水的资源化处理方法,本发明属于环境技术领域。其包括预处理、电沉积、化学沉淀和电氧化4个部分。目的是针对现有的电沉积法和化学沉淀法处理含铜含硅碱性废水存在的电极维护困难、易产生二次污染的不足之处,提供一种操作简单、维护方便、可高效回收铜和硅并降解COD的方法,以解决现有技术中存在的缺陷。该方法对废水中的铜、硅和COD的去除率分别为99.8%、94.3%和96.8%,处理过程中阳极表面无结垢,方法简单,可大批量处理含铜含硅碱性废水。
Description
技术领域
本发明属于环境技术领域,是关于一种基于电化学的含铜含硅碱性废水的资源化处理方法。
背景技术
化工行业催化剂生产过程中,分子筛车间会产生大量具有强碱性的含硅、铜和有机络合物的废水。在强碱性条件下,硅与铜络合物均可稳定存在,但随着pH降低,硅酸盐可形成H4SiO4析出,而部分铜络合物会随硅酸共沉淀形成危废,堵塞设备、管道。如何简单、快速在处理废水的同时实现铜和硅的资源化成为关注的焦点。
电化学法在含铜废水的处理中的应用已较为成熟,其原理是废水中的铜离子在外加电场的作用下迁移至阴极,并在阴极得电子还原为单质铜实现资源化回收。催化阳极通过涂层材料的直接氧化作用和活性氧物质对铜络合物进行破络合,提高阴极的电沉积效率。其优点是电化学法的工艺成熟,运行稳定,污泥产量少,在回收铜的同时对COD具有明显的降解作用,目前已在电镀废水、印刷电路板蚀刻废水和铜湿法冶金废水的处理方面大量应用。但当废水含有高浓度硅酸盐时,阳极表面会沉积H4SiO4,影响对铜有机物络合物破络合和COD降解,同时,电极的使用维护负担较重。因此在采用电化学法除铜时应避免硅酸盐的干扰,或对废水进行脱硅。
常用的废水除硅方法有添加钙盐、镁盐、絮凝剂或加入无机酸的方式,虽对除硅效果明显,但若未经除铜预处理,形成的沉淀会因含有大量的铜而形成危废。且由于催化剂生产排放的废水中的硅主要为已经解离的活性硅,若可再利用将比原料硅的反应活性更迅速,具有一定的回收价值。
因此,有必要开发一种既能有效回收铜和硅,又能降解COD,且方便维护,不产生危废的电化学处理方法。
发明内容
本发明的目的是针对现有的电沉积法和化学沉淀法处理含铜含硅碱性废水存在的电极维护困难、易产生二次污染的不足之处,提供一种操作简单、维护方便、可高效回收铜和硅并降解COD的方法,以解决现有技术中存在的缺陷。
本发明提出一种基于电化学的含铜含硅碱性废水的资源化处理方法,其特征在于包括以下步骤:
(1)预处理:将废水加入到预处理池,加强碱调pH或加氯盐,充分搅拌;
(2)电沉积:将步骤(1)中调pH或加氯盐后的废水排入电沉积池进行电沉积,在阴极回收铜;
(3)化学沉淀:将步骤(2)中所述除铜后的废水排入混合沉淀池,加入除硅沉淀剂,充分搅拌并沉淀一段时间后进行固液分离,回收硅;
(4)电氧化:将步骤(3)中得到的除硅废水排入电氧化池降解COD。
根据本发明的方法,优选的:
上述步骤(1)中,强碱为氢氧化钠或氢氧化钾,pH调节至12.9-13.5;
上述步骤(1)中,氯盐为氯化钠或氯化钾,投加量为0.5-3.0g/L。
上述步骤(2)中,阳极为Ti/RuO2-IrO2、Ti/TiO2-RuO2或PbO2电极,阴极为铜或不锈钢板,极板间距为1-10cm,电流密度为10-40mA/cm2;
上述步骤(3)中,沉淀剂为硫酸、盐酸、氯化钙或氯化镁;
上述步骤(3)中,沉淀剂为硫酸或盐酸时,pH应调至3.0-7.0;
上述步骤(3)中,沉淀剂为氯化钙或氯化镁时,投加钙或镁与硅的摩尔比为(0.39-1.2):1;
上述步骤(3)中,沉淀时间为100-120分钟;
上述步骤(3)中,固液分离采用板框压滤、带式压滤或真空抽滤;
上述步骤(4)中,阳极为Ti/RuO2-IrO2、Ti/TiO2-RuO2或PbO2电极,阴极为不锈钢或钛电极,极板间距为1-10cm,电流密度为10-40mA/cm2。
本发明提出一种基于电化学的含铜含硅碱性废水的资源化处理方法,在电沉积时,阳极和阴极反应原理如下:
阳极反应:
2OH--e-→O2+2H+ (3)
2Cl--2e-→Cl2 (5)阴极反应:
Cu2++e-→Cu (6)
2Cu2++H2O+2e-→Cu2O+2H+ (7)
Cu2O+2e-+H+→2Cu+H2O (8)
电沉积过程中,阳极析氧反应产生的H+在阳极表面与硅酸根结合形成H4SiO4沉积在阳极表面,如反应式(1-3)所示。但当废水初始pH调节至12.9以上,沉积的H4SiO4可再次溶解,如反应式(4)所示,有效避免对阳极的钝化。当溶液中存在Cl-时,析氯反应与析氧反应竞争,减少H+的产生量,避免H4SiO4形成。阴极具有还原性,络合物中的Cu(Ⅱ)可在阴极的电子直接还原为Cu(0)或先还原为Cu(Ⅰ),随后进一步被还原为Cu(0),如式(6-8)所示。
化学沉淀过程中,采用沉淀剂为H2SO4或HCl时,硅酸根可结合氢离子形成H4SiO4沉淀后被回收,当沉淀剂为钙盐或镁盐时,硅酸盐与钙、镁离子反应形成难溶于水的固体沉淀后被回收,反应原理如下:
电氧化过程中,由于在预处理或化学沉淀过程中引入Cl-,阳极析氯反应产生的活性氯可提高COD的降解效率。
本发明有如下特点:
1)废水中的铜和硅可分步回收,纯度高;
2)电沉积过程中阳极不结垢,维护方便;
3)预处理或化学沉淀部分引入Cl-,有利于电氧化除COD;
4)处理过程中不产生危废;
5)可处理多种含重金属和硅的废水。
附图说明
图1是摘要图;
图2是实施例1-4时间-铜去除率曲线图;
图3是实施例1-4电沉积回收铜的EDS图;
图4是实施例1-4化学沉淀产物的XRD谱图;
图5是实施例1-4废水初始pH调节前后阳极表面结垢情况对比;
图6是实施例14-18中pH-硅浓度曲线图;
图7是实施例22-24时间-COD去除率曲线图。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整的描述,显然,所描述的实施例仅是本发明的一部分实施例,不作为对技术方案的限制。在不冲突的情况下,本发明的实施例中的特征可以相互组合。任何一种可以实现本发明的技术方法均构成本发明涉及技术方案的一部分。
实施例1-4
(1)预处理:取废水500mL,其中铜浓度为600mg/L,硅浓度为3800mg/L,COD为12440mg/L,加入NaOH将pH调至13.2;
(2)电沉积:以1块5×6cm2的Ti/RuO2-IrO2阳极和2块具有相同面积的铜阴极,在极板间距为1cm,电流密度为10、15、20、30mA/cm2条件下电沉积除铜,反应4h后铜的浓度分别为183、36.5、1.8、1.6mg/L,阳极表面无结垢;
(3)化学沉淀:以CaCl2为沉淀剂,投加量为6g/L,充分搅拌,静置30min,充分沉淀,采用真空抽滤法对沉淀物脱水,将滤液与上清液混合得到脱硅废水,硅的去除率为89.7%;
(4)电氧化,取100mL脱硅废水,以1块3×5cm2的Ti/RuO2-IrO2阳极和2块具有相同面积的不锈钢阴极电氧化降解COD,在极板间距为1cm,电流密度为30mA/cm2的条件下电氧化去除COD,反应14h后COD浓度降至400mg/L,达到排放标准。
实施例5-7
如实施例1所述,不同的是:
步骤(1)中,在废水中加入NaOH将pH分别调至12.9,13.1,13.5;
步骤(2)中,电流密度为20mA/cm2,反应4h后铜的残留浓度为1.6、1.8、1.4mg/L,达到排放标准,阳极表面无结垢。
实施例8-10
如实施例1所述,不同的是:
步骤(2)中,采用电流密度为20mA/cm2,反应4h后得到除铜废水;
步骤(3)中,以CaCl2为沉淀剂,投加量为3、10、17g/L,硅的去除率分别为74.2%、90.6%、94.3%。
实施例11-13
如实施例8-10所述,不同的是:
步骤(3)中,以MgCl2为沉淀剂,投加量为3、10、17g/L,硅的去除率分别为65.2%、87.4%、92.6%。
实施例14-18
如实施例8-10所述,不同的是:
步骤(3)中,以HCl为沉淀剂调节废水pH至11.11、8.69、7、5.9、3.86,硅的去除率为7.74%、80.2%、94.3%、99.72%、99.94%。
实施例18-21
如实施例8-10所述,不同的是:
步骤(3)中,以H2SO4为沉淀剂调节废水pH至10.04、8.35、7.16、3.35,硅的去除率为54.29%、86.72%、95.16%、99.62%。
实施例22-24
如实施例1-4所述,不同的是:
步骤(2)中,采用电流密度为20mA/cm2,反应4h后得到除铜废水;
步骤(4)中,电流密度分别为10、20、40mA/cm2,各自反应22、22、16和10h后,COD去除率分别为82.8%、98.3%、96.8%、99.7%。
实施例25-28
如实施例1-4所述,不同的是:
步骤(1)中,pH未调节,为12.0,投加NaCl的量分别为0.5、10、2.0、3.0;
步骤(2)中,电流密度为20mA/cm2,反应4h后,铜的浓度分别降低至1.8、1.4、1.7、1.2mg/L。
实施例29
如实施例1-4所述,不同的是:
步骤(2)中,阴极采用不锈钢电极,反应4h后,铜的浓度降低至1.2mg/L。
实施例30
如实施例1-4所述,不同的是:
步骤(4)中,阴极采用铜电极,反应4h后,COD浓度降低至342mg/L。
实施例31
如实施例1-4所述,不同的是:
步骤(1)中,pH未调节,为12.0,投加KCl的量分别为0.5、10、2.0、3.0;
步骤(2)中,电流密度为20mA/cm2,反应4h后,铜的浓度分别降低至1.7、1.6、1.8、1.4mg/L。
Claims (8)
1.一种基于电化学的含铜含硅碱性废水的资源化处理方法,包括如下步骤:
(1)预处理:将废水加入到预处理池,加强碱调pH或加氯盐,充分搅拌;
(2)电沉积:将步骤(1)中调pH或加氯盐后的废水排入电沉积池进行电沉积,在阴极回收铜;
(3)化学沉淀:将步骤(2)中所述除铜后的废水排入混合沉淀池,加入除硅沉淀剂,充分搅拌并沉淀一段时间后进行固液分离,回收硅;
(4)电氧化:将步骤(3)中得到的除硅废水排入电氧化池降解COD;
通过权利要求1所述的一种基于电化学的含铜含硅碱性废水的资源化处理方法,经处理后的废水中铜、硅和COD的去除率分别为98.8%、94.3%和96.8%。
2.如权利要求1所述的一种基于电化学的含铜含硅碱性废水的资源化处理方法,其特征在于,所述步骤(1)中,强碱为氢氧化钠或氢氧化钾,pH调节至12.9-13.5。
3.如权利要求1所述的一种基于电化学的含铜含硅碱性废水的资源化处理方法,其特征在于,所述步骤(1)中,氯盐为氯化钠或氯化钾,投加量为0.5-3.0g/L。
4.如权利要求1所述的一种基于电化学的含铜含硅碱性废水的资源化处理方法,其特征在于,所述步骤(2)中,阳极为DSA电极,阴极为铜或不锈钢电极,极板间距为1-10cm,电流密度为10-40mA/cm2。
5.如权利要求1所述的一种基于电化学的含铜含硅碱性废水的资源化处理方法,其特征在于,所述步骤(3)中,沉淀剂为硫酸、盐酸、氯化钙或氯化镁。
6.如权利要求1所述的一种基于电化学的含铜含硅碱性废水的资源化处理方法,其特征在于,所述步骤(3)中,沉淀剂为硫酸或盐酸时,pH应调至3.0-7.0。
7.如权利要求1所述的一种基于电化学的含铜含硅碱性废水的资源化处理方法,其特征在于,所述步骤(3)中,沉淀剂为氯化钙或氯化镁时,投加钙或镁与硅的摩尔比为(0.39-1.2):1。
8.如权利要求1所述的一种基于电化学的含铜含硅碱性废水的资源化处理方法,其特征在于,所述步骤(4)中,阳极为Ti/RuO2-IrO2、Ti/TiO2-RuO2或PbO2电极;阴极为不锈钢或钛电极,极板间距为1-10cm,电流密度为10-40mA/cm2。
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