Chemical composition of biomass
2.6 CHEMICAL COMPOUNDS AND BIOMASS PROCESSING .1 Drying
One drawback of many processes involving biomass relates to its water content. The water content of freshly harvested green biomass is often as high as 50–60% water (wet basis). Drying is an energy consuming process but can be done at low temperature, meaning that surplus low-value and low-temperature (<95◦C) heat can be used. At industrial facilities and combined heat and power (CHP) plants, heat generated by the condensation of vapor produced during drying at high temperatures (>100◦C) is often reused to increase the energy efficiency of the drying processes.
Patzek and Pimentel (2005) illustrated the importance of moisture content in biomass. These authors discussed a case in which raw biomass with a natural moisture content of around 55% was upgraded by drying it to yield a fuel with a moisture content of 10% by weight. Because the heat of condensation was not recycled during the drying process, the net gain in available energy was low.
In the interval of 20–60% moisture content (wet basis) the weight of raw biomass needed, to produce heat in order to dry 1 kg of upgraded fuel to 10% moisture content, is more than doubled for each 10% going from the bottom of the interval to the top. The higher moisture content the lower net gain. At high moisture contents the concept without recovery of condensation heat starts to break down completely.
On the other hand, Wahlund et al. (2002) reported that biomass drying could be achieved with low energy input at a bio-based CHP facility. In this case, the biomass was dried using pressurized steam and a heat exchanger was used to transfer heat from the ‘dirty’ steam generated by moisture in the wood to ‘clean’ steam that could be used to generate power. In addition, the heat released during the condensation of the ‘dirty’ steam was recycled and reused in the drying process. Additional heat exchange below the vapor condensation point could further reduce the specific energy of drying and increase the net output of bioenergy in this process. Thus, the most effective drying process accounts only for heat exchange losses in the system.
These examples illustrate that controlling the moisture content of biomass is crucial for its industrial use and that the heat needed for drying should be reused in as many ways as possible in order to continuously increase the net output of upgraded fuel. This requires the development of integrated processes that allow for the efficient use of surplus heat; many current industrial and energy conversion processes produce a lot of surplus low-value, low-temperature heat that could be exploited for drying biomass.
There are of course other ways to reduce or overcome problems arising from the moisture content of biomass. One is delayed harvesting, which has been demonstrated for the rhizome grass, reed canary grass (Phalaris arundinacea L.), and for industrial hemp, by cropping in spring instead of autumn (Xiong et al., 2009). During late fall and winter, the above-ground biomass of these grasses dies, and over the course of the early spring, it dries out, at which point it is harvested. A notable advantage of such delayed harvesting is the low ash content of the biomass obtained and the favorable composition of the ash that is formed. Other systems used in forestry involve storing covered piles of logging residues in such a way that they self-dry over time in the air. A drawback of these outdoor storage systems is that some biomass is lost on standing due to biological and other degradation. In addition, infestations of mould and other bio-contaminants are hard to avoid and may be harmful downstream in the value chain.
2.6.2 Wet processing
Novel systems have been developed to avoid having to dry biomass completely. These typically focus on carrying wet biomass through all the steps in energy generation. Thus, the biomass is stored after pretreatment at low temperature with bio-preservatives such as polysaccharide-degrading enzymes (which can be added by treatment with yeasts) that maintain its condition and facilitate subsequent enzyme treatments (Passoth et al., 2009). It can then be subjected to fermentation e.g. ethanol and biogas production in sequence (Dererie et al., 2011). It is also possible use hydrothermal upgrading processes e.g. hydrothermal carbonization of lignocellulosic biomass (Hoekman et al., 2011). Gasification of wet biomass feedstocks using supercritical water oxidation has been studied and may become more practical following the discovery of new catalysts that improve reaction efficiency and product yield (Azadi and Farnood, 2011; Robbins et al., 2012).
2.6.3 Health aspects
Biomass in and of itself can be hazardous and cause health problems. Notably, it releases volatile species such as terpenes, aldehydes, and ketones that are collectively known as volatile organic compounds (VOCs). Banerjee (2001) has shown that during softwood drying, there are three mechanisms involved in the release ofα-pinene and other terpenes. Moreover, dissolved terpenes accounted for approximately 0.1% of the total quantity of vapor released during softwood drying.
Wajas et al. (2007) used headspace solid-phase micro extraction to analyze VOC emissions from
biomass. They found that vapors from different species had unique chemical compositions and that 64–98% of the eluted compounds were monoterpenes. Arshadi et al. (2009) have studied the emission of volatile aldehydes and ketones from wood pellets. Long-term exposure to high levels of VOCs may cause health problems. Thus, gaseous substances such as VOCs from biomass should also be monitored regularly, especially in industries that handle biomass. In addition, good ventilation should be maintained.
It is possible that stored biomass may undergo self-heating, which presents a risk of explosions and fires. If the moisture content of the biomass is sufficiently high, this initial self-heating often has biological causes, as thermophilic microorganisms increase the temperature of the fuel while decomposing it. At low moisture levels, which tend to suppress microbial growth, biomass may adsorb vapor from the ambient air, which can trigger self-heating due to differential rates of adsorption and vapor condensation. These initial heating processes can trigger auto-oxidation of the biomass, raising its temperature to the point that increasing quantities of VOCs and non-condensable gases like CO, CO2and CH4are released, greatly increasing the risk of explosions and/or fires. The temperature of stored biomass should therefore be monitored continuously and if it starts to rise, preventative measures should be taken to reduce the risk of fire.
Of the non-condensable gases, CO is the most hazardous because it prevents oxygen uptake by humans even at low atmospheric concentrations. Unprotected people exposed to an atmosphere containing around 800 ppm of CO will lose consciousness within 2 hours. At 12,800 ppm, death occurs within 1–3 minutes. Svedberg et al. (2004, 2008 and 2009) have studied VOCs and also cases where people were killed by emissions of non-condensable gases from biomass. These typically occur in environments where biomass is stored in rooms with no or very little ventilation, i.e. limited exchange of air. Such places are found in ships transporting biomass, in silos and in storage areas, etc. The solution is simple: increase the amount of ventilation and fresh air. People working in such environments must ensure that the levels of both CO and O2are safe (it is not enough to measure O2alone) before entering any space where biomass is stored in an enclosed area with little or no ventilation. Because CO can leak out to other rooms, the air in adjacent spaces should also be checked before entering. The safety measures for fuel pellets discussed in the Pellet Handbook (Obernberger and Thek, 2010) are valid for most biomass and should be implemented as a matter of course.
Another problem associated with handling biomass is the presence of dust as well as moulds and other microorganisms that grow on biomass. These are also hazardous. Explosions can occur if the concentration of dust in the air becomes too high, and prolonged inhalation of dust is harmful. Furthermore, microorganisms can be pathogenic and produce toxins and allergenic spores; exposure to these for even relatively short periods may result in sickness.
2.6.4 Bulk handling
It is well known that industrial processes involving solid biomass are significantly more problem-atic than those involving only gases or liquids. This point was highlighted three decades ago by the RAND Corporation (Merrow et al., 1981) and is still valid. The general conclusion of these reports was that the start-up costs and processing times for fluid processing plants exhibited little variation, with most being within 20% of the mean, whereas those for plants based on solids were 200 to 300% greater. After completion, fluid-processing plants typically operated at around 90%
of the designed throughput whereas solid-based plants tended to operate at around 50%. This is mainly due to the variable flow ability of solids compared to fluids. One should also keep in mind that viscoelastic solid biomass is harder to handle than hard solids such as gravel.
Feeding problems are a common reason for delayed start-ups and failure to sustain the designed-for production capacity. In comparison to fluid-based indusial processes, relatively little is known about biomass flow ability in different industrial processes and during internal transportation. As such, it will be important to study the tribology and rheology of solid biomass-derived materials in order to further their widespread adoption in industrial processes.
Figure 2.6. A van Krevelen diagram for un-treated biomass (open circles); Norway spruce wood chips torrefied at 260–300◦C for 8 to 25 minutes and commercial charcoal from softwood produced at about 450◦C (filled circles); and biochar produced at 600◦C (Lehmann et al., 2011) (diamonds).
The material with the highest average ratios is leaves from switch grass and sugarcane. Data on biomass and torrefied wood were kindly provided by Tao et al. (2012a) and Nordwaeger et al.
(2013 a and b), respectively.
Biomass is a visco-elastic and fibrous material and its bulk properties are generally difficult to predict because of its irregular shapes, wide particle size distributions, low bulk densities, and often high moisture contents. Further, biomass can have particles with very inconvenient shapes in which one or two dimensions are very much smaller than the third (e.g, straw, fibers and flakes);
this causes phenomena such as nesting. There are various mechanical problems associated with the bulk handling and flow characteristics of biomass, including bridging, compaction, and unwanted separation in silos and transporters. All of these are exacerbated by the presence of fine particles and dust, which also increase the risk of dust explosions.
The chemical composition of the material also affects its flow ability and processing. Samuels-son et al. (2009) and Nielsen et al. (2009) have shown that biomass samples with high concentrations of extractives in biomass will generate comparatively low wall friction at high pressures in systems such as pellet presses. High levels of organic acids and inorganic compo-nents in biomass will increase the wear on steel in transport canals, transporters, mills, presses, and so on.
2.6.5 Heat treatment of biomass
Pyrolysis is thermal treatment under anaerobic conditions, usually at temperatures of 450–550◦C or more. Torrefaction is a mild form of pyrolysis conducted at about 250 to 330◦C. In general, compared to raw and absolutely dried biomass, torrefaction produces material that has lost more of its mass (as a percentage) than its energy content. The oxygen-containing constituents of biomass have lower energy contents than other constituents. Consequently, the gases released during torrefaction typically have higher oxygen contents than the remaining biomass, as demonstrated by analyses of C, H and O levels in torrefied materials. A good overview of the torrefaction process can be obtained by constructing van Krevelen diagrams (van Krevelen, 1950) with the atomic O/C ratio on the horizontal axis and the H/C ratio on the vertical axis. A linear trend was observed in a series of experiments conducted using different torrefaction temperatures and treatment times (see Fig. 2.6).
Van Krevelen diagrams for other materials such as coal and anthracite have steeply sloping H/C trend lines when the O/C ratio is lower than 0.1, as shown by van der Stelt (2011). As such, it may be hard to obtain oxygen-free materials that still contain hydrogen by pyrolysis of biomass.
Figure 2.7. Changes in relative biomass atomic (molar) ratios after losses of C, H, O, CO CO2, H2O and CH4 in processes such as fermentation (biogas formation), torrefaction, pyrolysis, and gasification.
Furthermore, as indicated by the somewhat anomalous average value for bamboo (see Fig. 2.6), the starting atomic ratios in the untreated biomass may influence the product O/C and H/C ratios after treatment.
Charcoal, which is also known as biochar, is a carbon-rich product produced by pyrolysis of plant biomass at about 350–600◦C. The storage of biochar in soil has been suggested as a method for sequestering carbon from CO2 in the atmosphere and thus mitigating climate change. The attractiveness of this idea is increased by the fact that biochar enhances plant growth in many soil types, facilitating bioenergy production and increasing crop yields. Woolf et al. (2010) studied the technical potential for using pyrolysis on a global scale to produce biochar for storage in soils. They estimate that the maximum potential offset is 12% of current anthropogenic CO2 -C-equivalent emissions without endangering soil conservation habitat or food security. That is to say, a sustainable global implementation of biochar has the potential to negate approximately 1.8 Pg CO2-Ceof the 15.4 Pg CO2-Ceemitted annually.
In gasification, all of the hydrogen in the substrate can potentially be extracted for syngas production and for forming more complex products such as dimethylether (DME), which has the empirical formula CH3OCH3, an H/C ratio of 3 and an O/C ratio of 0.5. If hydrogen is trapped in the residual carbon after gasification, this directly reduces the efficiency of the process. This is especially true if the raw material has lower H/C ratios than the gasification products, which is the case for polymers (bio-plastics) consisting of CnH(1.5–2)n and other elements. As such, pretreatments such as torrefaction that are used to make biomass more suitable for gasification could reduce its H/C ratio. This in turn would reduce the product’s potential value. On the other hand, torrefaction could increase the scope for producing more suitable substrates that leave smaller quantities of carbon-containing residues during gasification. New pretreatments and approaches to gasification should therefore be developed to keep as much of the substrate’s hydrogen as possible in a reduced state and minimize the presence of hydrogen-containing biochar residues.
The results presented in Figure 2.6 and 2.7 can be combined to estimate the net effects of different processes on the basis of C, H and O analysis of samples. The dashed line in Figure 2.7 shows the linear relationship for torrefied samples presented in Figure 2.6. For these samples, both the H/C and O/C ratios decrease at higher temperatures and with prolonged treatment. The direction of this linear relationship indicates that torrefaction under anaerobic conditions induces a major overall reaction whereby the oxygen in biomass reacts with its hydrogen to produce water.
The torrefaction reaction is described in more detail in Chapter 7 of this book and was recently reviewed by van der Stelt (2011). Likewise it can be postulated from Figure 2.7 that the remaining material after biogas production, during which the main species lost from the biomass is CH4, will have a lower H/C ratio but probably an elevated O/C ratio, especially if the losses of CO,
Figure 2.8. The relationship between energy content and carbon content (C%) in biochar produced by pyrolysis (data from Woolf et al., 2010).
CO2and H2O are low in comparison to that of methane (CH4). This fermentation process also occurs in anaerobic environments.
It is indicated by van der Stelt (2011) that like natural peat produced in mires and mosses, natural lignite also has a somewhat higher H/C ratio than other thermally treated biomasses with comparable O/C ratios. This may also indicate that peat and lignite formation are both characterized by a relatively more rapid loss of oxygen than hydrogen. However, these formation processes are slow, occur at low temperatures, and may have a biological component. The data presented in Figure 2.7 suggest that the higher H/C ratio may be due to losses of CO2from the biomass.
Carbonization of biomass by different thermal and biochemical processes increases its gross calorific value. Figure 2.8 shows the linear relationship between energy and carbon content in biochar produced by pyrolysis.
The carbonization process for converting fresh biomass to biochar seems to be linear according to the van Krevelen diagram (van der Stelt, 2011), but the corresponding progression of “natural”
materials (lignite – coal – anthracite) is non-linear. Thus, thermal carbonization of biomass may be a natural first step that will facilitate the large-scale industrial use of biomass in existing coal-based plants as part of a broader effort to reduce the risk of irreversible climate change while avoiding damage to ecosystems and maintaining sustainable development that does not endanger food security, habitats, or soil conservation.
2.7 CONCLUSION
In conclusion, the chemical composition of biomass is complex and variable. Moreover, non-refined solid biomass has low flow ability and a low energy density whereas fossil oil and gas have good flow properties and oil and coal both have high energy densities. These factors, together with the health risks involved in handling raw and refined biomass, cause many problems that must be solved if biofuels are to replace fossil fuels on a large scale. It will be particularly important to monitor and control the inorganic contents of biomass, i.e. the ash-forming elements, since unfavorable compositions may cause operational problems during energy conversion. Thermal pretreatment of the organic components of biomass can homogenize feedstock quality, making it more like lignite or fossil coal.
We are currently on the doorstep of the industrialized biocarbon era. To cross the threshold, we will have to develop new knowledge and know-how in many sectors of society. We will also have to be patient and accept that there will initially be some drawbacks with the new systems because the problems to be solved along the way are more challenging than those encountered during the adoption of fossil fuels in the last century. However, we have a great advantage compared to the pioneers who first introduced widespread use of fossil fuels in that our technological sophistication and understanding of science have increased enormously. This puts us in a strong position as we strive to develop sustainably and to develop efficient and non-harmful methods for energy conversion.
2.8 QUESTIONS FOR DISCUSSION
• Why is biomass a suitable chemical resource for production of so many different types of products?
• How can biomass compete with oil and natural gas for production of plastics, textiles and other chemical products?
• What is the difference between cellulose, hemicellulose, starch and lignin?
• What do you believe biomass will be used for in the future? Any totally new applications?
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Arshadi, M., Geladi, P., Gref, R. & Fjallstrom, P.: Emission of volatile aldehydes and ketones from wood pellets under controlled conditions. Ann. Occup. Hyg. 53:8 (2009), pp. 797–805.
Arshadi, M., Geladi, P., Gref, R. & Fjallstrom, P.: Emission of volatile aldehydes and ketones from wood pellets under controlled conditions. Ann. Occup. Hyg. 53:8 (2009), pp. 797–805.