Biomass represents an abundant carbon-neutral renewable resource for the production of bioenergy and biomaterials, and its enhanced use would address several societal needs. Advances in genetics, biotechnology, process chemistry, and engineering are leading to a new manufacturing concept for converting renewable biomass to valuable fuels and products, generally referred to as the biorefinery. The integration of agroenergy crops and biorefinery manufacturing technologies offers the potential for the development of sustainable biopower and biomaterials that will lead to a new manufacturing paradigm.

http://science.sciencemag.org/content/sci/311/5760/484.full.pdf

The path forward for biofuels and biomaterials

Although fire is now rarely used in synthetic chemistry, it was not until Robert Bunsen invented the burner in 1855 that the energy from this heat source could be applied to a reaction vessel in a focused manner. The Bunsen burner was later superseded by the isomantle, oil bath, or hot plate as a source for applying heat to a chemical reaction. In the past few years, heating and driving chemical reactions by microwave energy has been an increasingly popular theme in the scientific community. This nonclassical heating technique is slowly moving from a laboratory curiosity to an established technique that is heavily used in both academia and industry. The efficiency of "microwave flash heating" in dramatically reducing reaction times (from days and hours to minutes and seconds) is just one of the many advantages. This Review highlights recent applications of controlled microwave heating in modern organic synthesis, and discusses some of the underlying phenomena and issues involved.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.200400655

Controlled microwave heating in modern organic synthesis.

▶ Addresses a wide range of timely environment, economic and energy topics ▶ A forum to review, analyze and stimulate the development, testing and implementation of mitigation and adaptation strategies at regional, national and global scales ▶ Contributes to real-time policy analysis and development as national and international policies and agreements are discussed and promulgated ▶ 94% of authors who answered a survey reported that they would definitely publish or probably publish in the journal again

Mitigation and Adaptation Strategies for Global Change

4.2.8. Reductive Coupling 3109 5. Reaction of Aromatic Compounds 3110 5.1. Electrophilic Substitutions 3110 5.2. Radical Substitution 3111 5.3. Oxidative Coupling 3111 5.4. Photochemical Reactions 3111 6. Reaction of Carbonyl Compounds 3111 6.1. Nucleophilic Additions 3111 6.1.1. Allylation 3111 6.1.2. Propargylation 3120 6.1.3. Benzylation 3121 6.1.4. Arylation/Vinylation 3121 6.1.5. Alkynylation 3121 6.1.6. Alkylation 3121 6.1.7. Reformatsky-Type Reaction 3122 6.1.8. Direct Aldol Reaction 3122 6.1.9. Mukaiyama Aldol Reaction 3124 6.1.10. Hydrogen Cyanide Addition 3125 6.2. Pinacol Coupling 3126 6.3. Wittig Reactions 3126 7. Reaction of R,â-Unsaturated Carbonyl Compounds 3127

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

and Fuels Changzhi Li,† Xiaochen Zhao,† Aiqin Wang,† George W. Huber,†,‡ and Tao Zhang*,† †State Key Laborotary of Catalysis, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China ‡Department of Chemical and Biological Engineering, University of WisconsinMadison, Madison, Wisconsin 53706, United States

Catalytic Transformation of Lignin for the Production of Chemicals and Fuels

Roles of water for chemical reactions in high-temperature water

Water near or above its critical point (374 C, 218 atm) is attracting increased attention as a medium for organic chemistry. Most of this new attention is driven by the search for more green or environmentally benign chemical processes. Using near-critical or supercritical water (SCW) instead of organic solvents in chemical processes offers environmental advantages and may lead to pollution prevention. Interest in doing chemistry in SCW is not entirely new, however. There has been much previous research in this area with applications in synthetic fuels production, biomass processing, waste treatment, materials synthesis, and geochemistry. Water near its critical point possesses properties very different from those of ambient liquid water. The dielectric constant is much lower, and the number and persistence of hydrogen bonds are both diminished. As a result, high-temperature water behaves like many organic solvents in that organic compounds enjoy high solubilities in near-critical water and complete miscibility with SCW. Moreover, gases are also miscible in SCW so employing a SCW reaction environment provides an opportunity to conduct chemistry in a single fluid phase that would otherwise occur in a multiphase system under more conventional conditions. The paper discusses the use of supercritical water in the following reactions:more » hydrogenation/dehydrogenation; C-C bond formation; rearrangements; hydration/dehydration; elimination; hydrolysis; partial oxidation; H-D exchange; decomposition; and oxidation.« less

Organic Chemical Reactions in Supercritical Water.

Supercritical fluids posses properties that make them attractive as media for chemical reactions. Conducting chemical reactions at supercritical conditions affords opportunities to manipulate the reaction environment (solvent properties) by manipulating pressure, to enhance the solubilities of reactants and products, to eliminate interphase transport limitations on reaction rates, and to integrate reaction and separation unit operations. Supercritical conditions may be advantageous for reactions involved in fuels processing, biomass conversion, biocatalysis, homogeneous and heterogeneous catalysis, environmental control, polymerization, materials synthesis, and chemical synthesis. Moreover, supercritical fluids can be used profitably in fundamental chemical investigations of intermolecular interactions and their influence on chemical processes. Work on chemical reactions in and with supercritical fluids is reviewed. We discuss both fundamental studies and applications of reactions at supercritical conditions, with focus on work published after 1985.

/pdf/reactions-at-supercritical-conditions-applications-and-1qoeqkmmtb.pdf

Reactions at supercritical conditions: Applications and fundamentals

We converted the marine microalga Nannochloropsis sp. into a crude bio-oil product and a gaseous product via hydrothermal processing from 200 to 500 °C and a batch holding time of 60 min. A moderate temperature of 350 °C led to the highest bio-oil yield of 43 wt %. We estimate the heating value of the bio-oil to be about 39 MJ kg−1, which is comparable to that of a petroleum crude oil. The H/C and O/C ratios for the bio-oil decreased from 1.73 and 0.12, respectively, for the 200 °C product to 1.04 and 0.05, respectively, for the 500 °C product. Major bio-oil constituents include phenol and its alkylated derivatives, heterocyclic N-containing compounds, long-chain fatty acids, alkanes and alkenes, and derivatives of phytol and cholesterol. CO2 was always the most abundant gas product. H2 was the second most abundant gas at all temperatures other than 500 °C, where its yield was surpassed by that of CH4. The activation energies for gas formation suggest the presence of gas-forming reactions other than steam...

Hydrothermal liquefaction and gasification of Nannochloropsis sp.

We produced crude bio-oils from the microalga Nannochloropsis sp. via reactions in liquid water at 350 °C in the presence of six different heterogeneous catalysts (Pd/C, Pt/C, Ru/C, Ni/SiO2−Al2O3, CoMo/γ-Al2O3 (sulfided), and zeolite) under inert (helium) and high-pressure reducing (hydrogen) conditions. To our knowledge, this is the first application of common hydrocarbon processing catalysts to microalgae liquefaction in water. In the absence of added H2, all of the catalysts tested produced higher yields of crude bio-oil from the liquefaction of Nannochloropsis sp., but the elemental compositions and heating values of the crude oil (about 38 MJ/kg) were largely insensitive to the catalyst used. The gaseous products were mainly H2, CO2, and CH4, with lesser amounts of C2H4 and C2H6. The Ru and Ni catalysts produced the highest methane yields. Only the zeolite catalyst produced significant amounts of N2. Typical H/C and O/C atomic ratios for the crude bio-oil are 1.7 and 0.09, respectively. In the presen...

Phillip E. Savage

Papers

Roles of water for chemical reactions in high-temperature water

Organic Chemical Reactions in Supercritical Water.

Reactions at supercritical conditions: Applications and fundamentals

Hydrothermal liquefaction and gasification of Nannochloropsis sp.

Hydrothermal Liquefaction of a Microalga with Heterogeneous Catalysts