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Fugitive Methane, Eating Elephants, and Brewing Quarantine Ethanol

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June 11, 2020

by Jim Lane (Biofuels Digest) … We left the discussion with a hint about the potential conversion of methane to methanol, which can serve as a powerful chemical building block or, in China most prominently, as a fuel. We’ll pick up from that point today.

Wolf Ron Cascone

Here’s some background on methane to methanol conversion from Wolf Cascone. And he responded with some provocative math on “fugitive methane”:

CO2 as a chemical has little or no value in most cases (ex beverage carbonation, etc.). CCS has no ROI, and CCU is challenging.  Yet, the EU intends to tax carbon at around €30/ton of CO2. Methane has, say, 23 times per mole the GHG potential as CO2.   Should its emissions be taxed at €30 x 23 x 16/44= €250/ton = $279/ton? Methane is now selling for $2/MM Btu = $128/ton.  A typical leak rate of 5% would add $14/ton, over a carbon tax of $91.5/ton.  Thus, the current taxed price of methane should be $233.5/ton = $3.65/MM Btu

 

You have to forgive Wolf Cascone about the unfamiliar English dialect that top science consultants write in. In science, standard English has been forbidden and everyone writes in a dialect known as TLA, which stands for Three Letter Acronym. So, CO2 is carbon dioxide, CCU is carbon capture and use, CCS is carbon capture and sequestration, GHG is greenhouse gas emissions, ROI is return on investment, BTU is British Thermal Unit, MM stands for millions.

Wolf Steve Weiss

Key ideas include a “seamless” (hate that word) transition to methane / methanol due to its match with current infrastructure (i.e. leverage trillions $); and an upside of moving to renewable methanol over time (e.g. by using renewable power to make hydrogen to combine with CO2). 

Wolf Weiss

You’re raising a fundamental policy issue, re taxing various emissions. Does someone estimate methane leaks from pipelines and at oilfields? Measure them? What happens if I can come in with some tech that grabs some of those emissions and turns them into a genuine carbon long-term product sink (a durable material/product)?

Wolf David Dodds

Very interesting is the interactive en-ROADS climate model, which can be found here.

Just close the box that says this is a beta product. I can’t speak to the algorithms used – although the assumptions are listed when you go to the detailed views of the different inputs. Playing around with all the detailed setting of this model, I could find only two things that really “moved the needle” and kept the global temperature increase to just 2.0C.

One was to reduce non-CO2 GHG emissions from agriculture by 50% and from industry by 90% (going to reductions greater than those values didn’t make any further difference). Two, a whopping carbon tax of at least $575/ton, starting from “zero” today and ramping up to that $575 in 10 years (by 2030). Nothing else really did much.

I have suggested in the past that fossil carbon should be taxed where it leaves the ground (pithead, wellhead), or where it enters the country (at station on a pipeline, railcar, tanker truck – including “finished petroleum products” such as chemicals and polymers).  Imposing the tax at the point of production (or at the port of entry) at the beginning of the value chain, rather than the consumers at the end, is far easier to do (and to enforce), and the fossil carbon – bearing its new cost from the tax liability – can go wherever the market directs it without need for any further regulation.

Wolfling Babul Patel

Taxing CH4 at source based on its GHG potential will be difficult. How would you assign a leakage factor at the source when NG is distributed all over the country and ownership of the gas changes from wellhead to trunk line to city gate to end users. If you tax methane as fuel with CO2 emissions, it has to be taxed may be at 50% to coal or 70% to diesel. I believe best way is to control leakage is through proper permitting and surveillance programs.

Wolf Cascone

Rep. Francis Rooney (R) of Florida (offered a)…bill (that) would create a carbon tax of $30 a ton. Imports from heavy emissions-producing countries like China would be taxed, while U.S. exports would be exempt to make sure our international competitiveness is not harmed.

 We have done taxes and cap and trade on various pollutants at every jurisdictional level for decades, including for SOx and NOx acid rain, NOx and VOCs in the SCAQMD and USGC, etc., and on COD and BOD in wastewater everywhere. We don’t let municipalities dumped sewage into rivers and the ocean. The idea of taxing harmful pollutants is baked into our economy and policies. Why is this different, and not an open sewer?

Wolf Dodds

I do recall the same language being used quite widely and publicly in the late 1960s to describe the behavior of “the chemical industry” that was dumping untreated industrial waste into waterways, and again in the 1970s when talking about acid-rain. That kind of language does have its uses, and is appropriate for some occasions.

Wolf Stone

I have to beg to differ with you Paul as related to ethanol as a fuel additive. Keep in mind that it is the lowest cost, highest octane, and oxygenate for high performance internal combustion engines. Further being a uniform molecule with optimized ignition it is one if not the most clean burning fuels. The engine designers such as Ricardo created the new small block high performance and mileage products based upon ethanol as a significant ethanol additive.

If ethanol is silly then what option would you propose. Certainly not aromatics that have profound environmental issues. Continued gasoline consumption is not environmentally sustainable.

Ethanol can be an essential building block for higher value products but keep in mind we need fuel solutions and from an emissions and environmental and health safety standpoint ethanol to me is the best immediate term option.

Wolf Bryan

My quarrel with fuel ethanol is NOT that it is a poor fuel. It is a good one, and could be an excellent one with engines optimized to take advantage of its properties. My issue is on the grander scale, in the sense that biology can use sugars to make molecules that are far more valuable than ANY fuel, while on the other hand, the much higher rates and “titers” in thermochemical conversion of LC biomass can lead us to multi-component mixtures that will serve perfectly well as fuels. To me, it’s sort of like saying that a 21-year-old Islay Single Malt tastes great with ginger ale and plenty of ice. I’m sure it does, but that’s not the best way to drink it.

If we are going to focus on one slice of the barrel to get the Bioeconomy off the ground (pun intended), why in the world should we start with the LOWEST VALUE slice? Let’s steal the premium chemicals market from the refiners first! Of course, the slanted playing field has forced us into the ethanol business and into fuels, but that doesn’t mean it’s RIGHT.

I hope that you don’t think we have the option of 100% replacement of liquid fuels by ethanol, at least not from fermentation. A 30% renewable blend is failure, or at best a stepping stone. The planet needs 90% renewable, and sure, maybe a third of that being ethanol is a good target, but what about the other two-thirds?

To take one example, we can make methanol from LC Biomass or bio-gas via conversion to syngas with very high Btu capture and with 100% commercial technology, then store and move methanol around as easily as we do crude oil or traditional liquid fuels. We can greatly enhance that process if we do have access to so-called green hydrogen, too. Blending the methanol directly is an option, but if you don’t like that, there is a proven commercial process for converting methanol to high-octane, low-aromatics, alkylate-like gasoline.

Lone Wolf Steve Slome

Another friend from Nexant, Steve Slome, jumps in at this point. Also as hungry for value as any Wolf, so we’ll consider him also Lone Wolf Slome.

Currently there is nothing easier to produce and cheaper than making ethanol as a fuel additive for gasoline. The case could be made for biogas and CNG vehicles, but the vehicles for the most part aren’t set up to use biogas. Thermochemical technologies are few and far between in actual commercial production. While I cede that we MAY be able to do better in the future, I’m not as bullish for a few reasons:

One, and this applies to sugar fermentations only, ethanol is a robust fermentation, one we have been working on for thousands of years.

Two, the high technical complexity of thermochemical technologies comes with a high capital cost, generally. As several high viability developers have outright failed, while others have struggled and changed models several times. Even if other technologies come about in the future, we need a bridge to the future from the present, and ethanol is that bridge.

Three, ethanol is also delicious. Checkmate other biofuels. 

Lone Wolf Slome

One, we still have to do something now until those technologies are available, and ethanol is better than gasoline.  Let’s not make perfect the enemy of good.

Two, if you can make anything that would generally fall into the gasoline pool, I would argue it is either better: a) fed to a naphtha cracker and turned into olefins for polymers or b) if it is an aromatic converted into any of a number of higher value downstream chemicals, than just burning them as a fuel—not to mention the environmental implications.  I’m not saying tear down the ethanol plants and start from scratch. It’s the ADDED capacity that I think should be looked at differently.

Wolf Stone

Plenty of great discussion and so many different perspectives. Steve make a great argument for ethanol as a fuel. Here are my points:

• Ethanol is not only a fuel. It is a performance additive that offers octane and oxygenate to existing fuel supply. It would be great to go to 100% replacement of gasoline. That is totally unrealistic since engagement across automobile manufactures, public opinion, supply chain capabilities, production capabilities, and political wills would not be aligned.

• We need to take baby steps as a plan to make progress. As one of my mentors taught me: How do you eat an elephant? A bite at a time.

• Having been a sports car racer and engine design follower the most likely approach to take steps further that automobile manufacturers would embrace and in fact have already suggested would be a 30% blend to offer a higher octane fuel that offers both performance and mileage. The auto folks then have a reason to support the change versus fight it. It also allows a phase out of gasoline volumes.

• We could then gradually increase the ethanol blend levels and possibly introduce butanol ethanol blends for total replacement of gasoline as a fuel.

I am totally supportive of replacing the entire barrel with producing renewable chemicals. My career has been focused on doing just that. Yet, repurposing ethanol plants to make chemicals is quite complex since most of, if not all the new fermentation processes are aerobic and require sterile conditions at a large scale. That is cap ex intensive and no slam dunk by any stretch of the imagination.

Wolf Dodds

Making ethanol is easy. It is the end point of an anaerobic pathway for extracting energy from carbohydrates that is common to a very wide array of micro-organisms. It also happens to be somewhat protective, in the sense that most micro-organisms that make it “in the wild” are reasonably resistant to its deleterious effect on cell membranes. So keeping an ethanol fermentation clean – or at least clean enough to make a useful amount of ethanol – is not very difficult.

Most ethanol plants today run to about 14% ethanol in about 48-52 hours or so, giving a productivity of about 3.5 g/L/hr. It is still the best whole cell process productivity. Poet has reported running to 17% ethanol, and a champagne yeast will run to 20%, but that last few percent takes far too long to be useful.

Further, for reasons that were not directed to making ethanol we are very, very good at growing corn. And all that carbon comes directly out of the atmosphere. And even if photosynthesis is not efficient, ethanol plants are! Theoretical yield of ethanol form a bushel of corn is 3.1 – 3.2 gallons, and plants today are running at around 2.9. And, is a source of income to the ag industry.

Wolf Stone

The big bonus going forward is valuable co products for high protein feeds. 

Wolf Dodds

Yes – the CO2 off the top of an ethanol fermentor is the best place to get CO2, but relative to fuel volumes, it is still small. And we need lots of hydrogen to go with it!  And protein is a big deal, and getting bigger. Protein is metabolically expensive to make.  And the world wants more – lots more.

(T)he world should use thermal processes for handling waste (you know where this is going….) and then feed biological process with the methanol to make things like protein or various fine chemicals that can be produced slightly off the central carbon pathways.  Methanol has an advantage in that it brings along lots of hydrogen in the molecule.

Lone Wolf Slome

Again, I couldn’t agree more!  For the chemical engineers, he’s referring to the redox balance, which isn’t managed by molecular hydrogen, but through metabolites such as NADH and FADH2.

The concept that we have discussed internally to clients is similar to the “cracker plus one” concept from the chemical industry.  It is where you don’t just build a cracker, you build the cracker plus one downstream derivative—whether it is EO, PE, or some other downstream derivative, you go one step down to maximize value.  This is a similar concept that we have suggested: “Central Metabolism plus One”.  You can go one step from central metabolism (e.g., succinic to BDO), without too much trouble—but much further and you will run into serious problems (e.g., genetic drift, low yields, etc).   READ MORE

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