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Elbersen Wageningen University & Research Centre (WUR) Institute Agrotechnology & Food Innovations-Biobased Products P.O. Box 17, 6700 AA Wageningen, the Netherlands e-mail: email@example.com ABSTRACT: In the bio-based economy, renewable herbaceous biomass such as straw and perennial grasses (e.g. Miscanthus, switchgrass and Reed Canary grass) will become important cellulosic feedstocks for conversion to biofuels, chemicals, electricity and heat. A significant fraction- up to one-fifth- of these herbaceous biomass consists of inorganic constituents, commonly referred to as ash, that can not be converted to energy. This paper reviews the occurrence and origin of mineral nutrients in biomass feedstocks and their impact on the whole production chain, including plant type, growing conditions, harvesting date and –method, storage, pre-processing, and conversion systems. The quantity and quality of ash in herbaceous biomass is shown to depend on a large amount of factors that all can be manipulated to a certain extent. Efforts to lower ash content or improve ash quality in herbaceous biomass however may have economic trade-offs that are case specific. An integrative approach to ash management in biomass delivery and conversion systems is proposed that will help develop strategies to reduce or overcome the impact of inorganic constituents in biomass conversion. Keywords: energy crops, ash, biomass resources, miscanthus, switchgrass 1 INTRODUCTION 2 OCCURRENCE AND ROLE OF INORGANIC CONSTITUENTS IN HERBACEOUS BIOMASS
10 9 Ash content (%) (% ) 8 7 6 5 4 3 2 1 0
Miscanthus- Miscanthus- Switchgrass Rapeseed Grass seed Grass seed A B straw straw-A straw-B Wheat straw Reed Canary Grass
In the bio-based economy, renewable herbaceous biomass such as straw and perennial grasses will become important cellulosic feedstocks for conversion to biofuels, chemicals, electricity and heat. A significant fraction of these herbaceous biomass consists of inorganic constituents, commonly referred to as ash, which can not be converted to energy. Not only the amount of ash, also the composition can be of great importance. Ash content can originate from the biomass itself or from collection and pretreatment methods and often lead to high disposal costs resulting in a negative economic impact on biomass conversion systems. Only in a few cases and under certain conditions, such as thermal conversion of rice hulls, have biomass ash residues become a marketable product. The negative impact of inorganic constituents in herbaceous biomass may be aggravated in biochemical conversion systems (such as production of cellulosic ethanol), where the use of inorganic chemicals during pretreatment adds to the total amount of non-convertible inorganic residues in the conversion system. This paper reviews research on occurrence and origin of mineral nutrients in biomass feedstocks in the whole production chain, including the effects on ash content and composition of: • Plant type • Plant fraction • Growing conditions • Harvesting time and -method • Handling systems • Pretreatment concepts (i.e. field leaching) • Conversion system The objective is to assess the evidence of the role of ash in biochemical and thermal conversion systems. In addition, methods to reduce or overcome the impact of inorganic constituents will be reviewed covering the whole production chain from agronomy, collection and handling, to pretreatment and conversion to products.
Figure 1: Ash content (% d.w.) of 8 herbaceous biomass grown on clay soils in the Netherlands (2005 harvest) Figure 1 shows the ash content of 8 herbaceous biomass types that were recently collected from commercial farms in the Netherlands. All samples were collected from crops grown on clay soils. Total ash content (% d.w.) is shown to vary enormously, from 2% for Miscanthus, to 8.5% for Reed Canary Grass. The wide variability in ash is in itself a potential bottleneck for biomass conversion, however, ash content alone cannot predict the potential impact of ash in herbaceous biomass types may have on thermo- or biochemical conversion. In order to understand better why and at what level specific inorganic constituents are found in herbaceous biomass, Table I reviews the occurrence of 5 main ash components (Si, K, Ca, S and Cl) that are generally thought to have an impact on biomass conversion system. Silicon has several beneficial effects to a large number of plant species. It increases leaf erectness, resulting in a reduced susceptibility against lodging. In addition, a high content of silicon in leaves increases the resistance of the tissue against fungal attacks, blast infection, and insect pests. Potassium is the macronutrient required by plants in the largest amount after nitrogen . The
Switchgrass grown on sandy soil consistently showed lower ash (51-73% reduction compared to clay soils) and potassium content (16-44%). As a result. stem.1 Plant type and -species C3 plants (e.0% Sulfur 0. and increased susceptibility to frost damage and fungal attack.potassium requirement for optimum plant growth is in the 1-5% dry matter weight range. calcium is a nutrient that has an important role in many essential processes including binding form.5% Chlorine 0. whereas rice straw is considered a difficult fuel due to the combination of high ash. and in long-distance transport within the plant . chloride has high mobility within the plant. Potassium is characterized by its high mobility in plants at all levels. C4 plants (sugar cane.3 growing conditions). phosphorus and potassium .15% Potassiuma 1–2% Calciumb 0. a byproduct of rice grain processing and a high ash-high silica material. b.0% of dry weight depending on growing conditions.  determined total ash and nutrient content of 5 switchgrass varieties on a clay and a sandy soil in the Netherlands (Figure 2). Calcium content of plants varies between 0. Potassium is not metabolized and forms only weak complexes in which it is readily exchangeable. Table I: Occurrence of inorganic constituents in biomass (% dry plant matter) Occurrence (%) Silica 0. node.2. Sulfur is a macronutrient required for plant growth and is increasingly being recognized as the fourth major plant nutrient after nitrogen. regulation of osmotic pressure.5 . Elbersen et al. which results in higher ash levels in crops grown on clay soils. Miscanthus. whereas stems only contained 12% ash (with 42% silica). Summers et al. Potassium is involved in a large number of essential processes for plant growth. The functions of sulfur in plant growth are closely related to the functions of the various organic structures of which sulfur is a constituent. and varies among plant species.2 . reed canary grass) exhibit a higher yield potential in temperate and cold climates and need more water to produce a similar amount of plant dry matter as compared to C4 plants. Calcium might be firmly bound to plant structure or is exchangeable at the cell walls. in mature leaves. main factors in the entire (primary) production to conversion chain are reviewed that affect the ash quantity and –quality in herbaceous biomass. the functional requirement for plant growth of most of these compounds is not known . between tissues. whereas results for chlorine were variable. Sulfur is incorporated into many organic structures. Chlorine plays an essential role in a number of processes. Chlorine in plants occurs mainly as a free anion or is loosely bound to exchange sites. are generally considered a good biomass fuel for combustion. plant species and organ . including amino acids. however some sulfate can be utilized without reduction . rain. protein synthesis. proteins. In general. photosynthesis. however. C3 plants generally contain a higher ash concentration as water uptake is directly related to deposition and uptake of Si and other inorganic constituents in plant biomass. In young plant shoots. 3. and high alkali content (leading to ash agglomeration) in the material.2 Plant fractions The distribution of ash and specific inorganic components in herbaceous biomass may vary significantly among different plant fractions. including wilting and sensitivity to drought stress. calcium might reach more than 10% Chlorine is a naturally abundant element and is taken up by plants in the form of chloride ion. wheat.1 and > 5. secretory processes. In addition. and average chlorine content in plants ranges from 0.1 . fertilizers. For instance rice hulls. maize. The supply of chlorine can be from a variety of sources including irrigation water.0% Notes: a. For example. C4 species exhibit lower ash concentrations compared to C3 plants (see also 3. is a very important factor in deposition of inorganic constituents in biomass. Cl-. and therefore concerns exist about chlorine toxicity in plants rather than chlorine deficiency. switchgrass) have a higher yield potential in Mediterranean and warm climates and use on average half as much water as C3 plants. Distribution of inorganic constituents among plant parts is often specific and can have a direct impact on the application of the biomass type. Like potassium. and air pollution generally exceeds the plant’s growth requirements. cell wall stabilization. As a result. panicle) and concluded that ash and silica content varied significantly among straw fractions: leaves contained 18-19% total ash (of which 76% consisted of silica). The difference in total ash content among these soil types can be largely explained by the higher soluble silica level in clay soils. including the opening and closure of stomata. and in particular its texture. 3. graminae require less sulfur for plant growth than leguminosae. soil type. including between individual cells. a number of chlorinated organic compounds have been found in plants.  determined total ash and silica in different botanical fractions of rice straw (leaf. SO42-.0% of dry plant weight. 3 FACTORS AFFECTING ASH QUANTITY AND – QUALITY IN HERBACEOUS BIOMASS In the following section.1 – 0.3 Growing conditions For any given species. vascular transport.1 and 0. and enzymes. The sulfur requirement for optimal plant growth varies between 0. including enzyme activation.2. high silica. K-deficiency in plants may lead to a variety of plant growth-inhibiting factors. . The majority of sulfate in the plant is reduced for incorporation into organic molecules.5% of dry plant weight. sorghum.2 . depending on species. while the potassium concentration in mature plants generally does not exceed 2% of dry matter. increased lodging. 3. It is taken up in particular by the roots in the form of sulfate.5. and cation-anion balance .g. membrane stabilization and regulation of osmotic pressure. up to 5% potassium may be found. Similar to potassium.
For leaching of wet-harvested. however effects on specific inorganic constituents and total ash have so far not been analyzed. char wash) has been proposed as well . For wet biomass streams.and Cl-containing fertilizers. and dewatering. including rice and wheat straw . and leaching (removal of soluble constituents by rain. Ash content is shown to be directly related to ash content in the biomass .g. and may be more feasible from a practical point of view.  proposed a combination of treatments that include crushing. The beneficial effects of leaching on combustion characteristics have been described for many herbaceous biomass types. in particular with regards to K. Techniques might include submersion in water. Cl) are particularly reduced due to effects of increased senescence and translocation (plant nutrients are removed from leaf and other tissues to under-ground parts). ensilage techniques have been proposed to allow for longer term storage prior to conversion. Finally. Applications where leaching can be integrated into an existing process would seem beneficial. For thermal conversion systems. dewatering. if microbial degradation in stored biomass occurs. 3. 17]. spring harvest. Knudsen et al. banagrass . Constraints for commercial application of leaching as a pre-processing step are the incremental costs of leaching. the contamination with extraneous matter in these fuels can be relatively easily monitored by performing total ash analysis. primary conversion (e. 3. the loss of organic matter will lead to an increase in inorganic constituents on a volumetric basis. and/or drying. handling after field operations may lead to increasing inorganic constituents in herbaceous biomass. enzymatic hydrolysis and fermentation of the carbohydrate fraction. chopped banagrass for thermal conversion. ash content is also highly influenced by water uptake by the plant-this explains for instance the high ash content in wetland species (e. evidence of contamination is more difficult to determine without specific elemental ash analysis which is normally not available at conversion facilities. the type and amount of fertiliser affects ash content and – quality in herbaceous biomass. Miscanthus) that are characterized by a high water use efficiency.w.). adding water to the crushed biomass to facilitate extraction).w. which is often performed to enhance field drying or optimize harvest operations.7 Thermochemical and biochemical conversion It is beyond the scope of this paper to fully assess the impact of inorganic constituents on biomass conversion systems. Removing elements after initial.5 Handling and Storage As with harvest.  proposed a process similar to cane diffusion. the impact of total ash and specific inorganic ash components on combustion or gasification has been extensively reported on [15. Turn et al. such as a high loss of plant matter (which reduces yields considerably) or an increase in total ash (due to losses of organic matter) .e.g. For many biomass types including cereal straws. and reduction of conversion efficiency due to higher fuel moisture content.). reed canary grass .g. or field leaching. as both may lead to contamination with soil. K and Cl content of 5 switchgrass varieties grown on a clay and a sandy soil in the Netherlands (1999-2000 harvest) As discussed earlier. rice) and low ash content in C4 species (e. high water requirements. Efforts to include a time window to allow for leaching by natural means (e. field operations prior to biomass collection (e. The processing or milling of sugar cane is an example of such a process: leaching of potassium and other elements occurs along with the extraction of sugar.g. an estimate is made of total ash content in the ligneous residue that is extracted following pretreatment. irrigation. in particular in field harvest operations that include swathing. most of the experience with handling and storage of biomass has been with woodfuels which have inherently low ash content (0-1% d. Delaying harvest however can also have important tradeoffs.3) from biomass on ash quality. imbibition (i.g.6 Pre-processing Given the beneficial effects of leaching of inorganic constituents (see 3. Given the low ash content. or too expensive to carry out at a regular basis. For leaching of wheat straw prior to combustion. combine harvesting of cereals) should be tuned to avoid submersion or flattening of straw. So far. K. and a higher total ash concentration will also impact the quality of the nonfermentable ligneous residue that is made available for thermal conversion. 3. Extending harvest dates later in the season generally leads to lower ash content.4 Harvest Both the total amount of ash as well as specific inorganic constituents in herbaceous biomass can be manipulated by the timing of harvesting. Swathing or raking may increase the amount of soil particles in the biomass. 16. as long as the biomass is stored at sufficiently low moisture contents(<20% d. which add to total ash composition .g. a number of authors have proposed a controlled washing or leaching step prior to conversion to remove troublesome elements from herbaceous biomass. mist or dew). Impacts of long-term storage of herbaceous biomass on ash are generally believed to be small. In herbaceous biomass however. and others. The selection of mechanical harvesting techniques may affect ash content and composition as well. In Figure 3. impact of ash and ash composition on conversion systems has not yet been widely studied. Specific constituents in herbaceous biomass may lead to fermentation inhibition (depending on the tolerance of the microorganism and the dry matter loading during fermentation). However. dew) are generally referred to as delayed harvesting. raking or curing the biomass prior to collection. For biochemical conversion systems. rain. A number of constituents (e. 3.7 Forestburg Summer CIR Blackwell Carthage 6 5 4 3 2 1 0 Ash (%) K (%) Clay soil Cl (%) Ash (%) K (%) Sandy soil Cl (%) Figure 2: Ash.
Georgia .. Alkali slagging problems with biomass fuels. and conversion systems.. 1998. Biomass and Bioenergy 20: 431-446 Turn et al.). 2001. St. Boocock (eds. Properties of Rice Straw as Influenced by Variety.A. 3rd revised edition. August 30-September 2 in Burlington.W. Academic Press.  Summers M. 1997. choice of harvest date.w. Turn.D. Switchgrass as an alternative energy crop in Europe. W. National Renewable Energy Laboratory. however measures to improve ash quality in herbacous biomass however may have economic trade-offs that are case specific.g. The Sulphur Institute. 2004. 1993. Functions of Potassium in Plants.M.C. Developments in Thermochemical Biomass Conversion. VR.5% 20 Ash in ligneous residu 15 10 5 0 2 4 6 Ash in Feedstock (% dm) 8 10 Figure 3: Total ash composition in ligneous residue following pretreatment.L. Georgia  Marschner. 1980. USA  Wallingford. plant fraction. 1980. et al. 1996.  Knudsen N. R. Mineral Nutrition of Higher Plants. H. Atlanta. in: Proceedings of the First Biomass Conference of the Americas. London.L. Potassium availability and uptake. sulfate). Biomass and Bioenergy 10:243-260  Burvall. 5 LITERATURE  Elbersen H. In: Potassium for Agriculture.nl  Jenkins B. Removal of inorganic constituents of fresh herbaceous fuels: processes and costs. H.  Jenkins B.1316-1330  Wallingford.0% 1. Proceedings of the International Conference. et al. Georgia  Tandon. Potash and Phosphate Institute. Proceedings Third Biomass Conference of the Americas. and D. et al.. 2001. et al. ASABE. harvest techniques. et al. Biomass and Bioenergy 12: 149-154. ASAE paper number 01-6078. Final report FAIR 5-CT97-3701. Atlanta. and is dependent on the amount of inorganic constituents added to the system during pretreatment (e. MI. Biomass and Bioenergy 25: 597-614 Jensen P.G. Joseph. In: Potassium for Agriculture. 1996. Atlanta.D. A.B. Potash and Phosphate Institute. et al. Combustion Characteristics of Leached Biomass. Functions of Potassium in Plants. including the potential for recycling of nutrients to the field. www.. Washington D. et al. 1991. Colorado  Baxter L. London. Blackie Academic and Professional. Efforts should be made to integrate this approach with beneficial uses of ash derived from biomass. In: Biomass for Energy and Industry. Montreal. W. enzymatic hydrolysis and fermentation of herbaceous biomass 4 CONCLUSIONS AND RECOMMENDATIONS The quantity and quality of ash in herbaceous biomass depends on a large amount of factors including plant type.0% 0. Germany  Miles et al.R. In: Bridgewater. In: Potassium for Agriculture. Season and Location. growing conditions. 2nd edition. 1980. 2002. United Kingdom  Munson..M. An integrative approach to ash management in biomass conversion systems is needed that will help develop strategies to reduce or overcome the impact of inorganic constituents in biomass conversion. pp..V. Wurzburg. Biomass and Bioenergy 12: 241-252 Bakker R. fertilisation.and may reach up to 20% d. 1993.switchgrass. Most of these factors can be managed to a certain extent to reduce total ash in biomass or to remove undesirable inorganic components. 1993 Biomass and Bioenergy 4(2):85-102. Golden. Potash and Phosphate Institute. 1997. Sulphur research and Agricultural Production in India. et al.S. 25 inorganic matter added for pretreatment: 2.O. Possibilities and evaluation of straw pretreatment. The amount of ash in the ligneous residu is also dependent on the selected upgrading technique for lignin: drying lignin will inevitably lead to a higher ash content then dewatering as soluble salts remain in the solid phase.
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