It’s 2014: get cracking!

Hydrotreating, catalytic cracking, pyrolysis, metathesis, supercritical, and catalytic reforming.

It’s the big new wave heading for biofuels and biobased chemicals at scale.

The secret word in the bioeconomy for 2014 starts with a C.

Carbon? Chemicals? Cellulosic? Close, but guess again.

Yep, it’s cracking. That is, breaking down the biobased feedstock with heat, pressure and catalysts, into targeted molecules for further processing, blending, or direct drop-in use as a hydrocarbon fuel. And we need to also toss in “treating,” a generally less harsh approach often used to upgrade biobased intermediates into fuels (e.g. hydrotreating).

The 2007-13 wave of fermentation technologies

2007-2013 was the age of fermentation — when gigantically complex technologies like enzymatic hydrolysis, and other types of fermentation aimed at using the fermentation abilities of selected biobased organisms to convert sugars or gases into fuels and chemicals.

In that period, we’ve seen fermentation technologies completely change the landscape of the fuels and chemicals economy. From the likes of POET-DSM, Abengoa, Novozymes, DuPont, Beta Renewables, Dyadic, Clariant, GranBio, Inbicon, Proterro, American Process, INEOS Bio, Genomatica, Cobalt, Joule, Verdezyne, Rivertop Renewables, Solazyme, Amyris, Gevo, LanzaTech, Raizen, Iogen and others Companies like Calysta Energy are coming along with methanotrophs that can work on natural gas.

Some companies fell by the wayside, some are just now reaching scale, some are already operating at scale and attracting titanic levels of investment as they move down their cost curve from nutraceuticals to speciality chemicals, to bulk commodity chemicals, and ultimately to fuels.

The energy landscape will never be the same — and those technologies have just begun to deploy across the multiple plant locations many of them are expected to have.

The next wave: thermal and catalytic technologies

But the next wave is coming.

With exotic-sounding costs as low as $1.15-$2.18 per gallon. That is, low enough for fuels at scale with a solid RPI for investors. Several of them drop in to existing refinery infrastructure.

How are they doing it? Using harsher approaches such as cracking and thermal deploymerization, or softer processes such as hydrotreating, reforming, or metathesis. Making, generally speaking, drop-in fuels.

Companies like: KIOR, Cool Planet, Avello, Avantium, Elevance, BioGasol, ECR Renewable Fuels, Sweetwater Energy, Annelotech, Virent, Enerkem, Renmatix, Licella, Midori, Dynamic Fuels, Neste Oil, Fulcrum Bioenergy, Ensyn, Velocys, Catchlight Energy, Primus Green Energy, Sapphire Energy, Sundrop Fuels, Pacific Pyrolysis and Renewable Energy Group are at the forefront of the revolution. Companies like Algenol are using hybrids — the best of each.

For years we have watched the technologies come along in their path out of the lab, to pilot projects, to demonstrations, to full commercial scale. More technologies will develop, and the technologies already reaching scale may well be transformed. Some may fall by the wayside.

The Big Biofuels Plays

But the trend is unmistakable. Especially if we focus in on the future of fuels technology, as opposed to the higher-priced markets where fermentation technologies have traditionally ruled (viz. pharma, and nutraceuticals like DHA — more recently in flavors and fragrances and other speciality chemicals).

There are and will continue to be significant fermentation technologies that will succeed in the fuels market, and there will continue to be thermal & catalytic technologies that will succeed in the speciality chemicals markets.

The newest and hottest fermentation technologies are generally heading, as a rule, more and more towards the chemical markets — for the short term or possibly for all time. Genomatica is just one example of the trend, Verdezyne and Rivertop also being examples of fermentation technologies that always aimed at chemicals.

Amyris, Gevo, Cobalt and Solazyme are examples of companies that plan ultimately to make fuels as well as chemicals, but are expected to focus primarily on chemicals in the near term except to the extent that fuels are subsidized or otherwise targeted with incentives or grants.

But that does not mean that because key fermentation technologies are shifting to biobased chemicals, that that is the primary trend in the industry for 2014. Though, to be sure, that was the trend for 2012 through the end of last year.

2014 in prospect

2014 will be different. The first wave of cellulosic fermentation technologies complete their half-decade-or-more development path from lab to commercial scale — Abengoa, POET-DSM, DuPont Industrial Biosciences and GranBio being just three expected to open a first commercial in the next year. Gevo, Beta Renewables, Amyris and INEOS Bio have already opened. All have had their issues in moving to steady-stage operations — none have indicated that their pathways are permanently blocked. Though some may fall behind, and be left behind.

A second wave of fermentation technologies will deploy over the next few years at commercial scale — LanzaTech, Gevo, Butamax, Solazyme among them.

But the next wave for the fuels market — as opposed to chemicals — is being built primarily around thermal & catalytic technologies.

The pace accelerates

Breakthroughs are coming at breakneck speed in the lab from the likes of the University of Wisconsin, Pacific Northwest National Lab, Argonne National Lab, Mississippi State, Iowa State, to name a few. We’ve seen breakthroughs at the likes of Ensyn, the CLG-ARA process, Velocys and more. Companies like Annelotech and Aveloo have been formed to take some of the technologies to market. We’ve yet to see exactly what will become of Chevron/Catchlight’s promising thermal depolymerization route.

Meanwhile, companies like Renmatix and Licella have been taking the opportunities in supercitical forward, with Renmatix moving at light speed.

Meanwhile, companies like Enerkem and KiOR are reaching scale now — though steady-state operations continue to elude the latter as it introduces a new version of its technology.

The promise of pyro

As Huamin Wang , Jonathan Male , and Yong Wang detail in a recent article in ACS Catalysis:

“Considerable worldwide interest exists in discovering renewable energy sources that can substitute for fossil fuels. Lignocellulosic biomass, the most abundant and inexpensive renewable feedstock on the planet, has a great potential for sustainable production of fuels, chemicals, and carbon-based materials. Fast pyrolysis integrated with hydrotreating, one of the simplest, most cost-effective, and most efficient processes to convert lignocellulosic biomass to liquid hydrocarbon fuels for transportation, has attracted significant attention in recent decades.

The pyro issues

However, Wang, Male and Wang offer this caution: “Effective hydrotreating of pyrolysis bio-oil presents a daunting challenge to the commercialization of biomass conversion via pyrolysis-hydrotreating. Specifically, the development of active, selective, and stable hydrotreating catalysts is problematic due to the poor quality of current pyrolysis bio-oil feedstock (i.e., high oxygen content, molecular complexity, coking propensity, and corrosiveness).

“Significant research has been conducted to address the practical issues and provide fundamental understanding of hydrotreating and hydrodeoxygenation (HDO) of bio-oils and their oxygen-containing model compounds, including phenolics, furans, and carboxylic acids. A wide range of catalysts have been studied, including conventional Mo-based sulfide catalysts and noble metal catalysts. Noble metal catalysts have been the primary focus of recent research because of their excellent catalytic performances and because they do not require the use of environmentally unfriendly sulfur. Recently, the reaction mechanisms of the HDO of model compounds on noble metal catalysts and their efficacy for hydrotreating or stabilization of bio-oil have been reported.”

The landscape includes:

KIOR: at scale, thermo-catalytic, fuels
Cool Planet, heading for scale based on modular design, unique pyrolysis-like fractionation process, fuels,
Avello, early-stage, pyrolysis, using Iowa State technology, fuels
Avantium, demo stage, advanced catalysis, chemicals
Elevance, commercial now, olefin metathesis, chemicals and fuels

BioGasol, commercial now, technology supplier, steam explosion
Sweetwater Energy, heading for scale, technology aggregator, steam explosion
Annelotech, early-stage, pyrolysis technology spun out of UMAss-Amherst
Virent, demo scale (Shell also has a pilot unit in Houston), catalytic bioforming, fuels and chemicals (BTX group)
Enerkem, commissioning first commercial, thermo-catalytic, fuels and chemicals (methanol, ethanol)

Renmatix, heading for scale, supercritical, sugar supplier
Licella, early-stage, pyrolysis, fuels
Midori, early-stage, thermal, renewable sugars
Dynamic Fuels, commercial now, hydrotreating, fuels
Diamond Green Diesel, commercial now, hydrotreating, fuels

Neste Oil, commercial now, hydrotreating, fuels
Fulcrum Bioenergy, heading for scale, thermo-catalytic, fuels
Ensyn, commercial scale, thermo-catalytic, fuels
Velocys, heading for scale, thermo-catalytic, fuels
Primus Green Energy, heading for scale, thermo-catalytic, fuels and chemicals

Algenol, demo stage, fermentation and pyrolysis, fuels and chemicals
Sapphire Energy, demo stage, hydrotreating, fuels
Sundrop Fuels, heading for scale, thermo-catalytic, fuels and chemicals
Pacific Pyrolysis, early-stage, pyrolysis, fuels
Renewable Energy Group, commercial scale, inorganic catalysts, fuels – own 50% of Dynamic Fuels

The Top 10 R&D developments

1. In Iowa, Iowa State engineers have upgraded their pilot plant for better studies of advanced biofuels. Machinery upgrades supported by $75,000 from the state-supported Leading the Bioeconomy Initiative at Iowa State will help engineers develop an even better understanding of the art of fast pyrolysis.

“The science of pyrolysis is what you can read in a book,” said Robert C. Brown, an Anson Marston Distinguished Professor in Engineering, director of Iowa State’s Bioeconomy Institute and the Gary and Donna Hoover Chair in Mechanical Engineering. “The art of pyrolysis is actually being able to make it work in continuous, pilot-scale reactors.” They have created “Pyrolyzer 2.0” at Iowa State’s BioCentury Research Farm just west of Ames. The improvements have bumped the pyrolyzer’s processing rate from 7 kilograms of biomass per hour to 10 kilograms per hour.

2. In Illinois, for the past four years, Argonne chemist Chris Marshall and his colleagues at the Argonne-led Institute for Atom-Efficient Chemical Transformations (IACT) have been searching for ways to improve the efficiency and selectivity of catalysts – precisely tailored chemicals that help to carry out a vast array of reactions.

3. In Georgia, ECR Renewable Fuels and Georgia Alternative Fuels, have been pursuing nanocatalysts and their effect on supercritical boundaries for several years. The goal? To reduce the temperature and pressure barrier at which liquids begin to demonstrate supercritical properties — using catalysis to reduce the energy levels.
“Our cellulosic ethanol process uses the supercritical heterogeneous catalytic process to pretreat cellulose,” said Alan Lawson, who heads the group. At a pilot and lab-scale, the technology is modeling along exciting lines.

“Supercritical fluid operating heat and pressures are now much lower due with the advanced catalysis technology. The critical point for our system is now less than 25 psi and 170F.”
As seen at lab and pilot-scale, Lawson says, “The process lowers our costs significantly to make a small scale system produce a very nice profit. We can now compete with mid-west ethanol on the East Coast. Our per pound sugar cost using biomass is about $0.04 per pound verses $0.125 per pound for corn ethanol. Our model is small cellulosic ethanol plants highly distributed over the East, at less than 10 million gallons per year.”

4. through 7. In Washington, the US Department of Energy announced four research and development projects to bring next generation biofuels on line faster and drive down the cost of producing gasoline, diesel, and jet fuels from biomass. The projects—located in Oklahoma, Tennessee, Utah, and Wisconsin—represent a $13 million Energy Department investment. It was an additional $1 million over the $12 million target when DOE set the project in motion last December.

The is is the CHASE Bio-Oil project, for those who recall its origins. CHASE – short for Carbon, Hydrogen, and Separation Efficiencies.

This funding project grew out of a stakeholder workshop held in December 2011 called “Conversion Technologies for Advanced Biofuels” (CTAB) and from a Request for Information circulated last November 2012.  The workshop itself stems from the DOE’s efforts to ensure it reaches its stated goal of producing cost-competitive drop-in biofuels at $3 per gallon by 2017.

The project is intended to move knowledge and understanding of basic or fundamental principles observed at Technical Readiness Level 1 into practical, applied research and development at TRLs 2-3 or beyond – regarding key technical barriers to improved yield and economic feasibility of producing biofuels via thermochemical, direct liquefaction pathways (i.e. fast pyrolysis, catalytic fast pyrolysis, hydropyrolysis, hydrothermal liquefaction, and solvent liquefaction).

Ceramatec will utilize an efficient electrochemical deoxygenation process to develop cost-effective technology to separate oxygen from bio-oil. This project will help produce hydrocarbon products suitable for further processing in conventional petroleum refineries.

Oak Ridge National Laboratory will use a microbial electrolysis process to efficiently remove the hydrogen from the water found in bio-oil. This technology will help reduce the corrosivity of bio-oil and improve the efficiency of converting hydrogen and biomass to biofuels. The University of Tennessee-Knoxville, Georgia Institute of Technology, Pall Corporation, OmniTech International, and FuelCellsEtc will also participate in this project.

The University of Oklahoma will investigate two methods—thermal fractionation and supercritical solvent extraction—to maximize the amount of renewable carbon and hydrogen that can be extracted from biomass and converted to a refinery-compatible intermediate and suitable for final upgrading to a transportation fuel. The multidisciplinary research team includes experts in catalysis, separation, life-cycle analysis and techno-economic assessment.

Virent will develop an innovative separation process which uses its BioForming technology to efficiently convert carbon from lignocellulosic biomass into hydrocarbon fuels. Virent will work to improve the overall carbon conversion efficiency of biomass—helping to reduce the cost of producing hydrocarbon biofuels that work with our existing transportation fuel infrastructure and are capable of meeting the Renewable Fuel Standard. Idaho National Laboratory will also bring their feedstock pre-processing capabilities to the project.

8. In Ohio, Battelle engineers and scientists have developed a mobile device that transforms residues such as wood chips or agricultural waste into bio-oil using catalytic pyrolysis. As currently configured, the Battelle-funded unit converts one ton of pine chips, shavings and sawdust into as much as 130 gallons of wet bio-oil per day. This intermediate bio-oil then can be upgraded by hydrotreatment into a gas/diesel blend or jet fuel. Battelle’s testing of the bio-based gasoline alternative suggests that it can be blended with existing gasoline and can help fuel producers meet their renewable fuel requirements. The Battelle bio-oil created by the mobile pyrolysis unit is similar to naturally occurring fossil oils harvested from underground.

9. In Louisiana, Cool Planet Energy Systems CEO Howard Janzen, flanked by Louisiana Gov. Bobby Jindal, announced the company will build three bio-refineries in Louisiana with a capital investment of $168 million. The project will consist of modular biomass-to-gasoline refineries in Alexandria, Natchitoches and a site to be determined. Cool Planet will create 72 new direct jobs, averaging $59,600 per year, plus benefits. Additionally, LED estimates the project will result in 422 new indirect jobs, for a total of 494 new jobs. The company estimates 750 construction jobs will also be created by the project.

Its not hard to see why everyone has been excited — sometimes laced with skepticism — about Cool Planet. With claimed operating costs of $1.00 to $1.15 per gallon, and adding another 13 cents or so for the capital costs (amortized over 15 years) – well, you get the picture. It’s drop-in, renewable gasoline, in prospect, for about half the price of the incumbent fossil fuels

10. About a year ago, a little-known company called Midori Renewables picked up some traction from the invited international selectors in the 50 Hottest Companies in Bioenergy. The promise of the technology was simple: a revolutionary way to deliver low-cost sugars — perhaps the most stubborn barrier between cellulosic biofuels as a triumph in the lab, and cellulosic biofuels as a triumph at the pump.

The technology may surprise. There’s no biology in it, really – no enzymes, no magic micro-organism — fungus, yeast, bacteria, protein, aqueous acid, or what have you. It is a solid material — though one temporarily shrouded in some mystery — but one that reportedly can be easily separated from the reaction and reused, resulting in a significantly lower cost solution than existing technologies.

“It’s a little like taking biomass and baking a cake,” said Baynes. “You mix it up with the catalyst, shove it into an oven — or, at scale, into a reactor. The sugars are melted of of the cellulose. You wash it with water, until you have a stream that looks like maple syrup, then you separate out all the solid residuals. It’s not hard for that step, because the trick is that we are using a very dense material that sinks very rapidly to the bottom of the reactor where it is recovered for re-use.

The Bottom Line: regarding irrational exuberance and irrational inexuberance

Nothing in today’s “Get Cracking” should beguile you from an ongoing interest in fermentation technologies. They are coming to scale, fast, and especially in the small chemical markets will be perhaps the dominant player for some time to come.

And nothing in “Get Cracking” should beguile you from an understanding that not all technologies succeed, none are built in a day, none are free, and achieving steady-state operations on a first commercial is not for the faint of heart.

And nothing in “Get Cracking” should beguile you from an understanding that the overwhelming issues in biofuels at scale remain market access, capital and feedstock — as we outlined earlier this month in “The End of the Great Big Easy.”

Having said that, by focusing on lignocellulosic feedstocks, producing drop-in fuels or intermediates (generally speaking) using lignin in many if not all cases, and by focusing on modular systems (in cases like Cool Planet, Velocys and more) — these technologies tend to address these perplexing issues in novel ways.

And, they are less dependent on structures such as the Renewable Fuel Standard to provide market access — though they benefit from that singularly transformative piece of energy legislation.

And by accessing novel feedstocks with immense productivity and no use of existing arable land – such as algae — or residues (such as MSW or animal fats), they are revolutionizing the environmental outlook as well as the economics of biofuels at scale.

But look at the number of them. It’s a wave. It’s a must-know, must understand.