CN106917104A - A kind of method of use BDD electrodes electro synthesis persulfate - Google Patents
A kind of method of use BDD electrodes electro synthesis persulfate Download PDFInfo
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- CN106917104A CN106917104A CN201710176058.5A CN201710176058A CN106917104A CN 106917104 A CN106917104 A CN 106917104A CN 201710176058 A CN201710176058 A CN 201710176058A CN 106917104 A CN106917104 A CN 106917104A
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- persulfate
- sulfuric acid
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- current density
- bdd
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- 238000000034 method Methods 0.000 title claims abstract description 21
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005341 cation exchange Methods 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- -1 electronic Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/29—Persulfates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
技术领域technical field
本发明属于环境工程技术领域，涉及一种用BDD电极电合成过硫酸盐的方法。The invention belongs to the technical field of environmental engineering and relates to a method for electrosynthesizing persulfate by using a BDD electrode.
背景技术Background technique
过硫酸盐S2O8 2-由于含有活性氧而在化学、纺织、电子、石油及食品领域得到了广泛的应用，如用作引发剂、催熟剂和漂白剂等。过硫酸盐的生产常用方法为电解法。通常利用铂电极或镀铂的钛电极在高于500mA/cm2的电流密度下电解硫酸根生成，但是此类方法常伴有水氧化的副反应产生而降低了电流效率同时会造成铂电极的溶出引入二次污染。此外过硫酸盐的不稳定性也会造成运输的困难限制了其应用。因此寻求一种更高效的电合成S2O8 2-方法有很大的市场需求。Persulfate S 2 O 8 2- has been widely used in the chemical, textile, electronic, petroleum and food fields due to its active oxygen content, such as initiator, ripening agent and bleaching agent. The common method of producing persulfate is electrolysis. Platinum electrodes or platinum-coated titanium electrodes are usually used to electrolyze sulfate radicals at a current density higher than 500mA/cm 2 , but this method is often accompanied by side reactions of water oxidation, which reduces the current efficiency and causes platinum electrodes. Dissolution introduces secondary pollution. In addition, the instability of persulfate will also cause difficulties in transportation and limit its application. Therefore, there is a great market demand for a more efficient electrosynthesis method of S 2 O 8 2- .
S2O8 2-的合成是阳极氧化的过程，因此阳极材料的选择至关重要。BDD电极因其高达3V的析氧电位、低背景电流和较好的化学稳定性和低吸附性的优点而在环境电化学领域应用广泛，如重金属的阴极回收，生物传感器和电化学分析测定等，但主要用于处理废水中的有机污染物。相比于金属电极，BDD电极由于高析氧电位的特性更易实现低电流密度下的电解合成S2O8 2-，因此具有很好的应用前景。此外，由于阳极氧化硫酸生成过硫酸是放热的过程，这易造成热不稳定的S2O8 2-分解而降低了电流效率，传统的单极室反应器硫酸根的转化效率只有不到5％。The synthesis of S 2 O 8 2- is a process of anodic oxidation, so the choice of anode material is very important. BDD electrodes are widely used in the field of environmental electrochemistry because of their high oxygen evolution potential of up to 3V, low background current, good chemical stability and low adsorption, such as cathode recovery of heavy metals, biosensors and electrochemical analysis and determination, etc. , but mainly used to treat organic pollutants in wastewater. Compared with metal electrodes, BDD electrodes are more likely to realize the electrolytic synthesis of S 2 O 8 2- at low current density due to the characteristics of high oxygen evolution potential, so they have a good application prospect. In addition, since the anodic oxidation of sulfuric acid to generate persulfuric acid is an exothermic process, which easily causes thermally unstable S 2 O 8 2- decomposition and reduces the current efficiency. The conversion efficiency of sulfate radicals in traditional single-pole chamber reactors is less than 5%.
发明内容Contents of the invention
基于此，本发明的目的是通过在分开的阳极室和阴极室和控制阳极室的温度的条件下利用BDD电解硫酸电合成过硫酸盐S2O8 2-，以实现电流效率的提高。Based on this, the purpose of the present invention is to realize the improvement of current efficiency by using BDD to electrolyze sulfuric acid to electrosynthesize persulfate S 2 O 8 2− under the conditions of separating the anode chamber and cathode chamber and controlling the temperature of the anode chamber.
本发明产生S2O8 2-的方法如下：以BDD电极为阳极、锆电极为阴极用阳离子交换膜隔开组成的装置为电解槽，阳极室和阴极室均为同浓度的2-5M的硫酸，循环流速为120-300L/h，控制电流密度为5-100mA/cm2，温度为9-20℃下电解合成。The method for producing S 2 O 8 2- in the present invention is as follows: the device with the BDD electrode as the anode and the zirconium electrode as the cathode separated by a cation exchange membrane is an electrolytic cell, and the anode chamber and the cathode chamber are both 2-5M of the same concentration. Sulfuric acid is electrolytically synthesized at a circulation rate of 120-300L/h, a controlled current density of 5-100mA/cm 2 , and a temperature of 9-20°C.
本发明具有以下的突出特点和有益效果：The present invention has the following outstanding features and beneficial effects:
(1)该方法可在分开的阳极室和阴极室和控温的条件下防止S2O8 2-因电解放热而分解。(1) This method can prevent S 2 O 8 2- from decomposing due to electrolysis under conditions of separate anode chamber and cathode chamber and temperature control.
(2)该方法可在相对较低的电流密度下电解硫酸产生S2O8 2-。(2) This method can produce S 2 O 8 2- by electrolyzing sulfuric acid at a relatively low current density.
(3)该方法对硫酸根的氧化效率与传统方法相比提高了2倍。(3) Compared with the traditional method, the oxidation efficiency of this method to sulfate radical is increased by 2 times.
附图说明Description of drawings
图1为不同电流密度下产生的S2O8 2-的量。Figure 1 shows the amount of S 2 O 8 2- produced at different current densities.
图2为不同电流密度下的电流效率。Figure 2 shows the current efficiency at different current densities.
具体实施方式detailed description
本发明通过以下实施例结合附图进一步详述。The present invention is further described in detail through the following embodiments in conjunction with the accompanying drawings.
(1)本发明的方法处理过程(1) method process of the present invention
以BDD电极(直径为10cm)为阳极，锆电极(直径为10cm)为阴极，阳离子交换膜组成电解槽，阳极室和阴极室的硫酸浓度均为2M，循环流速为200L/h，控制阳极和阴极室的温度为9℃，在电流密度为5-100mA/cm2，电解300min。The BDD electrode (10cm in diameter) is used as the anode, the zirconium electrode (10cm in diameter) is used as the cathode, and the cation exchange membrane forms the electrolytic cell. The temperature of the cathode chamber is 9°C, and the electrolysis is performed for 300 min at a current density of 5-100 mA/cm 2 .
(2)该实施例所获得效果(2) The effect obtained by this embodiment
该实例对比了不同电流密度条件下电解产生S2O8 2-的量，如图1所示，随着电流密度的增加，S2O8 2-的含量也在增加。当电流密度为5mA/cm2时，电解300min，产生的S2O8 2-的量为0.028M，而当电流密度为100mA/cm2时，电解300min，产生的S2O8 2-的量为0.26M。这与工业上高电流密度(500mA/cm2)相比，大大降低了工业成本。This example compares the amount of S 2 O 8 2- produced by electrolysis under different current densities. As shown in Figure 1, as the current density increases, the content of S 2 O 8 2- also increases. When the current density is 5mA/cm 2 , electrolysis for 300min, the amount of S 2 O 8 2- produced is 0.028M, and when the current density is 100mA/cm 2 , electrolysis for 300min, the amount of S 2 O 8 2- produced is The amount is 0.26M. This greatly reduces the industrial cost compared to the industrially high current density (500 mA/cm 2 ).
图2对比了不同电流密度条件下的电流效率。随着电流密度的增加电流效率呈现下降的趋势。当电流密度为5mA/cm2时，电流效率可达83％，而当电流密度增加到100mA/cm2时，电流效率降低到35％。Figure 2 compares the current efficiency under different current density conditions. The current efficiency shows a downward trend with the increase of current density. When the current density is 5mA/ cm2 , the current efficiency can reach 83%, and when the current density increases to 100mA/ cm2 , the current efficiency decreases to 35%.
Claims (3)
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| CN201710176058.5A CN106917104A (en) | 2017-03-17 | 2017-03-17 | A kind of method of use BDD electrodes electro synthesis persulfate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110902776A (en) * | 2019-11-23 | 2020-03-24 | 同济大学 | Method for generating sulfate radical free radical oxidation pollutants through in-situ electrocatalysis |
| CN120425380A (en) * | 2025-05-26 | 2025-08-05 | 浙江大学 | A persulfate-producing BDD-modified electrode and modification method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001192874A (en) * | 1999-12-28 | 2001-07-17 | Permelec Electrode Ltd | Method for preparing persulfuric acid-dissolving water |
| CN103380232A (en) * | 2010-12-21 | 2013-10-30 | 氯工程公司 | Electrically conductive diamond electrode, and sulfuric acid electrolysis method and sulfuric acid electrolysis apparatus each utilizing same |
| CN103384731A (en) * | 2011-02-28 | 2013-11-06 | 栗田工业株式会社 | Sulfuric acid electrolysis method and sulfuric acid electrolysis device |
| CN103518007A (en) * | 2011-03-08 | 2014-01-15 | 氯工程公司 | Apparatus for electrolyzing sulfuric acid and method for electrolyzing sulfuric acid |
-
2017
- 2017-03-17 CN CN201710176058.5A patent/CN106917104A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001192874A (en) * | 1999-12-28 | 2001-07-17 | Permelec Electrode Ltd | Method for preparing persulfuric acid-dissolving water |
| CN103380232A (en) * | 2010-12-21 | 2013-10-30 | 氯工程公司 | Electrically conductive diamond electrode, and sulfuric acid electrolysis method and sulfuric acid electrolysis apparatus each utilizing same |
| CN103384731A (en) * | 2011-02-28 | 2013-11-06 | 栗田工业株式会社 | Sulfuric acid electrolysis method and sulfuric acid electrolysis device |
| CN103518007A (en) * | 2011-03-08 | 2014-01-15 | 氯工程公司 | Apparatus for electrolyzing sulfuric acid and method for electrolyzing sulfuric acid |
Non-Patent Citations (2)
| Title |
|---|
| P-A. MICHAUD 等: "Electrochemical oxidation of water on synthetic boron-doped diamond thin film anodes", 《JOURNAL OF APPLIED ELECTROCHEMISTRY》 * |
| SUBRAMANIAN BALAJI 等: "Influence of cathode on the electro-generation of peroxydisulfuric acid oxidant and its application for effective removal of SO2 by room temperature electro-scrubbing process", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110902776A (en) * | 2019-11-23 | 2020-03-24 | 同济大学 | Method for generating sulfate radical free radical oxidation pollutants through in-situ electrocatalysis |
| CN120425380A (en) * | 2025-05-26 | 2025-08-05 | 浙江大学 | A persulfate-producing BDD-modified electrode and modification method |
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Application publication date: 20170704 |