Combined Froth Upgrading using in-Combined Froth Upgrading using in-situ Hydrogen from the Water Gas Shift situ Hydrogen from the Water Gas Shift

Reaction (WGSR)Reaction (WGSR)

Yuxiang(Tony) Rao and Flora T.T. Ng

Department of Chemical Engineering

University of Waterloo, Canada, N2L 3G1

Combined froth was treated at different reaction conditions in a 300cm3 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.

Experiments Experiments Experiments Experiments

Mo/H2

Mo/CO

Mo/CO/H2O (5ml)

Mo/CO/H2O (10ml)

Mo/Ni/V/CO/H2O (10ml)

Mo/Ni/CO/H2O (10ml)

Mo/Ni/CO

CO

CO/H2O (5ml)

CO/H2O (10ml)

All the liquid and solid oil products can be divided into four parts.

Light oil in trapper (liquid in gas sampling system)

Light oil + water (liquid outside liner)

Heavy oil (inside liner)

Soft solid (at the bottom of liner)

Experiments Experiments Experiments Experiments

X-Ray Fluorescence (XRF)

X-Ray Diffraction (XRD)

GC-Simulated Distillation (GC-SimDis)

CharacterizationCharacterization CharacterizationCharacterization

Water Effect to Pressure

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

Different amount of dirty water (0ml, 5ml and 10ml) from combined froth emulsion were added into the dry bitumen respectively. (Mo/CO)

Water Effect to Sulphur Removal

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

Water amount only show slightly effect on the sulphur removal performance. The sulphur content of fresh combined froth is 4.11wt% as confirmed by XRF.

Water Effect to Upgrading Product Fractions

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

Water amount played an important role in the upgrading product fractions. Adding more dirty water into the reactor will significantly inhibit the formation of soft solid and coke,but will also increase the system pressure.

Water Effect to Upgrading Product Fractions

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

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/H2O(5ml) Mo/CO/H2O(10ml)

Table 1. Toluene Insoluble (Coke and Metal)

Water Effect to Upgrading Products Qualities

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

GC-SimDis results of heavy oil product fractions treated at different water amount

Adding more dirty water (0ml-->5ml-->10ml) into the reactor will gradually improve the quality of heavy oil samples.

Feed Gas Effect to Sulphur Removal

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

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.

Feed Gas Effect to Upgrading Product Fractions

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

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)

Feed Gas Effect to Upgrading Products Qualities

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

Combined froth treated with pure hydrogen has slightly better quality than the one treated with pure CO.

Catalyst Effect to Sulphur Removal

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

Comparing with pure Mo catalyst and Mo/Ni/V catalyst, Mo/Ni catalyst has the best hydrodesulfurization ability.

Catalyst Effect to Upgrading Products Fractions

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

Mo/Ni catalyst has the best activity among those three catalysts.(less soft solid and water, more light oil)

Catalyst Effect to Upgrading Products Fractions

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

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/H2O (10ml)

Mo/Ni/CO/H2O (10ml)

Mo/Ni/V/CO/H2O (10ml)

Catalyst Effect to Upgrading Products Qualities

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

Mo/Ni catalyst produced more heavy fractions (pitch and heavy gas oil) than pure Mo catalyst and Mo/Ni/V catalysts.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)

Catalyst Effect to Upgrading Products Qualities

Results and Discussion Results and Discussion Results and Discussion Results and Discussion

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)

Sulphur Removal (without any catalyst)

Blank ExperimentsBlank ExperimentsBlank ExperimentsBlank Experiments

Without adding any catalyst, we still observed WGSR.Adding more water into the system (0ml-->5ml-->10ml) will slightly increase this hydrodesulfurization process.

Upgrading Product Fractions (without any catalyst)

Blank ExperimentsBlank ExperimentsBlank ExperimentsBlank Experiments

Adding more water into reactor (0ml-->5ml-->10ml) will result in producing less undesired soft solid fractions and more desired light fractions. Much more undesired soft solids were collected comparing with using Mo catalyst.

XRD ExperimentsXRD ExperimentsXRD ExperimentsXRD ExperimentsTable 3. XRD data for Sample: Coke -22 July 2009 (with Mo/Ni/V Catalyst)

Catalyst PDF# Wavelength(Å) 2 theta 2 theta 2 theta 2 theta

MOS2 770341 1.54184 14.434 38.208 34.121 41.044

MO3S4 270319 1.54184 13.708 34.037 46.778 41.740

MOS2 060097 1.54184 14.402 39.579 49.829

NiS 771624 1.54184 45.713 34.507 30.004 53.274

Ni17S18 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

Fe7S8 762308 1.54184 43.992 53.329 30.032

VS 732024 1.54184 34.373 26.612 27.564

Except for Mo,Ni,V, Fe was also detected in Coke (soft solid washed with toluene and then filtration )

XRD ExperimentsXRD ExperimentsXRD ExperimentsXRD ExperimentsTable 4. XRD data for Sample: Coke- 11 Sep 2009 (without any Catalyst)

Catalyst PDF# Wavelength(Å) 2 theta 2 theta 2 theta 2 theta

NiS 771624 1.54184 45.713 34.507 30.004 53.274

Ni17S18 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

Fe7S8 762308 1.54184 43.992 53.329 30.032

VS 732024 1.54184 34.373 26.612 27.564

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.

ConclusionsConclusionsConclusionsConclusions

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.

Pure hydrogen has only slightly better performance (sulfur removal, product quality) than CO, mainly due to its higher concentration.

Ni was proved to be a good promoter for Mo catalyst for upgrading reaction, adding V into Mo/Ni will inhibit the WGSR.

Blank experiments (without using any catalysts) confirmed that our catalysts did play an important role in upgrading process.

XRD experiments show that Ni,V and Fe metal ions exist in fresh combined froth and formed corresponding sulfide compounds after reaction.