膜科学与技术

酚醛树脂/活性炭基微孔炭膜制备及结构调控

作者：惠洪森，陈子尚，王崧鸿，熊鸽，王虹，同华，李建新

单位： 1.天津工业大学分离膜与膜过程国家重点实验室，分离膜科学与技术国家级国际联合研究中心，材料科学与工程学院，天津 300387；2.大连理工大学化工学院，大连市 116024

关键词：酚醛树脂；活性炭；微孔炭膜；电催化膜反应器；苯酚废水处理

出版年,卷(期):页码： 2020,40(1):131-138

摘要：

以酚醛树脂和活性炭为主要原料，甲基纤维素为粘结剂，聚乙烯醇缩丁醛（PVB）为造孔剂，采用压模成型及一步炭化法制备高比表面积酚醛树脂/活性炭炭基微孔炭膜（PRCM），通过调节原料配比及制备工艺参数等实现微孔炭膜结构的可控制备。结果表明，当酚醛树脂含量为45 wt.%，炭化温度1150 ℃，PVB添加量 20 wt.%时，酚醛树脂/活性炭微孔炭膜的抗折强度、电导率、孔隙率、纯水通量和比表面积分别为8.2 MPa、400.3 μs/cm、44.2%、93 L/m2?h和370.2 m2/g。此外，采用溶胶-凝胶法将纳米TiO2负载微孔炭膜制备电催化膜电极（TiO2/CM）。在相同配比和制备工艺条件下，对比煤基、煤沥青/活性炭以及酚醛树脂/活性炭三种原料所制备电催化炭膜的电化学和电催化降解苯酚性能。结果显示，TiO2/PRCM具有最优的电化学活性和催化降解效率。以其所构建的ECMR处理10 mmol苯酚废水时，COD和苯酚去除率分别可达86.5%和94.6%。这是因为PRCM具有较高的比表面积和石墨化程度，导致其具有较高的催化效率。酚醛树脂/活性炭炭基微孔炭膜在含酚废水过程中展现了良好的电化学和机械性能。

Activated carbon and phenolic resin as precursor material, carboxymethyl cellulose as binder and polyvinyl butyral as pore forming agent were employed to fabricate phenolic resin based carbon membrane (PRCM) with high specific surface area. When phenolic resin content was 45% and carbonization temperature was 1150 ℃, the bending strength, conductivity, porosity, specific surface area and pure water flux of resultant PRCM were 8.2 MPa, 400.3 μs/cm, 44.2%, 370.2 m2/g and 93 L/m2?h, respectively. Simultaneously, nano-TiO2 was loaded on PRCM to fabricate TiO2/PRCM catalytic membrane, which was used as anode to constitute FBECMR for 10.0 mmol/L phenolic wastewater treatment. The removal rates of phenol and COD obtained from TiO2/PRCM were up to 94.6% and 86.5%, respectively. The high efficiency and phenol removal obtained are ascribed to the high specific surface area and graphitization degree of PRCM. PRCM showed a good application in the treatment of phenolic wastewater.

第一作者简介：惠洪森（1990-），男，山东菏泽人，博士生，从事电催化膜反应器水处理研究。 *通讯作者：E-mail：waho7808@163.com；jxli@tiangong.edu.cn

参考文献：

[1]Yang Y, Qiao S, Zhou J T, et al. A novel porous-carbon-based hollow fiber membrane with electrochemical reduction mediated by in-situ hydroxyl radical generation for fouling control and water treatment [J]. Appl Catal B-Environ, 2019, 255:117772.
[2]Squire D. Reverse osmosis concentrate disposal in the UK [J], Desalination, 2000,132:47-54.
[3]Makabe R, Akamatsu K, Nakao S. Effect of electrolytes on stable permeation of submicron silica particles through microfiltration membranes [J]. Sep. Purif. Technol, 2018, 212:580–585.
[4]Renou S, Poulain S, Givaudan J G, et al. Amelioration of ultrafiltration process by lime treatment: Case of landfill leachate [J]. Desalination, 2009, 249:72-82.
[5]Chaudhari L B, Murthy Z V P. Treatment of landfill leachates by nanofiltration [J]. J. Environ. Manage, 2010, 91:1209-1217.
[6]Ding W D, Zhuo H W, Bao M T, et al. Fabrication of organic-inorganic nanofiltration membrane using ordered stacking SiO2 thin film as rejection layer assisted with layer-by-layer method [J]. Chem. Eng. J, 2017, 330:337-344.
[7]Wang, H, Wang, Y N, Li, X, et al. Removal of humic substances from reverse osmosis (RO) and nanofiltration (NF) concentrated leachate using continuously ozone generation-reaction treatment equipment [J]. Waste. Manage, 2016, 56:271-279.
[8]Bruggen V B, Lejon L, Vandecasteele C. Reuse, treatment and discharge of the concentrate of pressure-driven membrane processes [J], Environ. Sci. Technol, 2003, 137:3733-3738.
[9]Nederlof M, Paassen J A M, Jong R. Nanofiltration concentrate disposal: experiences in The Netherlands [J], Desalination, 2005, 178:302-312.
[10]Zhou J, Li W, Gu J S, et al. Surface modification of polypropylene membrane to improve antifouling characteristics in a submerged membrane-bioreactor: Ar plasma treatment [J]. Membr. Water. Treat, 2010, 1:83-92.
[11]Hai F I, Yamamoto K, Fukushi K. Performance of newly developed hollow fiber module with spacer in integrated anaerobic–aerobic fungi reactor treating textile wastewater [J]. Desalination, 2006,199:305–307.
[12]Cho B D, Fane A G. Fouling transient in nominally sub-critical flux operation of a membrane bioreactor [J]. J. Membr. Sci, 2002, 209:391–403.
[13]Wu J L, Le-Clech P, Stuetz R.M, et al. Effects of relaxation and backwashing conditions on fouling in membrane bioreactor [J]. J. Membr. Sci, 2008,324:26–32.
[14]Koseoglu H, Yigit N.O, Iversen V, et al. Effects of several different flux enhancing chemicals on filterability and fouling reduction of membrane bioreactor (MBR) mixed liquors [J]. J. Membr. Sci, 2008, 320:57–64.
[15]Pan Z L, Song C W, Li L, et al. Membrane technology coupled with electrochemical advanced oxidation processes for organic wastewater treatment: Recent advances and future prospects [J]. Chem. Eng. J, 2019, 376:120909.
[16]Liang P Y, Rivallin S. Cerneaux S, et al. Coupling cathodic Electro-Fenton reaction to membrane filtration for AO7 dye degradation: A successful feasibility study [J]. J. Membr. Sci, 510 (2016) 182–190.
[17]Yang Y, Li J X, Wang H, et al. An electrocatalytic membrane reactor with self-cleaning function for industrial wastewater treatment [J]. Angew Chem. Int Ed, 2011, 123(9):2196-2198.
[18]Hui H S, Hong W, Mo Y H, et al. A three-stage fixed-bed electrochemical reactor for biologically treated landfill leachate treatment [J]. Chem. Eng. J, 2019, 376, 121026.
[19]Tao P, Xu Y L, Song C W, et al. A novel strategy for the removal of rhodamine B (RhB) dye from wastewater by coal-based carbon membranes coupled with the electric field [J]. Sep. Purif. Technol, 2017, 179:175-183.
[20]Wei W, Qin G T, Hu H Q, et al. Preparation of supported carbon molecular sieve membrane rom novolac phenol–formaldehyde resin [J]. J. Membr. Sci, 2007, 303:80-85.
[21]熊鸽, 王虹, 惠洪森, 等. 活性炭基微孔炭膜制备及电化学性能 [J]. 膜科学与技术, 2019,39(5)37-44.
[22]Hui H S, Hong W, Mo Y H, et al. A fixed-bed electrochemical reactor with nano-TiO2 loading flat-sheet carbon membrane as anode for phenolic wastewater treatment [J]. Desalin. Water. Treat, 2018, 118:113-119.
[23]Song C W, Wang T H, Pan Y, et al. Preparation of coal-based microfiltration carbon membrane and application in oily wastewater treatment [J]. Sep. Purif. Technol, 2006, 51(1):80-84.
[24]Yang Y B, Zheng Q X, Jiang T, et al. Study on preparation of high strength formed coke [C]. International Congress on the Science & Technology of Ironmaking, 2009, 79:110-119.
[25]Kimberly A. T, Tony E. S. Mechanisms of the pyrolysis of phenolic rensin in a carbon/phenolic composite [J]. Carbon, 1995, 33(11):1509-1515.
[26]Kolarz B N, Wojaczyńska M, Kaczmarczyk J, et al. Influence of heat treatment conditions on the porosity changes of sulfonated styrene/divinylbenzene copolymers [J]. J. Polym. Sci. Pol. Phys, 1994, 32(12):1977-1990.
[27]Islam M N, Zhou W, Honda T. Preparation and gas separation performance of flexible pyrolytic membranes by low-temperature pyrolysis of sulfonated polyimides [J]. J. Membr. Sci, 2005, 261:17-26.
[28]杨永斌, 钟强, 姜涛, 等. 煤沥青型焦制备与固结机理[J]. 中南大学学报：自然科学版, 2016(7):2181-2188.
[29]Liu Z M, Zhu M F, Zhao L, et al. Aqueous tetracycline degradation by coal-based carbon electrocatalytic filtration membrane: Effect of nano antimony-doped tin dioxide coating [J]. Chem. Eng. J, 2017, 314:59-68.
[30]Liu Q L, Wang T H, Qiu J S, et al. A novel carbon/ZSM-5 nanocomposite membrane with high performance for oxygen/nitrogen separation [J]. Chem. Commun, 2006, 11: 1230-1232.
[31]Yang W, Yang W, Kong L N, et al. Phosphorus-doped 3D hierarchical porous carbon for high-performance supercapacitors: A balanced strategy for pore structure and chemical composition [J], Carbon, 2018, 127:557-567.
[32]Pang J, Zhang W F, Zhang H, et al. Sustainable nitrogen-containing hierarchical porous carbon spheres derived from sodium lignosulfonate for high-performance supercapacitors[J], Carbon, 2018, 132:280-293.
[33]Lee C H, Lee E S, Lim Y K, et al. Enhanced electrochemical oxidation of phenol by boron-doped diamond nanowire electrode [J], RSC Adv, 2017, 7:6229-6235.
[34]Kornienko G V, Chaenko N V, Maksimov N G. Electrochemical oxidation of phenol on boron–doped diamond electrode [J], Russ. J. Electrochem, 2011, 47:240-245.

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