1.0. Introduction 4044 2.0. Biomass Chemistry and Growth Rates 4047 2.1. Lignocellulose and Starch-Based Plants 4047 2.2. Triglyceride-Producing Plants 4049 2.3. Algae 4050 2.4. Terpenes and Rubber-Producing Plants 4052 3.0. Biomass Gasification 4052 3.1. Gasification Chemistry 4052 3.2. Gasification Reactors 4054 3.3. Supercritical Gasification 4054 3.4. Solar Gasification 4055 3.5. Gas Conditioning 4055 4.0. Syn-Gas Utilization 4056 4.1. Hydrogen Production by Water−Gas Shift Reaction 4056

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Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering.

Fast pyrolysis utilizes biomass to produce a product that is used both as an energy source and a feedstock for chemical production. Considerable efforts have been made to convert wood biomass to liquid fuels and chemicals since the oil crisis in mid-1970s. This review focuses on the recent developments in the wood pyrolysis and reports the characteristics of the resulting bio-oils, which are the main products of fast wood pyrolysis. Virtually any form of biomass can be considered for fast pyrolysis. Most work has been performed on wood, because of its consistency and comparability between tests. However, nearly 100 types of biomass have been tested, ranging from agricultural wastes such as straw, olive pits, and nut shells to energy crops such as miscanthus and sorghum. Forestry wastes such as bark and thinnings and other solid wastes, including sewage sludge and leather wastes, have also been studied. In this review, the main (although not exclusive) emphasis has been given to wood. The literature on woo...

Pyrolysis of Wood/Biomass for Bio-oil: A Critical Review

This paper provides an updated review on fast pyrolysis of biomass for production of a liquid usually referred to as bio-oil. The technology of fast pyrolysis is described including the major reaction systems. The primary liquid product is characterised by reference to the many properties that impact on its use. These properties have caused increasingly extensive research to be undertaken to address properties that need modification and this area is reviewed in terms of physical, catalytic and chemical upgrading. Of particular note is the increasing diversity of methods and catalysts and particularly the complexity and sophistication of multi-functional catalyst systems. It is also important to see more companies involved in this technology area and increased take-up of evolving upgrading processes. © 2011 Elsevier Ltd.

Review of fast pyrolysis of biomass and product upgrading

Biomass is an important feedstock for the renewable production of fuels, chemicals, and energy. As of 2005, over 3% of the total energy consumption in the United States was supplied by biomass, and it recently surpassed hydroelectric energy as the largest domestic source of renewable energy. Similarly, the European Union received 66.1% of its renewable energy from biomass, which thus surpassed the total combined contribution from hydropower, wind power, geothermal energy, and solar power. In addition to energy, the production of chemicals from biomass is also essential; indeed, the only renewable source of liquid transportation fuels is currently obtained from biomass.

The Catalytic Valorization of Lignin for the Production of Renewable Chemicals

Background Lignin, nature’s dominant aromatic polymer, is found in most terrestrial plants in the approximate range of 15 to 40% dry weight and provides structural integrity. Traditionally, most large-scale industrial processes that use plant polysaccharides have burned lignin to generate the power needed to productively transform biomass. The advent of biorefineries that convert cellulosic biomass into liquid transportation fuels will generate substantially more lignin than necessary to power the operation, and therefore efforts are underway to transform it to value-added products. Production of biofuels from cellulosic biomass requires separation of large quantities of the aromatic polymer lignin. In planta genetic engineering, enhanced extraction methods, and a deeper understanding of the structure of lignin are yielding promising opportunities for efficient conversion of this renewable resource to carbon fibers, polymers, commodity chemicals, and fuels. [Credit: Oak Ridge National Laboratory, U.S. Department of Energy] Advances Bioengineering to modify lignin structure and/or incorporate atypical components has shown promise toward facilitating recovery and chemical transformation of lignin under biorefinery conditions. The flexibility in lignin monomer composition has proven useful for enhancing extraction efficiency. Both the mining of genetic variants in native populations of bioenergy crops and direct genetic manipulation of biosynthesis pathways have produced lignin feedstocks with unique properties for coproduct development. Advances in analytical chemistry and computational modeling detail the structure of the modified lignin and direct bioengineering strategies for targeted properties. Refinement of biomass pretreatment technologies has further facilitated lignin recovery and enables catalytic modifications for desired chemical and physical properties. Outlook Potential high-value products from isolated lignin include low-cost carbon fiber, engineering plastics and thermoplastic elastomers, polymeric foams and membranes, and a variety of fuels and chemicals all currently sourced from petroleum. These lignin coproducts must be low cost and perform as well as petroleum-derived counterparts. Each product stream has its own distinct challenges. Development of renewable lignin-based polymers requires improved processing technologies coupled to tailored bioenergy crops incorporating lignin with the desired chemical and physical properties. For fuels and chemicals, multiple strategies have emerged for lignin depolymerization and upgrading, including thermochemical treatments and homogeneous and heterogeneous catalysis. The multifunctional nature of lignin has historically yielded multiple product streams, which require extensive separation and purification procedures, but engineering plant feedstocks for greater structural homogeneity and tailored functionality reduces this challenge.

https://lifelong.unt.edu/sites/default/files/EmeritusCollege/Spring2015/Handouts/Lignin%20co-products.pdf

Lignin valorization: improving lignin processing in the biorefinery.

Slow-release effect of N-functionalized kraft lignin tested with Sorghum over two growth periods

Abstract The common use of wood together with traditional chemical polymers opens new possibilities in the field of sustainable product development. Wood plastic composites (WPCs) are an ideal combination of these raw materials, which can be produced with standard plastic technology such as extrusion or injection moulding. Wood to plastic ratio in a WPC influences quality and price, thus adaptation of analytical tools for material testing and quality assurance is required. In this study, the suitability of analytical pyrolysis (Py) and differential scanning calorimetry (DSC) was investigated to quantify the amount of polypropylene (PP) in WPCs. The reliability of these methods was tested by analysing WPCs with different ratios of wood and PP. The amount of PP can be determined with DSC based on its melting point as the influence of wood is negligible in this context. The increment of typical PP markers and decrement of wood markers was observed and quantified in the pyrograms if the PP content in WPCs was elevated. Thus, the ratio of PP and wood can be reliably quantified by means of online and offline analytical pyrolysis.

Quantification of polypropylene (PP) in wood plastic composites (WPCs) by analytical pyrolysis (Py) and differential scanning calorimetry (DSC)

A continuous fluidized-bed plant (PDU-scale) for fast pyrolysis of lingnocellulosic biomass gives rise to bio-oil yields of 65 wt.-%. The average reactor gas residence time was 1.2 s only. The gas and charcoal yields were 15–20 wt.-%, respectively. The bio oils were chemically characterized. The main monomeric products of the thermal degradation of carbohydrates are acetic acid, hydroxyacetaldehyde, hydroxypropanone, and levoglucosan. The process described in this paper can also be used for disposal of inorganic-, metal-organic-, and chlorine-organic contaminated waste-wood. Inorganic compounds of wood preservatives are concentrated in the charcoal fraction and can be separated easily. Chlorine-organic wood preservatives are mostly degraded. The process has been positively tested as a technique for disposal, recycling, and exploitation of industrial biomass waste (wood waste, grinding grit, fibre sludge, cocoa shell and modern composites like HPL). Bio oil from fast pyrolysis can be used for the production of energy and chemical feedstock. Research for these purposes is ongoing.

Design, Construction, and Operation of a Fast Pyrolysis Plant for Biomass

Innovative extraction methods with supercritical CO 2 and liquid CO 2 have been employed to obtain value-added chemicals from a slow pyrolysis liquid. Sequential solvent extraction with hexane and acetone was carried out for comparison. Pyrolysis liquid was first adsorbed on silica (SiO 2 ) with weight ratios SiO 2 :oil of 100:40 and 100:80. Pyrolysis liquid and extracts were mainly characterized by GC–MS/FID, elemental analysis, and water content. Results show that scCO 2 extraction is mainly controlled by dissolution at the first 3 h during a 6-h extraction period and by combination of dissolution and diffusion at later extraction periods. Around 60–65% of the CO 2 and hexane extracts could be identified by GC compared to 49% of the starting pyrolysis liquid. GC data confirmed that, CO 2 extraction effectively enriched both non-aromatics and aromatic compounds. Hexane extracts contained lower contents of organic acids. Hexane enabled a complete extraction of aromatics. Chemical composition of extracts from scCO 2 and liquid CO 2 are very similar. Extraction with scCO 2 and liquid CO 2 proves to be an effective and innovative pre-treatment process for the production of chemicals from pyrolysis liquid.

Dietrich Meier

Papers

Slow-release effect of N-functionalized kraft lignin tested with Sorghum over two growth periods

Quantification of polypropylene (PP) in wood plastic composites (WPCs) by analytical pyrolysis (Py) and differential scanning calorimetry (DSC)

Design, Construction, and Operation of a Fast Pyrolysis Plant for Biomass

Comparison of supercritical CO2, liquid CO2, and solvent extraction of chemicals from a commercial slow pyrolysis liquid of beech wood

Reactions, characterization and uptake of ammoxidized kraft lignin labeled with 15N