Fuel 90 (2011) 34043409

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Fuel
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Experimental study on two-stage catalytic hydroprocessing of middle-temperature coal tar to clean liquid fuels
Tao Kan, Hongyan Wang, Hongxing He, Chunshan Li , Suojiang Zhang
State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, PR China

a r t i c l e

i n f o

a b s t r a c t
Special MoCo/c-Al2O3 and WNi/c-Al2O3 catalysts with different metal loadings were prepared applying new synthesis technologies that combine ultrasonic-assisted impregnation and temperature-programming methods. Clean liquid oil was obtained from middle-temperature coal tar via hydrogenation in two-stage xed beds lled with the laboratory made catalysts. The MoCo/c-Al2O3 catalyst with 12.59 wt.% Mo and 3.37 wt.% Co loadings, and the WNi/c-Al2O3 catalyst with 15.75 wt.% W and 2.47 wt.% Ni loadings were selected. The effects of pressure and liquid hourly space velocity on hydrogenation performance were investigated while other experimental conditions remained constant. Gasoline (6180 C) and diesel (180360 C) fractions were separated from the oil product and analyzed. The twostage reacting system was capable of removing nitrogen and sulfur from 1.69 and 0.98 wt.% in the feed to less than 10 ppm and 100 ppm, respectively in the products. The results indicated that the raw coal tar could be considerably upgraded through catalytic hydroprocessing and high-quality fuels were obtained. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 25 March 2011 Received in revised form 7 June 2011 Accepted 12 June 2011 Available online 22 June 2011 Keywords: Middle-temperature coal tar Hydroprocessing Oil Two-stage Catalyst

1. Introduction In view of growing concerns about the petroleum depletion crisis and rising fuel price, major efforts are being dedicated to the development of various usable energy sources to ensure energy security. China is one of the largest coal producers in the world and extensive studies have been focused on the fuel production from coal [14]. Abundant coal tar has been produced every year during coal carbonization and gasication [5]. The coal tar can be used as an alternative source for producing conventional liquid fuels (e.g., gasoline and diesel) through its hydrogenation. On the other hand, liquid fuel production is currently subject to strict environmental standards for transport liquid fuels and refractory feeds for reners [6]. Environmental and economic benets are inevitably linked to the hydroprocessing of coal tar to produce clean transport fuels with ultra-low heteroatom content. Coal tar is a complex mixture consisting of aliphatic, aromatic, alicyclic, and heterocyclic compounds. The complexity of coal tar has driven researches that focused on a pure model compound, such as naphthalene [710], phenanthrene [10], anthracene [11], and quinoline [12], rather than on a real fraction. Extensive investigations on thermodynamics and kinetics have been performed [1316]. Detailed reviews of studies on the reaction networks have been provided by Girgis and Gates [17]. The kinetics of the removal
Corresponding authors. Tel./fax: +86 10 82547800 (C. Li), +86 10 82627080 (S. Zhang). E-mail addresses: csli@home.ipe.ac.cn (C. Li), sjzhang@home.ipe.ac.cn (S. Zhang).
0016-2361/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2011.06.012

of sulfur compounds and other impurities has a critical effect on the optimization of process variables and the selection of catalyst for hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and hydrodeoxygenation (HDO) processes [6]. Although studies described above are helpful in understanding the behavior of certain compounds under hydroprocessing conditions, an overall picture of coal tar hydrogenation was not provided. At the temperature and pressure required for hydrotreatment, many undesirable reactions including dehydrogenation, polymerization, isomerization, and condensation would occur [18]. The performance of hydroprocessing units is greatly inuenced by the catalyst, type of reactor, process ow, and operating parameters. Physical properties such as the density, porosity, size, and shape of a catalyst are crucial parameters in hydroprocessing heavy feeds [19]. These parameters are feed dependent [20], implying that for certain coal tar feedstock, catalysts with special properties (usually high BET surface and large pore volume) are required. MoCo supported on alumina has long life, and under suitable conditions, enables the removal of a high degree of sulfur with little more than theoretical hydrogen consumption [21]. Also, in the study by Raje et al., the hydrotreatment of coal-derived naphtha was evaluated over unsupported transition metal sulde catalysts of Group VIII in the Periodic Table, and ruthenium sulde (RuS2) was found to be the most active catalyst for the heteroatom removal [22]. Furthermore, a low loading Ru/zeolite catalyst was believed to exceed the commercial MoCo and MoNi catalysts in HDN activity per weight of metal and price [23]. But it showed a much lower HDS activity. Tungsten sulde has been claimed as an effective catalyst

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for a wide variety of hydrocarbon reactions including the hydrogenation of olens and aromatics, and isomerization of naphthenes and parafns, as well as hydrocracking and hydrogenolysis [24]. It is believed that creating smaller particles of active metals will improve the catalysts activity. Some recent studies [2528] have discussed the synthesis of highly dispersed c-Al2O3-supported MoCo catalysts using energy from ultrasonic waves. The present study describes the bench scale two-stage hydroprocessing of middle-temperature coal tar using laboratory made MoCo and WNi catalysts supported on c-Al2O3 in the rst and second stages respectively. Impregnation and temperature-programming technologies were applied to prepare the catalysts. This work primarily aims to reduce heteroatoms (S, N, and O) and produce high-quality liquid fuels under varied reaction pressures and liquid hourly space velocities (LHSV). The coupling of hydroning for initial hydrogenation in the rst stage and hydrocracking for further hydrogenation and CAC bond cracking in the second stage showed promising results.

2.2. Feedstock The distillate (under 360 C) of the middle-temperature coal tar was used as feedstock in this study. Some properties of the feedstock are listed in Table 1. 2.3. Reaction system The hydroprocessing of the coal tar was carried out in a continuous two-stage xed-beds system. As shown in Fig. 1, the entire reaction system was mainly made up of three units, i.e., the reactant feeding, the hydrogenation, and the product separation and collection units. The reactant feeding unit consisted of a tar supply line and a high-pressure hydrogen supply line. The hydrogenation unit consisted of a preheater, a hydroning reactor, and a hydrocracking reactor. The middle section of each reactor tube was lled with 30 ml catalyst. The product separation and collection unit included a water cooler, a gasliquid separator, a lye washer and so on. 2.4. Operating procedure and product analysis

2. Experimental 2.1. Catalyst preparation and characterization Hydroning catalysts (MoCo/c-Al2O3) with different Mo and Co loadings were prepared and the synthesis procedure is described as follows: (1) Pretreatment. The commercial c-Al2O3 granules of 2040 mesh were used as the catalyst support. Higher surface area of the alumina granules was obtained after they were dipped in the 5 wt.% diluted HCl solution for 20 min. Then they were dried at 110 C for 2 h to get rid of the surface water, after which they were calcined at 500 C for 6 h to eliminate the water absorbed in the pores and stabilize the framework of the alumina. (2) Ultrasonic impregnation. The support was impregnated in an aqueous solution containing the required amount of ammonium molybdate [(NH4)6Mo7O244H2O] and cobalt nitrate [Co(NO3)26H2O] for 12 h. During the impregnation process, ultrasonic vibration with a frequency of 50 kHz was applied. Then the Mo and Co precursors will be highly dispersed on the pretreated cAl2O3 support using energy from ultrasonic waves. (3) Temperature-programmed treatment. The catalyst was heated in the air atmosphere to the temperature of 200 C and held for 3 h. Then it was heated to 350 C at a rate of 5 C/min and held for 3 h, which was nally heated to 500 C at a rate of 10 C/min and held at this temperature for 6 h. The hydrocracking catalysts (WNi/c-Al2O3) with different W and Ni loadings were also synthesized under the same procedure using the precursors of ammonium metatungstate hydrate [H40N10O41W12XH2O] and nickel nitrate [Ni(NO3)26H2O]. The amount of various metals present on the catalysts was analyzed using ICP-AES (IRIS Intrepid II XSP, ThermoFisher Co., Ltd.). The BET surface area and pore volume measurements of the catalysts were performed with adsorption equipment (Micromeritics) using N2 gas. X-ray diffraction (XRD) was performed using a diffractometer (XPert PRO MPD, PANalytical Co., Ltd.) with Cu Ka radiation ltered by a graphic monochromator at a setting of 40 kV and 40 mA. High resolution transmission electron microscopy (HRTEM, model: JEM-2100, JEOL Co., Ltd.) was also performed to investigate the structure of the catalysts. Catalysts with different metal loadings were evaluated in the tests of coal tar hydroprocessing. After preliminary screening tests, the hydroning catalysts (MoCo/c-Al2O3) with 12.59 wt.% Mo and 3.37 wt.% Co loadings, and the hydrocracking catalyst (WNi/cAl2O3) with 15.75 wt.% W and 2.47 wt.% Ni loadings showed better performance than did the other catalysts. Thus, they were nally used in the following experiment. Coal tar hydroprocessing was conducted as follows: (I) Pre-sulfidation of catalysts. The suldation of catalysts was performed at PH2 = 6 MPa, LHSV = 1.6 h1, and H2/oil ratio = 1000 using 2 wt.% dimethyl disulde in aviation kerosene and underwent a temperature-programmed procedure. (II) Hydroprocessing tests. All the experimental parameters were set at the respective desired values and the tests were conducted at a duration of 120 h. (III) The overall system was washed with ethanol after each run. The liquid product was distilled into gasoline (6180 C), diesel (180360 C) and residue oil (>360 C) fractions. The samples of gasoline and diesel fractions were then subjected to the following analyses: (i) determination of distillation range by the Engler distillation method (standard: ASTM D86); (ii) C and H elemental analyses on an Elementar VARIO ELIII (Germany), N and S analyses on KY-3000SN (Jiangsu Jiangyan KEYUAN Electronic Instrument Co. Ltd., standard: ASTM D5453 and D4629); (iii) density on DMA 5000 (Anton Paar, Austria); (iv) research octane number (RON) and anti-knock index (AKI) for gasoline; (v) cetane number and solidifying point for diesel; and (vi) detailed composition determined by capillary column GCMS analysis (Agilent 6890N with a 30 m 0.25 mm 0.25 lm HP-5MS capillary column). 3. Results and discussion 3.1. Catalyst characterization As shown in Table 2, both the MoCo/c-Al2O3 and WNi/cAl2O3 catalysts had a BET surface area of 200 m2/g and a pore
Table 1 Properties of coal tar fraction. Properties Elemental analysis (wt.%) C H N S Oa H/C molar ratio Distillation range (C) IBP 10% 50% 90% Density (20 C) (g mL1)
a

Value 84.86 8.39 1.69 0.96 4.10 1.19 118 196 261 306 1.0078

By difference.

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Fig. 1. Schematic diagram of the reaction system for coal tar hydrogenation.

volume of higher than 0.5 cm3/g. The XRD patterns (not shown here) of both fresh catalysts exhibited only very broad XRD lines of the c-Al2O3 support and did not show any obvious special peaks other than the c-Al2O3 support, indicating that for both catalysts, all the metal oxides were highly dispersed over the support and their particle sizes are below the detection limit of XRD. These results are well consistent with those of previous studies [6,2526]. The TEM micrographs of the fresh MoCo and WNi catalysts were shown in Fig. 2A and Fig. 2B respectively. The presulfurized MoCo and WNi catalysts were also analysed by TEM as exhibited in Fig. 2C and D. It could be concluded that the active metals and promoters were highly dispersed on the alumina support. 3.2. Comparison between intermedial and nal products In order to certify the necessity of two-stage hydroprocessing and the catalysis effect by the downstream WNi/c-Al2O3 catalyst, the intermedial product after the rst reactor was analysed and compared with the nal product after the second reactor. Both the products were distilled into gasoline, diesel, and residual oil fractions and the comparison between the intermedial and the nal products was shown in Table 3. Some heteroatom-containing compounds such as aniline, substituted phenols, and benzyl alcohols still remained in the intermedial product according to the GCMS analysis. These results indicated that the two-stage process and the downstream WNi/c-Al2O3 catalyst were essential for obtaining high hydroprocessing performance (e.g., yields and properties of gasoline and diesel products). 3.3. Effect of pressure on product properties The most important process variables, which generally affect the hydroprocessing performance, are temperature, pressure, hydrogen-to-oil ratio, and LHSV. Operation at very high temperatures is undesirable, and the catalyst should be operated at temperatures below 400 C [29]. In current study, the experimental conditions such as hydroning temperature (Thf) of 360 C, hydrocracking temperature (Thc) of 380 C, and hydrogen to coal tar volume ratio (H2/oil ratio) of 1600 were kept constant. Other conditions including reaction pressure

Table 2 Catalyst characterization. Catalyst Composition (wt.%) Mo MoCo/c-Al2O3 WNi/c-Al2O3 12.59 Co 3.37 W 15.75 Ni 2.47 BET area (m2/g) 217 192 Pore vol. (cm3/g) 0.58 0.52

P H2 and LHSV were varied in the range of 612 MPa and 0.4 1.2 h1 respectively to investigate their effects on the hydroprocessing performance. As shown in Table 4 the inuence of pressure on the hydroprocessing performance was investigated at stepwise pressures of 6, 8, and 12 MPa. The nitrogen conversion reached a very high level with a nitrogen content of only 3 ppm remained in the produced gasoline and 1 ppm in the diesel under the pressure of 12 MPa. These data indicated that HDN is a strong function of hydrogen pressure. The preferred reaction pathway for HDN reaction initially involves the saturation of the aromatic ring carrying the heteroatom (especially for compounds in which nitrogen is part of the aromatic ring) before CAN bond scission takes place [17,29,30]. The removal of nitrogen compounds contained in coal-derived naphtha was also well investigated by Liaw et al. [31]. The most signicant HDS for environmental attention exhibited the same changing trend as did the HDN. As the pressure was raised from 6 to 12 MPa, the sulfur content changed from 71 to 66 ppm and 54 to 24 ppm in the gasoline and diesel products respectively. The HDS reaction network proceeds by a similar mechanism through direct hydrogenolysis or through the hydrogenation of the aromatic ring prior to sulfur removal [29]. It can be also concluded from Table 4 that pressure inuences the HDN activity to a greater extent than the HDS activity, which indicated that the rate constant for HDN is higher than the value for HDS. In the kinetic study by Vishwakarma et al. [6], the higher HDN reaction rate than HDS could be explained as that the HDN was not inhibited by pore diffusion while the HDS was the opposite. On the other hand, basic nitrogen-containing compounds are well known to have strong inhibition effect on the HDS reaction. For a long time, the nature of the inhibition remained unclear but

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Fig. 2. TEM micrographs of catalyst samples: (A) the fresh MoCo catalyst; (B) the fresh WNi catalyst; (C) the presulfurized MoCo catalyst; and (D) the presulfurized WNi catalyst.

Table 3 Comparison between intermedial and nal productsa. Product properties Gasoline Intermedial product 13.7 Final product 20.1 71 14 1.81 Diesel Intermedial product 75.0 457 422 1.43 Final product 76.9 54 8 1.71

Yield (vol.%)

S & N analysis (wt.%) S (ppm) 244 N (ppm) 352 H/C molar 1.76 ratio

a Experimental conditions: P H2 = 6 MPa, Thf = 360 C, Thc = 380 C, LHSV = 0.4 h1, and H2/oil ratio = 1600.

recently scanning tunnelling microscopy (STM) and density functional theory (DFT) studies on the unsupported MoS2-based catalysts have provided new detailed atomic-scale insight into the nature of the inhibition effects, which revealed that the metallic like brim sites located adjacent to the edges were involved in the hydrogenation and CAS bond scission reactions in HDS [3235]. It was found that inhibition by nitrogen-containing compounds was due to not only blocking but also reducing the number of H atoms available for hydrogenation [36]. As to the supported catalysts, a few studies have investigated support effects by modelling promoted and unpromoted MoS2-based cluster structures on different facets of c-Al2O3, and in the latter studies different adsorption geometries and congurations were mapped out in great detail [34]. For the Co or Ni promoted Mo catalyst, the interactions among Mo, the promoter, and the support will exhibit more complexity. Comparing to the unsupported catalysts, such

investigations of the catalyst involving c-Al2O3 support are complicated further by the fact that the precise location of non-spinel sites in c-Al2O3 is not completely known and still under discussion [34]. As to the HDO, the oxygen contents in the gasoline and diesel products were evidently reduced to 0.51.5 wt.% (not shown in the tables) comparing to the oxygen content of 4.10 wt.% in the feed. The heating values of the produced fuels were strongly dependent on their oxygen content and the higher heating value (HHV) of the liquid fuels can be approximately calculated from elemental data using the corresponding equation [37]. At the same time, there also occurred an increase in H/C molar ratio and a reduction in the boiling range, indicating enhanced aromatic saturation and hydrocracking under higher pressure. The rate-controlling step in the hydrogenation reaction appears to be the orientation and adsorption of the reactants on the catalyst surface [11]. At higher pressure, more hydrogen gas dissolved into the reactant oil, moved onto the catalyst surface, participated in the hydrogenation reaction, and nally entered into the product. The decrease in density at higher pressure can be ascribed to the effect of a lower aromatic content caused by enhanced aromatic saturation. Increasing the pressure from 6 to 12 MPa resulted in the downgrade of RON and AKI for the gasoline product and cetane value for the diesel product. This downgrade may be caused by the excessive hydrogenation of the feedstock at higher pressure. 3.4. Effect of LHSV on product properties LHSV reects the contact time of the tar with the catalysts. For the same catalyst bed, a higher LHSV value will result in shorter contact time. In the serial tests, three typical LHSV values of 0.4,

3408 Table 4 Effect of pressure on properties of gasoline and diesel productsa. Product properties Effect of pressure on gasoline 6 (MPa) Yield (vol.%) 20.1 8 (MPa) 20.3 66 12 1.91 90 114 / / 283 0.8035 92.9 88.2 / / 12 (MPa) 22.3 66 3 1.98 80 113 / / 274 0.7941 91.2 86.7 / /

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Effect of pressure on diesel 6 (MPa) 76.9 54 8 1.71 / / 275 343 360 0.8863 / / 56.2 +4.3 8 (MPa) 73.2 44 2 1.80 / / 273 340 358 0.8750 / / 42.4 14.9 12 (MPa) 70.1 24 1 1.89 / / 253 320 355 0.8444 / / 35.6 29.1

S & N analysis (wt.%) S (ppm) 71 N (ppm) 14 H/C molar ratio 1.81 Distillation range (C) IBP 10% 50% 90% FBP Density (20 C) (gmL1) RON AKI Cetane value Solidifying point (C) 95 122 / / 286 0.8060 93.0 88.2 / /

Fig. 3. FT-IR spectra for (A) the coal tar; (B) the gasoline product and (C) the diesel product. Experimental conditions: P H2 = 6 Mpa, Thf = 360 C, Thc = 380 C, LHSV = 0.4 h1, H2/oil ratio = 1600.

is apparently necessary. At higher LHSV, maybe not enough time was provided to ensure the occurrence of certain reactions. 3.5. Components in gasoline and diesel products The organic components in the gasoline and diesel products were determined by GCMS analysis. The most abundant components in the gasoline product included C6AC8 hydrocarbons, such as cyclohexane, substituted cyclohexanes, and toluene. Methylcyclohexane (C7H14) appeared as the most outstanding component with a molar content of 12.48%. The gasoline fraction mainly consisted of monocyclic aromatics, alkenes, and saturated ring compounds. Bicyclic substituted naphthalenes with low contents were also detected. For the diesel product, more than 300 peaks were successfully detected. Various bicyclic and polycyclic aromatics (e.g., naphthalene, anthracene, and phenanthrene) as well as straight-chain alkanes with high carbon numbers (e.g., heptadecane) appeared in the diesel fraction. Hexadecane was the most abundant material with molar content of 2.36%. 3.6. Functional groups in gasoline and diesel products The FTIR analysis was were employed to study the organic groups existing in the coal tar, the gasoline, and diesel products as presented in Fig. 3. For the coal tar (Fig. 3A), the absorption band from 3690 to 3100 cm1, the peaks at 2920 cm1, 1460, and 1380 cm1, the peak at 1600 cm1, and the peaks at 812 and 752 cm1 were attributed to the OAH stretching vibrations, the presence of alkanes, the existence of C@C bonds, and the presence of polycyclic and substituted aromatic groups respectively. For the gasoline (Fig. 3B), and diesel (Fig. 3C) products, two similar FT-IR spectra with different intensities of peaks were obtained. Comparing to the coal tar, some changes occurred: (1) The disappearance of the band between 3690 and 3100 cm1 showed the removal of OAH group via HDO. (2) The peak at 2920 cm1 for the alkanes became stronger, accompanied by the relatively smaller peaks at 752 cm1, indicating the increasing content of alkanes and the reduction of aromatic groups. (3) The peak at 1600 cm1 almost vanished, indicating the decrease of the C@C compounds. 4. Conclusion Special hydroning (MoCo/c-Al2O3) catalyst with 12.59 wt.% Mo and 3.37 wt.% Co loadings and hydrocracking (WNi/c-Al2O3) catalyst with 15.75 wt.% W and 2.47 wt.% Ni loadings were prepared applying combined synthesis technologies of ultrasonic-as-

a Other experimental conditions: Thf = 360 C, Thc = 380 C, LHSV = 0.4 h1, and H2/oil ratio = 1600.

Table 5 Effect of LHSV on properties of gasoline and diesel productsa. Product properties Effect of LHSV on gasoline Effect of LHSV on diesel 0.4 (h1) Yield (vol.%) S & N analysis (wt.%) S (ppm) N (ppm) H/C molar ratio Distillation range (C) IBP 10% 50% 90% FBP Density (20 C) (gmL1) RON AKI Cetane value Solidifying point (C) 20.1 71 14 1.81 95 122 / / 286 0.8060 93.0 88.2 / / 0.8 (h1) 19.9 78 19 1.79 96 121 / / 290 0.8067 93.2 88.7 / / 1.2 (h1) 18.7 167 141 1.72 96 129 / / 279 0.8086 95.2 90.3 / / 0.4 (h1) 76.9 54 8 1.71 / / 275 343 360 0.8863 / / 56.2 +4.3 0.8 (h1) 72.2 67 51 1.67 / / 275 340 358 0.8895 / / 56.0 +5.1 1.2 (h1) 69.9 82 226 1.59 / / 273 342 365 0.8940 / / 53.6 +5.1

a Other experimental conditions: P H2 = 6 MPa, Thf = 360 C, Thc = 380 C and H2/oil ratio = 1600.

0.8 and 1.2 h1 were selected and other experimental parameters such as P H2 = 6 MPa, Thf = 360 C, Thc = 380 C, and H2/oil ratio = 1600 were kept constant. As shown in Table 5, the gasoline yield slightly decreased from 20.1% to 18.7% with increasing the LHSV from 0.4 to 1.2 h1. The sulfur and nitrogen concentrations in the gasoline product rose with increasing LHSV, accompanied by a drop in H/C molar ratio from 1.81 to 1.72 due to the less reaction time provided for HDS at higher LHSV. The density as well as the RON and AKI indexes was also slightly elevated with increasing the LHSV. However, the distillation range was not evidently inuenced by the LHSV. As can be concluded from Table 5, similar results were obtained for the diesel product. During the hydroprocessing of the coal tar, the hydrogenation reaction involving in three phases proceeds at a very slow rate. For this multistep hydrogenation reaction, enough reaction time

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sisted impregnation and temperature-programming. Clean liquid fuels were obtained from middle-temperature coal tar via hydrogenation in two-stage xed beds lled with the laboratory made catalysts. The effects of pressure and liquid hourly space velocity on hydrogenation performance were investigated. Gasoline (6180 C), and diesel (180360 C) fractions were separated from the oil product and analyzed. The two-stage reacting system was capable of removing nitrogen and sulfur from 1.69 and 0.98 wt.% in the feed to less than 10 ppm and 100 ppm, respectively in the products. The results showed that the raw coal tar can be considerably upgraded through catalytic hydroprocessing. More effective catalysts and investigations are still required to produce gasoline and diesel with lower sulfur content. Acknowledgements The authors are grateful to the National Natural Science Foundation of China (No. 21006113) and National Basic Research Program of China (973 Program No. 2009CB219900). References
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