CeOx掺杂TiO2-SiO2载体对Ag基柴油脱硫吸附剂性能的影响

XU Cheng-zhi; ZHENG Mei-qin; CHEN Keng; HU Hui; CHEN Xiao-hui

CeO_x掺杂TiO₂-SiO₂载体对Ag基柴油脱硫吸附剂性能的影响

许承志^{1, 2},
郑美琴^{1, 2},
陈铿^{1, 2},
胡晖²,
陈晓晖^{1, 2, ,}

1.
福州大学化肥催化剂国家工程研究中心, 福建福州 350002
2.
福州大学石油化工学院, 福建福州 350116

基金项目:

国家自然科学基金资助 21376055

详细信息

中图分类号: O643.36
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出版历程
- 收稿日期: 2016-03-08
- 修回日期: 2016-05-20
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-08-10

CeO_x doping on a TiO₂-SiO₂ supporter enhances Ag based adsorptive desulfurization for diesel

XU Cheng-zhi^{1, 2},
ZHENG Mei-qin^{1, 2},
CHEN Keng^{1, 2},
HU Hui²,
CHEN Xiao-hui^{1, 2
, ,}

1.
National Engineering Research Center of Chemical Fertilizer Catalysts, Fuzhou University, Fuzhou 350002, China
2.
School of Chemical Engineering, Fuzhou University, Fuzhou 350116, China

Funds:

国家自然科学基金资助 21376055

More Information

Corresponding author: Tel: +86-591-83731234-8607, E-mail: Xiao-hui chenxhfzu@fzu.edu.cn

摘要

摘要: 以钛酸丁酯的乙醇溶液为钛源, 硝酸铈的水溶液为沉淀剂, 采用共浸渍法制备CeO_x/TiO₂-SiO₂复合氧化物作为Ag基柴油脱硫吸附剂的载体, 探究CeO_x掺杂TiO₂-SiO₂载体对吸附剂结构及脱硫性能的影响.结果表明, 采用共浸渍法制备的CeO_x/TiO₂-SiO₂载体中, Ce物种和Ti物种均处于充分分散的状态, 掺杂CeO_x可促进Ag活性物种的分散, 还会促进金属态Ag活性物种的氧化, 形成高度分散的Ag氧化物 (Ag₂O₂) 活性中心, 从而提高吸附剂的脱硫性能 (22.5%).在静态吸附实验中, Ag-CeO_x/TiO₂-SiO₂对中国国II柴油 (硫含量952.9mg/kg) 的吸附硫容可达5.38mg/g, 在剂油比为1:10时可将中国国IV柴油 (硫含量39.0mg/kg) 中的硫含量降至10mg/kg以下, 达到中国国V柴油的标准.
- 真实柴油 /
- 吸附脱硫 /
- 氧化银 /
- CeO_x掺杂 /
- 高度分散
Abstract: In this work, the impact of CeO_x doping on a TiO₂-SiO₂ supporter on the Ag based adsorptive desulfurization for Chinese standard diesel was studied. The dispersion and valence states of Ce, Ti and Ag species were characterized, and the impact of Ce doping was investigated. The results indicated that Ce species and Ti species were dispersed evenly on the surface of SiO₂ via a novel co-impregnation method. Following CeO_x doping, the Ag species were in the form of oxides (about 5nm) instead of metallic Ag particles (about 35nm), which is due to the large amount of coordinative unsaturated sites provided by the interaction between CeO_x and TiO₂, as well as the oxidation-reduction property of CeO_x. The Ag in the active oxide state (Ag₂O₂) and dispersed evenly on the supporter could interact with sulfur compounds more favorably, and therefore showed a good performance in the adsorptive desulfurization. In both static batch and dynamic breakthrough desulfurization tests, Ag-CeO_x/TiO₂-SiO₂ was proved to be a more efficient adsorbent compared with Ag-TiO₂-SiO₂. It was found that the desulfurization performance of Ag-TiO₂-SiO₂ exhibited an excellent improvement (22.5%) after being doped with CeO_x. In the static equilibrium tests, the equilibrium sulfur capacity of Ag-CeO_x/TiO₂-SiO₂ was up to 5.38mg/g for CN-II diesel (sulfur content 952.9mg/kg) and the sulfur content of the CN-IV diesel (sulfur content 39.0mg/kg) after desulfurization was less than 10mg/kg, which could meet the CN-V standard.
- commercial diesel /
- adsorptive desulfurization /
- Ag oxides /
- CeO_x doping /
- adequate dispersion

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Figure 1 N₂-physisorption curves of different adsorbents and supports

a: SiO₂; b: TiO₂-SiO₂; c: Ag-TiO₂-SiO₂; d: CeO_x/TiO₂-SiO₂; e: Ag-CeO_x/TiO₂-SiO₂

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Figure 2 XPS Ti 2p spectra of CeO_x/TiO₂-SiO₂ and Ag-CeO_x/TiO₂-SiO₂

a: CeO_x/TiO₂-SiO₂; b: Ag-CeO_x/TiO₂-SiO₂

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Figure 3 XPS Ce 3d spectra of CeO_x/TiO₂-SiO₂ and Ag-CeO_x/TiO₂-SiO₂

a: CeO_x/TiO₂-SiO₂; b: Ag-CeO_x/TiO₂-SiO₂

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Figure 4 XRD patterns of different adsorbents

a: SiO₂; b: TiO₂-SiO₂; c: Ag-TiO₂-SiO₂; d: CeO_x/TiO₂-SiO₂; e: Ag-CeO_x/TiO₂-SiO₂

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Figure 5 TEM images of Ag-TiO₂-SiO₂

(a): bright field image; (b): HADDF-STEM image; (c), (d): HRTEM image

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Figure 6 TEM images of Ag-CeO_x/TiO₂-SiO₂

(a): BF image; (b): HADDF-STEM image; (c), (d): HRTEM image; (d) is the enlargement of the part enclosed by dotted lines in (c)

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Figure 7 Relative sulfur concentration (C/C₀) varies with adsorption time 3 g adsorbent was mixed with 90 mL CN-IV diesel fuel in a flask at 333 K and atmospheric pressure under vigorous stirring

●: Ag-TiO₂-SiO₂; ■: Ag-CeO_x/TiO₂-SiO₂

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Figure 8 Breakthrough curves of adsorbents obtained with CN-IV diesel at 298 K, atmospheric pressure and different LHSV

■: Ag-CeO_x/TiO₂-SiO₂ LHSV=0.3 h^-1;
●: Ag-CeO_x/TiO₂-SiO₂ LHSV=0.6 h^-1;
▲: Ag-CeO_x/TiO₂-SiO₂ LHSV=0.9 h^-1;
▼: Ag-TiO₂-SiO₂ LHSV=0.3 h^-1;
◆: Ag-TiO₂-SiO₂ LHSV=0.6 h^-1;
◀: Ag-TiO₂-SiO₂ LHSV=0.9 h^-1

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Figure 9 Contrasting the adsorption rate curves of CN-IV diesel and model diesel 3 g Ag-CeO_x/TiO₂-SiO₂ was mixed with 90 mL diesel fuel in a flask at 333 K and atmospheric pressure under vigorous stirring

●: CN-IV diesel; ■: model diesel

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Figure 10 Regeneration experiment of Ag-CeO_x/TiO₂-SiO₂ obtained with CN-IV diesel at 298 K, atmospheric pressure and 0.3 h^-1 of LHSV

■: fresh;
●: 1st recycling;
▲: 2nd recycling;
▼: 3rd recycling;
◆: 4th recycling;
◀: 5th recycling

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Table 1 Porous parameters of different adsorbents and supports

Sample ID	Surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Pore diameter d/nm
SiO₂	341.3	1.00	11.7
TiO₂-SiO₂	335.9	0.91	10.8
Ag-TiO₂-SiO₂	297.2	0.83	11.1
CeO_x/TiO₂-SiO₂	318.0	0.82	10.3
Ag-CeO_x/TiO₂-SiO₂	278.8	0.76	10.8

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Table 3 Static equilibrium test results of different adsorbents and supports

Adsorbent	A/F^b /(g·mL^-1)	Diesel	C_e^{a, b} /(mg·kg^-1)	η^{a, b} /%	C_S^{a, b} /(mg·g^-1)
SiO₂	1:30	CN-IV	30.6	21.6	0.21
TiO₂-SiO₂	1:30	CN-IV	26.5	32.0	0.31
CeO_x/TiO₂-SiO₂	1:30	CN-IV	25.6	34.4	0.35
Ag-SiO₂	1:30	CN-IV	27.6	29.3	0.29
Ag-TiO₂-SiO₂	1:30	CN-IV	23.1	40.8	0.40
Ag-CeO_x/TiO₂-SiO₂	1:30	CN-IV	19.7	49.5	0.49
Ag-CeO_x/TiO₂-SiO₂	1:20	CN-IV	14.8	62.0	0.41
Ag-CeO_x/TiO₂-SiO₂	1:10	CN-IV	8.1	79.1	0.26
Ag-CeO_x/TiO₂-SiO₂	1:30	CN-III	166.6	43.0	3.16
Ag-CeO_x/TiO₂-SiO₂	1:30	CN-II	738.5	22.4	5.38
Ag-TiO₂-Al₂O₃	1:30	CN-IV	29.3	25.0	0.25
^a all the desulfurization were processed at 333 K and atmospheric pressure, the adsorbents were mixed with the diesels under mechanical shaking for 48 h, respectively; ^b A/F represent adsorbent to diesel fuel ratios; C_e represent the equilibrium concentration; η is the desulphurization efficiencies; C_S represent the sulfur adsorption capacity

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Table 2 XPS binding energy of O 1s, Si 2p and Ce 3d peaks

Levels	Peak	Binding energy E_B/eV
Levels	Peak	reference	CeO_x/TiO₂-SiO₂	Ag-CeO_x/TiO₂-SiO₂
Ce 3d_5/2^a	v₀	880.6	-	-
	v	882.6	883.6	883.8
	v₁	885.45	-	-
	v₂	888.85	887.2	887.5
	v₃	898.4	899.9	900.5
Ce 3d_3/2^a	u₀	898.9	-	-
	u	901.05	902	902.3
	u₁	904.05	-	-
	u₂	907.45	905.8	906.1
	u₃	916.7	918.2	918.8
Si 2p^b		103.7	102.9	103.0
O 1s^b		533.2	532.9	533.1
^a: the reference binding energy of the ten Ce 3d peaks were from reference^[33]; ^b: the reference binding energy of O 1s and Si 2p in silica gel were from reference^[34]

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参考文献(37)

[1]	WU L, XIAO J, WU Y, XIAN S, MIAO G, WANG H, LI Z. A combined experimental/computational study on the adsorption of organosulfur compounds over metal-organic frameworks from fuels[J]. Langmuir, 2014, 30(4):1080-1088. doi: 10.1021/la404540j
[2]	PALOMINO J M, TRAN D T, HAUSER J L, DONG H, OLIVER S R. Mesoporous silica nanoparticles for high capacity adsorptive desulfurization[J]. J Mater Chem, 2014, 2(36):14890-14895. doi: 10.1039/C4TA02570A
[3]	XU X, ZHANG S, LI P, SHEN Y. Adsorptive desulfurization of liquid Jet-A fuel at ambient conditions with an improved adsorbent for on-board fuel treatment for SOFC applications[J]. Fuel Process Technol, 2014, 124:140-146. doi: 10.1016/j.fuproc.2014.03.001
[4]	XIAO J, WANG X, CHEN Y, FUJⅡ M, SONG C. Ultra-deep adsorptive desulfurization of light-irradiated diesel fuel over supported TiO₂-CeO₂ adsorbents[J]. Ind Eng Chem Res, 2013, 52(45):15746-15755. doi: 10.1021/ie402724q
[5]	HUSSAIN A S, TATARCHUK B J. Adsorptive desulfurization of jet and diesel fuels using Ag/TiO_x-Al₂O₃ and Ag/TiO_x-SiO₂ adsorbents[J]. Fuel, 2013, 107:465-473. doi: 10.1016/j.fuel.2012.11.030
[6]	QIN Y, MO Z, YU W, DONG S, DUAN L, GAO X, SONG L. Adsorption behaviors of thiophene, benzene, and cyclohexene on FAU zeolites:Comparison of CeY obtained by liquid-, and solid-state ion exchange[J]. Appl Surf Sci, 2014, 292:5-15. doi: 10.1016/j.apsusc.2013.11.036
[7]	KHAN N A, HASAN Z, JHUNG S H. Ionic liquids supported on metal-organic frameworks:Remarkable adsorbents for adsorptive desulfurization[J]. Chem Eur J, 2014, 20(2):376-380. doi: 10.1002/chem.v20.2
[8]	HUSSAIN A S, TATARCHUK B J. Mechanism of hydrocarbon fuel desulfurization using Ag/TiO₂-Al₂O₃ adsorbent[J]. Fuel Process Technol, 2014, 126:233-242. doi: 10.1016/j.fuproc.2014.05.006
[9]	HUSSAIN A S, MCKEE M L, HEINZEL J M, SUN X, TATARCHUK B J. Density functional theory study of organosulfur selective adsorption on Ag-TiO₂ adsorbents[J]. J Phys Chem C, 2014, 118(27):14938-14947. doi: 10.1021/jp503097y
[10]	LIU B, ZHU Y, LIU S, MAO J. Adsorption equilibrium of thiophenic sulfur compounds on the Cu-BTC metal-organic framework[J]. J Chem Eng Data, 2012, 57(4):1326-1330. doi: 10.1021/je300130s
[11]	YANG R T, HERNANDEZ-MALDONADO A J, YANG F H. Desulfurization of transportation fuels with zeolites under ambient conditions[J]. Science, 2003, 301(5629):79-81. doi: 10.1126/science.1085088
[12]	HE G, SUN L, SONG X, LIU X, YIN Y, WANG Y. Adjusting host properties to promote cuprous chloride dispersion and adsorptive desulfurization sites formation on SBA-15[J]. Energy Fuels, 2011, 25(8):3506-3513. doi: 10.1021/ef200723m
[13]	XU X, ZHANG S, LI P, SHEN Y. Equilibrium and kinetics of Jet-A fuel desulfurization by selective adsorption at room temperatures[J]. Fuel, 2013, 111:172-179. doi: 10.1016/j.fuel.2013.04.068
[14]	MA X, SPRAGUE M, SONG C. Deep desulfurization of gasoline by selective adsorption over nickel-based adsorbent for fuel cell applications[J]. Ind Eng Chem Res, 2005, 44(15):5768-5775. doi: 10.1021/ie0492810
[15]	VELU S, MA X, SONG C, NAMAZIAN M, SETHURAMAN S, VENKATARAMAN G. Desulfurization of JP-8 jet fuel by selective adsorption over a Ni-based adsorbent for micro solid oxide fuel cells[J]. Energy Fuels, 2005, 19(3):1116-1125. doi: 10.1021/ef049800b
[16]	SHEN Y, XU X, LI P. A novel potential adsorbent for ultra deep desulfurization of jet fuels at room temperature[J]. RSC Adv, 2012, 2(15):6155-6160. doi: 10.1039/c2ra20224g
[17]	TRIANTAFYLLIDIS K S, DELIYANNI E A. Desulfurization of diesel fuels:Adsorption of 4, 6-DMDBT on different origin and surface chemistry nanoporous activated carbons[J]. Chem Eng J, 2014, 236:406-414. doi: 10.1016/j.cej.2013.09.099
[18]	WANG L, YANG R T, SUN C L. Graphene and other carbon sorbents for selective adsorption of thiophene from liquid fuel[J]. AlChE J, 2013, 59(1):29-32. doi: 10.1002/aic.v59.1
[19]	BALTZOPOULOU P, KALLIS K X, KARAGIANNAKIS G, KONSTANDOPOULOS A G. Diesel fuel desulfurization via adsorption with the aid of activated carbon:Laboratory-and pilot-scale studies[J]. Energy Fuels, 2015, 29(9):5640-5648. doi: 10.1021/acs.energyfuels.5b01133
[20]	XU X, ZHANG S, LI P, SHEN Y. Desulfurization of Jet-A fuel in a fixed-bed reactor at room temperature and ambient pressure using a novel selective adsorbent[J]. Fuel, 2014, 117:499-508. doi: 10.1016/j.fuel.2013.09.074
[21]	GUO J, JANIK M J, SONG C. Density functional theory study on the role of ceria addition in Ti_xCe_1-xO₂ adsorbents for thiophene adsorption[J]. J Phys Chem C, 2012, 116(5):3457-3466. doi: 10.1021/jp2063996
[22]	TIAN F, SHEN Q, FU Z, WU Y, JIA C. Enhanced adsorption desulfurization performance over hierarchically structured zeolite Y[J]. Fuel Process Technol, 2014, 128:176-182. doi: 10.1016/j.fuproc.2014.07.018
[23]	WANG Y, YANG R T, HEINZEL J M. Desulfurization of jet fuel byπ-complexation adsorption with metal halides supported on MCM-41 and SBA-15 mesoporous materials[J]. Chem Eng Sci, 2008, 63(2):356-365. doi: 10.1016/j.ces.2007.09.002
[24]	HERNANDEZ-MALDONADO A J, YANG R T. Desulfurization of commercial liquid fuels by selective adsorption viaπ-complexation with Cu (I)-Y zeolite[J]. Ind Eng Chem Res, 2003, 42(13):3103-3110. doi: 10.1021/ie0301132
[25]	PERALTA D, CHAPLAIS G, SIMON-MASSERON A, BARTHELET K, PIRNGRUBER G D. Metal-organic framework materials for desulfurization by adsorption[J]. Energy Fuels, 2012, 26(8):4953-4960. doi: 10.1021/ef300762z
[26]	LIU X, WANG J, LI Q, JIANG S, ZHANG T, JI S. Synthesis of rare earth metal-organic frameworks (Ln-MOFs) and their properties of adsorption desulfurization[J]. J Rare Earths, 2014, 32(2):189-194. doi: 10.1016/S1002-0721(14)60050-8
[27]	NAIR S, TATARCHUK B J. Supported silver adsorbents for selective removal of sulfur species from hydrocarbon fuels[J]. Fuel, 2010, 89(11):3218-3225. doi: 10.1016/j.fuel.2010.05.006
[28]	WATANABE S, MA X, SONG C. Characterization of structural and surface properties of nanocrystalline TiO₂-CeO₂ mixed oxides by XRD, XPS, TPR, and TPD[J]. J Phys Chem C, 2009, 113(32):14249-14257. doi: 10.1021/jp8110309
[29]	SCIRE S, MINICO S, CRISAFULLI C, SATRIANO C, PISTONE A. Catalytic combustion of volatile organic compounds on gold/cerium oxide catalysts[J]. Appl Catal B:Environ, 2003, 40(1):43-49. doi: 10.1016/S0926-3373(02)00127-3
[30]	ZHANG Y, ANDERSSON S, MUHAMMED M. Nanophase catalytic oxides:I. Synthesis of doped cerium oxides as oxygen storage promoters[J]. Appl Catal B:Environ, 1995, 6(4):325-337. doi: 10.1016/0926-3373(95)00041-0
[31]	XIAO J, WANG X, FUJⅡ M, YANG Q, SONG C. A novel approach for ultra-deep adsorptive desulfurization of diesel fuel over TiO₂-CeO₂/MCM-48 under ambient conditions[J]. AlChE J, 2013, 59(5):1441-1445. doi: 10.1002/aic.14085
[32]	GONBEAU D, GUIMON C, PFISTER-GUILLOUZO G, LEVASSEUR A, MEUNIER G, DORMOY R. XPS study of thin films of titanium oxysulfides[J]. Surf Sci, 1991, 254(1):81-89.
[33]	ROMEO M, BAK K, FALLAH J E, NORMAND F L, HILAIRE L. XPS study of the reduction of cerium dioxide[J]. Surf Interface Anal, 1993, 20(6):508-512. doi: 10.1002/(ISSN)1096-9918
[34]	GROSS T, RAMM M, SONNTAG H, UNGER W, WEIJERS H M, ADEM E H. An XPS analysis of different SiO₂ modifications employing a C 1s as well as an Au 4f_7/2 static charge reference[J]. Surf Interface Anal, 1992, 18(1):59-64. doi: 10.1002/(ISSN)1096-9918
[35]	NAGPURE I, PITALE S S, TSHABALALA K, KUMAR V, NTWAEABORWA O, TERBLANS J, SWART H. Luminescence response and CL degradation of combustion synthesized spherical SiO₂:Ce nanophosphor[J]. Mater Res Bull, 2011, 46(12):2359-2366. doi: 10.1016/j.materresbull.2011.08.051
[36]	LARACHI F, PIERRE J, ADNOT A, BERNIS A. Ce 3d XPS study of composite Ce_xMn_1-xO_2-y wet oxidation catalysts[J]. Appl Surf Sci, 2002, 195(1):236-250.
[37]	SAMOKHVALOV A, NAIR S, DUIN E C, TATARCHUK B J. Surface characterization of Ag/titania adsorbents[J]. Appl Surf Sci, 2010, 256(11):3647-3652. doi: 10.1016/j.apsusc.2010.01.002

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CeO_x掺杂TiO₂-SiO₂载体对Ag基柴油脱硫吸附剂性能的影响

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CeO_x doping on a TiO₂-SiO₂ supporter enhances Ag based adsorptive desulfurization for diesel

Corresponding author: Tel: +86-591-83731234-8607, E-mail: Xiao-hui chenxhfzu@fzu.edu.cn

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