Refractory Cyclic Sulfidic Compounds in Deeply Hydrodesulfurized

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Refractory Cyclic Sulfidic Compounds in Deeply Hydrodesulfurized Diesels Meng Wang, Suoqi Zhao, Limin Ren, Yehua Han, Chunming Xu, Keng H. Chung, and Quan Shi Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.7b00007 • Publication Date (Web): 03 Mar 2017 Downloaded from http://pubs.acs.org on March 7, 2017

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Refractory Cyclic Sulfidic Compounds in Deeply Hydrodesulfurized Diesels Meng Wang †,‡, Suoqi Zhao†, Limin Ren†, Yehua Han†, Chunming Xu†, Keng H Chung§, and Quan Shi†*

†

State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China ‡

Research Institute of Petroleum Exploration and Development, PetroChina, Beijing

100083, China §

North Huajin Petrochemical Corporation, Panjin, Liaoning, 124000, China

ABSTRACT Sulfur compounds in deep hydrodesulfurization (HDS) derived diesels were effectively

separated

into

thiophenic

and

sulfidic

fractions

using

the

methylation/demethylation method and characterized by gas chromatography-mass spectrometry (GC-MS) and GC-sulfur chemiluminescence detector (SCD). Sulfidic fractions account for over 15 wt% of total residual sulfur, in which a series of refractory cyclic sulfidic compounds, 1,1-dimethylhexahydrodibenzothiophenes (1,1-DMH6DBTs) and 1,9b-dimethylhexahydrodibenzothiophenes (1,9b-DMH6DBTs) were found in the diesels and larger molecular weight homologues were identified Some homologue series of C1 to C4 alkyl substituted thiaadamantanes were detected in the HDS diesel. These cyclic sulfidic components are refractory to deep HDS, which require more prudent catalysis and reaction systems to achieve ultra-low sulfur diesel (ULSD) production.

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INTRODUCTION The common sulfur functional groups found in fossil fuels are thiols, sulfides, and thiophenes. Thiophenes are the refractory sulfur compounds which cause catalyst poisoning in refining operations, corrosion of refining equipments, fouling of vehicle exhaust converters, and sulfur emissions that are health hazardous.1 In the past 10 years, many countries have imposed more stringent environmental regulatory to reduce the sulfur contents in transportation fuels to less than 10 wppm.2 This has rejuvenated research and development work on catalysis and reaction engineering in the production of ultra-low sulfur diesel (ULSD).3-8 Moreover, the sulfur content of hydrocarbons for fuel cell application cannot exceed 1 wppm.9 Catalytic hydrodesulfurization (HDS) is the commonly used refinery process for removing sulfur in petroleum derived feedstocks. The HDS is carried out in high temperature and pressure reactor systems in the presence of hydrogen and metal catalysts.10 To achieve higher sulfur removal, the HDS is required to operate at a much higher reaction severity: higher temperature and pressure, and lower space velocity.11 Nevertheless, the HDS is not effective for removing highly refractory sulfur compounds. Hence, a better understanding of the residual refractory sulfur compounds in HDS derived products is critical to improve the HDS efficiency.12, 13 It is known that HDS is highly effective in removing thiols, sulfides, and benzothiophenes (BTs), but less effective for dibenzothiophenes (DBTs) removal. Since 1980s, many reports showed that the highly refractory sulfur compounds for HDS are DBTs with alkyl substituents at the 4- and/or 6-position (4-MDBT and 4,6-DMDBT).14-16 Considerable work has been devoted to develop more effective HDS for producing diesel which contain the refractory sulfur species.17-22 Advances in separation and analytical techniques enable the detailed analysis of residual sulfur compounds in deep HDS derived diesels.13, 23, 24 The alkylated DBTs in HDS derived diesels, which accounted for 13 and 76 wppm sulfur, were separated and


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analyzed. It was found that in addition to the 4-MDBT and 4,6-DMDBT, the DBTs with a methyl group at 1-position also show low HDS reactivity, due to the non-planarity of the aromatic rings led by the spatial requirements of the 1-methyl group.23 It was also found that the HDS derived diesels with 7 to 384 wppm sulfur, contained a series of polycyclic sulfides,

1,1,4a,6-tetramethyl-9-alkyl-1,2,3,4,4a,9b-hexahydrodibenzothiophenes

(1,1-DMH6DBTs, Compounds 1-3 in Figure 1).13 The 1,1-DMH6DBTs were isolated as their sulfone derivatives and characterized by nuclear magnetic resonance (NMR) and gas chromatography mass spectrometry (GC-MS). Charrié-Duhaut et. al.13 found that as the residual sulfur content of HDS derived diesels decreased, the relative concentration ratio of 1,1-DMH6DBTs to 4,6-DMDBT increased. This suggested that 1,1-DMH6DBTs are more resistant to HDS than 4,6-DMDBT.13 The two methyl groups at 4a- and 6- positions, as well as the cis ring junction in 1,1-DMH6DBTs, are steric hindered the sulfur atom from approaching the active sites on the catalyst surface.13 Andersson et. al.24 developed the PdII ligand-exchange chromatography to selectively separate 1,1-DMH6DBTs (compounds 1-4 in Figure 1) from a HDS derived diesel. An isomeric group of 1,1-DMH6DBTs, 1,9b-DMH6DBTs (compounds 6-8 in Figure 1) were found. The concentration of 1,9b-DMH6DBTs in the HDS derived diesel was similar to that of 1,1-substituted counterparts, indicating these two sulfur compounds had similar low HDS reactivities. The 1,1-DMH6DBTs and 1,9b-DMH6DBTs (denoted as H6DBTs) were postulated to derive from terpenoid precursors under certain geological environment.13 Yet, the origin of H6DBTs was speculative; since all the analyses were performed on HDS derived diesels.13, 24 Recently, a series of H6DBTs were found in a crude oil sample.25 This provided the evidence that H6DBTs are naturally occurring biomarker-like compounds.25


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1,1-DiMeH6DBTs

1: R = H 2: R = Me 3: R = Et 4: R = Pr 5: R = ...

1,9b-DiMeH6DBTs

6: 7: 8: 9:

(a)

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R=H R = Me R = Et R = ...

(b)

Figure 1. Molecular structures of hexahydrodibenzothiophenes (H6DBTs).

Even though H6DBTs are refractory to HDS, they are difficult to detect in crude oil because their concentrations are orders of magnitude lower than that of DBTs. Also, using the conventional analysis, such as chromatographic separation, the amount of sample is too small to allow comprehensive analysis of H6DBTs. However, with the recent developed methylation/demethylation method, it is capable of separating large amount of sample which allows enrichment of H6DBTs from ULSDs for molecular characterization and semiquantitation.25, 26 In work, attempts were made to separate H6DBTs and other HDS resistant sulfur compounds from ULSDs, reveal the molecular composition of these components, and evaluate the impacts of these components on HDS.

EXPERIMENTAL Samples and Reagents. A HDS derived diesel was obtained from the commercial HDS units of Sinopec Jingmen Refinery (JM-D: 17.6 mg/L sulfur, 0.8192 g/mL at 20°C). Another HDS derived diesel was obtained from PetroChina Dagang Refinery (DG-D: 29.5 mg/L sulfur, 0.8320 g/mL at 20°C). The chemical reagents, silver tetrafluoroborate (AgBF4, 99%, 55.4% Ag), methyl iodide (MeI, 99%), 4-dimethylaminopyridine (DMAP, 99%),

and

7-azaindole

(98%)

were

purchased

from

J&K

Chemical

Ltd.

High-performance liquid chromatography (HPLC)-grade n-hexane, acetonitrile (MeCN), dichloromethane (DCM), (Scharlau Chemicals S.A., Spain) were used as received.


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Selective Separation of Residual Thiophenic and Sulfidic Compounds from HDS Derived Diesels. The flow chart of selective separation of thiophenic and sulfidic compounds has been described elsewhere.25 The dosage of diesel samples was listed in Table 1. In general, the diesel sample was dissolved in 200 mL of DCM, and 5 molar equivalent of AgBF4 and 15 molar equivalent MeI (based on the sulfur content of the HDS diesel, similarly hereinafter) were added sequentially. The mixture was stirred in dark at room temperature for 24 h. This procedure was repeated once to ensure the high methylation conversion. After removing AgI precipitate by filtrating and evaporating DCM by a rotary evaporator, the left-over oily residue was mixed with 100 mL of n-hexane in a vial and the resulting mixture was cooled to 0 oC. The sulfonium salts precipitated and settled to the vial bottom by centrifugation. The sulfonium salts were separated by decanting the n-hexane supernatant. This procedure was repeated for 5 times and monitored by thin layer chromatography (n-hexane as developing solvent) until no components in n-hexane supernate could be detected by ultraviolet (UV) light under an UV lamp at 254 and 365 nm. The sulfonium salts collected, were dissolved in 5 mL of MeCN, and 10 molar equivalent of 7-azaindole was added to the solution. After stirred at room temperature for 24 h, the resulting mixture was extracted by n-hexane (3 × 5 mL). The combined n-hexane phase was concentrated under vacuum distillation and the thiophenic compounds (labeled as thiophenic fraction) were obtained using an open column silica gel chromatography (4 g 200-300 mesh silica gel in a 9 mm-diameter column, and 40 mL of n-hexane as eluent). For demethylation of the remaining sulfonium salts, ten molar equivalent of DMAP was added to the MeCN solution, and the solution was refluxed for 12 h. 10 mL of hydrogen chloride aqueous solution (2 N) was added to the demethylation mixture. The resulting mixture was extracted with n-hexane (3 × 5 mL). The combined organic phase was concentrated by evaporation, then subjected to open column chromatography (4 g of


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silica gel and 35 mL of n-hexane as eluent) to obtaint the sulfidic compounds (labeled as sulfidic fraction). The sulfidic fraction of DG-D was further fractionated to 7 subfractions (denoted SF 1-7) using an open column silica gel chromatography (4 g 200-300 mesh silica gel in a 9 mm-diameter column). A total of 35 mL n-hexane was used as the eluting solvent and each 5 mL eluent was collected as a subfraction. The HDS derived diesels were subjected to gas chromatography (GC) coupled with a sulfur chemiluminescence detector (SCD) for composition analysis. All the separated sulfur fractions were subjected to elemental and GC−MS analyses. GC−SCD, GC−MS and Elemental Analysis. The GC−SCD analysis was carried out in an Agilent 7890A GC equipped with a HP-5 column (30 m × 0.25 mm × 0.25 µm) column with an Agilent 355 SCD detector. The hydrogen and air flow rates were set at 46 and 66 standard-state cubic centimeters per minute (scm), respectively. The burner was set at 800°C at 377 Torr. The injector and the SCD temperature were set at 280 and 250°C, respectively. The GC-MS analysis was carried out in a Thermo-Finnigan Trace DSQ GC−MS with 70 eV electron impact (EI) ionization source. The scan mass range was 35-500 Da with a 1 s scan cycle. The injector was 280°C. A HP-5MS column (30 m × 0.25 mm × 0.25 µm) was used for GC−MS analysis. The column oven programs for both GC-SCD and GC-MS analysis were as follow: kept a constant temperature of 40 °C for 1 min, followed by ramps of 10 oC/min to 300 oC, then holding for 10 min. The sulfur content of sample was determined using an ANTEK 7000 Pyrofluorescence Analyzer (ANTEK Instruments) according to the ASTM D5453 method.

RESULTS AND DISCUSSION Table 1 shows the yields of thiophenic and sulfidic fractions obtained from HDS derived diesels, JM-D (17.6 mg/L sulfur) and DG-D (29.5 mg/L sulfur). The sulfidic


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fraction of DG-D was further separated into 7 subfractions. The amounts of sulfur in thiophenic and sulfidic fractions accounted for 64.5 and 15.9 wt%, respectively of total sulfur in JM-D, and 71.9 and 12.9 wt%, respectively of total sulfur in DG-D. Figure 2 shows the SCD chromatogram of JM-D and the GC-MS total ion chromatograms (TIC) of thiophenic and sulfidic fractions of JM-D. The GC-SCD and GC-MS data indicated that the thiophenic and sulfidic fractions of JM-D contained only sulfur compounds, no hydrocarbons or other non-sulfur compounds were detected in these fractions. The chromatographic peaks of JM-D and its thiophenic fraction were C0-C4+ alkyl dibenzothiophenes, which are known refractory sulfur compounds in HDS. In

the

sulfidic

fraction

of

JM-D,

the

abundant

compounds

were

dimethylhexahydrodibenzothiophenes (DMH6DBTs), including four homologues of 1,1-DMH6DBTs (Compounds 1-4) and one homologue of 1,9b-DMH6DBTs (Compound 6). The mass chromatograms and mass spectra of Compounds 1-4 and 6 in sulfidic fraction of JM-D are shown in Figures S-1 and S-2 (see Supporting Information), which are consistent with those found in deep HDS derived diesels and crude oils.24, 25 The selective separation enabled detailed compositional characterization of H6DBTs in oils with low sulfur content.

Figure 2. GC−SCD chromatogram of JM-D and GC−MS total ion chromatogram of thiophenic and sulfidic fractions of JM-D. The peak with an asterisk is 4-DMDBT.


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The SCD chromatogram of DG-D and the GC-MS total ion chromatograms (TIC) of thiophenic and sulfidic fractions of DG-D are shown in Figure S-3 (see Supporting Information). The data in Figure S-3 were consistent with those of JM-D in Figure 2, except DG-D had a higher sulfur concentration than JM-D. The sulfidic fraction of DG-D was further fractionated to 7 subfractions (SF 1-7). Figure 3 shows that the SCD and the total ion chromatograms of SF 1 were identical, indicating high-purity sulfur compounds. Majority of sulfur compounds were a series of 1,1-DMH6DBTs, including Compounds 1-4 and a larger molecular weight homologue (Compound 5 with

MW 302). Similar to SF 1, SF 2-5 also contained clean sulfidic

compounds (see Figures S-4, S-6, S-8, S-10, and S-12, respectively), consisting various homologues of 1,1-DMH6DBTs and 1,9b-DMH6DBTs. A larger molecular weight homologue of 1,9b-DMH6DBTs was found in SF 5 (Compound 9, MW 288). The mass chromatograms and mass spectra of H6DBTs identified in SF 2-5 are shown in Figures S-5, S-7, S-9, S-11 and S-13 (see the Supporting Information). Many compounds (Compounds a-h) with distinct chromatographic peaks were found in SF 5, showing similar but different fragmentation with H6DBTs in their mass spectra which are shown in Figure S-14 (see Supporting Information). These unidentified compounds are likely analogues of H6DBTs which warrant further investigation. No H6DBTs were detected in SF 6-7.


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Figure 3. SCD and GC-MS total ion chromatograms of SF 1 of DG-D, and GC-MS total ion chromatograms of SF 2-5. The peaks with asterisks are 4,6-DMDBT, C2-DBT and C3-DBT.

In SF 3, a cluster of low-intensity peaks was present to the left of the SCD chromatographic peaks of H6DBTs. These compounds were C1 to C3 alkyl substituted thiaadamantanes from GC-MS analysis. Figure 4 shows the chromatograms of thiaadamantanes. The detailed information of labeled peaks of mass spectra in Figure 4 is shown in Figures S-15 (see Supporting Information), which are consistent with those reported.27-30 Various homologues and isomers of C1 to C4 substituted thiaadamantanes were also detected, which were predominantly sulfur compounds in SF 6-7. The corresponding mass chromatograms and spectra are shown in Figures S-16 to 19 (see Supporting Information).


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Figure 4. GC-SCD chromatogram and GC-MS total ion chromatograms of SF 3 of DG-D, and mass chromatograms of thiaadamantanes in SF3.

Thiaadamantanes are the smallest members of the thiadiamondoid family, which are cage-like sulfidic compounds.27 They were found in crude oils from various geological formations around the world.25, 27, 29-31 Thiadiamondoids are believed to be generated from sulfurization of their adamantine precursors by thermal sulfate reduction in reservoirs at temperatures greater than 120°C.31-33

Even though the geochemical

significance of thiadiamondoids was widely discussed, their roles in refinery operations have been overlooked. This work shows that thiaadamantanes are refractory sulfidic compounds to HDS, which were unconverted under severe HDS conditions. The refractory nature of thiaadamantanes is likely due to their diamond-like fused ring structures, which are more thermally stable than the dibenzothiophenes.29 Although the thiaadamantanes are found in crude oils, it cannot be ruled out the possibility that these compounds are intermediate products from refining processes. Nevertheless, since thiaadamantanes are refractory to HDS, they will have significant impact on ULSD production via deep HDS. Therefore, it is recommended that refineries which are


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mandated to produce ULSD should pay attention in selecting feedstocks for their refinery operations. The concentration of thiadiamondoids in crude oil varies from several ppm to thousands ppm depending on the origin of crude oil.29, 31 Small amount of thiophenic compounds (chromatogram peaks labeled with asterisks in Figures 2 and 3) were founded in the sulfidic fractions of JM-D and DG-D. This does not means the separations were unsuccessful, in fact, the thiophenic compounds were in a very low concentration. As shown in Table 1, the sulfidic fraction accounted for 15.9 wt% (at least half of them were H6DBTs) of total residual sulfur in JM-D. As for DG-D, after deduction of the thiophenic compounds and the unidentified sulfur compounds in the sulfidic fraction, the refractory sulfidic compounds (including H6DBTs and thiaadamantanes) accounted for at least 4.5 wt% of total sulfur in DG-D. The results indicated that even under commercial deep HDS, significant amounts of H6DBTs (even more refractory than 4,6-DMDBT) and thiaadamantanes remained unconverted. In other words, since H6DBTs are native cyclic sulfidic compounds in crude oils,25 their concentration in the straight-run distillate fraction (light gas oil) could predetermine the ultimate sulfur concentration in diesel product, regardless of HDS reaction severity. Therefore, it is not economic viable to process feedstocks with high concentrations of H6DBTs and thiaadamantanes for ULSD production.

CONCLUSIONS The methylation/demethylation separation technique is effective in isolating sulfur compounds in deep HDS derived diesels into thiophenic and sulfidic fractions. A series of cyclic sulfidic compounds 1,1-DMH6DBTs and 1,9b-DMH6DBTs were found in the diesels and larger molecular weight homologues were identified. In addition, thiaadamantanes with C1 to C4 alkyl substituents were also present in the deep HDS derived diesels, indicating that thiaadamantanes are highly refractory sulfur compounds to deep HDS. Semi-quantitative results were obtained for the characterization of


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refractory cyclic sulfidic compounds in deep HDS diesels. Since DMH6DBTs and thiaadamantanes could be native species in crude oils, feedstocks with high concentrations of these sulfidic compounds are not suitable for ULSD production.

ASSOCIATED CONTENTS Supporting Information Additional information as noted in text. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected].

ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (NSFC 21236009, and 21376262). REFERENCES 1.

Granadeiro, C. M.; Ribeiro, S. O.; Karmaoui, M.; Valenca, R.; Ribeiro, J. C.; de Castro, B.; Cunha-Silva,

L.; Balula, S. S., Production of ultra-deep sulfur-free diesels using a sustainable catalytic system based on UiO-66(Zr). Chemical Communications 2015, 51, (72), 13818-13821. 2.

González-García, O.; Cedeño-Caero, L., V-Mo based catalysts for oxidative desulfurization of diesel

fuel. Catalysis Today 2009, 148, (1–2), 42-48. 3.

Gupta, M.; He, J.; Nguyen, T.; Petzold, F.; Fonseca, D.; Jasinski, J.; Sunkara, M., Nanowire catalysts for

ultra-deep hydro-desulfurization and aromatic hydrogenation. Applied Catalysis B: Environmental 2016, 180, 246-254. 4.

van Haandel, L.; Bremmer, M.; Kooyman, P. J.; van Veen, J. A. R.; Weber, T.; Hensen, E. J. M.,

Structure–Activity Correlations in Hydrodesulfurization Reactions over Ni-Promoted MoxW(1–x)S2/Al2O3 Catalysts. ACS Catalysis 2015, 5, (12), 7276-7287. 5.

Blanco-Brieva, G.; Campos-Martin, J. M.; Al-Zahrani, S. M.; Fierro, J. L. G., Effectiveness of

metal–organic frameworks for removal of refractory organo-sulfur compound present in liquid fuels. Fuel 2011, 90, (1), 190-197. 6.

Rashidi, F.; Sasaki, T.; Rashidi, A. M.; Nemati Kharat, A.; Jozani, K. J., Ultradeep hydrodesulfurization

of diesel fuels using highly efficient nanoalumina-supported catalysts: Impact of support, phosphorus, and/or boron on the structure and catalytic activity. Journal of Catalysis 2013, 299, 321-335.


Page 12 of 15

Page 13 of 15

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

7.

Hansen, L. P.; Ramasse, Q. M.; Kisielowski, C.; Brorson, M.; Johnson, E.; Topsøe, H.; Helveg, S., Atomic

‐Scale Edge Structures on Industrial‐Style MoS2 Nanocatalysts. Angewandte Chemie International Edition 2011, 50, (43), 10153-10156. 8.

Wang, L.; He, W.; Yu, Z., Transition-metal mediated carbon-sulfur bond activation and

transformations. Chemical Society Reviews 2013, 42, (2), 599-621. 9.

Shekhawat, D.; Berry, D. A.; Haynes, D. J.; Spivey, J. J., Fuel constituent effects on fuel reforming

properties for fuel cell applications. Fuel 2009, 88, (5), 817-825. 10. Babich, I. V.; Moulijn, J. A., Science and technology of novel processes for deep desulfurization of oil refinery streams: a review☆. Fuel 2003, 82, (6), 607-631. 11. Pacheco, M. E.; Martins Salim, V. M.; Pinto, J. C., Accelerated Deactivation of Hydrotreating Catalysts by Coke Deposition. Industrial & Engineering Chemistry Research 2011, 50, (10), 5975-5981. 12. Choudhary, T. V.; Gong, K.; Ellison, P.; Subbiah, A., A glimpse into the molecular journey inside an ultralow sulfur diesel reactor. ChemCatChem 2014, 6, (6), 1782-1787. 13. Charrié-Duhaut, A.; Schaeffer, C.; Adam, P.; Manuelli, P.; Scherrer, P.; Albrecht, P., Terpenoid-Derived Sulfides as Ultimate Organic Sulfur Compounds in Extensively Desulfurized Fuels. Angewandte Chemie International Edition 2003, 42, (38), 4646-4649. 14. Houalla, M.; Broderick, D. H.; Sapre, A. V.; Nag, N. K.; de Beer, V. H. J.; Gates, B. C.; Kwart, H., Hydrodesulfurization of methyl-substituted dibenzothiophenes catalyzed by sulfided Co  Moγ-Al2O3. Journal of Catalysis 1980, 61, (2), 523-527. 15. Kabe, T.; Ishihara, A.; Zhang, Q., Deep desulfurization of light oil. Part 2: hydrodesulfurization of dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. Applied Catalysis A: General 1993, 97, (1), L1-L9. 16. Ma, X.; Sakanishi, K.; Mochida, I., Hydrodesulfurization reactivities of various sulfur compounds in diesel fuel. Industrial & engineering chemistry research 1994, 33, (2), 218-222. 17. Hernández-Maldonado, A. J.; Yang, R. T., Desulfurization of Diesel Fuels by Adsorption via π-Complexation with Vapor-Phase Exchanged Cu(I)−Y Zeolites. Journal of the American Chemical Society 2004, 126, (4), 992-993. 18. Oyama, S. T.; Lee, Y.-K., The active site of nickel phosphide catalysts for the hydrodesulfurization of 4,6-DMDBT. Journal of Catalysis 2008, 258, (2), 393-400. 19. Gutiérrez, O. Y.; Klimova, T., Effect of the support on the high activity of the (Ni)Mo/ZrO2–SBA-15 catalyst in the simultaneous hydrodesulfurization of DBT and 4,6-DMDBT. Journal of Catalysis 2011, 281, (1), 50-62. 20. Bej, S. K.; Maity, S. K.; Turaga, U. T., Search for an Efficient 4,6-DMDBT Hydrodesulfurization Catalyst: A Review of Recent Studies. Energy & Fuels 2004, 18, (5), 1227-1237. 21. Sun, Y.; Prins, R., Hydrodesulfurization of 4, 6‐Dimethyldibenzothiophene over Noble Metals Supported on Mesoporous Zeolites. Angewandte Chemie International Edition 2008, 47, (44), 8478-8481. 22. Shen, J.; Semagina, N., Palladium Nanoparticle Size Effect in Hydrodesulfurization of 4, 6‐ Dimethyldibenzothiophene (4, 6‐DMDBT). ChemCatChem 2016, 8, (15), 2565-2571. 23. Schade, T.; Andersson, J. T., Speciation of Alkylated Dibenzothiophenes in a Deeply Desulfurized Diesel Fuel. Energy & Fuels 2006, 20, (4), 1614-1620. 24. Japes, A.; Penassa, M.; Andersson, J. T., Analysis of Recalcitrant Hexahydrodibenzothiophenes in


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Petroleum Products Using a Simple Fractionation Process. Energy & Fuels 2009, 23, (4), 2143-2148. 25. Wang, M.; Zhu, G.; Ren, L.; Liu, X.; Zhao, S.; Shi, Q., Separation and Characterization of Sulfur Compounds in Ultra-deep Formation Crude Oils from Tarim Basin. Energy & Fuels 2015, 29, (8), 4842-4849. 26. Wang, M.; Zhao, S.; Chung, K. H.; Xu, C.; Shi, Q., Approach for Selective Separation of Thiophenic and Sulfidic Sulfur Compounds from Petroleum by Methylation/Demethylation. Analytical Chemistry 2015, 87, (2), 1083-1088. 27. Hanin, S.; Adam, P.; Kowalewski, I.; Huc, A.-Y.; Carpentier, B.; Albrecht, P., Bridgehead alkylated 2-thiaadamantanes: novel markers for sulfurisation processes occurring under high thermal stress in deep petroleum reservoirs. Chemical Communications 2002, (16), 1750-1751. 28. Wei, Z.; Mankiewicz, P.; Walters, C.; Qian, K.; Phan, N. T.; Madincea, M. E.; Nguyen, P. T. H., Natural occurrence of higher thiadiamondoids and diamondoidthiols in a deep petroleum reservoir in the Mobile Bay gas field. Organic Geochemistry 2011, 42, (2), 121-133. 29. Wei, Z.; Walters, C. C.; Michael Moldowan, J.; Mankiewicz, P. J.; Pottorf, R. J.; Xiao, Y.; Maze, W.; Nguyen, P. T. H.; Madincea, M. E.; Phan, N. T.; Peters, K. E., Thiadiamondoids as proxies for the extent of thermochemical sulfate reduction. Organic Geochemistry 2012, 44, 53-70. 30. Jiang, N.; Zhu, G.; Zhang, S.; Wang, Z., Detection of 2-thiaadamantanes in the oil from Well TZ-83 in Tarim Basin and its geological implication. Chinese Science Bulletin 2008, (03), 396-401. 31. Gvirtzman, Z.; Said-Ahmad, W.; Ellis, G. S.; Hill, R. J.; Moldowan, J. M.; Wei, Z.; Amrani, A., Compound-specific sulfur isotope analysis of thiadiamondoids of oils from the Smackover Formation, USA. Geochimica et Cosmochimica Acta 2015, 167, 144-161. 32. Wei, Z.; Moldowan, J. M.; Fago, F.; Dahl, J. E.; Cai, C.; Peters, K. E., Origins of thiadiamondoids and diamondoidthiols in petroleum. Energy & Fuels 2007, 21, (6), 3431-3436. 33. Cai, C.; Amrani, A.; Worden, R. H.; Xiao, Q.; Wang, T.; Gvirtzman, Z.; Li, H.; Said-Ahmad, W.; Jia, L., Sulfur isotopic compositions of individual organosulfur compounds and their genetic links in the Lower Paleozoic petroleum pools of the Tarim Basin, NW China. Geochimica et Cosmochimica Acta 2016, 182, 88-108.


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Energy & Fuels

Table 1. Volume and sulfur content of HDS diesels used and the obtained sulfur fractions, as well as the calculated recovery yields of the separated sulfur fractions. HDS diesel JM-D (245 mL, S: 17.6 mg/L)

DG-D (240 mL, S: 29.5 mg/L)

a

Recovery Yield =

sulfur fraction thiophenic fraction sulfidic fraction thiophenic fraction sulfidic fraction SF 1 SF 2 SF 3 SF 4 SF 5 SF 6 SF 7 in total

volume, mL

sulfur content, mg/L

recovery yielda, %

10

278

64.5

1.0

685

15.9

25

204

71.9

1.0 1.0 1.0 1.0 1.0 1.0 1.0

152 49.2 162 97.0 131 219 100

2.15 0.70 2.29 1.37 1.85 3.09 1.41 12.9

× !"# $%&%&' ()* +,-.-' × !"# $%&%&()* +,-.-'


Refractory Cyclic Sulfidic Compounds in Deeply Hydrodesulfurized

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