碳纳米管改性海泡石多孔陶瓷及其高效油水分离性能研究

doi:10.15541/jim20190382

无机材料学报 ›› 2020, Vol. 35 ›› Issue (6): 689-696.DOI: 10.15541/jim20190382

碳纳米管改性海泡石多孔陶瓷及其高效油水分离性能研究

董龙浩¹,张海军¹(),张俊¹,吴文浩¹,贾全利²

^1. 武汉科技大学省部共建耐火材料与冶金国家重点实验室, 武汉 430081
^2. 郑州大学河南省高温功能材料重点实验室, 郑州 450052

收稿日期:2019-07-24 修回日期:2019-09-24 出版日期:2020-06-20 网络出版日期:2019-12-29
作者简介:董龙浩(1992-), 男, 硕士研究生. E-mail: donglonghao1125@163.com;
DONG Hailong (1992-), male, Master candidate. E-mail: donglonghao1125@163.com
基金资助:
国家自然科学基金(51872210);国家自然科学基金(51672194);湖北省教育厅高等学校优秀中青年科技创新团队计划(T201602);湖北自然科学基金创新群体项目(2017CFA004)

Carbon Nanotube Modified Sepiolite Porous Ceramics for High-efficient Oil/Water Separation

DONG Longhao¹,ZHANG Haijun¹(),ZHANG Jun¹,WU Wenhao¹,JIA Quanli²

^1. The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China
^2. Henan Key Laboratory of High Temperature Functional Ceramics, Zhengzhou University, Zhengzhou 450052, China

Received:2019-07-24 Revised:2019-09-24 Published:2020-06-20 Online:2019-12-29
Supported by:
National Natural Science Foundation of China(51872210);National Natural Science Foundation of China(51672194);Program for Innovative Teams of Outstanding Young and Middle-aged Researchers in the Higher Education Institutions of Hubei Province(T201602);Key Program of Natural Science Foundation of Hubei Province(2017CFA004)

摘要/Abstract

摘要：

为了有效地从油/水混合液体中回收油, 本工作以纤维状海泡石为原料, 硝酸镍为催化剂前驱体, 聚乙烯粉体为造孔剂和碳源, 采用冷冻干燥结合催化裂解法制备了超疏水/超亲油碳纳米管(CNTs)改性海泡石多孔陶瓷, 研究了固含量和催化热解温度对改性多孔陶瓷形貌的影响, 并表征了其在pH=1的强酸、pH=14的强碱、373 K高温和77 K低温等极端环境中的表面润湿性能及水油分离性能。结果表明: 催化剂前驱体溶液浓度为0.5 mol/L、海泡石的固含量为15wt%、催化热解温度为973 K且保温时间为2 h时所制备的CNTs改性多孔陶瓷具有最好的超疏水/超亲油性能, 其对柴油、白油、植物油和真空泵油的最高吸附量分别是其自身质量的15.7、20.8、23和25倍; 其连续油水分离时油通量高达250 kg·s ^-1·m ^-2, 且在5 h内分离效率及选择性不发生明显降低。

关键词: 海泡石多孔陶瓷, 冷冻干燥, 碳纳米管, 超疏水/超亲油, 油水分离

Abstract:

To efficiently recovery oil from oil/water mixed liquid, fibrous sepiolite, polyethylene powder and nickel nitrate was respectively used as raw mateials, carbon source and pore-forming agents, and catalyst precursor to prepare carbon nanotubes (CNTs) modified sepiolite porous ceramics by freeze-drying/catalytic pyrolysis method, and the effects of solid content and pyrolysing temperature on the morphology of the modified porous ceramics were studied. The water contact angle and oil-water separation performance in severly environment such as acid (pH=1), alkali (pH=14), and high (373 K) and low temperature (77 K) were also characterized. The results showed that when the concentration of catalyst precursor solution was 0.5 mol/L, the solid content of sepiolite was 15wt%, the catalytic pyrolysis temperature was 973 K, and the soaking time was 2 h, the as-prepared CNTs modified porous ceramics possessed superhydrophobic/superlipophilic nature, and their maximum adsorption capacity for diesel, paraffin oil, vegetable oil, and vacuum pump oil is respectively 15.7, 20.8, 23 and 25 times of their own weight. The oil flux during the continuous separation process is up to 250 kg·s ^-1·m ^-2, and the separation efficiency and selectivity can be maintained without significant decreasing within 5 h.

Key words: sepiolite porous ceramics, freeze drying, carbon nanotubes, superhydrophobic/superlipophilic, oil/water separation

中图分类号:

TQ174

董龙浩,张海军,张俊,吴文浩,贾全利. 碳纳米管改性海泡石多孔陶瓷及其高效油水分离性能研究[J]. 无机材料学报, 2020, 35(6): 689-696.

DONG Longhao,ZHANG Haijun,ZHANG Jun,WU Wenhao,JIA Quanli. Carbon Nanotube Modified Sepiolite Porous Ceramics for High-efficient Oil/Water Separation[J]. Journal of Inorganic Materials, 2020, 35(6): 689-696.

图/表 13

图1 海泡石多孔陶瓷的SEM照片

Fig. 1 SEM micrographs of the as-prepand sepiolite porous ceramics (a-b) Before CNTs modification; (c-d) Modified with CNTs

图2 不同固含量的CNTs改性海泡石多孔陶瓷的SEM照片和碳含量变化

Fig. 2 SEM micrographs and carbon content change of CNTs modified sepiolite porous ceramics with various solid contents (a) 10wt%; (b) 15wt%; (c) 20wt%; (d) Carbon content change

图3 不同固含量的CNTs改性海泡石多孔陶瓷的表面水润湿角

Fig. 3 The static water contact angle of CNTs modified sepiolite porous ceramics with various solid contents (a) 10wt%; (b) 15wt%; (c) 20wt%

图4 不同催化裂解温度时CNTs改性海泡石多孔陶瓷的SEM照片和碳含量变化

Fig. 4 SEM micrographs and carbon content change of CNTs modified sepiolite porous ceramics prepared at various pyrolysis temperatures (a) 923 K; (b) 973 K; (c) 1023 K; (d) Carbon content change

图5 973 K/2 h催化裂解聚乙烯所制备CNTs的TEM和HRTEM照片

Fig. 5 TEM and HRTEM images of CNTs resultant from pyrolysis of polyethylene at 973 K for 2 h under the optimal condition (a) Low transmission electron microscopy; (b) Tip of CNTs; (c) HRTEM images of the walls of CNTs

图6 CNTs改性海泡石多孔陶瓷对不同油的静态吸附性能

Fig. 6 Static adsorption capacities of CNTs modified sepiolite porous ceramics for different oils

表1 各种吸附材料吸附量的比较

Table 1 Comparison of adsorption capacity values of various adsorbent materials developed to date

Adsorbent material	Adsorbate	Modified substance	Adsorption capacity (g?g^-1)	Ref.
Sepiolite powders	Motor oil	-	0.174-0.184	[29]
Modified silica powders	Motor oil	1, 7-octadiene	0.330	[30]
Diatomite/silicalite-Ⅰcomposite powders	Benzene	Silicalite-Ⅰ	0.095-0.246	[31]
Modified diatomite porous ceramics	Toluene	Graphene/carbon nanobelts	1.090	[19]
Modified diatomite porous ceramics	Vacuum pump oil	Graphene/carbon nanobelts	1.025	[19]
Boron nitride aerogel	Salad oil	-	5	[32]
Modified alumina porous ceramics	Hexane	Polydimethylsiloxane	2	[33]
Modified rock wool	Diesel oil	Polydimethylsiloxane/silica	7	[34]
Polymethylsilsesquioxane aerogel	Hexane	-	6.2	[35]
Modified sepiolite porous ceramics	Hiesel oil	CNTs	15.7	This work
Modified sepiolite porous ceramics	Haraffin oil	CNTs	20.8	This work
Modified sepiolite porous ceramics	Vegetable oil	CNTs	23	This work
Modified sepiolite porous ceramics	Vacuum pump oil	CNTs	25	This work

图7 CNTs改性多孔陶瓷的孔径分布

Fig. 7 Pore size distribution of CNTs modified sepiolite porous ceramics

图8 连续性油水分离装置模拟图(a)和实物图(b~c)

Fig. 8 Schematic illustration (a) and images (b-c) of the continuously oil recovery instrument

图9 CNTs改性海泡石多孔陶瓷连续工作5 h的分离油通量

Fig. 9 The oil flux of CNTs modified sepiolite porous ceramics for paraffin oil/water mixture within 5 h

图10 CNTs改性多孔陶瓷在不同环境下的水接触角

Fig. 10 The static water contact angles of CNTs modified sepiolite porous ceramics in various environments (a) As-synthesized ceramic; (b) pH=1; (c) pH=13; (d) 373 K; (e) 77 K

图11 不同环境下CNTs改性多孔陶瓷的油水分离选择性

Fig. 11 Oil/water separation selectiviies of CNTs modified porous ceramics in various environments (1) As-synthesized ceramic; (2) pH =1; (3) pH=13; (4) Heating at 373 K for 4 h; (5) Freezing at 77 K for 4 h

图12 不含碳纳米管的多孔陶瓷的水接触角和油接触角

Fig. 12 Static water/oil contact angle of porous ceramics without CNTs (a) Water contact angle; (b) Oil contact angle

参考文献 41

[1]	ZHANG JUN, HAN LEI, ZHANG HAI-JUN , et al. Selective oil/water separation materials. Progress in Chemistry, 2019,31(1):146-155.
[2]	LIU KE-SONG, YAO XI, JIANG LEI . Recent developments in bio-inspired special wettability. Chemical Society Reviews, 2010,39(8):3240-3255. DOI URL
[3]	SU CHUN-PING, YANG HAO, SONG SHUANG , et al. A magnetic super-hydrophilic/oleophobic sponge for continuous oil-water separation. Chemical Engineering Journal, 2017,309:366-373. DOI URL
[4]	ZHANG LIN, LI HONG-QIANG, LAI XUE-JUN , et al. Thiolated graphene-based superhydrophobic sponges for oil-water separation. Chemical Engineering Journal, 2017,316:736-743. DOI URL
[5]	LIU CAN, YANG JIN, TANG YONG-CAI , et al. Versatile fabrication of the magnetic polymer-based graphene foam and applications for oil-water separation. Colloids and Surfaces A, 2015,468:10-16. DOI URL
[6]	SHI ZHUN, ZHANG WEN-BIN, ZHANG FENG , et al. Ultrafast separation of emulsified oil/water mixtures by ultrathin free- standing single-walled carbon nanotube network films. Advanced Materials, 2013,25(17):2422-2427. DOI URL
[7]	GUI XU-CHUN, ZENG ZHI-PING, LIN ZHI-QING , et al. Magnetic and highly recyclable macroporous carbon nanotubes for spilled oil sorption and separation. ACS Applied Materials & Interfaces, 2013,5(12):5845-5850. DOI URL
[8]	HAN LEI, DENG XIAN-GONG, LI FA-LIANG , et al. Preparation of high strength porous mullite ceramics via combined foam- gelcasting and microwave heating. Ceramics International, 2018,44(12):14728-14733. DOI URL
[9]	HAN LEI, LI FA-LIANG, HUANG LANG , et al. Preparation of Si₃N₄ porous ceramics via foam-gelcasting and microwave-nitridation method. Ceramics International, 2018,44(15):17675-17680. DOI URL
[10]	DENG XIAN-GONG, RAN SONG-LIN, HAN LEI , et al. Foam-gelcasting preparation of high-strength self-reinforced porous mullite ceramics. Journal of the European Ceramic Society, 2017,37(13):4059-4066. DOI URL
[11]	SHANG SHAN SHAN, HE XIONG, YANG YI , et al. Preparation of Ti₂AlN porous ceramics by organic foam impregnation process. Key Engineering Materials, 2016,697:163-168. DOI URL
[12]	QIAN HAO-RAN, CHENG XU-DONG, ZHANG HE-PING , et al. Preparation of porous mulliteceramics using fly ashcenosphere as a pore-forming agent by gelcastingprocess. International Journal of Applied Ceramic Technology, 2014,11(5):858-863. DOI URL
[13]	GE SHENG-TAO, LIN LIANG-XU, ZHANG HAI-JUN , et al. Synthesis of hierarchically porous mullite ceramics with improved thermal insulation via foam-gelcasting combined with pore former addition. Advances in Applied Ceramics, 2018,117(8):493-499. DOI URL
[14]	CHAU TRANG THE LIEU, LE DUNG QUANG TIEN, LE HOA THI , et al. Chitin liquid-crystal-templated oxide semiconductor aerogels. ACS Applied Materials & Interfaces, 2017,9(36):30812-30820. DOI URL
[15]	JESÚS M RODRÍGUEZ-PARRA, RODRIGO MORENO, MARÍA ISABEL NIETO . Effect of cooling rate on the microstructure and porosity of alumina produced by freeze casting. Serbian Chemical Society Journal, 2012,77(12):1775-1785. DOI URL
[16]	DU JIAN-CONG, ZHANG XING-HONG, HONG CHANG-QING , et al. Microstructure and mechanical properties of ZrB₂-SiC porous ceramic by camphene-based freeze casting. Ceramics International, 2013,39(2):953-957. DOI URL
[17]	XIA YONG-FENG, ZENG YU-PING, JIANG DONG-LIANG . Microstructure and mechanical properties of porous Si₃N₄ ceramics prepared by freeze-casting. Materials & Design, 2012,33:98-103.
[18]	REN LIN-LIN, ZENG YU-PING, JIANG DONG-LIANG . Preparation of porous TiO₂ by a novel freeze casting. Ceramics International, 2009,35(3):1267-1270. DOI URL
[19]	BI YU-BAO, HAN LEI, ZHENG YANG-FAN , et al. Lotus- seedpod-bioinspired 3D superhydrophobic diatomite porous ceramics comodified by graphene and carbon nanobelts. ACS Applied Materials & Interfaces, 2018,10(32):27416-27423. DOI URL
[20]	MA YING, ZHANG GAO-KE . Sepiolite nanofiber-supported platinum nanoparticle catalysts toward the catalytic oxidation of formaldehyde at ambient temperature: efficient and stable performance and mechanism. Applied Clay Science, 2016,288:70-78.
[21]	SUÁREZ M, GARCÍA-ROMERO E . Variability of the surface properties of sepiolite. Applied Clay Science, 2012,67:72-82.
[22]	LI TIAN, WANG LI-JUAN, WANG KAI-LEI , et al. The preparation and properties of porous sepiolite ceramics. Scientific Reports, 2019,9(1):7337. DOI URL
[23]	VICTORIA BERNARDO, FREDERIK VAN LOOCK, JUDITH MARTIN-DE LEON, et al. Mechanical properties of PMMA- sepiolite nanocellular materials with a bimodal cellular structure. Macromolecular Materials and Engineering, 2019,304(7):1900041. DOI URL
[24]	GUO ZHEN-HUA, LIU ZHONG-TAO, YANG FAN , et al. Application of sepiolite in wastewater treatment. Environmental Protection and Circular Economy, 2016,36(10):30-32.
[25]	MILT V G, BANUS E D, MIRÓ E E , et al. Structured catalysts containing Co, Ba and K supported on modified natural sepiolite for the abatement of diesel exhaust pollutants. Chemical Engineering Journal, 2010,157(2/3):530-538.
[26]	WANG JUN-KAI, DENG XIAN-GONG, ZHANG HAI-JUN , et al. Synthesis of carbon nanotubes via Fe-catalyzed pyrolysis of phenolic resin. Physica E, 2017,86:24-35.
[27]	WANG JUN-KAI, DENG XIAN-GONG, ZHANG HAI-JUN , et al. Carbon nanotube preparation by catalytic pyrolysis of phenolic resin with nickel nitrate. Materials for Mechanical Engineering, 2016,40(8):30-33.
[28]	SONG JIAN-BO, ZHANG HAI-JUN, WANG JUN-KAI , et al. High-yield production of large aspect ratio carbon nanotubes via catalytic pyrolysis of cheap coal tar pitch. Carbon, 2018,130:701-713.
[29]	RAJAKOVIĆ-OGNJANOVIĆ V, ALEKSIĆ G, RAJAKOVIĆ L . Governing factors for motor oil removal from water with different sorption materials. Journal of Hazardous Materials, 2008,154(1/2/3):558-563.
[30]	AKHAVAN B, JARVIS K, MAJEWSKI P . Hydrophobic plasma polymer coated silica particles for petroleum hydrocarbon removal. ACS Applied Materials & Interfaces, 2013,5(17):8563-8571.
[31]	YUAN WEI-WEI, YUAN PENG, LIU DONG , et al. A hierarchically porous diatomite/silicalite-1 composite for benzene adsorption/desorption fabricated via a facile pre-modification in situ synthesis route. Chemical Engineering Journal, 2016,294:333-342.
[32]	XUE YANG-MING, DAI PENG-CHENG, JIANG XIANG-FEN , et al. Template-free synthesis of boron nitride foam-like porous monoliths and their high-end applications in water purification. Journal of Materials Chemistry A, 2016,4(4):1469-1478.
[33]	DONG BING-BING, YANG MING-YE, WANG FEI-HONG , et al. Porous Al₂O₃ plates prepared by combing foaming and gel-tape casting methods for efficient collection of oil from water. Chemical Engineering Journal, 2019,370:658-665.
[34]	HAO WEN-TAO, XU JIAN, LI RAN , et al. Developing superhydrophobic rock wool for high-viscosity oil/water separation. Chemical Engineering Journal, 2019,368:837-846.
[35]	GEN HAYASE, KAZUYOSHI KANAMORI, MASASHI FUKUCHI , et al. Facile synthesis of marshmallow-like macroporous gels usable under harsh conditions for the separation of oil and water. Angewandte Chemie International Edition, 2013,52(7):1986-1989.
[36]	ZHANG AI-LI, ZHAI XIU-JING, FU YAN , et al. Reach on electrochemical lithium storage performance of carbon nanotubes. Journal of Inorganic Materials, 2004,19(1):244-248.
[37]	ZHENG YANG-FAN, ZHANG HAI-JUN, GE SHENG-TAO , et al. Synthesis of carbon nanotube arrays with high aspect ratio via Ni-catalyzed pyrolysis of waste polyethylene. Nanomaterials, 2018,8(7):556.
[38]	WENZEL ROBERT N . Resistance of solid surfaces to wetting by water. Industrial & Engineering Chemistry, 1936,28(8):988-994.
[39]	CAO SU-JIAO, QIU FANG, XIONG CHEN , et al. Superhydrophobic PES/PDA/ODTS fibrous mat prepared by electrospinning and silanization modification for oil/water separation. Journal of Applied Polymer Science, 2018,135(12):45923.
[40]	CHENG PENG, JING PENG, ZHANG SHI-YUAN , et al. A macroporous metal-organic framework with enhanced hydrophobicity for efficient oil adsorption. Chemistry-A European Journal, 2018,24(15):3754-3759.
[41]	GUPTA SHIVAM, TAI NYAN-HWA . Carbon materials as oil sorbents: a review on the synthesis and performance. Journal of Materials Chemistry A, 2016,4(5):1550-1565. DOI URL

碳纳米管改性海泡石多孔陶瓷及其高效油水分离性能研究

Carbon Nanotube Modified Sepiolite Porous Ceramics for High-efficient Oil/Water Separation

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