MANAGING ASH CONTENT AND -QUALITY IN HERBACEOUS BIOMASS: AN ANALYSIS FROM PLANT TO PRODUCT Robert R. Bakker and H.W.

Elbersen Wageningen University & Research Centre (WUR) Institute Agrotechnology & Food Innovations-Biobased Products P.O. Box 17, 6700 AA Wageningen, the Netherlands e-mail: robert.bakker@wur.nl 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 [1]. The

potassium requirement for optimum plant growth is in the 1-5% dry matter weight range, depending on species, while the potassium concentration in mature plants generally does not exceed 2% of dry matter. Potassium is characterized by its high mobility in plants at all levels, including between individual cells, between tissues, and in long-distance transport within the plant [2]. Potassium is not metabolized and forms only weak complexes in which it is readily exchangeable. Potassium is involved in a large number of essential processes for plant growth, including enzyme activation, protein synthesis, photosynthesis, regulation of osmotic pressure, vascular transport, and cation-anion balance [3]. K-deficiency in plants may lead to a variety of plant growth-inhibiting factors, including wilting and sensitivity to drought stress, increased lodging, and increased susceptibility to frost damage and fungal attack. Calcium content of plants varies between 0.1 and > 5.0% of dry weight depending on growing conditions, plant species and organ [2]. Calcium might be firmly bound to plant structure or is exchangeable at the cell walls. Like potassium, calcium is a nutrient that has an important role in many essential processes including binding form, cell wall stabilization, secretory processes, membrane stabilization and regulation of osmotic pressure. Sulfur is a macronutrient required for plant growth and is increasingly being recognized as the fourth major plant nutrient after nitrogen, phosphorus and potassium [4]. Sulfur is incorporated into many organic structures, including amino acids, proteins, and enzymes. It is taken up in particular by the roots in the form of sulfate, SO42-. The majority of sulfate in the plant is reduced for incorporation into organic molecules, however some sulfate can be utilized without reduction [2]. The functions of sulfur in plant growth are closely related to the functions of the various organic structures of which sulfur is a constituent. The sulfur requirement for optimal plant growth varies between 0.1 and 0.5% of dry plant weight, and varies among plant species. In general, graminae require less sulfur for plant growth than leguminosae. Table I: Occurrence of inorganic constituents in biomass (% dry plant matter) Occurrence (%) Silica 0.5 - 15% Potassiuma 12% Calciumb 0.1 - 5.0% Sulfur 0.1 0.5% Chlorine 0.2 - 2.0% Notes: a. In young plant shoots, up to 5% potassium may be found, b. in mature leaves, calcium might reach more than 10% Chlorine is a naturally abundant element and is taken up by plants in the form of chloride ion, Cl-. Chlorine in plants occurs mainly as a free anion or is loosely bound to exchange sites. In addition, a number of chlorinated organic compounds have been found in plants, however, the functional requirement for plant growth of most of these compounds is not known [2]. Chlorine plays an essential role in a number of processes, including the opening and closure of stomata. Similar to potassium, chloride has high mobility within the plant, and average chlorine content in plants ranges from 0.2 - 2.0% of dry

plant weight. The supply of chlorine can be from a variety of sources including irrigation water, rain, fertilizers, and air pollution generally exceeds the plants growth requirements, and therefore concerns exist about chlorine toxicity in plants rather than chlorine deficiency. 3 FACTORS AFFECTING ASH QUANTITY AND QUALITY IN HERBACEOUS BIOMASS In the following section, main factors in the entire (primary) production to conversion chain are reviewed that affect the ash quantity and quality in herbaceous biomass. 3.1 Plant type and -species C3 plants (e.g. wheat, sorghum, 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. As a result, 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. C4 plants (sugar cane, maize, Miscanthus, switchgrass) have a higher yield potential in Mediterranean and warm climates and use on average half as much water as C3 plants. As a result, C4 species exhibit lower ash concentrations compared to C3 plants (see also 3.3 growing conditions). 3.2 Plant fractions The distribution of ash and specific inorganic components in herbaceous biomass may vary significantly among different plant fractions. For example, Summers et al. [5] determined total ash and silica in different botanical fractions of rice straw (leaf, stem, node, 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), whereas stems only contained 12% ash (with 42% silica). Distribution of inorganic constituents among plant parts is often specific and can have a direct impact on the application of the biomass type. For instance rice hulls, a byproduct of rice grain processing and a high ash-high silica material, are generally considered a good biomass fuel for combustion, whereas rice straw is considered a difficult fuel due to the combination of high ash, high silica, and high alkali content (leading to ash agglomeration) in the material. 3.3 Growing conditions For any given species, soil type, and in particular its texture, is a very important factor in deposition of inorganic constituents in biomass. Elbersen et al. [6] determined total ash and nutrient content of 5 switchgrass varieties on a clay and a sandy soil in the Netherlands (Figure 2). Switchgrass grown on sandy soil consistently showed lower ash (51-73% reduction compared to clay soils) and potassium content (16-44%), whereas results for chlorine were variable. The difference in total ash content among these soil types can be largely explained by the higher soluble silica level in clay soils, which results in higher ash levels in crops grown on clay soils.

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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, 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, ash content is also highly influenced by water uptake by the plant-this explains for instance the high ash content in wetland species (e.g. rice) and low ash content in C4 species (e.g. Miscanthus) that are characterized by a high water use efficiency. Finally, the type and amount of fertiliser affects ash content and quality in herbaceous biomass, in particular with regards to K- and Cl-containing fertilizers. 3.4 Harvest Both the total amount of ash as well as specific inorganic constituents in herbaceous biomass can be manipulated by the timing of harvesting. Extending harvest dates later in the season generally leads to lower ash content. A number of constituents (e.g. K, 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), and leaching (removal of soluble constituents by rain, mist or dew). The beneficial effects of leaching on combustion characteristics have been described for many herbaceous biomass types, including rice and wheat straw [8], reed canary grass [9], banagrass [10], and others. Efforts to include a time window to allow for leaching by natural means (e.g. rain, dew) are generally referred to as delayed harvesting, spring harvest, or field leaching. Delaying harvest however can also have important tradeoffs, such as a high loss of plant matter (which reduces yields considerably) or an increase in total ash (due to losses of organic matter) [11]. The selection of mechanical harvesting techniques may affect ash content and composition as well, in particular in field harvest operations that include swathing, raking or curing the biomass prior to collection, which is often performed to enhance field drying or optimize harvest operations. Swathing or raking may increase the amount of soil particles in the biomass, which add to total ash composition [11]. For many biomass types including cereal straws, field operations prior to biomass collection (e.g. irrigation, combine harvesting of cereals) should be tuned to avoid submersion or flattening of straw, as both may lead to contamination with soil. 3.5 Handling and Storage As with harvest, handling after field operations may lead to increasing inorganic constituents in herbaceous biomass. So far, most of the experience with handling and storage of biomass has been with woodfuels which

have inherently low ash content (0-1% d.w.). Given the low ash content, the contamination with extraneous matter in these fuels can be relatively easily monitored by performing total ash analysis. In herbaceous biomass however, evidence of contamination is more difficult to determine without specific elemental ash analysis which is normally not available at conversion facilities, or too expensive to carry out at a regular basis. Impacts of long-term storage of herbaceous biomass on ash are generally believed to be small, as long as the biomass is stored at sufficiently low moisture contents(<20% d.w.). However, if microbial degradation in stored biomass occurs, the loss of organic matter will lead to an increase in inorganic constituents on a volumetric basis. For wet biomass streams, ensilage techniques have been proposed to allow for longer term storage prior to conversion, however effects on specific inorganic constituents and total ash have so far not been analyzed. 3.6 Pre-processing Given the beneficial effects of leaching of inorganic constituents (see 3.3) from biomass on ash quality, a number of authors have proposed a controlled washing or leaching step prior to conversion to remove troublesome elements from herbaceous biomass. Techniques might include submersion in water, dewatering, and/or drying. Removing elements after initial, primary conversion (e.g. char wash) has been proposed as well [12]. For leaching of wet-harvested, chopped banagrass for thermal conversion, Turn et al. [13] proposed a combination of treatments that include crushing, imbibition (i.e. adding water to the crushed biomass to facilitate extraction), and dewatering. For leaching of wheat straw prior to combustion, Knudsen et al. [14] proposed a process similar to cane diffusion. Constraints for commercial application of leaching as a pre-processing step are the incremental costs of leaching, high water requirements, and reduction of conversion efficiency due to higher fuel moisture content. Applications where leaching can be integrated into an existing process would seem beneficial, and may be more feasible from a practical point of view. 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. 3.7 Thermochemical and biochemical conversion It is beyond the scope of this paper to fully assess the impact of inorganic constituents on biomass conversion systems. For thermal conversion systems, the impact of total ash and specific inorganic ash components on combustion or gasification has been extensively reported on [15, 16, 17]. For biochemical conversion systems, 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), and a higher total ash concentration will also impact the quality of the nonfermentable ligneous residue that is made available for thermal conversion. In Figure 3, an estimate is made of total ash content in the ligneous residue that is extracted following pretreatment, enzymatic hydrolysis and fermentation of the carbohydrate fraction. Ash content is shown to be directly related to ash content in the biomass

and may reach up to 20% d.w., and is dependent on the amount of inorganic constituents added to the system during pretreatment (e.g. sulfate). 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.
25 inorganic matter added for pretreatment: 2.0% 1.0% 0.5%

20 Ash in ligneous residu

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10

0 2 4 6 Ash in Feedstock (% dm) 8 10

Figure 3: Total ash composition in ligneous residue following pretreatment, 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, plant fraction, growing conditions, fertilisation, choice of harvest date, harvest techniques, and conversion systems. Most of these factors can be managed to a certain extent to reduce total ash in biomass or to remove undesirable inorganic components, however measures to improve ash quality in herbacous biomass however may have economic trade-offs that are case specific. 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. Efforts should be made to integrate this approach with beneficial uses of ash derived from biomass, including the potential for recycling of nutrients to the field. 5 LITERATURE

[7] Elbersen H.W. et al, 2002. Switchgrass as an alternative energy crop in Europe, Final report FAIR 5-CT97-3701. www.switchgrass.nl [8] Jenkins B.M. et al, 1996. Biomass and Bioenergy 10:243-260 [9] Burvall, 1997. Biomass and Bioenergy 12: 149-154. [10]Turn, 1997. Biomass and Bioenergy 12: 241-252 [11]Bakker R.R. et al, 2004. Biomass and Bioenergy 25: 597-614 [12]Jensen P.A. et al, 2001. Biomass and Bioenergy 20: 431-446 [13]Turn et al. Removal of inorganic constituents of fresh herbaceous fuels: processes and costs, Proceedings Third Biomass Conference of the Americas, Montreal. [14] Knudsen N.O. et al, 1998. Possibilities and evaluation of straw pretreatment, In: Biomass for Energy and Industry, Proceedings of the International Conference, Wurzburg, Germany [15] Miles et al, 1993. Alkali slagging problems with biomass fuels, in: Proceedings of the First Biomass Conference of the Americas, August 30-September 2 in Burlington, VR, National Renewable Energy Laboratory, Golden, Colorado [16] Baxter L.L. et al, 1993 Biomass and Bioenergy 4(2):85-102. [17] Jenkins B.M. et al, 1996. Combustion Characteristics of Leached Biomass, In: Bridgewater, A.V. and D.G.B. Boocock (eds.), Developments in Thermochemical Biomass Conversion, Blackie Academic and Professional, London, pp.1316-1330

[1] Wallingford, W., 1980. Functions of Potassium in Plants, In: Potassium for Agriculture, Potash and Phosphate Institute, Atlanta, Georgia [2] Marschner, H., 1993. Mineral Nutrition of Higher Plants, 2nd edition; Academic Press, London, United Kingdom [3] Munson, R.D., 1980. Potassium availability and uptake, In: Potassium for Agriculture, Potash and Phosphate Institute, Atlanta, Georgia [4] Tandon, H.L.S., 1991. Sulphur research and Agricultural Production in India, 3rd revised edition, The Sulphur Institute, Washington D.C. [5] Summers M.D. et al, 2001. Properties of Rice Straw as Influenced by Variety, Season and Location, ASAE paper number 01-6078, ASABE, St. Joseph, MI, USA [6] Wallingford, W., 1980. Functions of Potassium in Plants, In: Potassium for Agriculture, Potash and Phosphate Institute, Atlanta, Georgia