Researchers develop high-rate, high-yield bacterial process to convert methane to methanol

Cartoon of the process. Click to enlarge.

Researchers at Columbia University have developed a biological process utilizing autotrophic ammonia-oxidizing bacteria (AOB) for the conversion of methane (CH₄) to methanol (CH₃OH). A paper on their work is published in the ACS journal Environmental Science & Technology.

In fed-batch reactors using mixed nitrifying enrichment cultures from a continuous bioreactor, up to 59.89 ¬± 1.12 mg COD/L (COD = chemical oxygen demand, an indirect measurement of organic compounds in water) of CH₃OH was produced within an incubation time of 7 h-approximately 10x the yield obtained previously using pure cultures of Nitrosomonas europaea. Themaximum specific rate of CH₄ to CH₃OH conversion obtained during this study was 0.82 mg CH₃OH COD/mg AOB biomass COD-d-1.5x times the highest value reported with pure cultures.

There are intense efforts globally to develop biobased fuels, chemicals, and energy. While ethanol has been of primary focus in the past few years, it should be noted that other chemicals and biofuels such as methanol can be also attractive. In addition to being used in gasoline blends, methanol can be used in fuel cells, combined with long-chain fatty acids and lipids to form biodiesel, or chemically dimerized to dimethyl ether (DME, also a fuel). Methanol is also one of the most widely used chemicals for enhancing denitrification in wastewater treatment. Methanol is commonly produced from natural gas, by chemical catalysis. The chemical pathway first involves the oxidation of CH₄ to CO₂ and H₂ and subsequent reduction of CO₂ to CH₃OH, and is quite economically and energy intensive and redundant.

Given that natural gas reserves are finite, it might be more sustainable to look toward alternate sources of CH₄ to produce CH₃OH, such as anaerobic digester gas, biogas, or landfill gas, which in addition contain moisture and CO₂. However, the primary limitation to the more widespread use of such gas mixtures is the cost and energy required to purify the CH₄ present and the challenges of handling a gaseous stream.

On the other hand, ammonia-oxidizing bacteria (AOB) can oxidize CH₄ to CH₃OH via the nonspecific action of the enzyme ammonia monooxygenase (AMO). The other benefit of using bacterial conversion of CH₄ to CH₃OH is that the contaminants such as moisture and CO₂, which need to be removed from anaerobic digestion gas or biogas for chemical conversion to CH₃OH, do not pose a limitation for biological conversion. In fact autotrophic AOB can also utilize the CO₂ contained in gas mixtures for cell synthesis.

-Taher and Chandran

The rationale behind using AOB to oxide methane instead of using methane-oxidizing bacteria (MOB) is rather straightforward, the authors note in their paper: MOB oxidize methane completely to CO₂, which cannot be used readily as a fuel. In other words, if MOB were to be used for methanol production, there would need to be some likely non-trivial engineering to selectively inhibit the metabolic pathways that further process CH₃OH.

AOB only oxidize CH₄ partially to CH₃OH-and possibly to trace amounts of formaldehyde (HCHO), which is highly toxic to AOB. Feedback inhibits any further oxidation of CH₃OH to HCHO.

AOB do not derive any energy or reducing equivalents from this process, and since AMO requires reducing power to function, continued CH₄ oxidation can likely be limited unless reducing power is supplied externally. NH₃ is not an ideal or direct source of reducing power, since it can competitively inhibit methane oxidation. The researchers posited that the use of an alternate reducing power source such as NH₂OH could promote AOB-mediated CH₄ oxidation to CH3OH. They also hypothesized that uncoupling NH₃ and CH₄ feeding strategies could promote CH₄ oxidation to CH₃OH by avoiding competition between these two substrates for AMO.

The results obtained highlight the metabolic versatility of AOB to convert CH₄ to CH₃OH and point to the possibility of developing engineered processes to promote the production and utilization of CH₄ as a chemical needed for enhanced denitrification. Once optimized, the successful implementation of this process could potentially allow wastewater treatment plants to offset some of their CH₃OH costs.

Consequently, the overall greenhouse footprint of wastewater treatment plants (by lowering CH₄ release as well as recovering CH₃OH) could be reduced. At the same time, through this microbially mediated approach, redundancies in currently followed chemical conversion of CH₄ to CH₃OH can be avoided. Further mechanistic and modeling studies are needed to understand the substrate and product fluxes during AOB mediated oxidation of CH₄ to CH₃OH oxidation and to maximize the kinetics and yield of CH₃OH.

-Taher and Chandran

Resources

• Edris Taher and Kartik Chandran (2013) High-Rate, High-Yield Production of Methanol by Ammonia-Oxidizing Bacteria. Environmental Science & Technology doi: 10.1021/es3042912

http://www.greencarcongress.com/2013/03/taher-20130322.htm

China-US team concludes duckweed biorefineries can be cost-competitive with petroleum-based processes

Researchers from the US and China have determined that a duckweed biorefinery producing a range of gasoline, diesel and kerosene products can be economically competitive with petroleum-based processes, even in some cases without environmental legislation that penalizes greenhouse gas emissions. A paper describing their analysis of four different scenarios for duckweed biorefineries is published in the ACS journal Industrial & Engineering Chemistry Research.

Duckweed, an aquatic plant that floats on or near the surface of still or slow-moving freshwater, is attractive as a raw material for biofuel production. It grows fast, thrives in wastewater that has no other use, does not impact the food supply and can be harvested more easily than algae and other aquatic plants. However, few studies have been done on the use of duckweed as a raw material for biofuel production.

The team, comprising researchers from Princeton University; Peking University; Institute of Process Engineering, Chinese Academy of Sciences; and PetroChina company, investigated four different thermochemical pathways for the production of gasoline, diesel, and kerosene from gasified duckweed synthesis gas as the intermediate:

• Low-temperature and high-temperature Fischer‚àíTropsch processes (LTFT and HTFT) using both iron and cobalt based catalysts. Clean syngas is converted to hydrocarbons via cobalt or iron-based catalysts operating at either low or high temperature. The residue/wax produced from FT synthesis is directed to a hydrocracker, and the vapor phase C3‚àíC22 hydrocarbons are sent for further upgrading.

• Methanol to hydrocarbons via the methanol-to-gasoline (MTG) or methanol-to-olefins (MTO) processes. The hydrocarbons are refined into the final liquid products using ZSM-5 catalytic conversion, oligomerization, alkylation, isomerization, hydrotreating, reforming, and hydrocracking.

Fischer‚àíTropsch (FT) synthesis flowsheet. Credit: ACS, Baliban et al. Click to enlarge.	Methanol synthesis and upgrading flowsheet. Credit: ACS, Baliban et al. Click to enlarge.

The team developed a process synthesis framework to select the refining pathway that will produce the liquid fuels at the lowest possible cost. The used the synthesis framework to determine the effect of refinery capacity and liquid fuel composition on the overall system cost, the refinery topological design, the process material/energy balances, and the lifecycle greenhouse gas emissions.

The researchers used four case studies focused on two target capacities (i.e., 1,000 and 5,000 bpd) and two product compositions (i.e., unrestricted and US demand ratios of gasoline, diesel, and kerosene) to demonstrate the capability of the process synthesis framework and determine the process design that has the lowest overall cost.

The price of crude oil for which the duckweed BTL refineries will be competitive is $100/bbl for the 1 kBD unrestricted study, $69/bbl for the 5 kBD unrestricted study, $105/bbl for the 1 kBD US ratio study, and $72/bbl for the 5 kBD US ratio study. An important highlight for these four studies is the strong use of methanol synthesis opposed to FT synthesis. The lack of inert production during methanol synthesis allows for the use of a large internal synthesis gas loop and less complex synthesis gas conversion design within the refinery. The methanol can be readily converted to gasoline, diesel, and kerosene using a ZSM- 5 catalyst.

A parametric analysis on the duckweed purchase price indicates that there exists a threshold price of duckweed above which the refinery will no longer be economically competitive with crude oil refining. This threshold level for duckweed purchase depends on the desired refinery capacity and will decrease as the capacity decreases.

If crude oil was priced around $105/bbl, then the 1 kBD refineries would be economically competitive with a duckweed purchase price of $50/dry metric ton. A reduction in the duckweed purchase price to $30/dry metric ton will make the 1 kBD duckweed refineries competitive at crude prices above $95/bbl. For the 5 kBD refineries, the process synthesis framework demonstrates the economic viability at a crude price above $72/bbl for duckweed purchase prices at $50/dry metric ton. If this purchase price was raised to $70/dry metric ton, the refineries would remain competitive at crude priced above $82/bbl.

-Baliban et al.

The US National Science Foundation and the Chinese Academy of Sciences provided funding for the research.

Resources

• Richard C. Baliban, Josephine A. Elia, Christodoulos A. Floudas, Xin Xiao, Zhijian Zhang, Jie Li, Hongbin Cao, Jiong Ma, Yong Qiao, and Xuteng Hu (2013) Thermochemical Conversion of Duckweed Biomass to Gasoline, Diesel, and Jet Fuel: Process Synthesis and Global Optimization. Industrial & Engineering Chemistry Research doi: 10.1021/ie3034703

http://www.greencarcongress.com/2013/03/arpa-e-to-issue-new-funding-op

http://www.greencarcongress.com/2013/03/duckweed-20130307.htm