Towards Realisation of Untapped Oil Resources via Enhanced THAI-CAPRI Process Using Novel Catalysts

Lead Research Organisation: University of Birmingham
Department Name: Chemical Engineering

Abstract

Extensive unexploited resources of heavy oil and bitumen exist, for example in Canada and Venezuela, as well as heavier deposits under the North Sea UK, which could potentially be utilized as the production of conventional light crude declines. Heavy oil and bitumen are more difficult to recover than conventional crude, requiring mining or specialized in-situ recovery techniques followed by upgrading to make them suitable for use as a fuel. Toe to heel air injection (THAITM) is an in-situ combustion and upgrading process in which air is injected to a horizontal well to feed combustion of a small fraction of the oil (up to 15 %). The heat generated causes the oil to flow along the well, where thermal upgrading reactions occur, leading to upgrading of the oil (by 4-6 API). CAPRI is a catalytic add-on to THAI in which catalyst is packed around the well to effect further catalytic upgrading reactions, such as hydrotreatment, however previous studies showed that the catalyst lifetime and process effectiveness are limited by coke deposition upon the catalyst. Additionally the costs and challenges of packing the well with pelleted catalyst prior to starting up also make the CAPRI process less economically attractive.
The current proposal seeks to develop cheap, effective nanoparticulate catalysts which could be conveyed into the well by air or as slurry during operation, thereby avoiding the requirement for packing the well with catalyst prior to start up and to reduce the amount of deactivation and bed blockage that occurs by coke deposition upon pelleted catalysts. Initially, readily available iron oxide nanoparticles will be tested as a base-case. Nanoparticulate catalysts will also be prepared by supporting the metal upon bacteria, using a method in which metal containing solution is reduced in the presence of a bacterial culture, followed by centrifuge and drying which kills the live bacteria. The method has the advantages of being able to utilize scrap metal solutions and thus facilitate recycling of metals from waste sources, and it may be tuned to engineer nanoparticles of desired size and properties (e.g. crystal structures). Here we seek to develop, test and scale up the production of biogenic Fe catalysts for the upgrading of oil in the THAI process. Furthermore, waste road dusts contain deposits of catalytic metals from the exhaust of vehicular catalytic converters and these will be converted into cheap mixed metal catalysts by economically proven biohydrometallurgical methods for testing in the THAI process.
Key to the effectiveness of utilizing nanoparticle catalysts will be the ability to contact them with oil in the mobile oil zone and flame front of the well, where the reaction is taking place. Studies of the rock void structure will be carried out using techniques such as X-Ray microtomography. Monte Carlo and Lattice Boltzmann simulations will be used to study the pneumatic conveying of particles into the reservoir and to study penetration and distribution of particles within the void space of the rocks. Conveying of slurry catalysts and process performance will be modeled using STARS reservoir simulation software.
Evaluation of the different catalysts will be performed experimentally under real conditions using a rig developed under a previous project. The effect of variables such as gas:oil ratio, temperature, pressure and gas composition will be studied experimentally, in order to select the best catalyst and understand the conditions required for maximum upgrading. The experiments will also indicate whether catalyst deactivation occurs during use and enable conditions to be tuned to avoid deactivation.

Planned Impact

The project will deliver new catalysts, technology and intellectual property, which will be highly marketable to industry. The project is of direct commercial relevance to Petrobank Energy and Resources Ltd, who are testing THAI-CAPRI technology in Alberta, and intend to carry out field trials of the process. The use of recycled materials such as metal wastes and road dusts to provide a cheap catalyst, together with deactivation resistance will improve the economics of the CAPRI process. The 'holy grail' would be if the upgraded bitumen has an API gravity approaching 20 degrees, where it can be pumped without using diluent, providing substantial cost savings. Other companies such as Shell, Exxon and Husky oil, have stakeholder interests in the oilsands and would be interested in technology to exploit them, which could occur through licensing of THAI-CAPRI technology.
The project is particularly timely. The rising oil prices and uprisings in Middle Eastern countries, increase concern for the security of supply of lighter crude oils and cost of transportation fuels. Plans by governments to re-introduce building programmes of nuclear power will be delayed or shelved by renewed debates following the recent disaster at Fukushima. The recovery and upgrading of Canadian heavy oils could provide a solution, being a reliable source of fuel from a stable country. However concerns exist about oilsands extraction and carbon dioxide emissions, in particular from mining and steam assisted gravity drainage methods, which require large volumes of natural gas to be used for steam generation. By contrast, the THAI-CAPRI process has a lower environmental impact because it does not require stripping of the forest land above the well and does not use external natural gas supplies to generate steam, thereby having a lower carbon emission.
The project team has considerable expertise in technology transfer activities, particularly Prof Macaskie, who holds a London Technology Network Business Fellowship, which targets various networking and outreaching events to access potential collaboration and exploitation events. Prof. Malcolm Greaves (co-inventor of the THAI CAPRI process) has 30 years experience of improved oil recovery techniques, has links with Petrobank in Canada, as well as other oil companies (e.g. Shell), which could provide routes for exploitation of the technology developed under this project.
The technology transfer and IP rights concerning the project will be managed by the Technology Transfer companies of the 4 Universities. The project will deliver three research fellows, who will be highly trained in bio-catalytic manufacture as well as skilled in surface analytical techniques, chemical synthesis and business development. It is expected that Joint Venture Licensing or spin out will occur around 2014.
The work will be widely disseminated through a range of events, which will include academic publications and conferences, technical presentations at subject group meetings (e.g. IChemE), media dissemination (radio and TV), and school visits. For example, the work of Angela Murray on road dust recovery has featured widely in the media, both in the national press and on BBC TV Midlands Today and previous work by Greaves and Wood on THAI CAPRI on BBC Radio 4 Material World. Pro-actively and following a hugely successful EPSRC delivery of impact award (clean energy) we will deliver an interactive workshop in to schools and also anticipate a Royal Society Summer Exhibition ('Oil can be green') combining this project with two concurrent projects ('Wood/Macaskie') on CO2 trapping into value products.

Publications

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Al-Marshed A (2015) Effectiveness of Different Transition Metal Dispersed Catalysts for In Situ Heavy Oil Upgrading in Industrial & Engineering Chemistry Research

 
Description The Toe-to-Heel Air Injection (THAI) Catalytic Process In-situ (CAPRI) was previously developed, investigated in an experimental project by the current team and tested in the field by Petrobank to comprise a pelleted refinery catalyst packed around a horizontal oil well to augment the thermal cracking reactions experienced through THAI with additional catalytic upgrading. However, catalyst deactivation can lead to limitation in the catalytic effect and shorten the lifespan of the catalyst. The present award investigated the use of dispersed catalyst that could be conveyed in to the well, or pumped as a slurry to the combustion front where it's needed for the upgrading reaction. It was found that the produced oil from dispersed ultrafine Co-Mo/Al2O3 catalyst (dp = 2.6 micron) exhibited superior light oil characteristics and quality than that produced with the fixed-bed of pelleted Co-Mo/Al2O3. The API gravity of the feed oil was 13.8 degrees and the produced oil showed an increase of 5.6 degrees in the fixed bed and 8.7 with the dispersed catalyst. The ultrafine particles presented high surface area to volume ratio, reducing the chances of pore plugging, have more accessible reaction sites per unit mass, and lead to enhanced cracking of macromolecules. Moreover, the reduction of sulphur of 38.6% and (Ni + V) content of 85.2% in the produced oil show greater heteroatom removal compared to 29% (sulphur) and 45.6% (Ni + V) observed in the product from the fixed-bed.
Significant upgrading has also been described for dispersed nanoparticulate hematite and several un-supported transition metal nanoparticles, namely MoS2, NiO and Fe2O3. Although the extent of upgrading was modest compared to thermal cracking, these dispersed materials significantly uppressed coke formation, with the remaining coke having a sponge-type character which may find use as an industrial fuel compared with typical coke materials generated from thermal cracking. These studies highlight the potential for the combination of dispersed nano-sized catalysts with the in situ upgrading offered by the CAPRI process, as an alternative to previously used pelleted hydroprocessing catalysts.
Methods developed to support catalytic metals as nanoparticles on bacterial supports can have advantages of utilising metals from scrap sources such as spent catalytic converters and electronic goods, and bacteria from second life processes such as fermentation. Bionanoparticles (BioNPs) were manufactured and tested for the upgrading of heavy oils, comprising Pd/biomass, biomagnetite and Pd augmented biomagnetite (Pd-BnM). The level of upgrading was comparable to commercially available and previously tested catalysts, but significant decreases in the coke content (3 wt% for 9.5 wt% Pd-BnM versus 10 wt% for thermal cracking) and associated increases in liquid content (~90 wt% for 9.5 wt% Pd-BnM versus ~79 wt% for thermal cracking) demonstrate the potential for the use of Pd-augmented biogenic magnetite as a catalyst in the THAI CAPRI process.
The reservoir itself contains metals in the sandpack which potentially could be mobilised in-situ and converted into an active catalyst. Preliminary tests were carried out to investigate the use of bacterica to convert reservoir metals in a sample of untreated oilsand into catalysts suitable for oil upgrading.
Exploitation Route The findings are of interest to oil companies. Primarily the work is of interest to the sponsor Touchstone exploration, who operated THAI oil wells in the Alberta oilsands of Canada. A presentation was made of the results of this project at their offices in March 2015. However their investment is now changing towards easier to recover oils, e.g. in Trinidad. Other companies are also interested in the technology and a workshop was held at Petrochina to present results of this project in August 2015. Companies could potentially use the findings of this research to guide the conditions and catalyst selection for use in further field trials of the THAI-CAPRI Process, and reduce costs of large scale trials by informed decisions based on the laboratory catalytic upgrading data gained through this project. Petrochina has since become a project partner in a related EPSRC project. Academics are also interested in the catalyst development, characterisation and testing that has been carried out in this project. The process inventor Dr Alex Turta is compiling a report on the research findings, including from this project, and future commercial opportunities for the THAI-CAPRI process.
Sectors Chemicals,Education,Energy,Environment,Transport

URL https://www.researchgate.net/publication/305815742_Upgrading_of_heavy_oil_by_dispersed_biogenic_magnetite_catalysts
 
Description The findings of the project have been presented at workshops to industrial oil companies involved in heavy oil extraction, namely Touchstone Exploration (Calgary, Canada, March 2015) and Petrochina (Beijing, China, August 2015). These companies will use the findings to inform their research on heavy oil extraction, and potential planning of field trials based on in-situ oil recovery techniques. Discussions have also been held with Repsol oil company (March 2015) who are interested in a related refinery upgrading process for heavy vacuum residue oils. The process inventor of CAPRI, Dr Alex Turta, has compiled a report including the findings and publication list from this project to act as a source of information for companies interested in the deployment of THAI-CAPRI in-situ oil recovery techniques. The deployment of the findings of this project in industry could eventually lead to more stable fuel supplies, and reduction of environmental emissions e.g. CO2, sulphur, polluted water, compared with alternative extraction technologies such as steam-based recovery techniques and surface mining.
First Year Of Impact 2015
Sector Chemicals,Education,Energy,Environment,Transport
Impact Types Economic

 
Description Electromagnetically-assisted Catalytic-upgrading of Heavy Oil (ECHO)
Amount £707,442 (GBP)
Funding ID EP/N032985/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Academic/University
Country United Kingdom
Start 11/2016 
End 10/2019
 
Description Touchstone Exploration 
Organisation Touchstone Exploration Inc.
Country Canada 
Sector Private 
PI Contribution Carrying out testing of in-situ upgrading of heavy oil using laboratory rigs under different experimental conditions. Testing of the heavy oil after recovery to determine the level of upgrading achieved.
Collaborator Contribution Touchstone Exploration have provided a contribution of £30,000 towards laboratory expenses (As promised in the original grant application). They have also provided samples of partially treated heavy oil from their in-situ combustion well at the Kerrobert Oilfield in Alberta Canada, and have provided virgin oilsand samples for additional tests.
Impact Data regarding upgrading of heavy oil, such as viscosity, API gravity, simulated distillation results of oils processed using different catalysts and process conditions such as temperature and pressure.
Start Year 2012
 
Description Association of Science Educators Annual Conference, University of Birmingham, 8th-11th January 2014 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach Regional
Primary Audience Schools
Results and Impact Also at this conference Dr Angela Murray was invited to give a talk (Friday 9th January 2014) in the conference lecture series 'Biology in the Real World.' The audience was comprised of both teachers and secondary school children. There were around 100 - 120 people at the two workshops. The teachers and pupils asked questions and were interested in the practical applications of engineering in the real world.

There has been an increase in interest in Applicant Visit Days at the University of Birmingham.
Year(s) Of Engagement Activity 2014
 
Description BBC World Service Radio Programme 27th January 2014 BBC World Service show 'The Forum' with Bridget Kendall (episode title 'Modern Alchemy'). Also broadcast on Radio 4, 22nd February 2014 at 11am. 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Media (as a channel to the public)
Results and Impact This show was recorded at the BBC studios in London and discussed the problems with our current rate of consumption of natural resources (especially metals) and presented potential ways to reduce this impact via various panel members research areas. The show was 45 minutes long and as it was broadcast on the World Service the audience would have been large (>500 in your categories list).

Raising the profile of UK Science, the University of Birmingham, EPSRC funded research to an international audience.
Year(s) Of Engagement Activity 2014
URL http://www.bbc.co.uk/programmes/b03vtcwn
 
Description Feature on the BBC One Show 
Form Of Engagement Activity A magazine, newsletter or online publication
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Media (as a channel to the public)
Results and Impact A feature presentation about metal recovery was made on the BBC One Show, by Dr Angela Murray, a postdoc in my group. This will have raised the profile of research at the University of Birmingham to a national audience.

Increasing number of undergraduates applying to study at the University of Birmingham in Chemical Engineering
Year(s) Of Engagement Activity 2014
URL http://www.bbc.co.uk/programmes/b03zcvm2
 
Description Otley Science Festival Tuesday 11th November 2014 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Public/other audiences
Results and Impact Dr Angela Murray was an invited speaker (one of three) for the Science Café Evening at the Otley Science Festival (organised by Marty Jopson mentioned above in outcome 4). Science Café's are after dinner talks organised to allow members of the public to question academics on their current research. My talk was entitled 'Where there's muck there's brass. Precious metals from road dust' and this one had a specific focus on heavy oil upgrading catalysts as our end product (as opposed to fuel cells, industrial catalyst etc.).

Questions from the audience. Increased interest in recycling of metals.
Year(s) Of Engagement Activity 2014
 
Description School visit (Wolverhampton) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact Raised level of interest in science from girls school. Positive comments from teacher.

High interest in science from girls attending the talk.
Year(s) Of Engagement Activity 2014