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Page added on March 15, 2014
New Catalyst Could Revolutionize Natural Gas
The Scripps Energy and Materials Center (SEMC)
Transformer. A catalyst made with thallium (orange) readily converts methane (gray and white molecule) into liquid methanol, a starting point for producing commodity chemicals and fuels.
Natural gas is great at heating our houses, but it’s not so good at fueling our cars—at least not yet. Researchers in the United States have discovered a new and more efficient method for converting the main components in natural gas into liquids that can be further refined into either common commodity chemicals or fuels. The work opens the door to displacing oil with abundant natural gas—and reducing both carbon emissions and society’s dependence on petroleum in the process.
Over the past several years, the United States and other countries have undergone an energy revolution as new drilling techniques and a process called hydraulic fracturing have made it possible to recover vast amounts of natural gas. Today, most of that gas is burned, either for heating homes or to drive electricity-generating turbines. But chemical companies have also long had the technology to convert the primary hydrocarbons in natural gas—methane, ethane, and propane—into alcohols, the liquid starting materials for plastics, fuels, and other commodities made by the train load. However, this technology has never been adopted on a wide scale, because it requires complex and expensive chemical plants that must run at temperatures greater than 800°C in order to carry out the transformation. Converting petroleum into those commodities has always been cheaper, which is why we’ve grown so dependent on oil.
Two decades ago, Roy Periana, a chemist at the Scripps Research Institute in Jupiter, Florida, started looking for metal catalysts that could transform natural gas into alcohols at lower temperatures. He knew he needed to find metals that were deft at breaking the carbon-hydrogen bonds that are at the heart of methane, ethane, and propane, short hydrocarbons known as alkanes, and then add in oxygen atoms that would transform the alkanes into alcohols. But all the catalysts he discovered—including platinum, rhodium, and iridium—are rare and expensive, and the technique was never commercialized.
Periana says that what he didn’t appreciate at the time was that to be a good catalyst, the metals need to do another job in addition to transforming C-H bonds into C-O bonds. That’s because in a reactor, these catalysts are surrounded by solvent molecules. So before a metal can break an alkane’s bond, the alkane must first nudge a solvent molecule aside. It turns out that the expensive metals Periana was using aren’t so good at that part of the process: They require extra energy to push the solvent molecules out of their midst. Periana’s team realized that the different electronic structure of more abundant “main group” metals means that they wouldn’t have to pay this energetic price, and, therefore, might be able to carry out the C-H to C-O transformation more efficiently.
It worked better than he expected, Periana says. When he and his colleagues at Scripps and Brigham Young University ran a methane reaction with thallium—a main group metal—alkanes pushed the solvent molecules aside 22 orders of magnitude faster than when the reaction was run with iridium, reducing the overall energy required by about one-third, they report online today in Science. The success brought other benefits as well. The reaction runs at 180°C, and works on all alkanes at the same time, unlike the conventional natural gas conversion technology that works on only one species of alkane at a time. That could make it far easier, and thus potentially cheaper, to build chemical plants to convert natural gas to liquids using the new approach.
“This is a highly novel piece of work that opens the way to upgrading of natural gas to useful chemicals with simple materials and moderate conditions,” says Robert Crabtree, a chemist at Yale University. But that way is not entirely clear yet, Periana cautions. For now, the chemistry works one batch at a time. To succeed as an industrial technology, researchers must work out the conditions to get it to work on a continuous basis, he says. If they do, it may one day make it cheaper to derive commodity chemicals and fuels from natural gas than from petroleum. And that would be an energy revolution indeed.
10 Comments on "New Catalyst Could Revolutionize Natural Gas"
rockman on Sat, 15th Mar 2014 2:26 pm
Not a new idea of course. In the 1970’s researchers at Mobil Oil discovered that an acidic zeolite called ZSM-5 was able to catalyze the conversion of methanol into both olefins and hydrocarbons in the gasoline range.
I watched this from far when I worked for the MOC in the mid 70’s. At the time they were focused on doing this in New Zealand since they had a good bit of NG without much market so it could be acquired cheap. Economics still didn’t work. So some folks say they can do it now at an economic level. That’s fantastic. Get back to me when they are selling a significant volume at a price lower than oil derived gasoline. In the meantime I’ll just assume their words are empty until I’m proven wrong.
It cost very little to publish a report stating one can economically do X compared to actually doing X. OTOH investing in the stock of such a company could be a great investment. Yeah, yeah…that’s the ticket. LOL.
Nony on Sat, 15th Mar 2014 3:59 pm
methane to methanol is not a new concept. Issue is making it commercial. (huge prize if you can.) I actually interviewed for a job with Exxon to try to develop it. (Should have taken it and chased LSU skirt, but that’s another story. Go tiger, go.)
I’m not an expert on the specific chemistry or even industrial chemical practices. But my first take, is beware, beware, beware Science and Nature magazines. They are full of hype. Serious scientists note this all the time (worst in life sciences). While this will not be a stem cell or Schoen type scandal (chemists generally react what they say they did), the applicability is likely way hyped. And if you read to the end of the piece, you’ll finally see the caveats.
My first concerns are that it appears that the reaction is not truly catalytic. (You have to regenerate the catalyst). Read the comments on the article and some old salt has the same criticism. He also has a bunch of concerns about the TFA and the Tl. I’m not worried about TFA (it’s less harsh than sulfuric). Tl, granted, is poisonous. But I wonder if that can be handled. The regeneration and the activity are more the concerns.
I do wonder about a solid carrier of the Tl, though. Hmm…puts me in mind of an old idea I had once.
J-Gav on Sat, 15th Mar 2014 4:19 pm
The conditional mode used at the end of the article says a lot: “And that WOULD BE an energy revolution indeed.” Good luck researchers! But I’m not yet in breathless anticipation …
rockman on Sat, 15th Mar 2014 4:38 pm
Considering the motivation inspired by $100/bbl oil folks are pursuing every possible alternative that comes close to making sense. After all it has us spending $billions chasing the shales. If whatever works can happen I have no doubt it will. But given we’re years into high priced oil I think it’s telling that we’re not seeing even the initial commercial development stage of any tech that will “save us”.
Northwest Resident on Sat, 15th Mar 2014 5:59 pm
By the time they get the “New Catalyst” into economically viable full production mode, we’ll have already harnessed fusion energy and mankind will be heading out to the stars to populate new worlds. So, why even bother?
Ok, that’s sarcastic. Still Saturday morning, so what the heck…
shortonoil on Sat, 15th Mar 2014 8:40 pm
The world now produces 117.5 tcf of NG per year. On an energy bases to replace the 72 mb/d of conventional crude now produced (by our calculations) would require another 207 tcf per year. With conventional NG production now declining by 24% per year, and shale gas wells having a 65% first year decline rate, it is not likely that there is going to be much NG to crude replacement over the next couple of decades.
The number of discoveries that get from the lab to an operating pilot plant can be measured in the less than 1% category. From the pilot plant to full scale commercial application is even less. But it’s like Rock said, it’s a good story to sell to potential investors!
http://www.thehillsgroup.org/
Nony on Sat, 15th Mar 2014 10:35 pm
1. Short, you all keep touting that first year decline from shale gas as if it means anything or is new info. Why do you think the % share of gas from shale is growing when the first year decline form it is higher than from conventional? It’s like saying hotels in Manhattan cost more than hotels in Texas. That still doesn’t tell you which overall market is larger.
2. If you took 10% of current gas production (either new production or even robbing existing markets by price competition) and changed it to useful liquid, it would give you an extra 5% oil equivalent. That would have HUGE impact on price, especially if OPEC could not keep discipline.
3. When I interviewed at ERDL in 1999 for a gig working on methane to methanol, they specifically talked about the issue of upstream gas that was flared. (I.e. free) And that if you could convert it to liquid, it would be easily gathered (since the oil was gathered).
***
This is a GINORMOUS market opportunity if you can get it to work economically. The only problem is, we can’t. 😉 But if you could…well…STFB, baby. Don’t poo poo that. It would be HAAAAYUGE.
Ronny on Sun, 16th Mar 2014 2:53 pm
I was at Exxon in the late 70’s. Our laboratory specialized in the development of catalysts for the production of methanol as well as hydrocarbons. We got patents on many of the processes discussed here, including thallium based catalysts for methanol production. THe economics didn’t work then as well as the toxicity issue of Thallium. It is difficult to prevent leaching of the thallium from the catalyst and consequent environmental issues resulting from it.
Nony on Sun, 16th Mar 2014 3:10 pm
1. Ronny were you at ERDL (BR)? Or in NJ?
2. I know very little about this, but was surfing on the net about it last night, prompted by this discussion. There is a JACS review of several different transition metal oxides as catalysts. Also a review of different coordination compounds. I didn’t find a good free overview (Wiki article not very good). There is something in some paywalled specialty encyclopedia. I guess I could pay for it or see if the state uni library has it.
2. I also saw that Shell had cancelled a US GTL plant, recently. But SASOL is going ahead with design work for a plant in Louisiana. The capital is not committed yet for the plant itself (10 billion +). But paying for design shows that it is more than just press release. I guess it’s just conceptual design at this stage, not detailed drawings. Still…
http://theadvocate.com/news/business/7682706-123/sasol-awards-technip-contract-for
I wonder how they can really make money unless gas gets a lot cheaper or diesel more expensive. I guess I wonder about the local pricing also (I heard gas is cheapest in some areas of the Marcellus), but maybe it is cheap in LA also.
3. Clueless question: is there value for converting the methane to formaldehyde or formic acid? IOW, obviously CO2 is too far. But if you could get selective oxidation that went further than methanol is that fine too? I have no idea how hard/easy it is to convert those back to methanol or what their pricing is on their own.
Nony on Sun, 16th Mar 2014 3:28 pm
4. Also, from a chemical standpoint, is it easier or harder to selectively oxidize methane or the larger alkanes. Obviously, C1 is the cheapest, but we are starting to get a glut of C2 (price tracking with methane, not with oil) and even C3 and C4.