一步法制备含W介孔碳材料及其氧化脱硫性能研究

侯良培; 赵荣祥; 李秀萍

一步法制备含W介孔碳材料及其氧化脱硫性能研究

1.
辽宁石油化工大学化学化工与环境学部石油化工学院, 辽宁抚顺 113001
2.
辽宁石油化工大学化学化工与环境学部化学与材料科学学院, 辽宁抚顺 113001

详细信息

通讯作者:
赵荣祥, E-mail:zylhzrx@126.com

中图分类号: TE624
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- 文章访问数: 92
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- PDF下载量: 4
- 被引次数: 0
出版历程
- 收稿日期: 2016-11-28
- 修回日期: 2017-01-16
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-03-10

One-step preparation of mesoporous carbon containing tungsten and its desulfurization performance

1.
College of Petrochemical Engineering, Liaoning University of Petroleum & Chemical Technology, Fushun 113001, China
2.
College of Chemistry & Material Science Engineering, Liaoning University of Petroleum & Chemical Technology, Fushun 113001, China

摘要

摘要: 以钨酸钠为钨源，以乙二胺四乙酸二钠为碳源经过高温煅烧制备了含W的介孔碳材料，采用XRD、SEM、FT-IR、BET对含钨的介孔碳材料进行表征。结果表明，煅烧后介孔碳材料的表面形成了粒状含有结晶水的氧化钨（WO₃·H₂O）。相比于纯的介孔碳材料，含钨介孔碳材料的总比表面积减小。以含W介孔碳材料为催化剂，H₂O₂作为氧化剂，1-丁基-3-甲基咪唑氟硼酸盐（[BMIM][BF₄]）离子液体作为萃取剂，组成萃取-催化氧化脱硫体系（ECODS）并研究其对模拟油中二苯并噻吩脱除效果。考察了氧化钨负载量、反应温度、H₂O₂加入量、催化剂用量、离子液体用量以及不同类型硫化物对二苯并噻吩脱除的影响。在最佳反应条件下，催化剂对二苯并噻吩（DBT）、4，6-二甲基二苯并噻吩（4，6-DMDBT）、苯并噻吩（BT）、噻吩（TH）和真实汽油的脱除率分别达到98.6%、65.6%、61.2%、57.8%和64.3%。催化剂回收利用五次之后脱硫率略有降低，仍高达95.2%。
- WO₃·H₂O /
- 催化氧化脱硫 /
- 萃取 /
- 离子液体
Abstract: A mesoporous carbon containing tungsten was prepared using Na₂WO₄ and EDTA-2Na as the source of tungsten and carbon and characterized by XRD, FT-IR, SEM and BET. The results show that the tungsten oxide with crystal water (WO₃·H₂O) is formed on the surface of mesoporous carbon. Compared with pure mesoporous carbon, the total surface area of mesoporous carbon containing tungsten decreases. An extraction-catalytic oxidation desulfurization (ECODS) system was constructed using mesoporous carbon containing tungsten as catalyst, H₂O₂ as oxidant and ionic liquids (ILs) 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] [BF₄]) as extraction agent. The effects of tungsten oxide loading, reaction temperature, the amount of H₂O₂, the amount of catalyst and ILs dosage and different types of sulfur compounds on the removal of DBT was studied. Under the optimal conditions, the removal rate of DBT reaches 98.6% for DBT, 65.6% for 4, 6-DMDBT, 61.2% for BT, 57.8% for TH and 64.3% for actual gasoline, respectively. The desulfurization rate is slightly decreased when the catalyst is reused five times.
- WO₃·H₂O /
- catalytic oxidation desulfurization /
- extraction /
- ILs

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图 1 催化剂的FT-IR谱图

Figure 1 FT-IR spectra of catalysts

a: W-10%/MC; b: MC

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图 2 不同负载量催化剂的XRD谱图

Figure 2 XRD patterns of different loading catalysts

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图 3 催化剂的SEM照片

Figure 3 SEM images of catalysts

(a): MC; (b): W-5%/MC; (c): W-10%/MC; (d): W-20%/MC

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图 4 氧化钨负载量对脱硫效果的影响

Figure 4 Effect of WO₃-loading on desulfurization efficiency reaction conditions:V_{(model oil)}=5 mL, t=60 ℃, V_(H₂O₂)=0.2 mL, V_(ILs)=1 mL, m_(catalyst)=0.02 g

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图 5 双氧水用量对脱硫效果的影响

Figure 5 Effect of H₂O₂ amount on desulfurization efficiency reaction conditions:V_{(model oil)}=5 mL, t=60 ℃, V_(ILs)=1 mL, m_(catalysts)=0.02 g

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图 6 反应温度对脱硫效果的影响

Figure 6 Effect of temperature on desulfurization efficiency reaction conditions: V_{(model oil)}=5 mL, V_(H₂O₂)=0.2 mL, V_(ILs)=1 mL, m_(catalysts)=0.02 g

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图 7 催化剂用量对脱硫效果的影响

Figure 7 Effect of catalyst amount on desulfurization efficiency reaction conditions:V_{(model oil)}=5 mL, t=70 ℃, V_(H₂O₂)=0.2 mL, V_(ILs)=1 mL

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图 8 催化剂对不同硫化物的脱除

Figure 8 Catalytic removal of different sulfides reaction conditions:V_{(model oil)}=5 mL, t=70 ℃, V_(H₂O₂)=0.2 mL, m_(catalyst)=0.02 g, V_(ILs)=0.25 mL

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图 9 催化剂对汽油的脱除

Figure 9 Catalytic removal of sulfur in gasoline reaction conditions: V_{(model oil)}=5 mL, t=70 ℃, V_(H₂O₂)=0.2 mL, m_(catalyst)=0.02 g, V_(ILs)=0.25 mL

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图 10 反应产物和DBT的FT-IR谱图

Figure 10 FT-IR diagram of reaction products and DBT

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图 11 反应机理示意图

Figure 11 Reaction mechanism

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表 1 不同负载量催化剂的比表面积及孔结构

Table 1 BET surface area and pore structure of catalysts under different loading conditions

Catalyst	Specific area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Pore size d/nm
MC	460.19	0.130	2.93
W-5%/MC	28.99	0.042	4.03
W-10%/MC	50.77	0.034	3.21
W-20%/MC	138.35	0.044	3.25

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表 2 离子液体用量对脱硫效果的影响

Table 2 Effect of ILs amount on desulfurization efficiency

ILs amount V/mL	S-removal η/%	ILs amount V/mL	S-removal η/%
0	24.4	0.5	99
0.2	93	1.0	98.4
0.25	98.6	1.5	98
reaction conditions：V_{(model oil)}=5 mL, t=70 ℃, V_(H₂O₂)=0.2 mL, m_(catalyst)=0.02 g

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表 3 不同硫化物的脱除

Table 3 Removal effect of different sulfides

Desulfurization system	S-removal η /%
Desulfurization system	4, 6-DMDBT	DBT	BT	TH
Catalyst +ILs+H₂O₂	65.6	98.6	61.2	57.8
ILs+H₂O₂	14.5	24.4	12.7	8.2
Catalyst +H₂O₂	9.8	12.2	8.6	7.3
H₂O₂	< 2	< 2	< 2	< 2

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表 4 催化剂和离子液体的循环使用对脱硫效果的影响

Table 4 Effect of the recycling catalyst and ILs on desulfurization efficiency

Cycle number	Desulfurization rate η /%	Cycle times	Desulfurization rate η /%
0	98.6	3	97.5
1	98.3	4	96.4
2	97.9	5	95.2
reaction conditions：V_{(model oil)}=5 mL, t=70 ℃, V_(H₂O₂)=0.2 mL, m_(catalyst)=0.02 g, V_(ILs)=0.25 mL

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参考文献(40)

[1]	YU F L, LIU C Y, XIE P H, XIE C X, YU S T. Oxidative-extractive deep desulfurization of gasoline by functionalized heteropoly acid catalysts[J]. RSC Adv, 2015, 5(104):85540-85546. doi: 10.1039/C5RA16013H
[2]	GB 17930-2013, Gasoline for motor vehicles[S].
[3]	ZHANG H, GAO J, MENG H, LI C X. Removal of thiophenic sulfurs using an extractive oxidative desulfurization process with three new phosphotungstate catalysts[J]. Ind Eng Chem Res, 2012, 51:6658-6665. doi: 10.1021/ie3004545
[4]	ZHU W S, WANG C, LI H P, WU P W, XUN S H, JIANG W, CHEN Z G, ZHAO Z, LI H M. One-pot extraction combined with metal-free photochemical aerobic oxidative desulfurization in deep eutectic solvent[J]. Green Chem, 2015, 17(4):2464-2472. doi: 10.1039/C4GC02425G
[5]	CAMPOS-MARTIN J M, CAPEL-SANCHEZ M C, FIERRO J L G. Highly efficient deep desulfurization of fuels by chemical oxidation[J]. Green Chem, 2004, 6(11):557-562. doi: 10.1039/b409882j
[6]	AGGARWAL S, KARIMI I A, LEE D Y. Reconstruction of a genome-scale metabolic network of Rhodococcus erythropolis for desulfurization studies[J]. Mol BioSyst, 2011, 7(11):3122-3131. doi: 10.1039/c1mb05201b
[7]	HUANG C P, CHEN B H, ZHANG J, LIU Z C, LI Y. Desulfurization of gasoline by extraction with new ionic liquids[J]. Energy Fuels, 2004, 18(6):1862-1864. doi: 10.1021/ef049879k
[8]	ZHAO K, CHENG Y, LIU H Y, YANG C P, QIU L, ZENG G M, HE H J. Extractive desulfurization of dibenzothiophene by a mixed extractant of N, N-dimethylacetamide, N, Ndimethylformamide and tetramethylene sulfone:Optimization by Box-Behnken design[J]. RSC Adv, 2015, 5(81):66013-66023. doi: 10.1039/C5RA12305D
[9]	LENK K Y, SUN Y Y, ZHANG X, XU W. Ti-modified hierarchical mordenite as highly active catalyst for oxidative desulfurization of dibenzothiophene[J]. Fuel, 2016, 174:9-16. doi: 10.1016/j.fuel.2016.01.070
[10]	ZHOU M D, MENG W Y, LI Y, WANG Q, LI X B, ZANG S L. Extractive and catalytic oxidative desulfurization of gasoline by methyltrioxorhenium in ionic liquids[J]. Energy Fuels, 2013, 28(1):516-521.
[11]	CHAMACK M, MAHJOUB A R. Synthesis and characterization of supported Cs₂H[PW₄Mo₈O₄₀] on iron oxide@mesoporous silica particles:Promising catalyst for oxidative desulfurization process[J]. Catal Lett, 2016, 146(6):1050-1058. doi: 10.1007/s10562-016-1731-8
[12]	SHIRANI M, SEMNANI A, HABIBOLLAHI S, HADDADI H. Synthesis and application of magnetic NaY zeolite composite immobilized with ionic liquid for adsorption desulfurization of fuel using response surface methodology[J]. J Porous Mater, 2016, 23(3):701-712. doi: 10.1007/s10934-016-0125-z
[13]	JAIN N, KUMAR A, CHAUHAN S. Chemical and biochemical transformations in ionic liquids[J]. Tetrahedron, 2005, 61(5):1015-1060. doi: 10.1016/j.tet.2004.10.070
[14]	VAN R F, SHELDON R A. Biocatalysis in ionic liquids[J]. Chem Rev, 2007, 107(6):2757-2785. doi: 10.1021/cr050946x
[15]	SONG C E, ROH E J. Practical method to recycle a chiral (salen) Mn epoxidation catalyst by using an ionic liquid[J]. Chem Commun, 2000, 31(35):837-838. https://www.researchgate.net/publication/237771721_Practical_Method_to_Recycle_a_Chiral_SalenMn_Epoxidation_Catalyst_by_Using_an_Ionic_Liquid
[16]	BÖSMANN A, DATSEVICH L, JESS A. Deep desulfurization of diesel fuel by extraction with ionic liquids[J]. Petrol Sci Technol, 2008, 26(9):973-982. doi: 10.1080/10916460600695496
[17]	ZHAO D S, WANG J L, ZHOU E P. Oxidative desulfurization of diesel fuel using a Brønsted acid room temperature ionic liquid in the presence of H₂O₂[J]. Green Chem, 2007, 9(11):1219-1222. doi: 10.1039/b706574d
[18]	WU Z Y, IQBAL Z, WANG X Q. Metal-free, carbon-based catalysts for oxygen reduction reactions[J]. Chem Sci Eng, 2015, 9(3):280-294. https://www.researchgate.net/publication/282890244_Metal-Free_Carbon-Based_Catalysts_for_Oxygen_Reduction_Reactions
[19]	LI X, ZHU H W, WANG A J, CHEN Y Y. Oxidative desulfurization of dibenzothiophene over tungsten oxides supported on SiO₂ and γ-Al₂O₃[J]. Chem Lett, 2013, 42(1):8-10. doi: 10.1246/cl.2013.8
[20]	LI X C, HUANG S X, XU Q R, YANG Y F. Preparation of WO₃-SBA-15 mesoporous molecular sieve and its performance as an oxidative desulfurization catalyst[J]. Transit Metal Chem, 2009, 34(8):943-947. doi: 10.1007/s11243-009-9285-x
[21]	TORRES-GARCIA E, CANIZAL G, VELUMANI S, RAMIREZ-VERDUZCO L, MURRIETA-GUEVARA F, ASCENCIO J. Influence of surface phenomena in oxidative desulfurization with WO_x/ZrO₂ catalysts[J]. Appl Phys A:Mater, 2004, 79(8):2037-2040. doi: 10.1007/s00339-004-2668-0
[22]	ZHAO R X, LI X P, SU J X, GAO X H. Preparation of WO₃/g-C₃N₄ composites and their application in oxidative desulfurization[J]. Appl Surf Sci, 2017, 392:810-816. doi: 10.1016/j.apsusc.2016.08.120
[23]	KATSUMATA H, TACHI Y, SUZUKI T, KANECO S. Z-scheme photocatalytic hydrogen production over WO₃/g-C₃N₄ composite photocatalysts[J]. Rsc Adv, 2014, 4(41):21405-21409. doi: 10.1039/c4ra02511c
[24]	SHI Y W, LIU G Z, WANG L, ZHANG X W. Efficient adsorptive removal of dibenzothiophene from model fuel over heteroatom-doped porous carbons by carbonization of an organic salt[J]. Chem Eng J, 2015, 259:771-778. doi: 10.1016/j.cej.2014.08.054
[25]	DING J, LIU Q Q, ZHANG Z Y, LIU X, ZHAO J Q, CHENG S B, ZONG B N, DAI W L. Carbon nitride nanosheets decorated with WO₃ nanorods:Ultrasonic-assisted facile synthesis and catalytic application in the green manufacture of dialdehydes[J]. Appl Catal B:Environ, 2015, 165:511-518. doi: 10.1016/j.apcatb.2014.10.037
[26]	QIU J H, WANG G H, ZHANG Y Q, ZENG D L, CHEN Y. Direct synthesis of mesoporous H₃PMo₁₂O₄₀/SiO₂ and its catalytic performance in oxidative desulfurization of fuel oil[J]. Fuel, 2015, 147:195-202. doi: 10.1016/j.fuel.2015.01.064
[27]	ZHUANG J Z, HU B, TAN J J, JIN X Y. Deep oxidative desulfurization of dibenzothiophene with molybdovanadophosphoric heteropolyacid-based catalysts[J]. Transit Metal Chem, 2014, 39(2):213-220. doi: 10.1007/s11243-013-9792-7
[28]	谢东, 何其慧, 苏阳洋, 王童薇, 许仁富, 胡柏星. MCM-41分子筛负载亚硒核过氧钨酸盐催化剂催化二苯并噻吩氧化脱硫[J].催化学报, 2015, 36(8):1205-1213. doi: 10.1016/S1872-2067(15)60897-X XIE Dong, HE Qi-hui, SU Yang-yang, WANG Tong-wei, XU Ren-fu, HU Bai-xing. Oxidative desulfurization of dibenzothiophene catalyzed by peroxotungstate on functionalized MCM-41 materials using hydrogen peroxide as oxidant[J]. Chin J Catal, 2015, 36(8):1205-1213. doi: 10.1016/S1872-2067(15)60897-X
[29]	ZHENG D, ZHU W S, XUN S H, ZHOU M M, ZHANG M, JIANG W, QIN Y J, LI H M. Deep oxidative desulfurization of dibenzothiophene using low-temperature-mediated titanium dioxide catalyst in ionic liquids[J]. Fuel, 2015, 159(6):446-453. https://www.researchgate.net/profile/Wenshuai_Zhu/publication/281720529_Deep_oxidative_desulfurization_of_dibenzothiophene_using_lowerature-mediated_titanium_dioxide_catalyst_in_ionic_liquids/links/562086fe08aea35f267e19ac.pdf
[30]	CEDEÑO-CAERO L, GOMEZ-BERNAL H, FRAUSTRO-CUEVAS A. Oxidative desulfurization of synthetic diesel using supported catalysts:Part Ⅲ. Support effect on vanadium-based catalysts[J]. Catal Today, 2008, 133(1):244-254. https://www.researchgate.net/publication/229175168_Oxidative_desulfurization_of_synthetic_diesel_using_supported_catalysts_Part_III_Support_effect_on_vanadium-based_catalysts
[31]	DAI B L, WU P W, ZHU W S, CHAO Y H, SUN J, XIONG J, JAING W, LI H M. Heterogenization of homogenous oxidative desulfurization reaction on graphene-like boron nitride with a peroxomolybdate ionic liquid[J]. RSC Adv, 2015, 6(1):140-147.
[32]	OTSUKI S, NONAKA T, TAKASHIMA N, QIAN W H, ISHIHARA A, IMAI T, KABE T. Oxidative desulfurization of light gas oil and vacuum gas oil by oxidation and solvent extraction[J]. Energy Fuels, 2000, 14(6):1232-1239. doi: 10.1021/ef000096i
[33]	LO W H, YANG H Y, WEI G T. One-pot desulfurization of light oils by chemical oxidation and solvent extraction with room temperature ionic liquids[J]. Green Chem, 2003, 5(5):639-642. doi: 10.1039/b305993f
[34]	李宇慧, 冯丽娟, 王景刚, 徐康文, 李春虎. MoO₃/Al₂O₃介孔催化剂在柴油氧化脱硫中的应用[J].石油学报 (石油加工), 2011, 27(6):878-883. http://www.cnki.com.cn/Article/CJFDTotal-SXJG201106007.htm LI Yu-hui, FENG Li-juan, WANG Jing-gang, XU Kang-wen, LI Chun-hu. Oxidative desulfurization of diesel oil by mesoporous catalyst MoO₃/Al₂O₃[J]. Acta Pet Sin (Pet Process Sect), 2011, 27(6):878-883. http://www.cnki.com.cn/Article/CJFDTotal-SXJG201106007.htm
[35]	ESSER J, WASSERSCHEID P, JESS A. Deep desulfurization of oil refinery streams by extraction with ionic liquids[J]. Green Chem, 2004, 6(7):316-322. doi: 10.1039/B407028C
[36]	ZHAO D S, SUN Z M, LI F T, LIU R, SHAN H D. Oxidative desulfurization of thiophene catalyzed by (C₄H₉)₄NBr·2C₆H₁₁NO coordinated ionic liquid[J]. Energy Fuels, 2008, 22(5):3065-3069. doi: 10.1021/ef800162w
[37]	TANG X D, HU T, LI J J, WANG F, QING D Y. Deep desulfurization of condensate gasoline by electrochemical oxidation and solvent extraction[J]. RSC Adv, 2015, 5(66):53455-53461. doi: 10.1039/C5RA06851G
[38]	SHIRAISHI Y, TACHIBANA K, HIRAI T, KOMASAWA I. Desulfurization and denitrogenation process for light oils based on chemical oxidation followed by liquid-liquid extraction[J]. Ind Eng Chem Res, 2002, 41(17):4362-4375. doi: 10.1021/ie010618x
[39]	DONG Y, NIE Y, ZHOU Q. Highly efficient oxidative desulfurization of fuels by Lewis acidic ionic liquids based on iron chloride[J]. Chem Eng Technol, 2013, 36(3):435-442. doi: 10.1002/ceat.v36.3
[40]	USUI Y, SATO K. A green method of adipic acid synthesis:Organic solvent-and halide-free oxidation of cycloalkanones with 30% hydrogen peroxide[J]. Green Chem, 2003, 5(4):373-375. doi: 10.1039/b305847f