Biomass-Based

National Renewable Energy Laboratory 1617 Cole Blvd. 

Task I Fluidizable Catalysts for Producing Hydrogen by Steam Reforming Biomass Pyrolysis Liquids, K. Magrini-Bair, S. Czernik, R. French, Y. Parent, M. Ritland, E. Chornet 

Task 2 Production of Hydrogen from Post-Consumer Wastes, S. Czernik, R French, C. Feik, E. Chornet 

Task 3 Hydrogen from Biomass for Urban Transportation, YD. Yeboah, K.B. Bota, Z. Wang, M. Realff, D. Day, J. Howard, D. McGee 

Task 4 Engineering Scale-Up of Renewable Hydrogen Production by Catalytic Steam Reforming of Peanut Shells Pyrolysis Products, R.J. Evans, S. Czernik, E. Chornet, C.J. Feik, R. French, S.D. Phillips 

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Ethyl Tertiary-Butyl Ether. Similar to methanol in the MTBE reaction, ethanol can react with isobutylene to produce ETBE. Which alcohol is used to make the ether is highly dependent on the relative cost of the alcohols. To make ethanol more economically competitive with methanol, the federal tax credit for biomass-based ethanol used in fuel also appHes to ethanol used to make ETBE in the United States (24). 

When implementing a biomass-based thermochemical conversion system, it is important to critically evaluate the feedstock characteristics such as cost, distribution, mass, and physical and chemical properties. The feedstock qualities must be considered when matching feedstocks with a proper conversion technology. 

Biomass-based processes for the production of hydrogen can be either thermochemical or biological and can produce this clean carrier directly or through an intermediate, storable product. Also, the use of coproducts has to be addressed to improve the process economics and in view of the sustainability of using this natural resource. A recent overview of the status of the different technologies is given in an IEA/NREL review5 and further by Czernik et al.8... 

Sensitivity analysis showed that the amount of com stover that could be harvested increased with root to shoot ratio (Fig. 8.4). If roots were not considered in the NHC value, then the estimated amount of above-ground biomass that could be safely harvested was about 35%, whereas if the root to shoot ratio was 1.00 then 70% of the above-ground biomass could be harvested. These findings are attributed to a relative increase in importance of the below-ground biomass. Based on these calculations, underestimating the root to shoot ratio will result in underestimating com stover removal rates, which, while having a positive influence on future... 

A large portion of the overall GHG emissions from the supply of biomass based fuels results from the formation of N20 in fertilised soils. To calculate N20 emissions, the European Soil Model is typically applied, developed by the European Joint Research Centre in Ispra (Italy). The data in Table 7.5 represent the average N20 emissions from the plantation of rapeseed in EU25 (R. Edwards, personal communication, Joint Research Centre (JRC), Ispra, August 2005). 

Biomass, via its photosynthesis, has provided energy for life for the longest period of its existence. Industrial processes that take-in biomass can be integrated with the natural photosynthesis/respiration cycle of vegetation. If used in this manner, biomass is a renewable energy source and, by its utilization, overall much less C02 is added to the atmosphere compared with the fossil fuel counterpart processes. When combined with C02 sequestration, biomass based processes can actually lower the C02 concentration in the atmosphere [11],... 

Current biodiesel can not be considered as a 100% biomass-based fuel as long as methanol is derived from petrochemical resources. A clean way to solve the biorelated problem is the conversion of glycerol waste from the transesterification process into syngas. In this context, glycerol reforming is a suitable target reaction worthy of study. 

Notably, several types of liquid biofuels exist or are under development and have the potential to replace fossil fuels, especially in the transportation sector. The focus is on organic fuels such as ethanol, butanol, methanol and their derivatives ETBE, MTBE, which can be produced by fermentation, but also biodiesel and liquid biogas, which can provide interesting biomass-based alternatives to diesel and LPG. 

The valorization of by-products in biomass conversion is a key factor for introducing a biomass based energy and chemistry. There is the need to develop new (catalytic) solutions for the utilization of plant and biomass fractions that are residual after the production of bioethanol and other biofuels or production chains. Valorization, retreatment or disposal of co-products and wastes from a biorefinery is also an important consideration in the overall bioreftnery system, because, for example, the production of waste water will be much larger than in oil-based refineries. A typical oil-based refinery treats about 25 000 t d-1 and produces about 15 000 t d 1 of waste water. The relative amount of waste water may increase by a factor 10 or more, depending on the type of feed and production, in a biorefinery. Evidently, new solutions are needed, including improved catalytic methods to eliminate some of the toxic chemicals present in the waste water (e.g., phenols). 

Several developments in the field of catalysis are required for the introduction of biomass-based raw materials in the chemical industry ... 

Table 2 reports the expected market development of major RRM-based products [7] notably, the potential market may significantly enlarge if the progressive introduction of biorefineries decreases the production costs, on one side, and increases the number of biomass-based products on the other side. 

A general conclusion is that incentives to convert conventional fossil fuel based technology into biomass based technologies are large, but implementation will be slowed down for several reasons. Firstly, there is the availability of biomass itself. The preferred feedstock should not compete with food production. Processes to convert such biomass practically into secondary energy carriers are not yet commercially available. In the mean time, technologies converting food related biomass will be implemented. But this will only occur for a limited period in the near future. 

Hydrothermal Carbonization (HTC), an alternative chemical pathway leading to a variety of carbonaceous materials, was presented in context with the generation of energy materials and energy hybrids. HTC is sustainable, as at least a majority of the precursors are biomass based, and the reaction takes place in pure water at mild tem-... 

Crude-Oil-Based Feedstock Biomass-Based Feedstock... 

Reijnders, L. 2006. Conditions for the sustainability of biomass-based fuel use. Energy Policy 34 863-876. 

There is a consensus amongst scientists that biofuels used in a sustainable manner result in no net increase in atmospheric carbon dioxide (CO ). Some would even go as far as to declare that sustainable use of biomass will result in a net decrease in atmospheric CO (Jefferson et al., 1991). This is based on the assumption that all the COj given off by the use of biomass fuels was recently taken in from the atmosphere by photosynthesis. Increased substitution of fossil fuels with biomass-based fuels would therefore help reduce the potential for global warming, caused by increased atmospheric concentrations of COj. 

During 1977, Canada consumed 658 million barrels of petroleum products ( 1). Products marked with an asterisk in Table I -motor gasoline and light, heavy and diesel fuel oil - account for 80% of the total production, and represent the main potential for biomass-based liquid fuel in Canada, almost 522 million barrels per annum. 

Various nonconventional reaction media have been intensively studied in recent years, including water [34], supercritical COj [35], Jluorous hiphasic [36], and ionic liquids [37] alone or in hquid-liquid biphasic combinations. The use of water and supercritical carbon dioxide as reaction media fits with the current trend toward the use of renewable, biomass-based raw materials, which are ultimately derived from carbon dioxide and water. 

Microorganisms capable of converting biomass pentose sugars to fuels and chemicals are essential for robust biomass-based processes. This session discussed recent technological developments and understanding that will allow for the construction of superior microorganisms. 

Flausoul PJC, Parvulescu AN, Lutz M, Spek AL, Bruijnincx PCA, Klein GRJM, Weckhuysen BM (2011) Mechanistic study of the Pd/TOMPP-catalyzed telomerization of 1,3-butadiene with biomass-based alcohols on the reversibility of phosphine alkylation. ChemCatChem 3 845-852... 

Parvulescu AN, Hausoul PJC, Bruijnincx PCA, Klein Gebbink RJM, Weckhuysen BM (2010) Synthesis of octyl-ethers of biomass-based glycols through two competitive catalytic routes telomerization and etherification. Catal Today 158 130-138... 

Amato, M. and Ladd, J. N. (1988). Assay for microbial biomass based on ninhy-drin-reactive nitrogen in extracts of fumigated soils. Soil Biol. Biochem. 20, 107-114. 

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