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Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
Postdoc Work at UWaterloo
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Postdoc Work at UWaterloo

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Postdoc Work at UWaterloo

Postdoc Work at UWaterloo

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  • 1. Yuxiang(Tony) Rao and Flora T.T. Ng Department of Chemical Engineering University of Waterloo, Canada, N2L 3G1 Combined Froth Upgrading using in-situ Hydrogen from the Water Gas Shift Reaction (WGSR)
  • 2. Experiments Combined froth was treated at different reaction conditions in a 300cm 3 batch-autoclave, stainless steel reactor . In total, 10 different types of reactions (including 3 blank experiments, no catalyst) were conducted for the combined froth upgrading experiments. All the experiments were conducted at 415 ° C for 2hrs with stirring. <ul><li>Mo/H 2 </li></ul><ul><li>Mo/CO </li></ul><ul><li>Mo/CO/H 2 O (5ml) </li></ul><ul><li>Mo/CO/H 2 O (10ml) </li></ul><ul><li>Mo/Ni/V/CO/H 2 O (10ml) </li></ul><ul><li>Mo/Ni/CO/H 2 O (10ml) </li></ul><ul><li>Mo/Ni/CO </li></ul><ul><li>CO </li></ul><ul><li>CO/H 2 O (5ml) </li></ul><ul><li>CO/H 2 O (10ml) </li></ul>
  • 3. Experiments <ul><li>All the liquid and solid oil products can be divided into four parts. </li></ul><ul><li>Light oil in trapper (liquid in gas sampling system) </li></ul><ul><li>Light oil + water (liquid outside liner) </li></ul><ul><li>Heavy oil (inside liner) </li></ul><ul><li>Soft solid (at the bottom of liner) </li></ul>
  • 4. Characterization <ul><li>X-Ray Fluorescence (XRF) </li></ul><ul><li>X- R ay Diffraction (XRD) </li></ul><ul><li>GC-Simulated Distillation (GC-SimDis) </li></ul>
  • 5. Results and Discussion <ul><li>Water Effect to Pressure </li></ul>Different amount of dirty water (0ml, 5ml and 10ml) from combined froth emulsion were added into the dry bitumen respectively. (Mo/CO)
  • 6. Results and Discussion <ul><li>Water Effect to Sulphur Removal </li></ul><ul><li>Water amount only show slightly effect on the sulphur removal performance. </li></ul><ul><li>The sulphur content of fresh combined froth is 4.11wt% as confirmed by XRF. </li></ul>
  • 7. Results and Discussion <ul><li>Water Effect to Upgrading Product Fractions </li></ul><ul><li>Water amount played an important role in the upgrading product fractions. </li></ul><ul><li>Adding more dirty water into the reactor will significantly inhibit the formation of soft solid and coke,but will also increase the system pressure. </li></ul>
  • 8. Results and Discussion <ul><li>Water Effect to Upgrading Product Fractions </li></ul>Table 1. Toluene Insoluble (Coke and Metal) Date Sep-02-2009 Aug-27-2009 Soft Solid(g) 7.7 5.35 Coke and metal(g) 0.7651 0.5347 Catalyst Mo/CO/H 2 O(5ml) Mo/CO/H 2 O(10ml)
  • 9. Results and Discussion <ul><li>Water Effect to Upgrading Products Qualities </li></ul>GC-SimDis results of heavy oil product fractions treated at different water amount <ul><li>Adding more dirty water (0ml--&gt;5ml--&gt;10ml) into the reactor will gradually improve the quality of heavy oil samples. </li></ul>
  • 10. Results and Discussion <ul><li>Feed Gas Effect to Sulphur Removal </li></ul><ul><li>Pure hydrogen has better hydrodesulphurization performance than pure CO, mainly due to the exist of higher concentrated hydrogen comparing with low concentrated in-situ hydrogen in pure CO experiment. </li></ul>
  • 11. Results and Discussion <ul><li>Feed Gas Effect to Upgrading Product Fractions </li></ul><ul><li>Using pure hydrogen as the feed gas will end up with getting more water than using pure CO, and only slightly less soft solid. (WGSR for CO) </li></ul>
  • 12. Results and Discussion <ul><li>Feed Gas Effect to Upgrading Products Qualities </li></ul><ul><li>Combined froth treated with pure hydrogen has slightly better quality than the one treated with pure CO. </li></ul>
  • 13. Results and Discussion <ul><li>Catalyst Effect to Sulphur Removal </li></ul><ul><li>Comparing with pure Mo catalyst and Mo/Ni/V catalyst, Mo/Ni catalyst has the best hydrodesulfurization ability. </li></ul>
  • 14. Results and Discussion <ul><li>Catalyst Effect to Upgrading Products Fractions </li></ul><ul><li>Mo/Ni catalyst has the best activity among those three catalysts.(less soft solid and water, more light oil) </li></ul>
  • 15. Results and Discussion <ul><li>Catalyst Effect to Upgrading Products Fractions </li></ul>Table 2. the effect of catalyst to upgrading product fractions Date Aug-27-2009 July-28-2009 July-22-2009 Water (g) 2.5 1 2.5 Light Oil Outside Liner(g) 10.65 12.55 12.52 Light Oil in Trapper(g) 27.89 39.95 16.76 Heavy Oil(g)   30.58 19.09 34.5 Soft Solid(g)   5.35 5.32 11.82 Total(g) 76.97 77.91 78.1 Yield (%) 82.73675 82.4551943 80.90632204 Catalyst Mo/CO/H 2 O (10ml) Mo/Ni/CO/H 2 O (10ml) Mo/Ni/V/CO/H 2 O (10ml)
  • 16. Results and Discussion <ul><li>Catalyst Effect to Upgrading Products Qualities </li></ul><ul><li>Mo/Ni catalyst produced more heavy fractions (pitch and heavy gas oil) than pure Mo catalyst and Mo/Ni/V catalysts. </li></ul><ul><li>This is due to its more concentrated heavy oil fractions.( 19.09g for Mo/Ni catalyst VS 30.58g for Mo catalyst and 34.5g for Mo/Ni/V catalyst) </li></ul>
  • 17. Results and Discussion <ul><li>Catalyst Effect to Upgrading Products Qualities </li></ul><ul><li>GC-SimDis data for Light oil fraction samples (outside liner) shows that the light oil fraction samples produced by Mo/Ni catalyst has best quality.(no pitch) </li></ul>
  • 18. Blank Experiments <ul><li>Sulphur Removal (without any catalyst) </li></ul><ul><li>Without adding any catalyst, we still observed WGSR. </li></ul><ul><li>Adding more water into the system (0ml--&gt;5ml--&gt;10ml) will slightly increase this hydrodesulfurization process. </li></ul>
  • 19. Blank Experiments <ul><li>Upgrading Product Fractions (without any catalyst) </li></ul><ul><li>Adding more water into reactor (0ml--&gt;5ml--&gt;10ml) will result in producing less undesired soft solid fractions and more desired light fractions. </li></ul><ul><li>Much more undesired soft solids were collected comparing with using Mo catalyst. </li></ul>
  • 20. XRD Experiments Table 3. XRD data for Sample: Coke -22 July 2009 (with Mo/Ni/V Catalyst) <ul><li>Except for Mo,Ni,V, Fe was also detected in Coke (soft solid washed with toluene and then filtration ) </li></ul>Catalyst PDF# Wavelength(Å) 2 theta 2 theta 2 theta 2 theta M O S 2 770341 1.54184 14.434 38.208 34.121 41.044 M O3 S 4 270319 1.54184 13.708 34.037 46.778 41.740 M O S 2 060097 1.54184 14.402 39.579 49.829 NiS 771624 1.54184 45.713 34.507 30.004 53.274 Ni 17 S 18 762306 1.54184 45.734 30.084 34.567 53.425 NiS 750613 1.54184 45.954 30.174 34.696 53.594 FeS 760965 1.54184 34.126 26.906 20.648 FeS 760962 1.54184 43.934 34.270 30.479 Fe 7 S 8 762308 1.54184 43.992 53.329 30.032 VS 732024 1.54184 34.373 26.612 27.564
  • 21. XRD Experiments Table 4. XRD data for Sample: Coke- 11 Sep 2009 (without any Catalyst) <ul><li>This experiment confirmed the existence of Ni,V and Fe in fresh combined froth and also explains the observed high activity without adding any catalyst. </li></ul>Catalyst PDF# Wavelength(Å) 2 theta 2 theta 2 theta 2 theta NiS 771624 1.54184 45.713 34.507 30.004 53.274 Ni 17 S 18 762306 1.54184 45.734 30.084 34.567 53.425 NiS 750613 1.54184 45.954 30.174 34.696 53.594 FeS 760965 1.54184 34.126 26.906 20.648 FeS 760962 1.54184 43.934 34.270 30.479 Fe 7 S 8 762308 1.54184 43.992 53.329 30.032 VS 732024 1.54184 34.373 26.612 27.564
  • 22. Conclusions <ul><li>Adding more water into the reactor will results in the increasing of system pressure and product quality, but has little effect on the sulfur removal ability. </li></ul><ul><li>Pure hydrogen has only slightly better performance (sulfur removal, product quality) than CO, mainly due to its higher concentration. </li></ul><ul><li>Ni was proved to be a good promoter for Mo catalyst for upgrading reaction, adding V into Mo/Ni will inhibit the WGSR. </li></ul><ul><li>Blank experiments (without using any catalysts) confirmed that our catalysts did play an important role in upgrading process. </li></ul><ul><li>XRD experiments show that Ni,V and Fe metal ions exist in fresh combined froth and formed corresponding sulfide compounds after reaction. </li></ul>

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