磷钨酸/纳米晶TS-1催化剂高效择形催化氧化脱硫

摘要/Abstract

摘要： 采用浸渍法合成了纳米晶TS-1负载磷钨酸的HPW-Nano-TS-1催化剂，31P MAS-NMR，FT-IR，UV-vis表征结果表明，合成的负载型催化剂上磷钨酸保持Keggin骨架结构。以模型有机硫化物的正辛烷溶液为模拟油的吸附脱硫试验结果表明，噻吩、苯并噻吩和二苯并噻吩在纳米晶TS-1及HPW-Nano-TS-1样品上吸附达到平衡的时间逐渐增加，饱和吸附量相应减少。磷钨酸的引入提高了纳米晶TS-1对于大分子有机硫化物二苯并噻吩的氧化脱除活性。在温度60 ℃的反应条件下，噻吩的脱除率高于98.0%，二苯并噻吩的脱除率为58.0%，3种模型有机硫化物氧化脱除由易到难的顺序为：噻吩>二苯并噻吩>苯并噻吩，与常规的TS-1沸石或者多酸催化剂的活性顺序存在明显的差异，这是纳米晶TS-1沸石对于有机硫分子氧化反应的择形作用、扩散效应和磷钨酸在催化氧化脱硫过程中的电子云密度综合作用的结果。

关键词: 择形催化, 氧化脱硫, 多金属氧酸盐, 纳米晶TS-1, 过氧化氢

Abstract: The catalyst (HPW-Nano-TS-1) with phosphotungstic acid (HPW) supported on nanocrystalline TS-1 was synthesized by impregnation method. The results of 31P MAS-NMR, FT-IR and UV-VIS characterization indicated that the preservation of the Keggin structure in HPW-Nano-TS-1 catalysts was confirmed. Catalytic oxidative desulfurization reaction and adsorption desulfurization over synthesized catalysts with model oil consisting of n-octane solution of organic sulfur was investigated. The time for the adsorption of thiophene, benzothiophene and dibenzothiophene over the nanocrystalline TS-1 and HPW-Nano-TS-1 samples gradually increased, and the saturated adsorption amount decreased accordingly. The introduction of HPW enhances the oxidative removal activity of nanocrystalline TS-1 for macromolecular dibenzothiophene. The removal rates of thiophene and dibenzothiophene were 98.5% and 58.0% at 60 °C, respectively. The order of removal of organic sulfide in the three models from easy to difficult is: thiophene > dibenzothiophene > benzothiophene, clearly different in the order of easy removal of benzothiophene from conventional microporous zeolite or polyoxometalate catalysts. It is due to the effects of shape-selectivity, diffusion effect as well as the electron cloud density of nanocrystalline TS-1 zeolite and HPW on the oxidation reaction of organic sulfur molecules.

Key words: Shape selectivity, oxidative desulfurization, polyoxometallate, nanocrystalline TS-1, hydrogen peroxide

中图分类号:

马康富佟欢廖林李彦昕王军霞左心语陈立东成卫国. 磷钨酸/纳米晶TS-1催化剂高效择形催化氧化脱硫[J]. 石油炼制与化工, 2019, 50(8): 38-45.

参考文献

(1) Song C, Ma X. New Design Approaches to Ultra-Clean Diesel Fuels by Deep Desulfurization and Deep Dearomatization[J]. Appl Catal B: Envir, 2003, 41(1):207-238.
(2) Oyama S T, Gott T, Zhao H. Transition Metal Phosphide Hydroprocessing Catalysts: A Review[J]. Catal Today, 2009, 143(1) :94-107.
(3) Craven M, Xiao D, Kunstmann-Olsen C, et al. Oxidative Desulfurization of Diesel Fuel Catalyzed by Polyoxometalate Immobilized on Phosphazene-Functionalized Silica[J]. Appl Catal B: Envir,2018, 231: 82-91.
(4) Bai R S,Sun Q M, Song Y, et al. Intermediate-Crystallization Promoted Catalytic Activity of Titanosilicate Zeolites[J]. J Mater Chem A ,2018, 6(18):8757-8762.
(5) Lu T L, Zou J P, Zhan Y Z, et al. Highly Efficient Oxidation of Ethyl Pyruvate Catalyzed by TS-1 Under Mild Conditions[J]. ACS Catal, 2018, 8:1287-1296.
(6) Kong L Y, Li G, Wang X S. Mild Oxidation of Thiophene over TS-1/H2O2[J]. Catal Today, 2004, 93 (9):341-345.
(7) Jing C Z, Li G, Wang X S, et al. Ti-HMS和TS-1分子筛结构和催化性能的对比研究[J]. J Catal, 2007, 28:170-174 [金长子, 李钢王祥生，等. Ti-HMS和TS-1分子筛结构和催化性能的对比研究[J]. 催化学报, 2007, 28(2): 170-174.]
(8) Du S T, Sun Q M, Wang N, et al. Synthesis of Hierarchical TS-1 Zeolites with Abundant and Uniform Intracrystalline Mesopores andTheir Highly Efficient Catalytic Performance for Oxidation Desulfurization[J]. J Mater Chem A, 2017, 5(17):7992-7998.
(9) Du S T, Chen X X, Sun Q M, et al. A Non-Chemically Selective Top-Down Approach Towards the Preparation of Hierarchical TS-1 Zeolites with Improved Oxidative Desulfurization Catalytic Performance[J]. Chem Commun, 2016, 52:3580-3583.
(10) Du S T, Li F, Sun Q M, et al. A Green Surfactant-assisted Synthesis of Hierarchical TS-1 ZeolitesGau with Excellent Catalytic Properties for Oxidative Desulfurization[J]. Chem Commun, 2016, 52(16):3368-3371.
(11) González J, Chen L F,Wang J A, et al. Surface Chemistry and Catalytic Properties of VOX/Ti-MCM-41 Catalysts for Dibenzothiophene Oxidation in a Biphasic System[J]. App Surf Sci，2016, 379:367-376.
(12) Jin C Z, Li G Wang, X S, et al. A Titanium Containing Micro/Mesoporous Composite and its Catalytic Performance in Oxidative Desulfurization[J]. Microporous Mesoporous Mater, 2008, 111:236-242.
(13) 程时富, 刘月明, 高金宝,等. Ti-MWW催化氧化脱除轻油中苯并噻吩和二苯并噻吩[J]. 催化学报, 2006, 27:547-549.
(14) Cho K S, Lee Y K. Effects of Nitrogen Compounds, Aromatics, and Aprotic Solvents on the Oxidative Desulfurization(ODS) of Light Cycle Oil over Ti-SBA-15 Catalyst[J]. Appl Catal B-Env, 2014, 147(1):35-42
(15) Shah A T, Li B S, Abdalla Z E, et al. Direct Synthesis of Ti-containing SBA-16-type Mesoporous Material by the Evaporation-Induced Self-Assembly Method and Its Catalytic Performance for Oxidative Desulfurization[J]. A J Colloid Inter Sci, 2009, 336:707-711.
(16) Lu H Y, Ren W Z, Liao W P, et al. Aerobic Oxidative Desulfurization of Model Diesel Using a B-type Anderson Catalyst [(C18H37)2N(CH3)2]3Co(OH)6Mo6O18?3H2O[J].
Appl Catal B: Envir, 2013, 138-139:79-83.
(17) Gao Y, Gao R M, Zhang G, et al.Oxidative Desulfurization of Model Fuel in the presence of Molecular Oxygen over Polyoxometalate Based Catalysts Supported on Carbon Nanotubes[J]. Fuel, 2018, 8:1287-1296.
(18) Craven M, Xiao Kunstmann-Olsen C, Kozhevnikova E F, et al. Oxidative Desulfurization of Diesel Fuel Catalyzed by Polyoxometalate Immobilized on Phosphazene-Functionalized Silica[J]. Appl Catal B: Envir, 2018, 231:82-91.
(19) Xun S H, Zhu W S, Zhu F X, et al. Design and synthesis of W-containing mesoporous material with excellent catalytic activity for the oxidation of 4,6-DMDBT in fuels[J]. Chem Eng J, 2015, 280: 256-264.
(20) 陈立东, 刘迪, 牛思祺, 等. 磷钨酸纳米ZSM-5复合催化剂的氧化脱硫反应性[J]. 应用化学, 2016, 33(3): 364-366.
(21) 陈立东, 佟欢, 王旭阳, 等. Keggin结构多阴阳离子构筑高活性多酸基氧化脱硫催化剂[J]. 应用化学, 2017, 34(11):1301-1306.
(22) Chen L D, Wang X S, Guo X W, et al. In Situ Nanocrystalline HZSM-5 Zeolites Encaged Heteropoly Acid H3PMo12O40 and Ni Catalyst for Hydroconversion of n-Octane [J]. Chem Eng Sci, 2007, 62(16):4469-4478.
(23) Song W C, Zuo Y, Xiong G, et al. Prehistoric Schistosomiasis Parasite Found in the Middle East[J]. Chem Eng J, 2014, 253:464-471.
(24) 姜春杰, 孙胜男, 王旭阳, 等. 甲醇脱水制二甲醚的杂多酸/纳米HZSM-5复合固体酸催化剂[J]. 化学学报, 2013, 71(5):810-814.
(25) Zhang Y Q, Wang R. Synthesis of Silica@C-dots/Phosphotungstates Core-Shell Microsphere for Effective Oxidative-Adsorptive Desulfurization of Dibenzothiophene with Less Oxidant[J]. Appl Catal B: Envir, 2018, 234:247-259.
(26) Xue T, Liu H P, Wang Y M, et al. Seed-induced Synthesis of Small-Crystal TS-1 Using Ammonia as Alkali Source[J]. Chin J Catal, 2015, 36:1928-1935.
(27) 袁明明, 李迪帆, 赵秀阁等.二氧化硅包覆的杂多酸在双氧水存在条件下催化氧化甘油[J].物理化学学报, 2018, 34: 886-895
(28) Yu X D, Guo Y N, Xu L L, et al. A novel preparation of mesoporous CsxH3?xPW12O40/TiO2 nanocomposites with enhanced photocatalytic activity[J]. Colloids Surf A, 2008, 316(1-3):110-118.
(29) Zuo Y, Song W C, Dai C Y, et al. Modification of Small-Crystal Titanium Silicalite-1 with Organic Bases: Recrystallization and Catalytic Properties in the Hydroxylation of Phenol[J]. Appl Catal A: Gen, 2013, 453: 272-279.
(30) Zhu K K, Hu J Z, She X Y, et al. Characterization of Dispersed Heteropoly Acid on Mesoporous Zeolite Using Solid-State 31P NMR Spin-Lattice Relaxation[J]. J Am Chem Soc, 2009, 131(28):9715-21.
(31) Kuang W, Rives A, Fournier M, et al. Structure and reactivity of silica-supported 12-tungstophosphoric acid[J]. Appl Catal A: Gen, 250(2003):221-229.
(32) Frédéric L. 31P MAS NMR Study of H3PW12O40Supported on Silica: Formation of(-SiO2)+(H2PW1240)-[J]. J Chem Soc Chem Commun, 1992, 0:756-757.
(33) Wang R, Zhang G F, Zhao H X. Polyoxometalate as effective catalyst for the deep desulfurization of diesel oil[J]. Catal Today, 2010, 149:117-121.
(34) Weisz P B, Frilette V, Intracrystalline and Molecular-Shape-Selective Catalysis by Zeolite Salts[J]. J Phys Chem ,1960, 64:382-382.
(35) Chen N Y,Garwood W E.Industrial Application of Shape-Selective Catalysis[J]. Catal Rev sci Eng, 1988, 28(2-3):185-264
(36) 武杰. 烃分子动力学直径与分子筛择形催化性能的相关性[J].化工进展, 2016, 35:167-173.]
(37) 贾玮玮, 刘靖, 谭涓. 分子筛催化剂上二异丙苯的择形催化裂化[J].石油化工, 2008, 37:998-1002.
(38) Doelle H J, Heering J, Riekert L, et al. Sorption and Catalytic Reaction in Pentasil Zeolites. Influence of Preparation and Crystal Size on Equilibria and Kinetics[J].Journal of Catalysis,1981, 71:27-40.
(39) Misono M. Unique Acid Catalysis of Heteropoly Compounds (Heteropolyoxometa lates) in The Solid State[J]. Chem Commum, 2001, 0: 1141-1153.
(40) Otsuki S, Nonaka T, Takashima N, et al. Oxidative Desulfurization of Light Gas Oil and Vacuum Gas Oil by Oxidation and Solvent Extration[J]. Energy Fuels, 2000, 14(6):750-3.
(41) 于凤丽, 王睿.有机-无机型杂多酸相转移催化氧化脱硫性能研究[J]. 化学学报，2014, 72 (1):105-113]
(42) Lu H Y, Deng C L, Ren W Z,et al. Oxidaive Desulfurization of Model Diesel Using [(C4H9)4N]6Mo7O24 as a Catalyst in Ionic Liquids[J]. Fuel Process Tenc, 2014, 119(1): 87-91.
(43) Mu?oz M, Romanelli G, Botto I L, Al13–[X–Mo/WOn] (X = Al, Co, V, P) Composites as Catalysts in Clean Oxidation of Aromatic Sulfides[J]. Appl Catal B: Environ, 2010,100 (1): 254-263.
(44) Nisar A, Lu Y, Zhuang J, et al. Polyoxometalate Nanocone Nanoreactors: Magnetic Manipulation and Enhanced Catalytic Performance[J]. Angew Chem Int Ed, 2011, 50: 3187-3192.

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