Baltic Bioenergy and Industrial Charcoal

BIOCOAL PRODUCTION, PROPERTIES AND USES

Mari Rautiainen, Mikko Havimo and Kristaps Gruduls

The Development of the Bioenergy and Industrial Charcoal (Biocoal) Production (Report of BalBiC -project cb46) Report 1/2012 Production and Logistics

Title: Biocoal production, properties and uses This report has been written in project The Development of the Bioenergy and Industrial Charcoal (Biocoal) Production (BalBiC ) partially financed by Central Baltic INTERREG IV A Programme 20072013. The content of the publication reflects the authors views and the Managing Authority cannot be held liable for the information published by the project partners. Publisher: University of Helsinki, Department of Forest Sciences Authors: Mari Rautiainen1, Mikko Havimo1 and Kristaps Gruduls2 1) Department of Forest Sciences, Faculty of Agriculture and Forestry, University of Helsinki, P.O. Box 27, FIN-00014 Helsingin yliopisto, Finland 2) Latvian State Forest Research Institute Silava, 111, Rigas str, Salaspils, LV 2169 Latvia Printer: Unigrafia Viikki, Infokeskus, Helsinki 2012

Table of Contents
1 Introduction ............................................................................................................. 5 1.1 1.2 1.3 2 2.1 2.2 2.3 2.4 3 3.1 3.2 3.3 3.4 3.5 3.6 4 4.1 4.2 4.3 4.4 4.5 Thermal degradation of biomass ................................................................... 5 Effect of process conditions on carbonization ................................................ 7 Carbonization and feedstock properties ...................................................... 11 Biocoal as fuel.............................................................................................. 13 Activated carbon.......................................................................................... 13 Charcoal in metallurgy ................................................................................. 14 Charcoal in agriculture and soil amendment ................................................ 14 Charcoal-making kilns .................................................................................. 17 The Carbo Twin-retort ................................................................................. 17 Euro kiln ...................................................................................................... 18 Lambiotte .................................................................................................... 18 Wagon retorts ............................................................................................. 19 Torrefaction plants ...................................................................................... 19 Charcoal production in the Nordic and Baltic countries ............................... 23 Latvia ........................................................................................................... 23 Estonia ......................................................................................................... 24 Sweden ........................................................................................................ 25 Finland ......................................................................................................... 25

Applications of biocoal ........................................................................................... 13

Production technologies......................................................................................... 16

Global charcoal production .................................................................................... 22

References .................................................................................................................... 26

PREFACE The use of bioenergy is increasing in the Nordic and Baltic countries. Climate change, increasing petroleum prices and the ambitious 20-20-20 target of the European Union are the drivers behind growing consumption and demand for bioenergy. Growing demand puts pressure on procurement of bioenergy. For example, large portions of stands suitable for forest residue collection are already in use. To fulfil the growing demand, bioenergy must be transported for long distances. Transporting forest bioenergy for long distances is unattractive, since the calorific value for wood is rather low in comparison to coal and other traditional fuels. Biocoal is a refined form of forest bioenergy. The calorific value and other properties for biocoal are better than those for untreated wood. The higher energy density of biocoal enhances transport and storage, allowing longer transport distances and use of remote raw material sources. Biocoal also has coal-like properties. This makes it a more suitable fuel for power plants designed for coal. Biocoal is here understood to include charcoal and torrefied wood. Charcoal has been made since ancient times, and several technological solutions exist. Torrefied wood is less well known product, but the production process is quite similar to charcoal making. Currently, several pilot plants and technological demonstrations of torrefaction technology are running in Europe. The aim of this report is to furnish the background on biocoal making by reviewing the literature on biocoal production and end use. The report was produced within BalBiC project Work Package 4. BalBiC is a joint project of the University of Helsinki, Latvian State Forest Institute Silava and Forestry Development Centre Tapio. The project was partly funded by Central Baltic Interreg IV A programme.

1 Introduction
Biocoal is a solid fuel made from biomass in a pyrolysis process. Depending on the process conditions, the solid product of pyrolysis is called charcoal or torrefied wood. In this study we refer to these two products as biocoal. Biocoal is CO2 neutral and a renewable fuel. It has several advantages over other biobased fuels, e.g. high energy content and coal-like properties. These make it attractive fuel for existing coal-fired power plants. Biocoal is produced during a process called pyrolysis, in which wood or other organic material is heated in the absence of oxygen. Heating degrades chemical substances of biomass thermally, breaking the long-chain polymer compounds of wood into smaller organic molecules. The pyrolysis process produces three main end products: solid biocoal, pyrolysis oil and non condensable gases. If the highest temperature in the process is above 300 C, the solid product is charcoal. At lower temperatures, torrefied wood is formed. The difference between these products is discussed later. Charcoal can be used in a wide range of applications, from soil enrichment to absorption agent, although the main end use of char is as a fuel. Pyrolysis oil and non condensable gases from the process are also combustible, and refining of pyrolysis oil into transportation fuel is currently being studied intensively. Non condensable gases have less economical or technical importance than char or pyrolysis oil, partly because the energy content of the gas is quite low. Non condensable gases are commonly used to fuel the pyrolysis process. Interest in pyrolysis has increased dramatically during the last 10 years. High oil prices and dependency on foreign energy sources are some of the drivers that have fostered the development of pyrolysis processes and technologies. Another driver is climate change, which forces the development of new CO2 neutral energy sources. Biocoal and pyrolysis oil are considered CO2 neutral if the raw material is biomass from sustainably managed sources. Here, we review biocoal production processes, raw materials and their current uses in the Nordic and Baltic countries. We have included process conditions, such as temperature and pressure, and various production technologies. Wood is the most common raw material for biocoal production, and the effect of various wood raw materials on biocoal properties is discussed. The statistics of biocoal production and use are also reviewed. Finally some case studies from Latvia and Finland are presented. 1.1 Thermal degradation of biomass Heating of biomass in an inert atmosphere causes thermal cracking of organic molecules. At elevated temperatures, some of the chemical bonds between atoms break down, forming light gaseous compounds and solid char. Breaking of the chemical bonds is an endothermic reaction and consumes energy; therefore, an initial heating is required. However, after bond breakage, new chemical bonds are formed. The formation of these bonds releases energy. After the initial heating phase, more energy is released from the new bond formation than is needed to break bonds. The process becomes exothermic and starts to release heat. 5

Thermal cracking of biomass depends on the process temperature. This can be illustrated with thermogravimetric analyses, in which wood or other biomass is heated and the mass of the sample is measured continuously. Figure 1. shows thermogravimetric analysis of dry Norway spruce (Picea abies) wood. There is a sharp drop in the sample mass when the temperature rises from 240 to 340 C. The lost mass is transformed into gaseous components, such as CO2, CO and various organic substances 1-2. At temperatures above 480 C the mass of the sample has become quite stable, and only small losses occur at higher temperatures. For example, the carbon content of the solid residue is 89% if the process is halted at a temperature of 680 C.3 If the temperature is further increased, only the carbon content increases by a few percentage points. Wood constituents have different thermal decomposition rates. Hemicelluloses are the most sensitive to thermal decomposition, and their mass decreases rapidly as temperature increases above 230 C.4 Cellulose is more heat-tolerant. It decomposes significantly only at temperatures above 260 C. When the temperature rises to above 290 C, over 45% of cellulose is consumed.4 Lignin is the most heat-tolerant of wood main components. Low temperatures below 230 C cause small decreases in lignin mass, but the main losses occur in temperatures above 300 C.4 The stages of charcoal formation can be briefly summarized as follows.5 Temperatures between 20 and 110 C. Wood absorbs heat and gives off moisture. The temperature remains around 100 C until wood is bone dry. Temperatures between 110 and 270 C. The final traces of water escape from wood. Decomposition starts, producing some gases, acetic acid and methanol. Heat is continuously absorbed. Temperatures between 270 and 290 C. Exothermic decomposition starts. Breakdown of chemical components continues spontaneously, producing heat, gases and some tar. Temperatures between 290 and 400 C. Breakdown of wood constituents continues. Tars begin to predominate substances produced. Temperatures above 400 C. At 400 C, transformation to charcoal is practically complete. However, some breakdown products are still trapped inside the charcoal; these can be driven off by heating the charcoal further.

1,0

0,8

Relative mass, %

0,6

0,4

0,2

0,0 0 200 400 600

o

800

Temperature, C

Figure 1. Thermogravimetric analysis of spruce sample. The sample is heated in an inert atmosphere, and the mass is recorded continuously.

1.2 Effect of process conditions on carbonization Several methods are available for industrial-scale charcoal production. The process conditions differ among methods, but the same basic physical principles can be applied to all charcoal production facilities. Temperature is the most important process condition in carbonization. Usually the highest temperature reached in the carbonization, called peak temperature, is used to describe the process. Solid product yield, heating value, carbon content and many other properties are dependent on peak temperature. Depending on the peak temperature, carbonization can be divided into two classes. At temperatures between 200 and 300 C, the process is called torrefaction, and the solid product is torrefied wood.6 In temperatures above 320 C, conventional charcoal is formed.7 Torrefied wood and charcoal can be made with the same methods; the main difference is lower peak temperature. The resulting solid products still differ considerably. The yield of solid products decreases when the peak temperature of the process increases. For example, the solid yield is 38% in 277 C, and drops to 25% when peak temperature reaches 877 C 8. The product yield approaches a given level asymptotically.9 Figure 1 illustrates the yield as a function of temperature. At the temperature range of torrefaction, the solid yield can be over 90%.10 On the other hand, at low temperatures, the heating value of the solid product remains low, and, therefore, the high yield may not be beneficial enough.

33

Higher heating value, MJ/kg

32

31

30

Logistic regression equation Measured heating value

29

28 200 400 600 800

o

1000

Temperature, C

Figure 2. Higher heating value of softwood charcoal produced at different temperatures. Drawn after data from Demirbas8.

The above-mentioned studies have been made in the laboratory, where the process is quite easy to control. It is reported that in industrial-scale reactors, the control of peak temperature may be difficult.7, 11 This is because after the initial heating phase the pyrolysis begins to produce heat. This extra heat can increase the peak temperature in the reactor beyond the intended level. Extra heat can be controlled by cooling the reactor, but in most charcoal-making processes cooling is not practical. If the temperature cannot be controlled, the final peak temperature is dependent on the process conditions, and can be different even within the same charcoal kiln.7 Therefore, traditional charcoal makers report the peak temperature in quite broad limits.

Table 1. Properties of torrefied wood and charcoal. mf = moisture-free, maf = moistureand ash-free.
Higher heating value (MJ/kg) 16 2 1 2 3 2 87 86 85 82 69 7.2 5.6 1 2 3 1 2 3 1 2 3 1 2 1 2 1 2 1 2 3 1 2 3 1 2 3 92 90 87 88 85 83 78 72 69 96 94 94 93 88 85 91 90 89 86 85 84 79 76 75 44 36 29 26 24 19 19 19 20 21 32 32 17 18 18 19 19 19 19 21 22 23 18 18 18 18 18 19 19 7.5 8.2 8.4 8.4 8.4 8.5 8.6 8.7 8.8 9.0 18 29 27 31 33 35

Peak temperature (C) Birch12 untreated 230 250 250 250 280 800 1000 Pine12 untreated 230 230 230 250 250 250 280 280 280 Pine13 untreated 230 230 250 250 280 280 Willow14 untreated 230 230 230 250 250 250 280 280 280 Eucalyptus dunnii15 untreated 300 350 450 600 650

Holding time (h)

Solid yield (wt%), maf

Carbon content (wt%, maf) 46 51 52 52 53 57 90 94 47 50 50 52 51 52 52 56 59 60 48 49 49 50 50 53 53 44 46 46 46 46 46 46 46 46 47 47 66 73 79 87 88

Ash content (wt%, mf) 0.60 0.64 0.65 0.67 0.75 4 5.1 0.15 0.16 0.16 0.16 0.16 0.17 0.18 0.20 0.21 0.23 0.23 0.23 0.23 0.24 0.24 0.40 1.40 1.41 1.43 1.48 1.51 1.52 1.60 1.66 1.69 0.6 1.3 1.7 2.1 2.0 2.1

High peak temperatures improve the heating value of the solid product (Fig. 2). The oxygen content decreases when the temperature increases, and the remaining solids contain more carbon, which, in turn, increases the heating value.16 Table 1 lists the heating values for a number of raw materials and peak temperatures. The higher heating value for dry wood is approximately 18 MJ/kg. The same value for torrefied wood is from 21 to 24 MJ/kg (Table 1.). If the peak temperature is raised to 1000 C, the higher heating value of charcoal increases to 32 MJ/kg,14 which is similar to good-quality coal. High heating values give good energy density per mass or volume unit. This is beneficial for the transport and storage of carbonized biomass: high-energy density fuels need less cargo space and storage facilities. On the other hand, the yield of the carbonization process decreases when the temperature and heating value increase. The producer must therefore decide whether it is better to have low yields and high energy content, or vice versa. Heating rate is another process condition that affects the properties of the solid product. Conventional pyrolysis designed for charcoal making commonly utilizes low heating rates, typically ranging from 0.1 to 1 C/s. This ensures high solid product yields 16-17. High production rates of pyrolysis oil and gaseous products can be achieved with fast pyrolysis or flash pyrolysis techniques.17 In these processes heating rates are very fast: in flash pyrolysis even up to 1000 C/s.14, 18 These extreme heating rates require very fine particle size and complex technology. The solid char yield is low. Low solid yields, fine particle size and complex technology make fast and flash pyrolysis unsuitable for charcoal making. Conventional pyrolysis (carbonization) is defined as having heating rates from 0.1 to 1 C/s. Within these limits, the solid yield and properties also vary. High yields can be obtained with low heating rates, but on the other hand, it is not practical to utilize very low heating rates.16 Along with peak temperature and heating rate, the time during which the biomass is held at the peak temperature, called the holding time, is another process condition that determines the properties of biocoal. Longer holding times decrease the yield of solid char. According to Pach et al.,19 yield of solids is observed to be approximately 13% higher in holding time of 1 hour than 3 hours in treatment temperature of 280 C. Ferro et al.,13 researched the effect of 1 and 2 hour holding times on torrefied products. They concluded that at temperatures lower than 280 C, the holding time has only slight impact (1%) on solid yield. Holding time has a slightly positive impact on heating value. The heating value increases with the increase in temperature and holding time.19 However, the increase is quite small even when the holding time is tripled; therefore, it is not economical to utilize long holding times. In batch-type charcoal-making kilns, such as the Missouri kiln used in the United States, the holding time is seldom controlled. After the initial heating phase, the kiln is left to heat up to the peak temperature. The peak temperature is not maintained by external heating or interrupted by forced cooling; the kiln is merely left to cool down due to con10

duction of heat to the atmosphere. When the charcoal is sufficiently cool, the kiln is unloaded. The whole cycle can take from 7 to 12 days.7 In charcoal-making processes that operate on a continuous basis, the holding time can be controlled by speeding up or slowing down the unloading rate of the reactor. In principle the holding time should be relatively short, since it determines the efficiency of the pyrolysis process. Experiments show that elevated pressure increases charcoal yield, although thermochemical equilibrium calculations predict no increase in carbon yields. For example, if the peak temperature is 450 C and pressure is increased from atmospheric to 1.0 MPa, charcoal yield improves by 7 percent points.20 According to Antal and Grnli16 the discrepancy between thermochemical calculations and experiments can be explained by secondary carbon formed from tarry vapours. In the pyrolysis reactor part of the gaseous tar components decompose to solid char. This process occurs also without overpressure, but at elevated pressures the decomposition process is more pronounced. 1.3 Carbonization and feedstock properties We have reviewed so far the effect of various process conditions on charcoal making and properties of charcoal. We now focus on raw materials and their effect on the process. Nearly all types of organic materials can be used in charcoal making. Peat, bones, straw and wood are suitable raw materials, and even manure can be pyrolysed into charcoal 21-22 . In the Nordic and Baltic countries, wood has been the most important raw material and will also continue to be so. Agricultural by-products are regionally important in those areas of the world where intensive farming or food industry produces large amounts of coconut shells, rice husks and other biomasses.22 In Nordic and Baltic countries these by-products could also be interesting raw material sources, but there seems to be a lack of studies on suitable non wood raw materials in the area. Moisture in biomass is probably the most important raw material property. High moisture content consumes more energy in the initial heating phase, since biomass dries before the temperature rises to the range at which pyrolysis begins. The satisfactory raw material moisture content in traditional kilns is 15 20 % 16. In continuous processes, such as in the Lambiotte kiln, the optimal raw material moisture content is 10%. Principally, drying can be performed in the pyrolysis reactor, but control of the process and equipment efficiency can be improved by drying beforehand. The moisture content of forest biomass is often greater than what the charcoal makers want. For example, stumpwood moisture content averages 53 % after harvesting, from which it can decrease to 31% in couple of months.23 However, it is difficult to attain moisture contents below 20% without artificial drying. Current bioenergy procurement in the Nordic and Baltic countries includes chipping of wood raw material. The size of the chips is important in biocoal production, since larger particles give higher yields.16 This is attributed to the formation of secondary char from gaseous tar components. Inside large wood blocks, gaseous components escape slowly, 11

and there is more time for the tar components to pyrolyse into char, which is then trapped inside the wood block. Although larger wood blocks have somewhat higher yields, it is probably more practical to use currently available chipping equipment and not produce larger wood blocks with specialized comminution machines. Teh density of wood varies considerably among tree species, and also within a species. Wood density has no effect on the carbonization yield.24 On the other hand, denser hardwoods are reported to give strong charcoal that burns more slowly than charcoal from less dense softwoods.22 Forest biomass contains small amounts of inorganic elements that are harmful to power plant equipment. Chlorine and potassium are the most important harmful elements. Chlorine can cause severe corrosion in boilers.25 Potassium forms deposits on the boiler surfaces, where it forms thick layers that decrease heat transfer and reduce boiler efficiency.25 Laboratory tests made with straw, which contains high amounts of chlorine and potassium, indicate that these elements can be reduced with pyrolysis. Jensen et al.26 showed in laboratory-scale tests that large amounts of chlorine were released from straw biomass at temperatures between 200 and 400 C. If the same is applicable to forest residues, carbonization could lower the amount of harmful elements in fuel feed. Lowering the concentration of chlorine and potassium during the carbonization process could give a significant competitive edge for charcoal.

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2 Applications of biocoal
2.1 Biocoal as fuel Biocoal is used mainly as a fuel. Charcoal has several applications, but torrefied wood is intended only for fuelling power plants. Charcoal can be used in metallurgy, soil amendment and in the chemical industry as an adsorbent. The largest application is still fuel, especially in the developing countries, where charcoal is used in households as a cooking fuel.22 Currently, the amount of charcoal and torrefied wood used in industrial power generation is negligible, but interest in both is increasing rapidly. An important reason for development of biocoal production is existing coal-fired power plants. These can seldom use, at least in large proportions, wood and other biomasses.27 Biomasses are fibrous materials and cannot be easily ground in mills intended for coal grinding.27 Biocoal has coal-like handling properties, and coal-fired power plants could probably use it without large investments in new technology.28 Charcoal and torrefied wood have several advantages over unprocessed biomass. Both have high energy density and low moisture content. High energy density is beneficial when fuel must be transported long distances, since it decreases costs per Joule transported. Furthermore, low moisture content similarly decreases transport costs, since it is not rational to transport excessive amounts of water within the biomass. Another advantage is the improved storage properties of biocoal. Outdoor storage of untreated biomass for long periods results in dry mass losses caused by microbial activity and fungal decay.29 Charcoal is highly resistant towards biological decay.30 It could probably be stored outdoors in large piles, thereby reducing investments in storage silos and buildings. According to Ciolkosz and Wallace 28 the same storage properties can be claimed for torrefied wood, since it is hydrophobic. However, as the authors pointed out, this claim has not been conclusively proven. The storage properties of charcoal and torrefied wood should be extensively studied. The aim is not only to verify the moisture uptake and mass losses, but also to map the possible harmful effects of storage. Large amounts of charcoal can self-ignite, a phenomenon that is not completely understood, but has been observed in sea transport of charcoal.16 The self-ignition seems to require wet charcoal and is related to the high reactivity of charcoal.16 2.2 Activated carbon Activated carbon is an adsorbent made from charcoal and is used to remove organic and inorganic substances from liquids and gases. It is widely used in water treatment, metal extraction, gas and air filters and similar applications. Production of activated carbon begins with carbonization of biomass. The charcoal produced is then activated with steam or CO2 in temperatures above 800 C.31 The activation is actually selective burning of the interior of the charcoal particle, which leads to 13

higher porosity. At temperatures from 800 to 950 C, both steam and CO2 are mild oxidants and eliminate carbon atoms from the charcoal particle in reactions that produce CO or CO and H2.31 In principle, oxygen can also be used as an oxidizing agent, but the control of rapid and highly exothermic oxygen-carbon reaction is difficult, thus making the use of oxygen unpractical.32 The high adsorbing capacity of activated carbon is based on its exceptionally large surface area. It can range from 500 to 1500 m2 g-1 of activated carbon.33 Molecules are bound to the surface of untreated activated carbon by van der Waals forces. Most organic molecules are well adsorbed by activated carbon, but it is not a good adsorbent of inorganic substances. The adsorbing capacity of activated carbon can be changed by various chemical treatments.33 2.3 Charcoal in metallurgy Charcoal was used as a reducing agent in iron making before the Industrial Revolution. During the 19th century coke, made with dry distillation process from coal, replaced charcoal in ironmaking. Today, charcoal is used in metallurgy in only a few special applications. In comparison to coke, charcoal has a lower fixed carbon content, higher content of volatiles and low ash content.34 Due to its low ash content and lack of sulphur, charcoal is considered as an ideal reducing agent for iron making 35. On the other hand, charcoal has lower mechanical strength than coke.34 This is a problem in large blast furnaces and other systems in which mechanical strength is needed to have bed permeability.35 However, in small blast furnaces mechanical strength is not an issue; e.g., small blast furnaces in Brazil use charcoal extensively. 36 The price of charcoal is another problem. For example, in Norway it is estimated that price of charcoal is two or three times higher than that of coke.16 At current price level, the use of charcoal is profitable only in regions of world where wood for charcoal making is cheap and widely available. Brazil is the most notable example of the industrial use of charcoal in metallurgy. In 1997, 23 million m3 of charcoal were used for pig iron production in Brazil, of which 75% came from eucalyptus plantations.36 Pig iron producers in Brazil are often small independent companies operating blast furnaces with an annual capacity between 60 000 and 400 000 tonnes.36 There are still larger plants from 400 000 to 4.1 million tonnes capacity, which can use either coke or charcoal in their processing. Other industrial users of charcoal seem to be scarce, but at least in Norway charcoal is used in the production of silicon and silicon ferroalloy.34 In these products, charcoal has some process benefits. Charcoal is imported to Norway from South America and Asia. 34 2.4 Charcoal in agriculture and soil amendment Addition of charcoal to agricultural fields may improve crop yields.37 The addition of charcoal has gained notable interest in recent years. The reason is not only the im14

provement of crop yields, but also reduction of carbon emissions into the atmosphere, if charcoal made from biomass is added to the soil. Charcoal addition to soil could be one mechanism for mitigating climate change. Crop yields may increase after soil amendment with charcoal by up to 320%, but there are also occasions in which the effect of charcoal addition is nil.38 Most studies on soil amendment with charcoal have been made in the tropical countries, and there is a lack of data on the use of charcoal in the Northern Hemisphere.

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3 Production technologies
There is a wide range of technologies available for the production of biocoal. Common to all these technologies is the requirement of heating the biomass for reaching and maintaining the desired peak temperature. Heating can be performed by combusting part of the feedstock loaded into the reactor, heating the reactor externally or by conveying hot flue gases into the reactor. At low temperatures, thermal degradation is an endothermic process, i.e. it consumes energy. If temperature is increased by heating, an exothermal degradation process begins. In this phase, biomass produces more heat than it consumes. Heating may still be needed, since part of the energy is lost by convection, conduction and radiation. These losses are dependent on several factors, including insulation and ambient temperature. Controlled combustion of the feedstock in the reactor is the oldest method for supplying heat to the process. For example, when kilns are used, part of the biomass in the kiln is ignited and then burnt slowly. The rate of combustion is controlled by opening and closing air inlets. The burning biomass heats up the rest of the feedstock. When all biomass in the kiln has reached the temperature at which exothermal degradation begins, the air inlets can be closed, and the pyrolysis process proceeds on its own. External heating of the reactor and recirculation of flue gases are more advanced methods than partial combustion of the feedstock. The two former methods utilize pyrolysis gases for heating the biomass. The pyrolysis oil can be condensed from the gases for later use, or if it is not feasible, all gases can be used for heating. In some exceptional cases, e.g. in the start-up phase, additional fuels are used, but under normal conditions pyrolysis gases are the heat source.39 In this method, the gases from the reactor are commonly collected and utilized in heating the reactor from the outside. The pyrolysis oil can be condensed from the gases for later use, or if it is not feasible, all gases can be used for heating. External heating is often used in continuous processes, where there is a constant need for heating fuel. Hot flue gases can also be used to heat the feedstock. A common operational method is to collect the gases from the reactor, condense the pyrolysis oil from the gases and then burn non condensable gases in a combustion chamber.40 The hot flue gases from the combustion chamber are then conveyed into the pyrolysis reactor. Carbonization or combustion technologies can also be divided according to the heating method. Heating can be internal, external or recirculated. In internal heating systems raw material is combusted under a controlled air inlet. This is the most common and traditional method of charcoal production. Kilns operated by internal heating include traditional kilns e.g. earth mound, concrete and pit kilns, but portable, movable and fixed metal kilns are also used. In external heating systems, retort is heated outside and there is no air inlet into the retort. Examples of this method include metal retorts such as the Van Marion Retort. In heating with recirculated heating gas, hot gas passes through the raw material charge. Charcoal and by-product yield is high, but the method is more expensive than those mentioned above.41 16

3.1 Charcoal-making kilns Kilns made from bricks, metal or concrete can be used for charcoal making. After earth mound kilns and pits, which have been used since ancient times, they provide the simplest method for producing charcoal. Various kiln types are actively used in the developing countries.22 Traditionally, kilns operate in batch mode in which the feedstock is first charged in the kiln. The kiln is then heated and the feedstock pyrolyses into charcoal. After a cooling phase, charcoal can be unloaded. The production cycle is typically quite long; e. g. 8 days in a 50-m3 brick kiln.22 Unloading and loading the kiln is labour-intensive work, and therefore in the industrialized countries other charcoal-making technologies are more common. The Missouri kiln, also known as the concrete kiln, is an example of a batch kiln type. It was developed in the state of Missouri in the U.S.A. and was standardized in 1960. This batch-type kiln is rectangular and made of concrete fitted with large steel doors. The large doors allow loading and unloading of the kiln with a front-end loader,16 which considerably reduces the need for labour. The flue gases are conveyed to the atmosphere by chimneys and are not commonly used for heating. Flue gases can still be led to an afterburner to reduce emissions from the carbonization.16 Typically, the volume of the Missouri kiln is 180 m3, and production is 16 tonnes of charcoal during a 3-week production cycle.42 The charcoal yield with the Missouri kiln varies between 20% and 30%. 16 3.2 The Carbo Twin-retort The Twin-retort is a semi-continuous system developed in the Netherlands in the 1990s. The following description of the retort system is from Reumerman and Frederiks.43 One Twin-retort unit consists of several 5-m3 vessels and an insulated oven. The oven can fit two vessels at a time. The system is placed into a hall, where an overhead crane is used to lift the vessel in and out of the oven. The Twin-retort is operated by placing a vessel loaded with wood into the oven. At the same time, another vessel in the oven is already at the pyrolysis temperature. The flue gases from the latter vessel are burned and used to externally heat the unpyrolysed vessel. No external heating source is required, except in the start-up phase. Carbonization of one vessel commonly requires 12 hours, after which the vessel is lifted from the oven for cooling. Cooling of the vessel requires from 20 to 24 h. Several vessels are needed, since some of them are in the oven, some are cooling, and some are in the loading or unloading phase. Since loading of wood and unloading of charcoal is done outside of the oven, the utilization of the oven is efficient. One Twin-retort module produces 900 tonnes of charcoal per year. The yields are typically 33%, which is better than with traditional kilns. Plants are operated in several countries, of which one is located in Prnu, Estonia.

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3.3 Euro kiln Another semi-continuous kiln type is the Euro kiln operated in Latvia by Arheo Ltd. The unit has an arrangement similar to that of the Twin-retort. The unit consists of two ovens (Fig. 3) and several steel containers. A steel container is first loaded with wood and then placed in an oven. Pyrolysis gases from the other oven are combusted in a burner, and hot flue gases from the burner are used to heat the oven loaded with fresh wood.

Figure 3. A Euro kiln unit of Arheo Ltd. in Preili, Latvia. The unit consists of two ovens and a pyrolysis gas burner. The unit is operated by an alternate method: one unit is in the pyrolysis stage while the other is in the heating stage. Hot pyrolysis gases from the unit in the pyrolysis stage are combusted and used to heat the oven in the heating stage. Photo by Arheo Ltd.

One Euro kiln batch produces 1 t of charcoal. The production cycle requires from 40 to 48 hours. The heating stage requires from 6 to 12 hours, depending on moisture content and tree species. Pyrolysis stage requires from 10 to 12 hours, and cooling 24 hours. The peak temperature of the process is from 450 to 490 C, and holding time of the peak temperature from 4 to 5 hours. The Arheo Company produces 70 tonnes of charcoal per month with Euro kilns. Birch is the main raw material. The main market areas for the company are Latvia, Lithuania and the Scandinavian countries. Export markets are important for the company, and 70% of the production is exported. 3.4 Lambiotte Lambiotte is considered by some authors as the most successful technology for continuous carbonization.5, 40 The technology was originally developed in the 1940s, and there exist two variants of the process. The SIFIC process is equipped with by-product recovery, whereas in the other system, named CISR, it is omitted. In Lambiotte retort drying, carbonization and cooling are performed in a long, vertical retort. Wood is loaded into the upper part of the retort, from where it slowly moves downwards as the carbonization proceeds. From the middle section of the retort hot gases are injected into the retort; these travel upwards to the top of the retort, simulta18

neously heating wood that is flowing downwards. Hot gases for heating are produced by burning pyrolysis gases from the retort in a separate burner. 5 In the bottom section of the retort, hot charcoal is cooled by injecting cooled combustion gases or other inert gas into the retort. The gases injected into the bottom rise upwards, cooling the hot charcoal. The cooling gases are drawn off at the middle of the retort, just below the point where the hot gases are injected into the retort.5 In the SIFIC variant, tars and other condensable liquids are recovered from the flue gases by coolers and scrubbers.39 The CISR variant is not equipped with recovery units. It is also smaller than the SIFIC.5 The Lambiotte retort is an efficient continuous process: annual production is typically from 2 000 to 6 000 tonnes of charcoal.44 On the other hand, the process is notable for its high investment costs. The high cost especially concerns the SIFIC variant 5. Currently there are two SIFIC Lambiotte retorts operating in Latvia.44 The plants produce electricity along with charcoal. For example, the large plant producing 8 000 tonnes of charcoal also generates 1 000 kW of electricity. 3.5 Wagon retorts Wagon retorts or tunnel retorts rely on wagons loaded with wood. The carbonization occurs in large heated tunnels equipped with rails. There are two main types of wagon retorts. In small retorts, the wagon loaded with wood is pushed into the tunnel. Wood is carbonized by heating the tunnel. When the carbonization process has finished, the wagon is pulled out of the tunnel and allowed to cool. In large wagon retorts, the process has been developed towards semi-continuous operation. In these retorts the tunnel can hold several wagons at a time, because the tunnel is divided by steel doors into compartments. Different compartments for drying, carbonization and cooling are common. The plant is operated by pushing wagons from one compartment into another. After the wagons have been moved to the compartments, steel doors are closed and the processes in the compartments occurs. The wagon retort process is considered to be technically simple, and produces goodquality charcoal with small amounts of fines.5 The main problems with the wagon retort process are the high maintenance costs of the steel wagons and the shell of the tunnel. 5 Wagon retorts were common before the second world war, but are no longer in wide use.5, 45 One still is reported to be operating in Croatia. 39 In Sweden, a company named Skogens Kol also operates a wagon retort system. The company considers itself as the largest industrial manufacturer of charcoal in Scandinavia.46 3.6 Torrefaction plants Torrefaction is basically a process similar to charcoal making. In both, biomass is heated in an inert atmosphere, which leads to thermal degradation. The difference between

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torrefaction and charcoal making is the peak temperature; in torrefaction the temperature remains below 300 C. Torrefaction devices are currently being developed in several countries, but there are as yet no commercially operated torrefaction mills. However, there are several demonstration plants that are able to produce torrefied wood on a small scale. Currently, torrefaction plants are being developed, either by modifying existing technology or by designing completely new reactors. Several companies, mainly manufacturers of drying technology, have chosen to modify their existing devices to torrefaction plants. For example, an United States-based company Wyssmont built a torrefaction reactor from their continuously operating dryer.47 Another torrefaction reactor based on existing dryer technology is the ACB process developed by an Austrian consortium.48 The process is being developed from the rotary drum dryer of Andritz AG (Gratz, Austria), and is currently in the demonstration phase. The demonstration plant can produce 1 tonne of torrefied biomass per hour.49 The temperatures in the torrefaction process are lower than in charcoal making, which makes the application of existing drying technology easy. Problems can arise when the temperatures are near or above the exothermal limit. If good control of heat generated in exothermal degradation is not applied, the process may show runaway temperatures, resulting in too severely torrefied biomass.11 In addition, there are also devices designed from the start for biomass torrefaction. One such device is the PATRIG pilot plant designed and built by the Energy Research Centre of the Netherlands (ECN).50 The plant includes drying, torrefaction and pelletization devices. Torrefaction is done in a moving-bed reactor. The reactor type is claimed to be of low cost, compact and able to provide high heating rates.50 The throughput of the reactor, reported as the amount of input material, is from 50 to 100 kg/h.

Figure 4. Combined torrefaction and pelletization plant. The raw material is first dried to uniform moisture content. Flue gases from the torrefaction process can be used in drying and torrefaction, but some additional fuel may be needed for drying, especially if moist raw material is used.

The energy density of torrefied wood is higher than that of raw biomass, especially when compared on a mass basis (e.g. J/kg). The energy density of torrefied wood, when compared on the basis of volume (e.g. J/m3), is near the energy density of wood.11 This can be improved by compacting torrefied wood into pellets (Fig. 4). Most planned torrefaction plants also include pelletization phase.49-50 The high energy density improves the 20

economics of transport and storage of torrefied wood, since less cargo space and storage volume is needed.51

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4 Global charcoal production

Food and Agriculture Organization (FAO) collects global statistics on charcoal production. In some countries, including Finland, there are no official statistics for charcoal production (see below for charcoal statistics in Finland). For these countries, the FAO estimates the total charcoal production, or uses unofficial figures. Among the largest producers are several developing countries (e.g. Ethiopia and Nigeria), which do not compile official production statistics. For these countries, production is estimated, which may result in some significant errors in the total world production. The FAO statistics estimate that the global production of charcoal was 47.1 million tonnes in 2010. Figure 5 shows the production in different parts of the world. The production is concentrated in Africa, which accounts for 62% of the total production. In Africa, charcoal is often made with traditional earth mound and pit kilns, and charcoal making is frequently practised by farmers. 22 Charcoal is mainly used as a fuel for preparing food. Brazil is the world largest producer of charcoal accounting for 11% (5 million t) of the total production in 2010. In Brazil, charcoal is frequently used in metallurgy for the production of pig iron (see section 2.3). Nigeria and Ethiopia are the second and third largest producers, both accounting for approximately 8% of the total production. Europe produced 600 000 tonnes of charcoal in 2010, which was only 1.3% of the world production. Large amounts of charcoal have previously been used in the industrial countries, but it has been replaced by coal, coke and synthetic materials.5, 22 In some niche areas, such as production of activated carbon, charcoal can still compete with other materials. However, the currently developing biobased economy may increase the future use of charcoal.

22

Africa
62 %

Oceania
0,1 % 1,3 %

Asia
16 %

Europe

Americas
21 %

Figure 5. Global charcoal production in 2010. The data is from FAO statistical database .

4.1 Charcoal production in the Nordic and Baltic countries Latvia and Estonia produce most of the charcoal produced in Scandinavia and the Baltic countries (Fig. 6). They also export charcoal to the Nordic countries and other parts of Europe. Production in the other Nordic countries except Sweden is negligible or not surveyed.

10000

8000

Volume (tonnes)

6000

4000

2000

0 Latvia Estonia Lithuania Sweden

Figure 6. Production of charcoal in the Baltic and Nordic countries.52 Production in Finland, Denmark, Norway and Iceland is either negligible or not surveyed.

4.2 Latvia FAO statistics show that Latvia is the largest charcoal producer and exporter of the Nordic and Baltic countries. Production of charcoal was over 10 000 tonnes annually from 23

2000 until 2007. In 2003 and 2004 production was over 16 000 tonnes. After 2007, production declined to under 8000 tonnes, but is showing an increase in 2010 by production of 9100 tonnes. There is a lack of official statistics on charcoal production in Latvia; therefore information must be collected from a wide range of other sources. It is known that during the first period (1918-1940) of Latvias independence, the forest department made attempts to encourage charcoal production from state forests, because there were no markets for yearly overproduced firewood. As a result, charcoal production evolved, mainly in the region of Liepaja and the forest districts of Liepna, Sauka, Ainai, Vecsalaca, Sl tere and Kurs i.53 Information on charcoal production during the Soviet period (1940 1991) is poor and it is known that in the late 1980s charcoal production nearly stopped.54 After regaining independence in 1991, production of charcoal evolved and in 2000 there were 35 plants producing charcoal with potential production capacity of 16 000 tonnes annually.55 Currently it is difficult to estimate the total number of charcoal producers in Latvia. It is known that there are several small-scale charcoal producers, e.g. R jienas kokogles Ltd., Latkora Ltd., B rbeles kokogle Ltd., but the biggest industrial charcoal producers in Latvia are: nu Karbons Ltd. produces charcoal from deciduous trees, using Lambiotte technology (see chapter 3.4 Lambiotte). Annual production capacity is from 2 000 to 6 000 t.56 Arheo Ltd. - produces charcoal from deciduous trees (birch and alder). Production capacity is 70 t per month.57 KRK Vidzeme Ltd. is the largest producer of charcoal in Latvia and uses equipment with production capacity 3 500 t y-1.58 Balt Carbon Ltd. is a producer of SIFIC/Lambiotte retorts in Latvia and has set up a cogeneration plant in Ug le (Western Latvia). The capacity is 8 000 t of charcoal and 1 000 KW of electricity, and in Kaplava (Eastern Latvia), the capacity is 2 000 t of charcoal per year and 250 KW of electricity.59

4.3 Estonia Estonia is the second largest charcoal producer and exporter of the Nordic and Baltic countries. The production peak in the last decade was in 2006, when 6 600 tonnes of charcoal were produced, after which the production quantities declined. The export quantity has been around 3 000 - 5 000 tonnes.52 Ala Sevabrik O have two charcoal production plants in Estonia, one located in Valga and the other in Jrvamaa, producing a total of 200 tonnes of charcoal per month for barbequing. The company uses deciduous wood, including aspen and alder. Ala Sevabrik O has been in the markets since 2001 and they are using carbonization technology from the Netherlands.60 24

4.4 Sweden Production has been quite stable in the last 10 years. From 2001 until 2007 it was 1 000 tonnes annually.52 Skogens kol is the only industrial-scale grill charcoal and briquette producer in Scandinavia.46 The company, founded 1876, has a long tradition in charcoal making. Deciduous wood, including alder, aspen and birch, are the raw materials used by the company to produce charcoal. Skogens kol uses the wagon retort method. The wood is heated indirectly and combustion gases are used in the process. Logs are dried 68 months before chipping and carbonizing. 4.5 Finland Charcoal production statistics in Finland are not compiled, because Statistics Finland, the governmental organization responsible for compiling statistics, surveys industrial production by sampling companies that have more than 10 employees. Charcoal-making companies in Finland have fewer than ten employees, and are rejected in the sampling procedure. Therefore there are no official statistics for charcoal production in Finland. 61 Although official statistics are lacking, there are still some production estimates. Newspaper Kaleva estimated that there are 20 charcoal producers in Finland. 62 The companies produce small quantities for local markets. Finnish barbeque markets are dominated by Russian and Baltic producers: their percentage of the charcoal market is assumed to be 90%.62 The situation for Finnish companies is difficult, since production costs in Finland are considerably higher than in neighbouring countries, and also because consumers are not willing to pay higher prices for domestic products.62-63 Of the Finnish charcoal producers, the company named RPK Hiili is probably the largest: it produces 250 tonnes of grill charcoal per year.63 The company operates two interconnected retorts. Pyrolysis gases from one retort are used to heat the feedstock in the other retort. Carbonization phase requires 2024 hours when the moisture content is around 40%. Carbonization time depends on the moisture of the wood. The cooling phase requires 24 hours.

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