陈圣¹,陈辉²,许金山³,许晓斌³,许军¹,曹发海¹

• 1:华东理工大学 大型工业反应器工程教育部工程研究中心，上海 200237
• 2:中国石油化工股份有限公司，北京 100728
• 3:中石化齐鲁分公司研究院，山东 淄博 255400

摘要(Abstract)：

传统加氢脱硫往往难以脱除重油中的噻吩类硫化物。利用噻吩类硫化物氧化后的极性增加，在超临界甲醇条件下强化其在极性溶剂中的溶解度，可深度脱除重油中的噻吩硫。以二苯并噻吩（DBT）与十四烷为模型油，甲醇为超临界介质，考察了无催化时反应条件对超临界氧化脱硫性能的影响，不同催化氧化体系的脱硫效率。利用红外光谱、气相色谱-质谱联用对反应产物进行分析以研究脱硫机理。结果表明，在无催化时，反应温度260℃、反应压力8.5~9.0 MPa、反应时间3 h、过氧化二叔丁基作氧化剂且氧硫摩尔比为3：1时，噻吩模型物的脱硫率最高，达42%。在催化氧化体系中，催化剂用量与硫的摩尔比为1：10时催化剂使用效率最高，3种脱硫效果较好的催化氧化体系脱硫率分别达到了47%、45%、45%。FTIR、GC-MS结果表明二苯并噻吩被氧化为相应亚砜并转移至甲醇相，从而实现了硫化物的脱除。

关键词(KeyWords)： 超临界甲醇;氧化脱硫;二苯并噻吩;正十四烷;模型物

Abstract:

Keywords:

基金项目(Foundation):

作者(Author): 陈圣¹,陈辉²,许金山³,许晓斌³,许军¹,曹发海¹

DOI: 10.3969/j.issn.1003-9015.2020.03.011

参考文献(References)：

• [1] GUO K, LI H, YU Z. In-situ heavy and extra-heavy oil recovery:A review[J]. Fuel, 2016, 185:886-902.
  [2] AL-HAJ-I H, MORSI B I. Desulfurization of petroleum coke:A review[J]. Industrial & Engineering Chemistry Research, 1992, 31(8):1835-1840.
  [3] CHEN Z, MA W, WEI K, et al. Detailed vacuum-assisted desulfurization of high-sulfur petroleum coke[J]. Separation & Purification Technology, 2017, 175:115-121.
  [4] EDWARDS L C, NEYREY K J, LOSSIUS L P. A review of coke and anode desulfurization[M]. Cham:Springer; 2016.
  [5] JAVADLI R, DE K A. Desulfurization of heavy oil-oxidative desulfurization (ODS) as potential upgrading pathway for oil sands derived bitumen[J]. Energy & Fuels, 2011, 26(1):594-602.
  [6] HOUDA S, LANCELOT C, BLANCHARD P, et al. Oxidative desulfurization of heavy oils with high sulfur content:A review[J]. Catalysts, 2018, 8(9):344.
  [7] WANG Z, CHEN S L, PEI J, et al. Insight into the intraparticle diffusion of residue oil components in catalysts during hydrodesulfurization reaction[J]. AIChE Journal, 2014, 60(9):3267-3275.
  [8] CHANDRA S V. An evaluation of desulfurization technologies for sulfur removal from liquid fuels[J]. RSC Advance, 2012, 2(3):759-783.
  [9] SHAFI R, HUTCHINGS G J. Hydrodesulfurization of hindered dibenzothiophenes:An overview[J]. Catalysis Today, 2000, 59(3/4):423-442.
  [10] JANG J G, LEE Y K. Promotional effect of Ga for Ni₂P catalyst on hydrodesulfurization of 4,6-DMDBT[J]. Applied Catalysis B:Environmental, 2019, 250:181-188.
  [11] DOOLEY K M, LIU D, MADRID A M, et al. Oxidative desulfurization of diesel with oxygen:Reaction pathways on supported metal and metal oxide catalysts[J]. Applied Catalysis A:General, 2013, 468:143-149.
  [12] ABDALLA Z, LI B. Preparation of MCM-41 supported (Bu₄N)₄H₃(PW₁₁O₃₉) catalyst and its performance in oxidative desulfurization[J]. Chemical Engineering Journal, 2012, 200:113-121.
  [13] LYU H, ZHANG Y, JIANG Z, et al. Aerobic oxidative desulfurization of benzothiophene, dibenzothiophene and 4,6-dimethyl-dibenzothiophene using an Anderson-type catalyst[(C₁₈H₃₇)₂N(CH₃)₂]₅[IMo₆O₂₄] [J]. Green Chemistry, 2010, 12(11):1954-1958.
  [14] ZHANG W, ZHANG H, XIAO J, et al. Carbon nanotube catalysts for oxidative desulfurization of a model diesel fuel using molecular oxygen[J]. Green Chemistry, 2014, 16(1):211-220.
  [15] SAMPANTHAR J T, XIAO H, DOU J, et al. A novel oxidative desulfurization process to remove refractory sulfur compounds from diesel fuel[J]. Applied Catalysis B:Environmental, 2006, 63(1/2):85-93.
  [16] ZHANG H, GAO J, MENG H, et al. Removal of thiophenic sulfurs using an extractive oxidative desulfurization process with three new phosphotungstate catalysts[J]. Industrial & Engineering Chemistry Research, 2012, 51(19):6658-6665.
  [17] TIMKO M T, SCHMOIS E, PATWARDHAN P, et al. Response of different types of sulfur compounds to oxidative desulfurization of jet fuel[J]. Energy & Fuels, 2014, 28(5):2977-2983.
  [18] FRAILE J M, GIL C, MAYORAL J A, et al. Heterogeneous titanium catalysts for oxidation of dibenzothiophene in hydrocarbon solutions with hydrogen peroxide:On the road to oxidative desulfurization[J]. Applied Catalysis B:Environmental, 2016, 180:680-686.
  [19] TIMKO M T, GHONIEM A F, GREEN W H. Upgrading and desulfurization of heavy oils by supercritical water[J]. The Journal of Supercritical Fluids, 2015, 96:114-123.
  [20] CARR A G, CLASS C A, LAI L, et al. Supercritical water treatment of crude oil and hexylbenzene:An experimental and mechanistic study on alkylbenzene decomposition[J]. Energy & Fuels, 2015, 29(8):5290-5302.
  [21] SARKAR B, KWEK W, VERMA D, et al. Effective vacuum residue upgrading using sacrificial nickel(II) dimethylglyoxime complex in supercritical methanol[J]. Applied Catalysis A:General, 2017, 545:148-158.
  [22] KWEK W, KHAN M K, SARKAR B, et al. Supercritical methanol as an effective medium for producing asphaltenes-free light fraction oil from vacuum residue[J]. The Journal of Supercritical Fluids, 2018, 133:184-194
  [23] KANG J, MYINT A A, SIM S, et al. Kinetics of the upgrading of heavy oil in supercritical methanol[J]. The Journal of Supercritical Fluids, 2018, 133:133-138.
  [24] SAVAGE P E. Organic chemical reactions in supercritical water[J]. Chemical Reviews, 1999, 99(2):603-622.
  [25] BAIKER A. Supercritical fluids in heterogeneous catalysis[J]. Chemical Reviews, 1999, 99(2):453-474.
  [26] YUAN P Q, CHENG Z M, JIANG W L, et al. Catalytic desulfurization of residual oil through partial oxidation in supercritical water[J]. The Journal of Supercritical Fluids, 2005, 35(1):70-75.
  [27] MURATA S, MURATA K, KIDENA K, et al. A novel oxidative desulfurization system for diesel fuels with molecular oxygen in the presence of cobalt catalysts and aldehydes[J]. Energy & fuels, 2004, 18(1):116-121.
  [28] VENKATASHWAR R T, SAIN B, KAFOLA S, et al. Oxidative desulfurization of HDS diesel using the aldehyde/molecular oxygen oxidation system[J]. Energy & Fuels, 2007, 21(6):3420-3424.
  [29] ZHU W, WU P, CHAO Y, et al. A novel reaction-controlled foam-type polyoxometalate catalyst for deep oxidative desulfurization of fuels[J]. Industrial & Engineering Chemistry Research, 2013, 52(49):17399-17406.
  [30] GARCIA-GUTIERREZ J L, LAREO G C, GARCIA-GUTIERREZ P, et al. Oxidative desulfurization of diesel using promising heterogeneous tungsten catalysts and hydrogen peroxide[J]. Fuel, 2014, 138:118-125.
  [31] ZHOU X, ZHAO C, YANG J, et al. Catalytic oxidation of dibenzothiophene using cyclohexanone peroxide[J]. Energy & fuels, 2007, 21(1):7-10.
  [32] SHEN C, WANG Y J, XU J H, et al. Synthesis of TS-1 on porous glass beads for catalytic oxidative desulfurization[J]. Chemical Engineering Journal, 2015, 259:552-561.
  [33] YANG C, ZHAO K, CHENG Y, et al. Catalytic oxidative desulfurization of BT and DBT from n-octane using cyclohexanone peroxide and catalyst of molybdenum supported on 4A molecular sieve[J]. Separation and Purification Technology, 2016, 163:153-161.
  [34] LIU S, WANG B, CUI B, et al. Deep desulfurization of diesel oil oxidized by Fe(VI) systems[J]. Fuel, 2008, 87(3):422-428.
  [35] AL-ABDULY A, SHARMA V K. Oxidation of benzothiophene, dibenzothiophene, and methyl-dibenzothiophene by ferrate(VI)[J]. Journal of Hazardous Materials, 2014, 279:296-301.
  [36] CASTILLO K, PARSONS J G, CHAVEZ D, et al. Oxidation of dibenzothiophene to dibenzothiophene-sulfone using silica gel[J]. Journal of Catalysis, 2009, 268(2):329-334.
  [37] WANG J, ZHAO D, LI K. Oxidative desulfurization of dibenzothiophene using ozone and hydrogen peroxide in ionic liquid[J]. Energy & Fuels, 2010, 24(4):2527-2529.
  [38] RAO T V, KRISHNA P M, PAUL D, et al. The oxidative desulfurization of HDS diesel:Using aldehyde and molecular oxygen in the presence of cobalt catalysts[J]. Petroleum Science and Technology, 2011, 29(6):626-632.
  [39] DUMONT V, OLIVIERO L, MAUGE F, et al. Oxidation of dibenzothiophene by a metal-oxygen-aldehyde system[J]. Catalysis Today, 2008, 130(1):195-198.
  [40] LU H, GAO J, JIANG Z, et al. Oxidative desulfurization of dibenzothiophene with molecular oxygen using emulsion catalysis[J]. Chemical Communications (Camb), 2007(2):150-152.
  [41] ZHANG Y, LV H, WANG L, et al. The oxidation of benzothiophene using the Keggin-type lacunary polytungstophosphate as catalysts in emulsion[J]. Journal of Molecular Catalysis A:Chemical, 2010, 332(1/2):59-64.
  [42] RODRIGUEZ-CABO B, RODRIGUEZ H, RODIL E, et al. Extractive and oxidative-extractive desulfurization of fuels with ionic liquids[J]. Fuel, 2014, 117:882-889.
  [43] ELLIOTT D C, SEALOCK JR L J, BAKER E G. Chemical processing in high-pressure aqueous environments. 2. Development of catalysts for gasification[J]. Industrial & Engineering Chemistry Research, 1993, 32(8):1542-1548.
  [44] NAWAF A T, GHENI S A, JARULLAH A T, et al. Improvement of fuel quality by oxidative desulfurization:Design of synthetic catalyst for the process[J]. Fuel Processing Technology, 2015, 138:337-343.
  [45] OTSUKI S, NONAKA T, TAKASHIMA N, et al. Oxidative desulfurization of light gas oil and vacuum gas oil by oxidation and solvent extraction[J]. Energy & Fuels, 2000, 14(6):1232-1239.
  [46] ZHANG B, JIANG Z, Li J, et al. Catalytic oxidation of thiophene and its derivatives via dual activation for ultra-deep desulfurization of fuels[J]. Journal of Catalysis, 2012, 287:5-12.