BIOMASS TORREFACTION

R. Zanzi1, D. Tito Ferro2, A. Torres3, P. Beaton Soler2 and E. Bjrnbom1 Department of Chemical Engineering and Technology, Chemical Reaction Engineering, Royal Institute of Technology (KTH), 100 44 Stockholm, Sweden. telephone: +46 8 - 790 8257, fax: +46 8 - 696 0007 e-mail : rolando@ket.kth.se 2 Universidad de Oriente, C.P. 90 500 Santiago de Cuba, Cuba 3 Universitat de Barcelona, 08007 Barcelona, Spain

ABSTRACT: This paper presents a work on biomass torrefaction performed in a laboratory unit with a reactor tube of a length of 0.5 m and an inner diameter of 0.04 m. The experiments are conducted with miscanthus, birch, salix as well as with wood and straw pellets. The reactor was heated to the selected temperature (230C, 250C or 280C) and kept at the final temperature for a period of 1, 2 or 3 hours. The effect of the raw material, temperature, and residence time on the properties of the torrefied products is studied. The torrefied biomass products are characterized with elemental composition, energy content, moisture content, ash content and volatile fraction. The gaseous products are also analysed. The type of biomass influenced the product distribution. During torrefaction biomass undergoes changes in physical and chemical properties. The fixed carbon content and energy density increase with both time and temperature of torrefaction, while the yield on a weight basis decreases. The torrefied biomass has hydrophobic properties and a higher calorific value than the raw material. Keywords: biomass pre-treatment, biomass densification, pyrolysis. 1 INTRODUCTION stoves, residential heating, manufacture of improved solid fuel products such as fuel pellets, compacted fireplace logs and barbecue briquettes for commercial and domestic uses [3,4,5]. Torrefied biomass can be also used as fuel for industrial applications. With a 30-35% fixed carbon content, torrefied wood has a promising potential as a reducer. [4]. Torrefied biomass can be blended with coal and co-fired in a Pulverized Coal Boiler (PBC). Important advantage of torrefied wood compared to untreated wood is its uniformity. Due to the low moisture content of torrefied wood the transport cost is lower and the quality as a fuel better. It is easily packaged and transported, and thus constitutes an efficient fuel. The properties of torrefied biomass should lead to an improved operation in gasifiers for which the stability of the process is important [3]. 2 EXPERIMENTAL

Biomass has some disadvantages as fuel (low calorific value, high moisture content, hygroscopic nature, smoking during combustion). Torrefaction is a feasible method for improvement the properties of biomass as a fuel. It consists of a slow heating of biomass in an inert atmosphere to a maximum temperature of 300 C [1]. The treatment yields a solid uniform product with lower moisture content and higher energy content compared to those in the initial biomass. The process may be called mild pyrolysis, with removal of smoke producing compounds and formation of solid product, retaining approximately 70% of the initial weight and 80-90% of the original energy content [2]. The generic term of torrefied biomass defines a group of products resulting from the partially controlled and isothermal pyrolysis of biomass occurring in a temperature range of 200-230C and 270-280C. When the biomass is heated, drying takes place first. Further heating removes new amount of water from chemical reactions through thermo-condensation process, which occurs at temperatures over 160C, as well as the formation of carbon dioxide gas begins. At temperatures between 180C and 270C an exothermical reaction takes place, as well as the degradation of hemicelluloses goes on. Biomass begins to be brown and gives off moisture, carbon dioxide and large amounts of acetic acid with some phenols. These compounds have low energy value. Biomass retains most of its energy potential, it loses its hygroscopic properties and becomes more friable than untreated biomass. About 280C the reaction is entirely exothermic and the gas production is increased, carbon monoxide and hydrocarbons are developed. Phenols, cresols and other heavier products are formed. Temperatures over 300C are not recommended because the pyrolysis process starts instead of the wanted torrefaction process [3]. Torrefied products can substitute charcoal in a number of applications such as fuel for domestic cooking

In each experiment 65 g of the biomass sample were subject to torrefaction at atmospheric pressure. A nitrogen flow (5 litre/hour) was used to keep the reaction in absence of oxygen. The reactor was heated and kept at the selected final temperature (230C, 250C and 280C) during different periods of time (1, 2 or 3 hours) and then the electrical heaters were switched off. After the treatment the samples are left to cool down. Before each experiment 12 litres of nitrogen was led through the system to remove the air. The collected torrefied solid product was weighed and characterized. The influence of the experimental conditions (temperature and residence time) on the product distribution and on the properties of the products was studied. 2.1 Biomass Birch, salix, miscanthus, as well as two types of densified biomass, straw and wood pellets, were selected as raw materials. The wood pellets are 6-8 mm diameter and 5-15 mm length. The straw pellets have a diameter between 8-9 mm and a length between 5-30 mm. The ash

and moisture contents of the raw materials are shown in Table I. Table I: Raw materials Biomass Birch Salix Miscanthus Wood pellets Straw pellets Ash wt% mf 0.2 0.4 0.3 0.3 4.6 Moisture wt% 3.1 3.3 2.8 6.0 7.7

Table II: Distribution of torrefaction products Biomass Yield of Products ash T t solid liquid gas wt% C h in wt%maf mf Birch 230 1 93.2 6 0.8 0.26 230 2 92 7 1 0.27 230 3 91.8 7.2 1 0.27 250 1 88 10.8 1.2 0.28 250 2 87.3 11.3 1.4 0.29 250 3 86 12 2 0.29 280 1 79 19 2 0.32 280 2 78 19 3 0.32 280 3 77 20 3 0.33 Salix 230 1 91 8 1 1.40 230 2 90 9 1 1.41 230 3 89 10 1 1.43 250 1 85.5 13 1.5 1.48 250 2 85 13 2 1.51 250 3 84 13 3 1.52 280 1 79 18 3 1.60 280 2 76 20 4 1.66 280 3 75 20 5 1.69 Miscanthus 230 1 89 10 1 3.20 230 2 89 10 1 3.20 230 3 87 11 2 3.25 250 1 83 15 2 3.39 250 2 82 15 3 3.44 250 3 80 16 4 3.52 280 1 69 24 7 4.10 280 2 67 25 8 4.23 280 3 66 26 8 4.30 Straw pellets 230 1 95.0 5.0 0.1 4.75 230 2 93.6 6.2 0.2 4.81 230 3 92.4 8.3 0.3 4.89 250 1 90.0 9.8 0.3 5.00 250 2 89.1 10.5 0.4 5.07 250 3 86.9 12.2 0.6 5.18 280 1 79.9 19.1 1.0 5.60 280 2 76.5 21.1 1.6 5.80 280 3 74.9 22.5 2.0 5.93 Wood pellets 230 1 96.5 3.5 0.06 0.23 230 2 95.5 4.4 0.10 0.23 230 3 94.6 5.3 0.15 0.23 250 1 94.4 5.5 0.15 0.23 250 2 93.3 6.5 0.20 0.24 250 3 92.5 7.2 0.30 0.24 280 1 89.4 10.0 0.60 0.25 280 2 86.7 12.3 1.00 0.25 280 3 85.8 12.9 1.30 0.26 T: temperature, t: residence time at the final temperature, h: hours maf: moisture and ash free, mf: moisture free The torrefaction process aims at a hydrophobic product, which prevents it from regaining humidity from the air during storage. After a period of time of 1 month in storage the moisture content of the torrefied samples was 1,7% for birch and miscanthus, 2.2% for salix and 1% for straw pellets and wood pellets. The moisture content is much less compared to the content of moisture of the raw material (see table I)

2.2 Equipment The equipment used in the experiments, shown in Fig. 1, included a cylindrical reactor equipment with a device for removal of the liquid products and measurement of the gaseous products. The reactor tube is heated by electric heaters. The reactor consists of two cylinders. The sample is placed in the removable inner cylinder with a net in the bottom. The outer cylinder is cone shaped at the bottom and connected to a metal tube with a screw, that makes it easier to open and clean. The volatiles are cooled in a water-cooled condenser, where the tar and the water phase are condensed. The gas is led through a cotton filter and a gasmeter and then collected in a bag. The gas composition is analyzed by a gas chromatograph for CO2, CO, N2, CH4, and C2hydrocarbons (ethane, ethene and acetylene).

Figure 1: Equipment 3 RESULTS AND DISCUSSION

3.1 Distribution of torrefaction products Table 2 shows the yield of products obtained in the performed experiments. The type of biomass influenced the product distribution. The samples of wood (birch and salix) gave more solid products and less tar and water than miscanthus. Compared to unprocessed raw materials, pelletized biomass produce more solid and less gas. As expected, when the temperature increases from 230C to 280C, the yield of the solid torrefied product decreases while the yield of gas, tar and water increases. An increase of the duration of the heating at the final temperature from 1h to 3h results also in a decrease of the yield of torrefied biomass and in an increase of the volatiles.

3.2 Chemical composition of the solid products The elemental analysis of the raw material and the torrefied products (table III) shows that the content of carbon increases at higher temperature of the torrefaction while the contents of hydrogen and oxygen decrease. Losses in hydrogen and oxygen are due to the formation of water and carbon monoxide and dioxide. Table III: Elemental composition of torrefied biomass Biomass T t C H N C h in wt%maf Birch raw 47.40 0.16 6.11 230 1 48.20 0.16 5.93 230 2 48.72 0.14 5.88 230 3 48.82 0.13 5.76 250 1 49.50 0.13 5.69 250 2 49.86 0.12 5.68 250 3 50.05 0.12 5.65 280 1 51.25 0.11 5.63 280 2 52.00 0.11 5.62 280 3 52.50 0.11 5.62 Salix raw 44.21 0.27 5.95 230 1 45.64 0.31 5.86 230 2 45.71 0.36 5.83 230 3 45.76 0.38 5.78 250 1 45.75 0.40 5.78 250 2 45.97 0.40 5.71 250 3 46.11 0.40 5.61 280 1 46.30 0.42 5.61 280 2 46.36 0.44 5.60 280 3 46.90 0.44 5.54 Miscanthus raw 43.5 0.9 6.49 230 1 44.42 0.81 6.05 230 2 45.43 0.79 5.97 230 3 45.98 0.75 5.97 250 1 47.40 0.69 5.84 250 2 47.80 0.67 5.78 250 3 48.40 0.66 5.75 280 1 51.31 0.64 5.65 280 2 52.00 0.65 5.54 280 3 52.10 0.65 5.43 Straw pellets raw 47.5 6.4 0.63 230 1 47.8 6.3 0.66 230 2 47.9 6.3 0.69 230 3 48.1 6.2 0.69 250 1 49.0 6.1 0.79 250 2 49.6 6.1 0.80 250 3 49.6 6.1 0.80 280 1 52.8 6.1 0.85 280 2 53.8 6.0 0.92 280 3 55.5 5.9 0.95 Wood pellets raw 48.5 6.6 0.05 230 1 49.8 6.3 0.09 230 2 50.4 6.3 0.09 230 3 50.6 6.2 0.11 250 1 50.7 6.2 0.12 250 2 50.8 6.2 0.12 250 3 51.0 6.2 0.12 280 1 52.5 6.2 0.12 280 2 53.0 6.2 0.13 280 3 54.1 6.2 0.14 O: oxygen is assessed by difference O 46.33 45.71 45.26 45.29 44.68 44.34 44.18 43.01 42.27 41.77 49.57 48.19 48.10 48.08 48.07 47.92 47.88 47.67 47.60 47.12 49.11 48.72 47.81 47.30 46.07 45.75 45.19 42.40 41.81 41.82 45.5 45.2 45.1 45.0 44.1 43.5 43.5 40.3 39.3 37.7 44.9 43.8 43.2 43.1 43.0 42.9 42.6 41.3 40.7 39.6

Table IV: Energy content of torrefaction products Biomass Birch T t CV 8.93 9.30 9.52 9.53 9.86 10.03 10.12 10.70 11.07 CVp CVb 1.04 1.07 1.07 1.10 1.12 1.13 1.20 1.24 ER H/C 0.04 0.04 0.03 0.03 0.03 0.03 0.03 0.03 0.03 O/C 0.73 0.71 0.70 0.70 0.68 0.67 0.66 0.63 0.61

11.32 1.27 0.98 0.03 0.60 raw 7.48 0.07 0.84 230 1 8.24 1.10 1.00 0.08 0.79 230 2 8.35 1.12 1.00 0.09 0.79 230 3 8.40 1.12 1.00 0.10 0.79 250 1 8.42 1.13 0.96 0.10 0.79 250 2 8.52 1.14 0.97 0.10 0.78 250 3 8.58 1.15 0.96 0.10 0.78 280 1 8.70 1.16 0.92 0.11 0.77 280 2 8.76 1.17 0.89 0.11 0.77 280 3 9.02 1.21 0.90 0.11 0.75 Miscanthus raw 8.19 0.25 0.85 230 1 8.44 1.03 0.92 0.22 0.82 230 2 8.90 1.09 0.97 0.21 0.79 230 3 9.12 1.11 0.97 0.20 0.77 250 1 9.71 1.19 0.98 0.17 0.73 250 2 9.87 1.20 0.99 0.17 0.72 250 3 10.15 1.24 0.99 0.16 0.70 280 1 11.56 1.41 0.97 0.15 0.62 280 2 11.90 1.45 0.97 0.15 0.60 280 3 11.93 1.46 0.96 0.15 0.60 Straw raw 17.8 1.62 0.72 pellets 230 1 17.90 1.00 0.95 1.59 0.71 230 2 17.9 1.00 0.94 1.57 0.71 230 3 17.9 1.00 0.93 1.55 0.70 250 1 18.21 1.02 0.92 1.50 0.67 250 2 18.43 1.03 0.92 1.48 0.66 250 3 18.46 1.04 0.90 1.48 0.66 280 1 20.02 1.12 0.90 1.38 0.57 280 2 20.40 1.14 0.88 1.34 0.55 280 3 21.04 1.18 0.88 1.26 0.51 Wood raw 18.58 1.64 0.69 pellets 230 1 18.77 1.01 0.98 1.52 0.66 230 2 19.02 1.02 0.98 1.49 0.64 230 3 19.03 1.02 0.97 1.47 0.64 250 1 19.05 1.03 0.97 1.47 0.64 250 2 19.12 1.03 0.96 1.47 0.63 250 3 19.24 1.04 0.96 1.46 0.63 280 1 19.87 1.07 0.96 1.41 0.59 280 2 20.13 1.08 0.94 1.40 0.58 280 3 20.68 1.11 0.96 1.36 0.55 CVp : Calorific Value of torrefied solid product CVb : Calorific Value of initial biomass ER: energy recovery = CVp * solid yield / CVb H/C: number H atoms/number of C = (%H/1) / (%C/12) O/C: number of O /number of C = (%O/16) / (%C/12) Salix At higher temperature, the content of C in the solid product increases while the contents of H and O decrease. H/C and O/C atomic ratios decrease with the temperature. The calorific value (CV) of the solid product increases with the temperature and at longer

raw 230 1 230 2 230 3 250 1 250 2 250 3 280 1 280 2 280 3

0.97 0.98 0.98 0.97 0.98 0.97 0.95 0.97

residence time. The calorific values are calculated using the elemental composition of the samples [6]: CV = 0.34%C + 1.40%H 0.16%O (MJ/kg) The degree of carbonization (CVp/CVb) is assessed as a ratio between the calorific value of the torrefied biomass product and the calorific value of the raw material. The degree of carbonization increases with the temperature. 3.3 Composition of the gaseous products Table V shows the composition of the gas obtained in the torrefaction (nitrogen and water free basis). Table V: Composition of the gaseous products. Biomass Birch

the CO2 content in the gaseous mixture decreased (Table V). Longer residence time produce the same effect on the composition of the gaseous product than a higher temperature treatment. 4 CONCLUSIONS

T C

t h

CH4

230 1 0.08 230 2 0.10 230 3 bdl 250 1 0.08 250 2 0.09 250 3 0.13 280 1 0.14 280 2 0.18 280 3 0.27 Salix 230 1 bdl 230 2 bdl 230 3 bdl 250 1 bdl 250 2 0.06 250 3 0.07 280 1 0.09 280 2 0.13 280 3 0.19 Miscanthus 230 1 0.03 230 2 0.03 230 3 0.04 250 1 0.04 250 2 0.04 250 3 0.05 280 1 0.05 280 2 0.11 280 3 0.15 Straw 230 1 bdl pellets 230 2 bdl 230 3 bdl 250 1 0.08 250 2 0.11 250 3 0.12 280 1 0.13 280 2 0.15 280 3 0.23 Wood pellets 230 1 bdl 230 2 bdl 230 3 0.22 250 1 0.23 250 2 0.28 250 3 0.29 280 1 0.34 280 2 0.37 280 3 0.52 bdl: below detention limit

C2 CO2 in vol % bdl 85.81 0.04 84.2 0.04 84.07 0.06 83.09 0.07 81.90 0.08 81.24 0.10 78.29 0.10 74.75 0.14 72.70 bdl 88.51 bdl 87.62 bdl 84.1 0.03 83.62 0.03 81.88 0.08 81 0.1 77 0.12 76.85 0.13 72.46 0.18 84.38 0.20 78.65 0.21 74.99 0.22 73.60 0.22 71.99 0.27 71.87 0.30 71.20 0.45 64.11 0.46 61.34 77.0 0.04 0.05 76.2 0.06 75.9 0.07 73.2 0.08 73.0 0.15 72.7 0.13 71.6 0.35 71.0 0.43 68.5 0.05 78.7 0.06 78.4 0.07 75.4 0.07 74.3 0.08 72.3 0.09 70.8 0.09 70.2 0.12 66.2 0.15 64.5

CO 14.11 15.66 15.89 16.77 17.94 18.55 21.47 24.97 26.89 11.49 12.38 15.9 16.35 18.03 18.85 22.81 22.9 27.22 15.41 21.12 24.76 26.14 27.75 27.81 28.45 35.33 38.05 23.0 23.8 24.0 26.7 26.9 27.0 28.1 28.5 30.8 21.25 21.59 24.29 25.4 27.3 28.8 29.4 33.3 34.9

The type of biomass influenced the product distribution. The samples of wood (birch and salix) gave more solid products and less tar and water than the studied agricultural residue (miscanthus). Compared to unprocessed raw materials, pelletized biomass produce more solid and less gas. The yield of solid product decreases while the yield of gas, tar and water increases with the temperature and the residence time. The content of carbon in the solid product increases at higher temperature of the torrefaction and longer residence time while the content of hydrogen and oxygen decrease, increasing the calorific value of the torrefied biomass. The content of CH4, H2, CxHy, and CO in the product gases increases when the temperature is increased while the content of CO2 decreases. The moisture content of the torrefied biomass is much less compared to the content of moisture in the raw material. 5 ACKNOWLEDGEMENTS

The authors acknowledge the financial supports of the Swedish Agency for Research Cooperation with Developing Countries, Department for Research Cooperation (Sida-SAREC) and the European Community (ALFA Programme). 6 REFERENCES

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[3] J. Bourgeois and J. Doat, Proceedings Conference on bioenergy, Gteborg, Vol.3, (1985), 153. [4] P. Girard and N. Shah, Developments on Torrefied Wood an Alternative to Charcoal, REUR Technical Series No. 20, Charcoal Production and Pyrolysis Technologies, (1991) 101. [5] S. Battacharya, S. Jungtiynont, P. Santibuppakul and V. Singamsetti , Some aspects of screw press briquetting, Int. Workshop on Biomass Briquetting, New Delhi, (1995). [6] Ruyter, H.P., Coalification model, Fuel 61,1982, 1182.

A higher treatment temperature favoured the production of CO, methane and C2 hydrocarbons while