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Renewable plastic precursor could reduce cost of cellulosic ethanol by >$2/gallon

A team of chemical and biological engineers at the University of Wisconsin–Madison has developed a new chemical pathway a way to produce from biomass a valuable compound—1,5-pentanediol, a plastic precursor primarily used to make polyurethanes and polyester plastics—that they estimate could lower the cost of cellulosic ethanol by more than two dollars per gallon.

The highly efficient approach devised by Professor George Huber and collaborators is much cheaper than a previously reported method—direct hydrogenolysis of tetrahydrofurfuryl alcohol (THFA)—and represents the first economically viable way of producing 1,5-pentanediol from biomass. A paper on their work is published in the journal ChemSusChem.

A process for the synthesis of 1,5-pentanediol (1,5-PD) with 84% yield from furfural is developed, utilizing dehydration/hydration, ring-opening tautomerization, and hydrogenation reactions. Although this process has more reaction steps than the traditional direct hydrogenolysis of tetrahydrofurfuryl alcohol (THFA), techno-economic analyses demonstrate that this process is the economically preferred route for the synthesis of biorenewable 1,5-PD.

2-Hydroxytetrahydropyran (2-HY-THP) is the key reaction pathway intermediate that allows for a decrease in the minimum selling price of 1,5-PD. The reactivity of 2-HY-THP is 80 times greater than that of THFA over a bimetallic hydrogenolysis catalyst. This enhanced reactivity is a result of the ring-opening tautomerization to 5-hydoxyvaleraldehyde and subsequent hydrogenation to 1,5-PD.

—Brentzel et al.

Furfural is first hydrogenated into THFA, which is then dehydrated in the gas phase to produce dihydropyran (DHP) with 87% yield. The DHP is then hydrated to 2-HY-THP and 2-HY-THP dimers in yields up to 100 % in the aqueous phase (20 wt % DHP in water) without a catalyst at temperatures from 343 to 403 K (70 to 130 ˚C). 2-HY-THP is a cyclic hemiacetal that undergoes ring-opening tautomerization in the aqueous phase to form 5-HY-Val.

The hydrogenation of 5-HY-Val in the presence of the 2-HY-THP monomers and dimers with a Ru catalyst results in 97% overall yield of 1,5-PD from DHP.The researchers refer to this routeas the dehydration, hydration, and hydrogenation (DHH) pathway.

Huber
Comparison of costs and MSPs for the DHH pathway with the direct hydrogenolysis pathway. Source: Click to enlarge.

Plant biomass is typically about 40% oxygen by weight, while petroleum oil is less than 0.1% oxygen. Huber’s approach uses the oxygen already inherent in the biomass to produce high value oxygenated commodity chemicals that can be used to make performance polymer materials such as polyurethanes and polyesters.

The study’s foundational discovery, its new pathway for chemical production, also provides fundamental chemistry that could be applicable to a wide cross-section of products. For example, the same pathway could be used to produce two other plastic precursors—1,4 butanediol and 1,6-hexanediol—currently derived from petroleum and which together represent an annual market of more than $6 billion.

The team will continue to refine their work, collecting the data needed to scale their process up to pilot plant testing. The Wisconsin Alumni Research Foundation (WARF) is in charge of licensing the technology.

Huber was joined in the collaborative study by UW–Madison engineering professors James Dumesic and Christos Maravelias, experts in a catalysis and techno-economic modeling, respectively, graduate students Zachary Bentzel (the paper’s first author) and Kevin Barnett, and postdoctoral researcher Kefeng Huang.

The development is the latest in an ongoing effort at UW–Madison to create commodity chemicals currently derived from petroleum out of biomass. These bio-derived chemicals could serve as high value co-products of the biofuels manufacturing process, improving the economics of the cellulosic bio-refinery.

Resources

  • Zachary J. Brentzel, Kevin J. Barnett, Dr. Kefeng Huang, Prof. Christos T. Maravelias, Prof. James A. Dumesic and Prof. George W. Huber (2017) “Chemicals from Biomass: Combining Ring-Opening Tautomerization and Hydrogenation Reactions to Produce 1,5-Pentanediol from Furfural” ChemSusChem doi: 10.1002/cssc.201700178

Comments

mahonj

What is MSP in this context ?

Other than that, it sounds good to me if they can scale it.

SJC

“We’ve had companies asking more about this exciting way to economically produce a valuable chemical from sustainable sources”

It is still a lab idea, when Dupont and Poet take interest it might be scaled up.

Trees

MSP probably "manufacturer suggested price".
Furfural has been in the R&D news of cellulosic for a few years now. A new class of solvents that has an interesting pathway (break through) for economic production.

The chemical market is more attractive and pays better than the ethanol. Ethanol industry has understood the direction of the business that will pull processing in multiple directions. Fuel, food, chemicals, feed, power, and biomass. Each plant has different approach to profit and it will get more complicated and interesting in the future with multiple pathways. Grain ethanol is the stabilizing profit center with resources to improve efficiency and increase value of coproducts. Actually, one company is setting up an ethanol process to utilize waste CO2 from power plants and cement processing.

The fuel component of ethanol is now ethanol and diesel. Biomass is another possibility for internal use in boiler fuel or pellet sales. They want to have ability to flex production to best return product. The DDGs are even being formulated to add value per balance nutrition feed supply, but that is another business. Raw material suppliers are another developing sector. New efficient process, storage, and transport services to supply the industry. Whether it be wood, grass, cane, or beets.

Trees

Just a comment on energy technology. If keep up on enterprising developments and if one can sort through the fluff some observations appear;

1. Natural gas is remarkably universal fuel. Clean, inexpensive, efficient, reliable and easy to store and transport. It can be renewable, hydrogen infused, and used in all sectors requiring energy.

2. Wind and solar have a huge handicap given the low utilization and lack of dispatch. Also, the variability and seasonal change of power production. It does have good value if sited properly and within particular productive zones of country. We can engineer around some of the weakness at a cost and inconvenience.

3. The grid is not a particularly good way to distribute high BTU power needs. It will improve over long time periods of high investment.

4. BEV is gaining respect and has a lot to offer consumers as technology improves the performance and lowers cost. It will be interesting how the new technology can improve city life.

5. Point of use generation of power should be more attractive, but will face much head wind with utilities and power plants that want to eliminate competition. It will be interesting if crony capitalism will handle the development. Will politicians work for the people or big influence? This is the roof top solar and CHP power that has enormous production capability. CHP is extremely underutilized and under developed. It could be regulated that new permanent natural gas devices that routinely produce low grade heat must produce power. I know these heat alone devices can operate in the 98% efficiency range, but they, also, can run in that range while producing power. Owr power plants have no use for low grade heat. It is a waste product. So, the efficiency upgrade kicks in by replacing low efficient power plants. Especially the ones that utilize the steam turbine. The CHP devices can be controlled by smart grid for flexible power production needs. Space heating and water heating should all be CHP generators. It is not complex technology, nor expensive. At least if production volumes increase.

6. Ethanol is way under utilized as a excellent source of stored energy for transportation. Hybrid optimised ethanol vehicles running cellulosic fuel has tremendous environmental value all around. Heavy truck or high torque engines may benefit the most as BEV will make good inroads to the light vehicle requirements.

SJC

The RFS in 2007 encouraged cellulose ethanol but it took Dupont and others to actually make it happen. More incentives should be offered.

Trees

Reflecting upon the ethanol industry, I think it was the success of corn ethanol that acted to support the industry. The success of corn with distribution, proven quality, and sustained production. This allowed a movement to continually improve image and cost. Currently, corn ethanol is bootstrapping cellulosic production. That will have a major impact upon the technology per the sustained increasing production. The whole industry is going through a learning curve.

SJC

Captain Obvious.

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