The chemistry of asphaltenes

My oil sands book, now on Kindle.

Rather amazingly, in my little world, AmazonI recently posted my award-winning book Bitumen: The people, performance and passions behind Alberta's oil sands, on Kindle; here's a link. 

This book covers the written record of Alberta's oil sands - the world's second-largest petroleum resource - from 1715 to the present day. The focus is on men and women who contributed to the enormous scientific and technological advances that enabled the oil sands sector to become a petroleum giant. Equally, it reviews recent developments that make much of the sector at best marginally economic.

According to renowned petroleum historian Earle Gray, the book "is a powerful addition to the corpus of writing about Canada’s petroleum industry. But it is more than history: it is an account of current challenges and visions of future possibilities. While he focuses on the vast oil deposits in the Alberta oil sands, he also sheds wide-ranging light on other aspects of the Canadian petroleum industry’s history.

"The author "has woven his story from an impressive array of diverse sources, as well as intensive and extensive research," Gray continues in his foreword. "The result is a must-read for anyone interested not only in the history of the Canada’s oil business, but perhaps more importantly, Canada’s economic history."

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Does a study of asphaltenes move the oil sands industry forward? It depends: Are  you in an academic lab or an industrial one?

By Peter McKenzie-Brown

Dr. Paul Hazendonk of the University of Lethbridge specializes in nuclear magnetic resonance (NMR), a discipline related to sub-atomic physics, which is basic science. He’s passionate about the importance of fundamental research which, in his view, doesn’t get the respect it deserves.

Investing entirely in applied science is like “eating our seed grain,” he says. “The good ideas originate with basic science. You have to be patient. If you aren’t generating new ideas, ultimately you’re going to run the well dry.”

Academically prolific – he has received two dozen research grants, published 66 peer-reviewed papers and given 125 technical presentations – Hazendonk was the lead researcher in a team that presented published its findings in a highly technical paper in the American Chemical Society journal Energy and Fuels, which Hazendonk calls “the premier journal in oil chemistry for fossil fuels.” The paper describes in chemical terms the architecture and inter-molecular interactions of asphaltenes – the most complex and gunkiest constituent of bitumen. Chemically speaking, asphaltenes include elemental carbon, hydrogen, nitrogen, oxygen and sulfur, plus molecules of nickel, iron and vanadium, for example.

The next stage of his work will be to get better NMR images of the structure of asphaltenes through the wonders of fluorine chemistry.  “We want to distributes fluorine evenly through the asphaltene molecules, and we want to make sure it doesn’t chew up the molecules – fluorine is even is even more reactive than oxygen. If we want to better understand this molecule, we need to be able to read fluorine signals because they give us a much more easy to read profile. We’re going to introduce 1% fluorine to replace 1% hydrogen, and that is going to make the spectra a lot less blurry, a lot easier to walk across than when you’re using hydrogen. We’ve got to be careful that we just got the right conditions. It will take a few years of the graduate student’s life to get those conditions just right….” And life in the lab goes on.

In a news release about this publication, the university’s public relations department went over the top, suggesting that this discovery would contribute enormously to the oilsands business – enabling the industry to cut costs by reducing the “energy overhead” involved getting bitumen out of the ground, transporting and upgrading it.

“Excuse the pun,” says Hazendonk, “but we have to focus our energies. Right now [the industry is] throwing a lot of heavy guns at bitumen extraction, when just a rifle might suit. There are a lot of things we just don’t know – for example, the amount of energy that goes into all the processes. The only way you can reduce some of these costs, really, is to have a better understanding of how asphaltenes work.”  He adds that more efficient operations lead to fewer greenhouse gas emissions, making the sector more environmentally sustainable. “The better you understand the basics, the cleaner the petroleum product [you can produce]. If the petroleum isn’t clean, it’s harder to transport, harder to pipeline because asphaltene particles aggregate, cling together. [In pipelines] they can be like cholesterol in arteries, creating blockages. The metals they contain can gunk up refinery catalysts. Sometimes they actually shut the processes down.”

The problem with academia

If these claims about the implications of this study seem too good to be true, that’s because they are. At least that’s the position of Randy Mikula, one of the paper’s authors. The oilsands consultant describes this statement as “typical of what comes out of the university’s PR department. They try to make a big deal out of what is really just interesting science. Unfortunately, it’s all too common. They tend to forget that they are there to train highly qualified people and hopefully those highly qualified people would go out and do the kinds of things that are being claimed in that press release. The fundamental science represented in this paper has nowhere near that big an impact.”

“This is just one piece of the puzzle,” he continues. “It isn’t going to solve the argument about the structure of asphaltenes. It’s an interesting approach, with nuclear magnetic resonance, but the suggestion in the press release that we are creating a revolution is leading us down the primrose path. We’ll see what the rest of the technical community thinks about it. [In my view] it’s a niche contribution at best.”

Anil Jain is another serious critic of these claims. Like Hazendonk, Jain has a PhD in chemistry, with a specialty in catalytic reactor design and operations. However, he also has a strong background in industrial research and development. He first worked with Union Carbide, then for Petro Canada, where his career path took him from research to refinery management, oilsands operations and then finance. After the merger, he retired from Suncor as senior director of supply chain services.

The paper is fine, he says. “I assume it is peer-reviewed and all that. The problem is with the press release, which is really overhyped. It’s all generic stuff. The suggestion that it is going to quickly have an impact on the oil sands industry just doesn’t make sense. [And while the] use of a fluoride apparatus to study [asphaltenes] may be helpful, so what? Is it important to nail this stuff down to the nth degree? Do we really need to know how much the molecule resonates and how much it spins and that kind of thing? At some point you have to say ‘I understand it well enough,’ and then move on.” Now he’s on a roll.

“Let’s look at the stages of research,” he says. “You begin with analytical work, which is what is being done in this paper. Let’s assume that this work is successful. Then you go through five stages. The first is a bench-scale effort. [This gives you] some hypotheses about what can happen from a piece of research.” At that point, a typical corporation conducts tests to see whether they can go from that step to a technology that will improve the upgrading process.

Perhaps the bench-scale tests will justify pilot plant experiments. “This is significantly larger, and it can involve a lot of equipment and machines.” If that works, “you build a demonstration facility, which will maybe cost $50 or $100 million. The idea is to demonstrate that the idea will really work. And if it does, you apply it to a large-scale plant. When I was working on the upgrading of bitumen we often looked at reports on asphaltenes, and did research that took us through all of those stages – bench scale, pilot plants and so on. But our focus was not to understand asphaltenes in the analytical sense. We wanted to work around the issue – to make the business work better.”

How often do new ideas work? The numbers are Darwinian. “Think about it this way,” says Jain. “Suppose the analytical work produces 1,000 ideas. Out of that, maybe 100 will make it to bench-scale testing. Maybe 20 will make it to the pilot plant stage, five to the demonstration plant and one to the final, commercial stage.”

There are many reasons why ideas don’t work. “Maybe they are unsuccessful technically. Maybe there are better, cheaper solutions.” Whatever the case, it’s important to understand that seeing an idea collapse into the scrapheap of history doesn’t mean failure. “Think about cancer. How many times have we heard about a breakthrough in cancer research? We hear about it all the time, but cancer is still with us. What happens is that the media get all excited and publish the headline. They are way ahead of the science.”

Mikula agrees. “The distance between fundamental research and commercial application can be huge. It can take many, many, many years. One of the problems the academic community faces is that the oil industry compared to many other parts of the resource sector is very, very high-tech. They do a lot of research in-house, and they do it confidentially – perhaps by contracting the work out to other research institutions. I wouldn’t be in the least surprised if some of the higher-end research facilities are already familiar with this result, but for reasons of their own haven’t published it.”

Spending in the lab…

“A lot of organizations, both public and private, are doing this kind of research,” he adds. “Researchers are constantly publishing papers, and a huge amount of information is in the public domain. However, there is an awful lot of information that is not made public. The reason, of course, is that so much work is funded by corporations with commercial interests, who want to gain a competitive advantage over their peers. As Jain puts it, companies fund research “with the hope that one day they can realize a significant return on their investment. Those companies don’t want their competitors to know what they’re doing.”

A recent report on corporate R&D funding listed four oilsands companies and one gas company among Canada’s 25 top 2012R&D spenders. The top spenders were CNRL ($270 million), Cenovus ($264), Imperial Oil ($201), Syncrude ($157) and EnCana ($127). Suncor, which for some reason didn’t appear on the 100-company list, budgeted $175 million for R&D spending in 2013, but it is also heavily involved in advanced (and expensive) field tests and demonstration projects.

 “It’s the bread-and-butter” of these companies to do research “and patent the stuff at the appropriate time,” says Anil Jain. He cautions against expecting a quick payout. Companies don’t apply for patents until a technology is “close to commercialization, or when they think their information might be at risk of being leaked out. Assuming these things don’t fizzle out in the early years, [commercial applications] might take 30, 40, 50 years to materialize.”

In Canada, the petroleum industry’s top R&D spenders invested about $1 billion in research in 2012, compared to $1.9 billion for Bombardier and $1.5 billion for Blackberry. When the oilsands are such a vital part of the Canadian economy – bitumen exports alone now make up 4% of Canada’s GDP – why did they put such a small amount into R&D funding?

According to Randy Mikula this is partly because most big oil companies are multinational. Exxon, BP, Total and Shell, for example, are the parent companies of oilsands operators, and they conduct much of lab work elsewhere. Shell and Total have labs all around the world, including facilities in Calgary, and Exxon subsidiary Imperial Oil also has a lab in Calgary.

Of course, in terms of scientific research into the oil sands, the granddaddy of them all is the University of Alberta, which in 1921 hired Karl Clark to investigate the oil sands. Today, more than 1,000 U of A researchers study the oilsands and their environmental effects.

Syncrude has an Edmonton research facility focused entirely on the oil sands. “There’s tremendous work being done there, with a lot of it being contracted out,” according to Mikula – for example, to the CANMET (Canada Centre for Mineral and Energy Technology) research centre at nearby Devon, Alberta. This federally-funded 130-person lab specializes in oil sands and heavy oil, focusing in areas the organization describes as extraction and tailings; water management; multiphase systems; upgrading oil sands and heavy oil; and future fuels and emissions. CANMET Devon works on about 150 client-sponsored projects a year, with partners the agency describes as “small [clients] to major international energy corporations.”

And in the field

Based on Anil Jain’s model of five stages of research and development, the big spending on the oilsands isn’t done in the laboratory, but in the field. Here’s an illustration of a potential game-changer that would involve big spending in the field.

In a recent research report, Calgary-based Peters & Co. discussed eight emerging and developing technologies being tested in SAGD operations. Oilsands Review readers will be familiar with electro-magnetic heating; solvent injection; thermal cracking and solvent de-asphalting to turn bitumen into pipeline-ready heavy oil; the application of heated solvents; the injection of non-condensable gas with steam; the addition of solvents to steam; and steam flooding.

Not so the SHORE process, which the Peters’ organization says may offer “the potential for the most significant game-changer.” Developed by two research groups within ExxonMobil, the acronym SHORE refers to “slurrified heavy oil recovery extraction.” This experimental in situ technique has three stages.

First, the operator produces a bitumen-sand-water slurry from an in situ oilsands formation by pumping high-pressure water into the reservoir. This relieves stress caused by overburden and increases the reservoir’s porosity and permeability. Second, the slurry is processed at surface to extract bitumen. According to a paper delivered to the Society of Petroleum Engineers, the project would likely recover more than 50% of the bitumen produced per well, with wells producing some 1,000 to 2,000 barrels per day. “The high well production rates translate to draining of any given reservoir volume in 2-3 years,” added the authors. Finally, the cleaned tailings, sand and other wastes would be injected back into the reservoir.

“We have developed a first principles numerical model of the process that fully accounts for fluid flow and sand flow under reservoir conditions to simulate and understand the process, according to the SPE paper. “We have also developed a large scale…laboratory system to demonstrate the technical feasibility of the process under reservoir conditions.”

The eight authors caution that “the technology is still in the early stages of development, but the laboratory and numerical modeling efforts demonstrate promising technical potential of the process at a field-scale. The ability of the process to work in thinner and more geologically complex reservoirs than other in situ processes, and with lower CO2 and surface footprints than thermal and mining processes, could make this an attractive alternative recovery process for shallow to intermediate depth, in situ bitumen resources.”

The conclusion Peters & Co. reaches is also cautious, but enthusiastic. The firm says the process could “allow for the development of substantial volumes of resources (thin pay or low saturation or at shallow but un-mineable depths) that cannot be recovered with any other existing technology. That said, it will take…time and capital to develop [it] to commerciality.”