PROGRESS REPORT

INDUSTRIAL RESEARCH CHAIR ON ADVANCED UPGRADING OF BITUMEN

Research Advisory Committee Meeting

May 5, 2004

Chair Holder: Murray R Gray

Department of Chemical and Materials Engineering

University of Alberta, Edmonton, AB T6G 2G6

Phone: (780) 492-7965 FAX: (780) 492-2881

1. Personnel

The table on the next page summarizes the personnel currently working on the Chair and related programs, and indicates their project areas. A total of seven full-time graduate students are working on projects under the chair program, along with a research manager, a research technician and a summer student.

Recruitment for 2004:

A new post-doctoral fellow has been recruited for the research on coke-liquid agglomerates (Project #4, description attached). Mr. Chunbao Xu will join the project in July, after completing his PhD on fluidized bed preparation of fine particles at the University of Western Ontario, under the supervision of Dr Jesse Xu.

New graduate students are being recruited for 2005, in anticipation of continuing Chair programs in three main areas: Project 4, Reaction and Transport in Coke-Residue Agglomerates, Project 8, Molecular Behavior of Bitumen Model Compounds, and a new project on high-temperature cracking of bitumen fractions.

2. Renewal of Chair Program in 2005

Potential additional industry partners have been contacted, but no commitments have been received to date. The following developments may impact the scope of upgrading research at U of A, and indirectly affect the chair program:

q  Alberta Ingenuity Proposal for an Oilsands Centre

q  Energy INet

q  Ongoing negotiations of Faculty of Engineering with companies

In order to avoid interruption of research activities, submission of an application to NSERC in May 2004 is recommended, based on the commitments from Syncrude and AERI.

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Research Personnel – NSERC Upgrading Chair Program
Researcher
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Position

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Project

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Start Date

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Anticipated Completion

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Funding1

Wa’el Abdallah / PhD Student / Surface studies of Nitrogen Compounds on Mo (110) / Jan 2002 / July 2005 / Chair
Oswaldo Asprino / MSc student / Adhesion and Fluid Properties During Bitumen Conversion / Sept 2002 / Sept 2004 / Chair
Weidong Bi / MSc Student / Role of Fine Solids in Kinetics of Coke Formation / Sept 2002 / Dec 2004 / Chair
Paul Chernick / MSc student / Biocatalysts for opening of ring compounds / Sept 2003 / Aug 2005 / NSERC
Dagles Diaz / MSc student / Mechanisms of Salt Decomposition in Upgrading of Oilsands Bitumen / Oct 2003 / Dec 2005 / CRD
Pedro Gonzalez / MSc student / Mechanisms of Aerosol Formation and Removal in Upgrading Processes / May 2002 / July 2004 / Chair
Tuyet Le / Technician / Mechanisms of Salt Decomposition in Upgrading of Oilsands Bitumen/ / Ongoing / CRD + Chair
Dr Felainiana Rakotondradany / Research manager / Molecular Behavior of Bitumen Model Compounds / Feb 2004 / Feb 2005 / Chair
Jeff Sheremata / PhD Student / Molecular representation of bitumen fractions / Jan 2001 / July 2005 / Chair
Part time and temporary researchers
Lisa Boddez / Undergraduate student / Adhesion and Fluid Properties During Bitumen Conversion / May 2004 / Aug 2004 / Chair
Richard McFarlane / MSc Student / High-Temperature Phase Behavior of Bitumen Residue Fractions (with JM Shaw) / Jan 2004 / Jan 2005 / -

1. Chair – NSERC Chair Program (Syncrude + AERI); CRD = Collaborative Research and Development Grant, Champion + NSERC; NSERC = NSERC post-graduate scholarship

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2. Description of Active Research Projects

2.1 Coking and Thermal Cracking

(1) Adhesion and Fluid Properties During Bitumen Conversion

Researcher: Oswaldo Asprino (MSc Candidate); Collaborators: JAW Elliott, W.C. McCaffrey and I Huq (Syncrude).

This research uses the novel apparatus developed under the chair program to measure fluid properties during thermal cracking and coking. This phase of the work is focusing on the role of the feed composition. Our hypothesis is that the heaviest fraction, the asphaltenes, controls the fluid properties during reaction. This project is measuring surface tension and viscosity of asphaltenes during reaction, and has already resulted in a new method for measuring contact angle of molten asphaltenes.

(2) Mechanisms of Aerosol Formation and Removal in Upgrading Processes

Researcher: Pedro Gonzalez (MSc Candidate); Collaborators: W.C. McCaffrey and C. McKnight (Syncrude).

The upgrading of oilsands bitumen is characterized by the migration of solids, such as clays and coke fines, into downstream units despite the expected thermodynamic behaviour. This migration, along with a variety of fouling phenomena, may be linked to the formation of aerosols in the upgrading process, which then migrate downstream. This study will investigate the fundamentals of aerosol formation in bitumen processing, supporting future research on the capture and deposition of aerosols.

(3) Role of Fine Solids in Kinetics of Coke Formation

Researcher: Weidong Bi (PhD Candidate); Collaborator: W.C. McCaffrey.

The presence of fine solids has a significant impact on the initial kinetics of coking. Our hypothesis is that this kinetic effect is due to the dispersion of the coke phase by the fine solids, which controls the thickness and agglomeration of the coke. This project will use a novel mesophase carbon material as a base for forming coke, in order to study the formation of coke in a controlled geometry in liquid suspension.

(4) Reaction and Transport in Coke-Residue Agglomerates (Coking and Thermal Cracking)

Collaborators: Ed Chan, Syncrude; Research staff: Dr Chunbao Xu (PhD, UWO July 2004) and Tuyet Le (Technician)

In a variety of processes, including fluid coking, proposed short-contact time coking and proposed catalytic processes, liquid residue feed is contacted with hot solids to initiate reaction. The behavior of the liquid droplets and solid feed in a variety of experiments suggests that the initial state of the liquid feed in fluid coker is a warm solid-liquid agglomerate. As this agglomerate circulates in a reactor bed, it will heat up to reactor temperature, it may pass liquid on to other bed particles, and it may break up due to internal or hydrodynamic forces. Work in collaboration with Syncrude Research would use an existing 3” pilot coker to study these processes under controlled conditions. By introducing agglomerates of known size and liquid saturation, their behavior under reaction conditions can be defined. This study would set the desired performance of a coker feed system in terms of liquid-solid agglomerate size and liquid saturation. It would also add to our knowledge of the interplay between heat transfer, mass transfer and momentum transfer in upgrading processes.

2.2 Bioprocessing

(5) Biocatalysts for opening of ring compounds

Researcher: Paul Chernik (MSc – NSERC Postgraduate Scholarship); Collaborator: Julia Foght, Biological Sciences.

The synthetic oil from the oilsands is rich in aromatic compounds, which is undesirable for fuel quality, particularly for manufacturing diesel and jet fuels that give good performance The aromatics are easily hydrogenated at high pressure, but the performance is inferior to equivalent fuels containing more linear chains. Opening of the rings is desirable, therefore, to give straight chain alkanes. Unfortunately, the available catalysts are very inefficient in this process, and give low yields of the desired product, along with high yields of unwanted butane. Bacteria commonly synthesize and degrade ring compounds that are remarkably similar to the saturated ring compounds in products from the oilsands. These compounds, structurally similar to cholesterol and other steroids, are common components of the cell membranes and cell walls of some organisms. Consequently, microorganisms likely possess interesting biocatalytic activity towards compounds containing saturated rings of carbon compounds. The objective of this project is to develop novel biocatalysts for opening saturated ring compounds, such as the structures found in products from the oilsands.

2.3 Chloride and Inorganic Compounds in Upgrading

(6) Mechanisms of Salt Decomposition in Upgrading of Oilsands Bitumen

Researcher: Dagles Diaz (MSc), Tuyet Le (Technician. Half time); Collaborators: A Wu (Syncrude), P. Eaton and S. Wang (Champion Technologies).

Bitumen from the Alberta oilsands contains significant concentrations of organic acid components, known as naphthenic acids. Bitumen can also contain chloride salts, depending on the salinity of the water during extraction or in situ production, and clay minerals. In the presence of steam, the chloride salts, clays and organic acids may combine synergistically to promote the formation of hydrochloric acid, causing significant corrosion in downstream equipment. Despite the importance of these compounds to product quality and upgrader operation, their behaviour under upgrading conditions has been studied very little. We propose a program of research to investigate the behaviour of these organic acids, clays and chloride salts, in order to develop new methods for removing these components or blocking their impact.

2.4 Bitumen Chemistry

(7) Molecular representation of bitumen fractions

Researcher: Jeff Sheremata (PhD); Collaborators: William McCaffrey, Heather Dettman (NCUT), Keng Chung (Syncrude).

Sheremata is able to construct sets of molecules that represent all of the data from elemental analysis and proton and 13C-NMR. Previous work by Mike Klein in the US gave representations of sets of molecules to represent petroleum residue fractions, but our work represents the first time that data from 13C-NMR have been fully utilized to give representations that agree with extensive work by Strausz on asphaltene and bitumen chemistry. In particular, Sheremata has succeeded in developing computer-generated molecular representations that include alkyl and sulfur bridges between aromatic groups. This work provides a basis for kinetic and thermodynamic models for bitumen based on realistic molecular components.

(8) Molecular Behavior of Bitumen Model Compounds

Researcher: Felaniaina Rakotondradany, Research Manager (from Feb 1, 2004); Collaborators: H. Fenniri (National Institute for Nanotechnology).

We propose to use an exciting combination of chemical synthesis and nanotechnology to explore new strategic paths for catalytic processing. By synthesizing model compounds to represent the components of the vacuum residue and asphaltene fractions, we can determine the mechanisms of thermal reactions, such as coke formation, and reactions on catalyst surfaces. Exciting opportunities include the development of new separation methods for characterizing bitumen based on affinity interactions with synthesized compounds, and using pure compounds to image how molecules interact with catalyst surfaces, using scanning probe microscopy with atomic-level resolution. This approach would allow us to use the methods of nanotechnology to understand how large bitumen molecules interact with catalyst surfaces, and discover completely new approaches to develop catalysts for residue processing. Subsequent work in this area would progress in collaboration with Dr Alan Nelson and Dr Hicham Fenniri (NINT).

(9) High-Temperature Phase Behavior of Bitumen Residue Fractions

Research Staff: Richard McFarlane (MSc); Collaborator: J.M. Shaw.

Following the approach of Sheremata in defining bitumen as a mixture of molecular species, this project would calculate the pressure-volume-temperature behavior of vacuum residue materials at 200-350 °C using a group additivity method. The predicted results would then be compared to experimental results. This research would provide a completely new approach to predicting the thermodynamic behavior of high-boiling fractions, rather than relying on the extrapolation of data from lower boiling fractions. For example, the correlations that form the basis for commercial software packages such as HYSYS were originally developed for gas oils.

2.5 Secondary Upgrading

(10) Surface studies of Nitrogen Compounds on Mo (110)

Research Staff: Wa’el Abdallah (PhD); Collaborators: Alan Nelson

This project is exploring the adsorption and denitrogenation reaction networks of basic and non-basic organonitrogen species on model catalyst surfaces. Using surface science techniques and molecular simulations, Ph.D. student Wa’el Abdallah is studying the adsorption of pyridine and pyrrole on Mo(110) and C/N-modified Mo(110) to develop fundamental insight into HDN reaction networks. This work has given us new insight into the detailed interactions of pyridine with a metal surface. Through additional studies, this approach will serve to; (1) determine the correlation between surface composition and activity, (2) identify the molecular adsorption species and reactive intermediates, and (3) investigate the way in which carbidic (and nitridic) overlayers affect reaction networks and surface species. The development of new catalysts that are selective to C-N bond scission, through and understanding of catalyst fundamentals, is the ultimate purpose of this research.

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