磁性可回收氟化石墨烯破乳材料的制备及乳液分离性能

doi:10.7503/cjcu20180559

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (3): 508.doi: 10.7503/cjcu20180559

磁性可回收氟化石墨烯破乳材料的制备及乳液分离性能

徐海燕^1,², 任嗣利³, 贾卫红^1,², 王金清^1,²()

1. 中国科学院兰州化学物理研究所固体润滑国家重点实验室, 兰州 730000
2. 中国科学院大学材料与光电研究中心, 北京 100049
3. 江西理工大学资源与环境工程学院, 赣州 341000

收稿日期:2019-08-10 出版日期:2019-01-24 发布日期:2019-01-24
作者简介:
联系人简介: 王金清, 男, 博士, 研究员, 博士生导师, 主要从事二维材料的制备及表/界面行为研究. E-mail: jqwang@licp.cas.cn
基金资助:
国家自然科学基金(批准号: 51574217和51675514)资助.

Preparation of Magnetically Recyclable Fluorinated Graphene and Its Demulsification Performance for Emulsified Oily Wastewater^†

XU Haiyan^1,², REN Sili³, JIA Weihong^1,², WANG Jinqing^1,^2,^*()

1. State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences,Beijing 100049, China
3. School of Resources and Environmental Engineering, Jiangxi University of Science and Technology,Ganzhou 341000, China

Received:2019-08-10 Online:2019-01-24 Published:2019-01-24
Contact: WANG Jinqing E-mail:jqwang@licp.cas.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.51574217, 51675514).

摘要/Abstract

摘要：

以氟化石墨烯(FG)为原料, 首先制备了水合肼还原的具有一定亲水性的氟化石墨烯(HFG), 然后采用溶剂热法制备了可磁性分离的四氧化三铁负载的氟化石墨烯复合破乳材料(HFG-Fe₃O₄). 分别利用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FTIR)、 X射线粉末衍射仪(XRD)和X射线光电子能谱仪(XPS)对HFG-Fe₃O₄的形貌、结构和化学性质进行了表征. 最后研究了HFG-Fe₃O₄对含油废水的破乳性能, 探讨了影响其破乳性能的主要因素, 并对其破乳机理进行了分析. 结果表明: HFG-Fe₃O₄是一种表面负载有Fe₃O₄纳米颗粒的二维片状材料, 在最佳剂量为600 mg/L时对酸性和中性含油废水具有良好的破乳效果. 在酸性和中性条件下, 主要是利用HFG-Fe₃O₄与含油废水之间的静电吸引力以及HFG-Fe₃O₄与沥青质之间的π-π相互作用实现油-水分离. 但是, 在碱性条件下, HFG-Fe₃O₄与油滴之间的静电斥力将急剧增大, 最终导致破乳效率降低. 此外, 将磁性回收的HFG-Fe₃O₄循环利用4次后其乳液分离效率并没有明显下降, 表现出优异的循环稳定性.

关键词: 氟化石墨烯, 乳化含油废水, 油-水分离, 可回收性, 破乳机理

Abstract:

Fluorinated graphene(FG) was firstly reduced by hydrazine hydrate to form the hydrophilic FG(HFG), and then magnetic Fe₃O₄ nanoparticles were further grafted onto the surface of HFG to synthesize HFG-Fe₃O₄ composite. The morphology, structure and chemical property of the samples were characterized by TEM, SEM, FTIR, XRD and XPS. In addition, the demulsification performance of HFG-Fe₃O₄ for oily wastewater was investigated and some affecting factors were discussed in detail. Moreover, the demulsification mechanism of HFG-Fe₃O₄ was proposed as well. The results show that the HFG-Fe₃O₄ is one kind of two-dimensional sheet-like material with Fe₃O₄ nanoparticles being uniformly distributed on its surface. The HFG-Fe₃O₄ has good demulsification performance on acidic and neutral oily wastewater, and its optimum dosage is 600 mg/L. Under the acidic and neutral conditions, the electrostatic attraction between HFG-Fe₃O₄ and the oily wastewater, as well as the π-π interaction between HFG-Fe₃O₄ and asphaltenes are the main forces promoting the oil separation from oily wastewater. However, the electrostatic repulsion between HFG-Fe₃O₄ and oily wastewater increases drastically under the alkaline condition, and ultimately results in the reduction of demulsification efficiency. What’s more, HFG-Fe₃O₄ still has excellent demulsification performance after 4 cycles, suggesting it has superior recyclability.

Key words: Fluorinated graphene, Emulsified oily wastewater, Oil-water separation, Recyclability, Demulsification mechanism

中图分类号:

O647.32

TrendMD:

徐海燕, 任嗣利, 贾卫红, 王金清. 磁性可回收氟化石墨烯破乳材料的制备及乳液分离性能. 高等学校化学学报, 2019, 40(3): 508.

XU Haiyan,REN Sili,JIA Weihong,WANG Jinqing. Preparation of Magnetically Recyclable Fluorinated Graphene and Its Demulsification Performance for Emulsified Oily Wastewater^†. Chem. J. Chinese Universities, 2019, 40(3): 508.

图/表 13

Scheme 1 Preparation process of HFG-Fe3O4

Fig.1 TEM images of Fe3O4 nanoparticles(A), HFG(B), HFG-Fe3O4(C) and EDS of HFG-Fe3O4(D)

Fig.2 SEM images of Fe3O4 nanoparticles(A), HFG(B), HFG-Fe3O4(C), the element mapping regions of HFG-Fe3O4(D) and the corresponding element mapping images of HFG-Fe3O4(E—I)(E) C; (F) O; (G) F; (H) N; (I) Fe.

Fig.3 FTIR spectra of the samples

Fig.4 XRD patterns of the samples

Fig.5 XPS spectra of the samples

Table 1 Surface species of FG, HFG and HFG-Fe3O4 samples determined by XPS analysis

Sample	Atomic ratio(%)
Sample	C	O		F		N		Fe
FG	54.62		1.74		43.64
HFG	86.95		3.31		4.47		5.27
HFG-Fe₃O₄	63.93		26.47		0.36		0.71		8.53

Fig.6 TGA curves of Fe3O4(a), HFG(b) and HFG-Fe3O4(c) samples(A) and magnetic hysteresis loops of Fe3O4(a) and HFG-Fe3O4(b) at room temperature(B)The insets in (B) show the magnetic separation-redispersion results of HFG-Fe3O4(a and b).

Fig.7 Zeta potentials of HFG,HFG-Fe3O4 and emulsified oily wastewater at various pH levels

Fig.8 Effects of HFG-Fe3O4 dosage and pH value of oily wastewater on demulsification performance of HFG-Fe3O4(A) pH=2.0, c(HFG-Fe3O4)/(mg·L-1) from a to i: 0, 50, 100, 200, 300, 400, 500, 600,700. (B) pH=2.0; (C) pH=4.0; (D) pH=6.0.

Fig.9 Reusability of HFG-Fe3O4 at pH=2.0

Fig.10 POM images of the emulsified oily wastewater(A), the newly formed floccule(B), the newly formed oil phase(C), the oil phase after magnetic separation and settlement(D), the newly separated water phase(E), and the separated water phase after being treated by a magnet(F)

Scheme 2 Demulsification mechanism of HFG-Fe3O4

参考文献 37

[1]	Gao H., Duan Y. Q., Yuan Z. H., Chem. J. Chinese Universities, 2016, 37(6), 1208—1215
	(高虹, 段月琴, 袁志好. 高等学校化学学报, 2016, 37(6), 1208—1215)
[2]	Li Q. T., Sun W., Zhang Q., Chem. J. Chinese Universities, 2017, 38(3), 464—470
	(李钦涛, 孙文, 张芹. 高等学校化学学报, 2017, 38(3), 464—470)
[3]	Gao R., Li F., Li Y., Wu T., Chem. Eng. J., 2017, 309, 513—521
[4]	Cao Z., Hao T., Wang P., Zhang Y., Cheng B., Chem. Eng. J., 2017, 309, 30—40
[5]	Peng J., Liu Q., Xu Z., Masliyah J., Energ. Fuel., 2012, 26, 2705—2710
[6]	Duong P.H. H.., Chung T. S.,J. Membrane Sci., 2014, 452, 117—126
[7]	Gu J., Xiao P., Chen J., Zhang J., ACS Appl.Mater. Interfaces, 2014, 6, 16204—16209
[8]	Hu G., Li J., Zeng G., J. Hazard. Mater., 2013, 261, 470—490
[9]	Kayvani F. A., Rhadfi T., McKay G., Al-marri M., Chem. Eng. J., 2016, 293, 90—101
[10]	Santander M., Rodrigues R. T., Rubio J., Colloid Surface A, 2011, 375, 237—244
[11]	Chanthamalee J., Wongchitphimon T., Luepromchai E.,Water Air Soil Pollut., 2013, 224, 1601—1613
[12]	Liu J., Zhao Y. P., Hu B., Ren S. L., Chem. Ind. Eng. Process, 2013, 32, 891—897
	(刘娟, 赵亚溥, 胡斌, 任嗣利. 化工进展, 2013, 32, 891—897)
[13]	Cao J. P., Zhang S., Han B. L., J. Beijing University Chem. Technol.( Natural Science), 2011, 38, 52—57
	(曹建苹, 张胜, 韩宝丽. 北京化工大学学报(自然科学版), 2011, 38, 52—57)
[14]	Cunha R. E. P., Fortuny M., Dariva C., Santos A. F., Ind. Eng. Chem. Res., 2008, 47, 7094—7103
[15]	Fang S., Chen T., Wang R., Xiong Y., Chen B., Duan M., Energ. Fuel., 2016, 30, 3355—3364
[16]	Liu J., Li X. C., Jia W. H., Li Z. Y., Zhao Y. P., Ren S. L., Energ. Fuel., 2015, 29, 4644—4653
[17]	Wang H. J., Liu J., Xu H. Y., Ma Z. W., Jia W. H., Ren S. L., RSC Adv., 2016, 6, 106297—106307
[18]	Bettinger H. F., Chem. Phys. Chem., 2003, 4, 1283—1289
[19]	Bai R., Zhao J. P., Li Y., Surf. Technol., 2014, 43, 131—136
	(白瑞, 赵九蓬, 李垚. 表面技术, 2014, 43, 131—136)
[20]	Wang X., Shi Y., Graff R. W., Lee D., Gao H., Polymer, 2015, 72, 361—367
[21]	Li S., Li N., Yang S., Liu F., Zhou J., J. Mater. Chem. A, 2014, 2, 94—99
[22]	Lü T., Chen Y., Qi D., Cao Z., Zhang D., Zhao H. T., J. Alloy. Compd., 2017, 696, 1205—1212
[23]	Lü T., Zhang S., Qi D., Zhang D., Vance G. F., Zhao H. T., Appl. Surf. Sci., 2017, 396, 1604—1612
[24]	Hamwi A., Phys. Chem Solids, 1996, 57, 677—688
[25]	Yang T. Z., Shen C. M., Li Z., Zhang H. R., J. Phys. Chem. B, 2005, 109, 23233—23236
[26]	Jian X., Wu B., Wei Y., Dou S. X., ACS Appl. Mater. Interfaces, 2016, 8, 6101—6109
[27]	Ye X. Y., Ma L. M., Yang Z. G., Wang J. Q., Wang H. G., Yang S. R., ACS Appl. Mater. Interfaces, 2016, 8, 7483—7488
[28]	Jiang X., Wang F., Cai W., Zhang X., J. Alloy. Compd., 2015, 636, 34—39
[29]	Wang Y., Lee W. C., Manga K. K., Ang P. K., Lu J., Liu Y. P., Adv. Mater., 2012, 24, 4285—4290
[30]	Bharathidasan T., Narayanan T. N., Sathyanaryanan S., Sreejakumari S. S., Carbon, 2015, 84, 207—213
[31]	Xu H. Y., Jia W. H., Ren S. L., Wang J. Q., Chem. Eng. J., 2019, 337, 10—18
[32]	Liu J., Zhao Y. P., Ren S. L., Energ. Fuel., 2015, 29, 1233—1242
[33]	Yeung A., Dabros T., Masliyah J., Czarnecki J., Colloid Surface A, 2000, 174, 169—181
[34]	Dabros A.Y. T.., Masliyah J.,J. Colloid Inter. Sci., 1999, 210, 222—224
[35]	Costa L. M., Stoyanov S. R., Gusarov S., Tan X., Gray M. R., Energ. Fuel., 2012, 26, 2727—2735
[36]	Bouhadda Y., Bormann D., Sheu E., Bendedouch D., Krallafa A., Daaou M.,Fuel., 2007, 86, 1855—1864
[37]	Pacheco-Sánchez J. H., AÄ lvarez-Ramírez F., Martínez-Magadán J. M., Energ. Fuel., 2004, 18, 1676—1686

磁性可回收氟化石墨烯破乳材料的制备及乳液分离性能

Preparation of Magnetically Recyclable Fluorinated Graphene and Its Demulsification Performance for Emulsified Oily Wastewater^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 37

相关文章 4

编辑推荐

Metrics

本文评价

[1]	高翼飞, 肖长发, 冀大伟, 黄阳正. 熔融纺丝-拉伸法制备PVDF中空纤维膜及其油-水分离性能[J]. 高等学校化学学报, 2021, 42(6): 2065.
[2]	刘鹏昌, 来华, 成中军, 刘宇艳. 超浸润形状记忆海绵的制备及油-水分离性能[J]. 高等学校化学学报, 2021, 42(3): 894.
[3]	彭新艳, 刘云鸿, 李嘉文, 冯乙胧, 王汉春. 单宁酸/两性离子改性油-水分离膜的制备及性能[J]. 高等学校化学学报, 2020, 41(6): 1337.
[4]	高乃伟, 马强, 贺泳霖, 王亚培. 基于离子液体的绿色电子器件[J]. 高等学校化学学报, 2020, 41(5): 901.

磁性可回收氟化石墨烯破乳材料的制备及乳液分离性能

Preparation of Magnetically Recyclable Fluorinated Graphene and Its Demulsification Performance for Emulsified Oily Wastewater†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 37

相关文章 4

编辑推荐

Metrics

本文评价

Preparation of Magnetically Recyclable Fluorinated Graphene and Its Demulsification Performance for Emulsified Oily Wastewater^†