Hemicellulose pyrolysis

Influence of Metal Ions on Oxygen Chemisorption and Ignition of Chars. We have carried out extensive studies of the influence of metal ions in wood on pyrolysis mechanisms (5.6) and this approach has now been extended to oxygen chemisorption of the chars. The metal ions occur in wood predominantly as the counterions of the uronic acid components of the hemicelluloses (12). We have shown that they can be almost completely removed by very mild acid treatment without any other major change in the chemistry of the wood. Table II shows that the major metal ions in cottonwood are Ca, K and Mg. The acid-washing process removed 98X of the metal ions in... 

Various solvents are being investigated to dissolve lignocellulosic materials. Some approaches focus on the selective depolymerization and extraction of lignin and hemicellulose as pre-treatment to produce clean cellulose fibers for subsequent fermentation or for pulping. Other approaches attempt to dissolve the whole lignocellulose with or without depolymerization. The liquefaction processes that are carried out at high temperature (>300 °C), and produce a complex oil mixture, are discussed above with the pyrolysis processes. 

Another approach to produce chemicals via degraded molecules is the fast pyrolysis of biomass at high temperatures in the absence of oxygen. This gives gas, tar and up to 80 wt.% of a so-called bio-oil liquid phase, which is a mixture of hundreds molecules. Some of compounds produced by pyrolysis have been identified as fragments of the basic components of biomass, viz. lignin, cellulose and hemicellulose. The bio-oil composition depends upon the nature of starting... 

Miller, R. S. and Bellan, J. (1997) A generalized biomass pyrolysis model based on superimposed cellulose, hemicellulose and lignin kinetics. Comb. Sci. and Techn., 126, 97-137. 

Pyrolysis of biomass is defined as the chemical degradation of the biopolymers (cellulose, lignin and hemicellulose) constituting the wood fuel which initially requires heat. As can be seen in Figure 51, all reaction pathways making up the pyrolysis are not endothermic, which implies that some of the pyrolysis reactions generate heat. However, overall the pyrolysis process is endothermic. 

Complex pyrolysis chemistry takes place in the conversion system of any conventional solid-fuel combustion system. The pyrolytic properties of biomass are controlled by the chemical composition of its major components, namely cellulose, hemicellulose, and lignin. Pyrolysis of these biopolymers proceeds through a series of complex, concurrent and consecutive reactions and provides a variety of products which can be divided into char, volatile (non-condensible) organic compounds (VOC), condensible organic compounds (tar), and permanent gases (water vapour, nitrogen oxides, carbon dioxide). The pyrolysis products should finally be completely oxidised in the combustion system (Figure 14). Emission problems arise as a consequence of bad control over the combustion system. 

The pyrolysis reactions involved in hemicellulose, i.e., xylan, are similar to those involved in cellulose pyrolysis. 

In principle, most types of biomass can be used as a raw material in the pyrolysis process [14]. Most of the research has been carried out using different wood as feedstock, although more than 100 different types of biomass have been tested [14]. Besides wood, these materials include forest residues, such as bark black liquor and agricultural residues such as straw, olive pits, and nut shells [12, 14], Additionally, pure biological polymers cellulose (linear polymer of D-glucose units), hemicellulose (heteropolymers of different hexoses and pentoses), and lignin (heteropolymer of p-coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol [19]) - have been tested as raw materials in the pyrolysis. 

Bio-oil from rapid pyrolysis is usually a dark brown, free-flowing liquid having a distinctive smoky odor. It has significantly different physical and chemical properties compared to the liquid from slow pyrolysis processes, which is more like a tar. Bio-oils are multicomponent mixtures comprised of different size molecules derived primarily from depolymerization and fragmentation reactions of the three key biomass building blocks cellulose, hemicellulose, and lignin. Therefore, the elemental composition of biooil resembles that of biomass rather than that of petroleum oils. Basic properties of biooils are shown in Table 33.7. More detail on fuel-related characteristics is provided in the literature.571... 

Pyrolysis in inert atmosphere between 400 and yOO C produces water vapour, CO2, combustible gases CO, H2, CH and a multitude of organic vapours from the biopolymers cellulose (C6(H 0)s), hemicellulose (Cj(H20)4) and lignin. An impression of the complex product spectrum especially of the condensable organic vapours is given in Fig. 6. The remainder is a black char, mainly consisting of carbon and inorganic ash oxides. 

Studies have focused on pyrolysis of wood s separated poXymene constituents , i.e., powdered wood, cellulose, hemicellulose and lignin (e.g. Antal, et al 198S Nunn, et at 1985). The effects that minor components such as extractives have on whole biomass pyrolysis products have not often been studied, except for ash (e,g Richards and Zheng, 1991). 

Biomass is composed of various components such as cellulose, hemicellulose, lignin, extractives and mineral water. The composition of biomass plays a definitive role in altering the product distribution and their properties [2-3J. As is shown in earlier publications [4-S] different biomass, on pyrolysis, give different product yield with different product properties. In order to choose a biomass for a particular process (carbonisation, liquefaction, gasification or adsorbent char) knowledge on the product distribution and properties for various biomass are essential. 

All the processes of biomass thermal eonversion (pyrolysis, gasification and combustion) begin with elementary steps of decompositions of each of the components of the starting material (cellulose, hemicellulose and lignin). It is hence necessary to well understand the kinetics of the corresponding fast elementary... 

Miller R.S, and Bellan J. (1997) A Generalized Biomass Pyrolysis Model Based on Surinqjosed Cellulose, Hemicellulose and Lignin Kinetic. Combust. Sci. Tech.,m, 97-112. 

The pyrolysis of wheat straw could be expected to be described by a superposition model, i.e. described by a number of parallel first order reactions, representing the decomposition of the biomass constituents (cellulose, hemicellulose and lignin) [4,5]. In this work, a superposition model has been used, in which the pyrolysis is assumed to be described by N independent first order reactions (for i=l, 2,..., N) ... 

As part of the answer lies in ability to describe the volatility of biomass tars, the work was primarly undertaken to get some insights into this area. Due to the very complex nature of pyrolysis tars, there are not suitable estimation methods available -experimental data are needed for further development of these techniques. The experimental data are needed to increase our understanding of this phenomenon. In this paper, we present results from tobacco, hemicellulose and lignin tars. 

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