IEA Bioenergy Task 34 ‐ Pyrolysis

Sweden’s representative PyNe Issue 35 July 2014 in Task 34 ISSN 2040-2759

By Magnus Marklund of ETC in Piteå, Sweden

IEA Bioenergy Task 34 is pleased to introduce the country leader for our newest member, Sweden

The Swedish Energy Agency intends, through its participation in IEA Bioenergy, to work to strengthen Swedish knowledge and interests in the international arena and to enable Swedish actors to receive international knowledge about bioenergy via networking. The Swedish National Team Leader of IEA Bioenergy Figure 1: Magnus Marklund, Managing Director at ETC, studies a Task 34, Magnus Marklund, is now fractionated oil sample obtained from the ablative pyrolysis oil cyclone and leading the international monitoring staged condensation system at ETC. of general Swedish interests and opportunities for technology development and the pyrolysis activities performed at develop international cooperation commercialisation of fast pyrolysis ETC. within the Task. Pilot-scale of biomass. Magnus is currently the experimental R&D work on fast Managing Director at ETC in Piteå, “The main overall aim of Sweden’s pyrolysis in Sweden is currently Sweden, and his main background participation is to push for an being performed at the Royal is in gasification with the more expansion of the use of the Institute of Technology (KTH), recent addition of pyrolysis through pyrolysis route in Sweden and to (Continued on page 2)

Inside this issue

Task 34 Members 2 International Events 35-37

Pyrolysis Around the World 3-32 Publications 38

Conference Review 33-34 Contact the Editor 39 Published by Aston University European Bioenergy Research Institute

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 1 Sweden’s representative in Task 34 ...continued

dealing with catalytic steam FB made zeolite catalysts function in new initiatives on pyrolysis pyrolysis, and at ETC around upgrading pyrolysis oil to high- activities in Sweden in order to ablative cyclone pyrolysis,” says grade hydrocarbon compounds are regain momentum for the possible Magnus. being performed at Luleå University implementation of fast pyrolysis in of Technology together with ETC. the Swedish industry. Ongoing The current focus of experimental More around the latter will be discussions between researchers, work at KTH is on confronting the presented in upcoming issues of industry and public agencies will challenges of reducing the internal PyNe and more on the KTH work hopefully result in fruitful joint oxygen present in the pyrolysis oil on their catalytic steam pyrolysis activities by the end of this year,” to levels suitable for the existing process can be found in a separate Magnus concluded. petrochemical industry, and at ETC article by Efthymios Kantarelis in to understand the underlying the current issue. phenomena and observable facts related to condensation and “Since BillerudKorsnäs decided to cooling of pyrolysis oil. discontinue their NER300 pre-study on production of green oil at the Furthermore, studies on how tailor end of last year, we are in need of

Members of IEA Bioenergy Task 34: 2013-2015

Finland Anja Oasmaa VTT Technical Research Centre of Finland Liquid Biofuels Biologinkuja 3-5, P.O. Box 1000, Espoo, FIN02044 VTT, FINLAND USA T: +358 20 722 5594 E: [email protected] Doug Elliott Pacific Northwest National Germany Laboratory (PNNL) Dietrich Meier 902 Battelle Boulevard Thünen Institute of Wood Research P.O. Box 999 Leuschnerstr. 91b, D-21031 Hamburg, Richland GERMANY Washington, 99352 T: +49 40 73 962 517 E: [email protected] USA T: +1 509 375 2248 E: [email protected] Netherlands Bert van de Beld BTG Biomass Technology Group BV Josink Esweg 34, 7545 PN NETHERLANDS T: +31 53 486 1186 E: [email protected]

UK Tony Bridgwater Aston University European Bioenergy Research Institute School of Engineering and Applied Science Birmingham B4 7ET, UK Doug Elliott T: +44 121 204 3381 E: [email protected] Task 34 Leader Sweden Magnus Marklund Energy Technology Centre (ETC) Industrigatan 1, 941 38 Piteå, SWEDEN Box 726, 941 28 Piteå, SWEDEN T: +46-911-23 23 85 E: [email protected]

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 2 Review of developments of fast pyrolysis in mobile processing systems

Doug Elliott of Pacific Northwest National Laboratory Figure 1: ABRI-Tech’s 1t/d mobile pyrolysis system. (PNNL) in the USA discusses the development of mobile pyrolysis units The more common vision for fast pyrolysis of biomass for the production of liquids involves moderate-scale, site-based processing systems. However, there remains considerable interest in the development of small-scale systems for mobile processing of isolated biomass resources. Much of this work involves some variation on an auger driven reactor, but other concepts are also under development. A key consideration for these units is attainment of fast pyrolysis conditions of short heat-up and cool-down time in order to recover Figure 2: The Agri-Therm field deployable unit (up to 5t/d). a primary product bio-oil in high yield. byproduct with condensates short review we will highlight Laboratory studies have confirmed including a heavy tar product, several of the current development that fast pyrolysis can be achieved “settled tar”, and a lower density efforts under consideration by the in a laboratory scale twin-auger aqueous phase, “pyroligneous Task participants. reactor when using a heat carrier acid.” While the focus of Task 34 is 1 medium. More often the auger fast pyrolysis to produce a single Fransham and Badger2 have been reactors are reported as char phase primary pyrolysis bio-oil at the forefront of this development production systems. Slow pyrolysis product, the formation of effort for many years. Their auger is well-known as the method for secondary pyrolysis products (gas systems are now available through production of char from biomass, and two-phase liquids) may also be two separate companies, ABRI- which also produces a gas of interest to our readers. In this (Continued on page 4)

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 3 Review of developments ...continued

US Department of Agriculture was described in this newsletter just last issue.9 A 2t/d mobile “A key consideration processing plant based on the circulating fluid-bed catalytic for mobile pyrolysis pyrolysis process, tested in the units is attainment of laboratory at ERRC, is being assembled at the laboratory in fast pyrolysis Wyndmoor, Pennsylvania. conditions of short Industrial partners include Siemens, who is designing controls heat-up and for on-farm pyrolysis systems, and cool-down time.” PQ/Zeolyst who is collaborating in Figure 3: Transportable fluid-bed the scale-up of the production of pyrolyser from Virginia Polytechnic the catalyst materials. Institute and State University. pyrolyser which has been A recent demonstration was made optimised for production of bio-oil. 3 Tech and Renewable Oil of two mobile technologies for Although there is limited data on 4 International. They have each built biomass pyrolysis at Stevenson, the operations of these units, the several small demonstration Washington, USA. The Western demonstration required collection systems which have been operated Renewable Technologies system10 of data and product analyses to for short periods of time. Detailed acquired from Biogreen® involves a validate the systems and those product yields and qualities are not heated horizontal helical screw results will be forthcoming. readily available and concerns conveyor without a central drive remain that the operation does not shaft. The screw acts in part as an A Dutch system, PyroFlash, has fall into the definition of fast ablative heater and is electrically recently been in the news.12 The pyrolysis because of longer heated by resistance. The 1t/h details of the reactor system are residence times in the hot zone. A throughput is designed for an 8-h not publically available. The discussion of the ABRI-Tech day of operation with a daily developer, Nettenergy, describes a equipment development effort was maintenance period. The reactor mobile processing system (2t/d) published in an earlier issue of this can be operated at a range of that makes a range of product 5 newsletter. temperatures to maximise bio-oil liquids, solids, and gas. Although yield, or char or gas as they claim on their website to have The mobile pyrolysis system of alternatives. The Amaron Energy a “not slow pyrolysis” process, 11 Berutti and Briens was introduced unit is a 0.5t/d rotary kiln (Continued on page 5) in this newsletter in 2007.6 The Agri-Therm unit7 is a field deployable unit (up to 5t/d) consisting of annular bubbling fluidised beds; the inside bed is for combustion with internal transfer tubes wherein the biomass particles are heated and then injected into the outer bubbling bed for pyrolysis.

Another transportable fluid-bed pyrolyser from Virginia Polytechnic Institute and State University was also reported earlier in this newsletter. That unit was developed to process poultry litter as a means of disposal and energy recovery. A 1-5t/d unit was designed and constructed in 2008.8 Figure 4: Members of the FarmBio3 consortium pose in front of the 2 metric tonne per day mobile pyrolysis unit which is under construction at ERRC in The effort at the Eastern Regional Wyndmoor, Pennsylvania. Research Center (ERRC) of the IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 4 Review of developments ...continued based on the product descriptions, this unit would not be a fast pyrolysis system.

The group at Fraunhofer UMSICHT in Oberhausen, Germany, is developing a different concept for a mobile pyrolysis system based on the PYTEC ablative pyrolysis system.13 The ablative system, also described in the last issue of this newsletter,14 would be used in the field for pyrolysis of straw following harvest. The liquid yield from the unit would be collected and transported to a central point for utilisation or further upgrading. Figure 5: Design study for a “mobile” flash pyrolysis plant from UMSICHT. The technology is being developed in a laboratory scale unit (15kg/h), and a functional mobile model (100kg/h) is also in development with MBB Fertigungstechnik GmbH. Based on the design calculations at UMSICHT it appears the cost of bio-oil would be about the same as baled straw at the field edge. Further cost savings for bio-oil transportation versus straw bale transport would improve the economics.

A similar ablative pyrolysis system Figure 6: The European Bioenergy Research Institute’s Energy Harvest unit is also under development in in India. Russia. The EnergoLesProm company15 has a small EBRI is also building two 20kg p/h Contact demonstration plant (50kg/h) for mobile intermediate pyrolysis units Doug Elliott their mobile autonomous – ‘Pyrofabs’ – which will be Pacific Northwest National technology for processing low operational throughout North West Laboratory (PNNL) grade wood to liquid fuel. Europe later this year as part of its 902 Battelle Boulevard

EU INTERREG IVB project, P.O. Box 999, Richland, In the UK, the European Bioenergy BioenNW. The units will Washington, 99352 Research Institute (EBRI) at Aston characterise the suitability of a USA University is developing a range of range of biomass for pyrolysis from mobile pyrolysis units. EBRI Belgium, France, Germany, the T: +1 509 375 2248 currently has a 20kg p/h Netherlands and the UK. A larger E: [email protected] intermediate pyrolysis mobile unit 100kg p/h mobile unit is also under operating in the Punjab region of construction and will be located in www.pnnl.gov India. It is demonstrating an the West Midlands. alternative to open field burning by utilising the residues from rice and In summary, mobile fast pyrolysis wheat harvests to produce oil, gas has been under development for and biochar. This ‘Energy Harvest’ over a decade. Numerous small research project is engaging (1-5t/d) demonstration plants have groups of Indian farmers and been built and operated. None villagers who are receiving training have since moved to commercial for operating the unit themselves operation for applications to (more details later in this issue.) lignocellulosic biomass.

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 5 Review of developments ...continued

References 6. Berruti, F.; Briens, C. Converting www.amaronenergy.com 1. Brown, J.N.; Brown, R.C. Process agricultural wastes into valuable 12. nettenergy website: optimization of an auger pyrolyzer green fuels and green chemicals www.nettenergy.com with heat carrier using response PyNe #23, September 2007, pp 3- 13. Meier, D.; Schöll, S.; Klaubert, H.; surface methodology Bioresource 4. Markgraf, J. Practical results from Technology 103 2012 405-414. 7. Agri-Therm website: www.agri- PYTEC's biomass-to-oil (BTO) 2. Badger, P.C.; Fransham, P. Use of therm.com pocess with ablaive pyrolyser and mobile fast pyrolysis plants to 8. Agblevor, F. Transportable diesel CHP plant. In: Bio€ - success densify biomass and reduce pyrolysis: a solution to poultry litter and visions for bioenergy, biomass handling costs—A disposal PyNe #24 June 2008 pp Bridgwater, A. V., Ed. CPL preliminary assessment. Biomass 10-11. Scientific Publishing Service Ltd.: Bioenergy 30 2006 321-325. 9. Boateng, A and Mullen, C. 2007. 3. ABRI-Tech website: FarmBio3 consortium: USDA-ARS 14. Schulzke, T. Development of on- www.advbiorefineryinc.ca and partners to demonstrate on- site flash pyrolysis units for stalk- 4. ROI website: farm pyrolysis biorefining. PyNe like biomass. PyNe #34 January www.renewableoil.com #34 January 2014, pp 11-12 2014, pp 22-24. 5. Fransham, P. Transportable 10. Western Renewable Technologies 15. Energolesprom website: http:// bioenergy systems. PyNe #28 website: www.wrtpyrolysis.com en.energolesprom.ru/ December 2010, pp 24-27. 11. Amaron website: Use of the Pyroformer™ in the Energy Harvest Project

Bioenergy that is sustainably Intermediate Pyrolysis. The produced has the potential to process used is depicted as a flow mitigate climate change and to sheet in the Figure 1 below. bring about rural development and socioeconomic improvement. The The Pyroformer™ (Pyrolysis Pyroformer™ technology based on reactor) is a coaxial screw system Intermediate Pyrolysis developed through which the pellets made by the European Bioenergy from different agricultural residue Research Institute (EBRI) at Aston biomass are fed via a feed storage University is being used to convert hopper. Pellets are conveyed the agricultural residues that are through the inner screw from one being currently burnt openly on end to the other end of the reactor. fields in India. This technology The residence time of the pellets converts the agricultural residues can be carefully controlled by the after harvest to useful products speed of the screw. At the end of such as bio-oil and biochar which the reactor the vapour leaves the in turn could be used for energy reactor through the vapour outlet Sudhakar Sagi of generation. The project “Energy which will be condensed later in a the European Harvest” was conceptualised to be condenser. The feed pellet that is multi-faceted in that apart from eventually transformed into char Bioenergy Research meeting rural energy needs and partly falls into the outer screw and reducing CO2 emissions, it would partly into the char container. The Institute, Aston galvanise self-reliance, local char in the outer screw is then employment, gender and health transported back into the reactor University, UK, related issues in addition to land and allowed to mix with the fresh offers an insight reclamation. The focus was to pellets that are fed into the reactor. meet the energy needs of these The char thereby achieves two into Energy Harvest services for the rural population aims: (i) better heat transfer as the and stop open burning. char is already hot and (ii) the char mobile pyrolysis in also acts as a catalyst to promote India Intermediate pyrolysis better reactions inside the reactor The core of the project is the which help in reduction of tar demonstration unit based on (Continued on page 7)

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 6 Use of the Pyroformer™ ...continued

demonstration in the village . The unit was demonstrated for a period of two months (September 2013 to October 2013).

The total capacity of the heaters installed on the Pyroformer is 12kW. The motors require additional power to rotate the screws of the Pyroformer and also for the feed hopper. The additional power requirement, including the chiller and the pump for the condenser together with screws, is 2kW. In total the power requirement of the plant is 14kW. However, once the desired temperature for the pyrolysis process is reached the power Figure 1: Flowsheet of the intermediate pyrolysis technology for conversion consumption of the plant is of straw. minimal. In simple terms the power required by the plant at the start up formation. The reactor is carefully but then the quality of the products is around 14kW and once the set monitored with respect to the is also affected. temperature is reached the plant reaction temperature by electrical consumes around 3 to 4kW. heaters with precise temperature Mobile unit demonstration controls. As part of the project planning the The total straw converted during technology was made mobile so this period was around 700kg. The One of the products of the process, that it could be demonstrated in the char was also distributed among the pyrolysis vapour, is directed to villages. The mobile pyrolysis plant the rural women who use firewood a quenching unit where it is is shown in Figure 2. The mobile for domestic cooking. The quenched using diesel as a unit was stationed in the feedstock was converted into quenching medium which is re- Khuaspura village of the Rupnagar stable products such as blended oil circulated in a closed loop until the District Punjab state of India. The (pyrolysis oil blended with required blend of pyrolysis liquid in village has a population of around conventional diesel), biochar and diesel is reached. Once the blend 3000. The mobile unit was non-condensable gas fractions. is reached the blended oil is stationed at the community centre, Pictures of the products are shown collected and fresh diesel oil is put which is operated as a school in the Figure 3. into the condenser. The oil during the day and as a community collected is used for running the centre in the evenings. The centre Results dual fuel engine. Not all the vapour had not been connected to the The simple mass balance of the generated can be condensed to oil. mains supply and so the school whole process states what goes in The non-condensable gas that had no power. The Energy Harvest and what comes out. For a unit cannot be condensed is used to Project provided continuous power (Continued on page 8) run the engine on dual fuel mode. supply to the school during its Alternatively there is also a flaring system as a safety measure.

The process parameters for straw conversion are a temperature of 380°C and a residence time of 3 minutes for the straw pellets inside the reactor. The product yields at these conditions were 34% char, 33% condensable oil, and 33% non -condensable gas (by difference). The yields can be changed by Figure 2: Mobile Pyrolysis unit in the village Khuaspura. changing the process conditions IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 7 Use of the Pyroformer™ ...continued

processing the residues through intermediate pyrolysis. The feed was pelletised prior to the pyrolysis process. This was taking place at around 120°C. The pellets produced were very hard and highly densified. This can be described as like a pre-treatment step similar to torrefaction. The 3 Figure 3: Feedstock, blended oil and biochar. density of the straw is 840kg/m . The feedstock straw has a heating value of 16 -17MJ/kg with a moisture content of roughly 5%.The bio-oil blend of 20% has a heating value of 37MJ/kg. The biochar has a heating value of 20MJ/kg. The pH of the biochar is around 9.

The locally produced bio-oil was utilised not only for producing power by running the engine, but also was distributed to the local farmers for them to run on the small scale leister engines installed on their farms for lifting water required for irrigation. Experiments were carried out in both modes by running the engine on pure diesel as well as with various blend ratios of pyrolysis oil and diesel. This study was required to compare the behaviour of the engine as well as the consumption rates of the fuel. From the results it has been observed that the rate of consumption of the blended fuel was not very different from the pure diesel.

Dual Fuel Engine The capacity of the installed engine in the container is 20kW (25kVA). The engine used for the demonstration of the Pyroformer technology is a Greaves make G 11 series, water cooled, four stroke, multi cylinder with direct injection compression ignition. The alternator is a state of the art self- excited, self-regulated and brushless design. AVR controlled Figure 4: FTIR spectra of rice straw and biochar. voltage gives excellent voltage regulation. The entire genset mass of biomass such as 1 acre of oil, 680kg of biochar, and the rest consists of the engine close- field generating 2 tonnes of rice by difference is the non- coupled with an alternator along straw, we get roughly 660kg of bio- condensable gas fraction from (Continued on page 9)

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 8 Use of the Pyroformer™ ...continued

increased with an increase in feedstock throughput. The results of the engine testing are depicted in Figures 5 and 6 for wheat and rice straw feedstock respectively. Trials are ongoing with rice straw processing and have processed around 1200kgs. The char produced has been given to Punjab Agricultural University who will be evaluating the fertilising capability of the char in a detailed scientific study and applying biochar to the fields in large scale. Figure 5: Chart of the fuel consumption at various blending ratios for wheat The field for the biochar trials at the straw. PAU is shown in Figure 7 below.

Feedback from the villagers The villagers were all very interested in the whole demonstration and participated actively. The villagers also expressed interest in actively participating if the unit will remain stationed there for much longer. In fact, there were few farmers who were not planning to burn the field from the coming harvest season. We did however observe during the harvest season that 4 to 5 Figure 6: Chart of the fuel consumption at various blending ratios for wheat farmers did stop burning the field straw. when rice was harvested. Figure 8 shows pictures taken during the with a control panel, all housed The engine was tested for blends demonstration phase in the village inside a canopy. The canopy is an up to 20% with a running time Khuaspura. Since we were acoustic enclosure that attenuates close to 250hrs. The engine was providing electricity to the the genset sound within statutory inspected on a regular basis and it community centre the villagers limits in India. The control panel is showed no signs of deterioration. made use of it for their weekly fitted with an electronic controller The engine was also tested via a village meetings. They requested for display and protection. dual fuel mode of operation by that the project remain in the The dual fuel installed on the injecting the non-condensable gas village, and said they will co- engine offers an affordable and fraction. The results showed that operate with us in every way efficient means of operating diesel we could displace the liquid fuel up possible. engines utilising both liquid and to 20%. This could also possibly be (Continued on page 10) gaseous fuel. This system allows for operation on natural gas up to a maximum of 75% of the fuel required to maintain the desired speed and load. The dual fuel system operates by blending both diesel fuel and natural gas in the combustion chamber. This is achieved using a fumigated gas- charge design, whereby gaseous fuel is pre-mixed with engine intake -air and delivered to the combustion chamber via the air- Figure 7: Field for biochar trials at PAUL Ludhiana. intake valve. IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 9 Use of the Pyroformer™ ...continued

Acknowledgement The Project team would like to thank Oglesby Charitable Trust for their generous financial as we all as moral support so that the project could take this shape today.

Contact Sudhakar Sagi c/o Aston University European Bioenergy Research Institute Figure 8: Community Centre and school being powered as part of the School of engineering and Applied village demonstration. Sciences Birmingham B4 7ET, UK

E: [email protected]

W: www.aston.ac.uk/eas/research/ groups/ebri/ Lignin pyrolysis in a circulating fluidised bed - influence of temperature and char holdup on product distribution Miika Franck (pictured), Ernst-Ulrich Hartge, Stefan Heinrich, Joachim Werther, all of Hamburg University of Technology, and Dietrich Meier of Thünen Institute of Wood Research, discuss results from their recent study of influences on the pyrolysis of Kraft lignin

In this project the pyrolysis of Kraft riser was 2m in height and 80mm demister, a platen type heat lignin in a circulating fluidised bed in diameter. The lignin was fed exchanger and an electrostatic was studied. The focus lay on the pneumatically by nitrogen into the precipitator. pyrolysis mechanism and on the pyrolyser. The bed was fluidised influences of temperature and char with a mixture of nitrogen and The gas composition of the accumulation in the bed on liquid steam. Solids were separated from permanent gases was continuously product yields and composition. the gas by a primary cyclone and monitored. In addition side stream The yield and composition of recirculated via a standpipe and a samples were taken just before the gaseous products and char were syphon. Char and ash were further scrubber and were analysed offline also investigated (detailed separated by a secondary cyclone, to determine the oil yield and information in (Franck et al., before the hot vapours were composition. The oil was analysed 2014)). quenched in a scrubber operated by gas chromatography (GC) and with a water/sodium hydroxide gel permeation chromatography For the experimental investigations solution. The gases left the (GPC) for oligomeric substances the setup shown in Figure 1 was scrubber with temperatures below (Franck et al., 2012). used. The circulating fluidised bed 90°C, and passed through a (Continued on page 11)

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 10 Lignin pyrolysis ...continued

During each experiment, the initial bed material (quartz sand) was coated with the char remaining from the pyrolysis process. The bed material (BM) and the material caught by the secondary cyclone (C2) were analysed for each experiment to determine the char content and composition. Therefore after the experiment the reactor was cooled down in an inert atmosphere until its temperature was below 300°C. The bed material cooled down further and was then taken from the reactor at an ambient temperature. Char may influence the process since char itself and the contained alkaline and alkaline earth metals have a catalytic effect (Richards and Zheng, 1991). In a technical application of the process the char might be used as source for process inherent energy by combustion, as the pyrolysis process itself is endothermic (Franck et al., 2011). Figure 1: Experimental pyrolysis plant (80mm riser diameter, 2m height).

In this work the influence of pyrolysis temperature on the nitrogen volume flow for pneumatic result is that the bed material is product yields and composition lignin feeding was 3.8Nm³/h, the finally coated with char. The char was studied in the range between steam mass flow was 12kg/h and layer of the particle in the centre of 550 and 700°C. To identify the the superficial gas velocity at the Figure 2 is fractured. The char influence of the char in the riser bottom was 5.5±0.3m/s. The (Continued on page 12) pyrolysis reactor Kraft-lignin was nitrogen volume flow through the continuously fed into the reactor gas distributor was adjusted to and pyrolysed at 650°C maintain a constant superficial gas (Experiments B1 to B3, cf. Figure. velocity at the reactor bottom of 4). At different times side stream 5.5m/s. samples were taken and analysed.

For all experiments the feeding RESULTS rate of lignin was 2±0.3kg/h, the Solids properties and pyrolysis mechanism Figure 2 shows BM particles with “In this work the the char layer. It can be concluded that during the pyrolysis of lignin in influence of pyrolysis the circulating fluidised bed, the temperature on the lignin makes contact with the bed product yields and material. Molten lignin deposits on the bed material form a char layer composition was as a result of the pyrolysis studied in the range reactions taking place at the Figure 2: SEM image of bed particle surface level. This material (BM) from Experiment B2, between 500 and assumption is in good agreement particle in the centre showing char 750°C.” with the softening temperature of lignin of ~120 to 180°C coating fracture, scale bar at 40µm. (Nowakowski et al., 2010). The

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 11 Lignin pyrolysis ...continued layer is not stable when subjected Exp. B1 to mechanic stress due to impact 70 on the reactor wall or cyclone wall Oil Exp. B2 or collision with other particles. The 60 % Exp. B3 fragments can be found in the material separated from the gas in 50 the secondary cyclone. It consists yield, mainly of small plate like char 40 fragments and a few primary particles not caught by the primary Gas cyclone. 30

Effect of char on product yield 20 The yields of oil, gas and char for Char the three experiments B1 to B3 10 with the duration of lignin feeding Instantaneous can be seen in Figure 3. The 0 duration of lignin feeding was 68 min for B1 and 130 min and 012345 117 min for B2 and B3 Accumulated lignin feed, kg respectively. During experiment B1 two samples were taken, while in experiments B2 and B3 four Figure 3: Effect of accumulated mass of lignin fed into the reactor on the samples were taken in a sequence. yield of oil, gas and char (single points) for the experiments B1 to B3. The yields are plotted against the lignin amount fed into the reactor from startup up to the middle of the sampling period. The char 1.5 produced is approximately 74 min proportional to the lignin amount ‐ 7 min fed into the reactor, and stays mainly in the reactor as the above 1 mentioned char layer that builds up 22 min on the bed material. As the bed 122 min material is taken from the reactor frequency, after each experiment only the 0.5 yield of char at the end of the whole feeding can be determined.

It can be seen that the char yield is Relative slightly lower for the shorter 0 experiment B1 (less lignin fed into 2 3 4 5 the reactor). The gas yield 10 10 10 10 increases with rising char holdup and the oil yield decreases. It can Molar mass, g/mol be clearly seen that the char (with its components) has a strong influence, decreasing the oil yield Figure 4: Molecular weight distribution of oil samples from experiment B2. by 7 to 10%-points for the experiments B2 and B3.

This effect can also be seen in increasing time and thus an increases with time in the reactor. Figure 4 showing the molecular increasing char amount in the However, the alkaline and alkaline weight distribution of the four oil reactor. earth metals also influence the samples of experiment B2 obtained product yield and composition. Due by gel permeation The cracking of oil and gas to to the pulping process Kraft lignin chromatography. The distribution smaller molecules may be caused contains high amounts of sodium shifts to smaller molar size with by the char, the amount of which (Continued on page 13)

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 12 Lignin pyrolysis ...continued

Circulating Fluidized Beds and 60 Fluidization (CFB X) 2011: Engineering Conferences Pyrolysis oil International, New York, pp. 241- %

248. 50 2. Franck, M., Hartge, E.-U., Heinrich, S., Werther, J., Eidam, P., Fortmann, I., Meier, D. 2012.

yield, 40 Gewinnung von Phenolen aus Lignin Gas durch Flash-Pyrolyse in einer zirkulierenden Wirbelschicht (ZWS) 30 – Prozessentwicklung und Produktanalytik, in Proceedings of the DGMK-Fachbereichstagung 20 Konversion von Biomassen: DGMK, Char Hamburg, pp. 35-43. 3. Franck, M., Hartge, E.-U., Heinrich, S., Werther, J., Meier, D. 2014. 10 Lignin Pyrolysis in a Circulating Instantaneous Fluidized Bed – Influence of Temperature and Char Formation on 0 Bed Material, in Proceedings of the 11th International Conference on 500 550 600 650 700 750 Fluidized Bed Technology: Chemical Industry Press, Beijing, pp. 733-738. Temperature, °C 4. Nowakowski, D. J., Bridgwater, A. V., Elliott, D. C., Meier, D., Wild, P. de 2010. Lignin fast pyrolysis: Results from an international Figure 5: Effect of temperature on product yield. collaboration. Journal of Analytical and Applied Pyrolysis 88, pp. 53–72. 5. Richards, G. N., Zheng, G. C. 1991. Influence of metal ions and of salts (here 3g/kg) which accumulates in 0315559A and 031A233C). The on products from pyrolysis of wood: the char having a sodium content responsibility for the content of this Applications to thermochemical of 9g/kg for experiment B2. work lies with the authors. processing of newsprint and Effect of pyrolysis temperature on biomass. Journal of Analytical and product yield Contact Applied Pyrolysis 21, pp. 133–146. Miika Franck Figure 5 shows the effect of Hamburg University of Technology temperature on product distribution (TUHH) for the three products pyrolysis Institute of Solids Process gas, oil and char. The vapour Engineering and Particle residence time in the hot zone of Technology the CFB pyrolysis plant was Denickestraße 15 - R2503 shorter than 1s. 21073 Hamburg Germany It can be seen that the effect of temperature manifests in the T: +49 40 43878 3282 maximum oil yield of 49% at E: [email protected] 650°C. With rising temperature the gas yield almost doubles from 17 www.spe.tu-harburg.de to 32%, while the char yield decreases from 24 to 13%. References 1. Franck, M., Hartge, E.-U., Heinrich, Acknowledgement S., Lorenz, B., Werther, J. 2011. This work has been carried out Energetic Optimization of the Lignin within the framework of the cluster Pyrolysis for the Production of Aromatic Hydrocarbons, in Biorefinery2021, funded by the Proceedings of the Tenth German Federal Ministry of International Conference on Research and Technology (FKZ

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 13 Renewable wood-based biofuels for shipping: ReShip

ReShip is a new research project 2017 and is funded by industry which aims at developing partners and the Research Council renewable wood-based biofuels for of Norway. shipping. Alternative sustainable transportation fuels are needed in Sustainable transport fuel from the transport sector to reduce wood feedstocks greenhouse gas emissions. In In Norway, low quality wood marine transport, there is a fractions like forest residues and particular need to develop low- energy wood represent a sulphur fuel alternatives due to significant potential resource for upcoming regulations demanding bioenergy production. This significantly reduced sulphur resource is currently not much content in marine fuels from used due to costly logistics and low January 2015. profitability in direct combustion. However, cost-efficient logistics Kai Toven of the The overall objective of ReShip is can be obtained for such to develop cost-competitive feedstocks by converting the Paper and Fibre pyrolysis oil based multicomponent biomass into energy dense Research fuels which meet the performance pyrolysis oils in decentralised requirements of marine diesel pyrolysis plants. Institute (PFI), engines. The project is led by the Paper and Fibre Research Institute Crude pyrolysis liquids are not Norway, and Tony (PFI) in Norway and includes suitable for direct use in diesel Bridgwater from industry partners along the whole engines. Compared to petroleum- value chain, from forest owners to based fuel oils, the pyrolysis liquids the European end users in shipping. Research are acidic, rich in oxygenated and development partners in the functional groups, hard to ignite Bioenergy project are PFI, Aston University and of relatively low calorific value. and the Norwegian University of In addition, fast pyrolysis oils Research Science and Technology (NTNU). contain unstable compounds such Institute, Aston The project is running from 2013 to (Continued on page 15) University, UK, introduce us to the ReShip Project

Figure 1: ReShip aims to produce multi-component fuels for the shipping industry.

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 14 ReShip ...continued

Figure 2: The ReShip concept. as aldehydes, ketones and requirements of marine diesel Contact carboxylic acids, which may cause engines. The project concept is Kai Toven increased viscosity, phase illustrated in Figure 2. If successful, Paper and Fibre Research Institute separation and changed chemical the concept can be adapted to an (PFI) composition upon storage. industrial scale at low cost, as both Høgskoleringen 6B Pyrolysis oils can be upgraded mild upgrading and fuel blending NO-7491 Trondheim directly to transport fuel quality by processes are favourable from a Norway hydro-deoxygenation, high- cost perspective. pressure hydrogenation and T: +47 95 21 17 04 catalytic cracking of pyrolysis Key topics which will be addressed E: [email protected] vapours. However it is a challenge in ReShip are bio-oil stabilisation to develop cost effective technology, multi-component fuels, www.pfi.no techniques as rather extensive and engine testing. The research upgrading is required. activities are being led by Dr. ing. Kai Toven, Lead Scientist in ReShip concept Biorefining and Bioenergy at PFI The ReShip project is based on an and Professor Tony Bridgwater, Tony Bridgwater innovative approach for producing Head of the European Bioenergy Aston University partly upgraded storage stable Research Institute at Aston European Bioenergy Research pyrolysis oil from wood feedstocks, University, UK. Institute and for developing pyrolysis oil- School of Engineering and Applied based multi-component fuels which Science meet the performance Aston Triangle Birmingham B7 4ET, UK

T: +44 121 204 3381 E: [email protected] “Key topics which will be addressed in ReShip are bio-oil stabilisation technology, www.aston.ac.uk/eas/research/ groups/ebri/ multi-component fuels and engine testing.”

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 15 Application of pyrolysis oil in the OP16 gas turbine - development of a low calorific fuel combustor

Martin Beran and Figure 1: The OP16 gas turbine. Lars-Uno Axelsson OPRA Turbines develops, of a new combustor for pyrolysis oil manufactures, markets and and other low-calorific fuels. This conclude their maintains generator sets in the research project was partly 2MW power range using the OP16 sponsored by the province of discussion - series of gas turbines. The OP16 Overijssel, the Netherlands, as part begun in PyNe gas turbine, shown in Figure 1, is of the BE2O project. an all-radial design, which provides Issue 33 - of robustness, reliability and the Combustor for pyrolysis oil highest efficiency in its class. A key Based on the results obtained from research and feature of the OP16 gas turbine is the initial feasibility study a new development at the ability to utilise a wide range of combustor was developed (patent fuels. As part of OPRA’s pending, patent application No. US OPRA Turbines in continuous efforts to extend the 2012/0111014).The main features fuel capability of the OP16 gas of the combustor are a significantly the Netherlands turbine, a research and increased volume of the reaction development project was initiated zone and the use of an enhanced focusing on the utilisation of cooling method of the flame tube pyrolysis oil. The overall aim of the walls. From the feasibility study it R&D project was to develop a was found that the flame tube film combustor suitable for the efficient cooling significantly disturbs the combustion of pyrolysis oil. The combustion process of the higher viscosity, lower energy pyrolysis oil. Hence it was density and limited chemical necessary to develop a new stability of the pyrolysis oil means strategy for the cooling of the flame that it requires different fuel tube wall. This new cooling handling in comparison to strategy, together with the use of conventional liquid fuels. thermal barrier coating on the flame tube inner wall, allows the A feasibility study on the use of surface temperature to be kept pyrolysis oil in the OP16 gas relatively high and improves the turbine was presented in an earlier combustion process of the PyNe newsletter (Issue 33, June pyrolysis oil. 2013). This article presents the continuation of the R&D project, focusing on the design and testing (Continued on page 17)

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 16 Application of pyrolysis oil in the OP16 gas turbine… continued

Results from the test campaign OPRA’s atmospheric combustion test facility, shown in Figure 2, was used for the tests. For these tests pyrolysis oil from pine wood provided by BTG Bioliquids was used. The test campaign focused on the operability range of the new combustor as well as on the effect of different fuel injection strategies. The target for the new combustion chamber was to burn pure Figure 2: Low calorific fuel combustor installed in OPRA’s combustion test pyrolysis oil between 70% and 100% load, which was also facility. achieved. At loads below 70% a mixture of pyrolysis oil and ethanol spray shall be approximately 50% means that the so called fuel, NOx, has to be used. The ethanol is also of the maximum allowed droplet is produced during the combustion used for cleaning the fuel system diameter for diesel No. 2. process. If all the nitrogen and injectors when the engine is contained in the fuel is converted shut down. The exhaust gas emissions were to NOx, this would make up for measured for several fuels over the about 60% of the total NOx During the rig testing several air complete load range. Table 1 produced during pyrolysis oil blast nozzles and pressure nozzles shows the NOx and CO emissions combustion. Hence, from an were used. The main purposes at full load for diesel, ethanol and environmental perspective it would here were to investigate the impact pyrolysis oil converted to 15% O2. be beneficial to decrease the of the droplet size on the pyrolysis Although the low-calorific nitrogen content in the fuel. oil burning process and to define combustor can burn high-calorific the limits for the maximum allowed fuels, such as diesel and natural Conclusions droplet diameter as a function of gas, the NOx emissions will be With the development of the new the operating condition. The air higher due to the longer residence combustor OPRA has an efficient blast nozzle produces a fairly time caused by the larger and reliable solution for the constant droplet size independent combustor volume. To make a fair utilisation of pyrolysis oil in the of the fuel flow, whereas the comparison the emission values for OP16 gas turbine. The new droplet size for the pressure nozzle diesel are obtained from a combustor can also be used for shows a strong dependency on the conventional gas turbine other (ultra) low calorific liquid and fuel flow. In addition, a pressure combustor. The NOx emissions gaseous fuels such as syngas, nozzle is highly sensitive to from low-calorific fuels are ethanol, biogas and waste gas. abrasion and erosion due to the generally lower than from particles present in the fuel and the conventional fuels, which can be Contact high velocity in the small nozzle seen when comparing the ethanol Martin Beran passages. Therefore, a pressure and diesel results. However, E: [email protected] atomiser is not recommended for pyrolysis oil and diesel show pyrolysis oil burning. From the similar NOx levels. It should be Lars-Uno Axelsson extensive tests performed it was noted that pyrolysis oil contains E: [email protected] found that the maximum allowed about 0.4%wt nitrogen that is droplet diameter for pyrolysis oil chemically bounded in the fuel. It OPRA Turbines BV Opaalstraat 60 Table 1: Exhaust gas emissions at full load converted to 15% O2. For 7554 TS Hengelo ethanol and pyrolysis oil the data was obtained from the low-calorific The Netherlands fuel combustor, whereas for diesel the data was obtained from the conventional combustor. T: +31 74 245 2121

Diesel No. 2 Ethanol Pyrolysis Oil

NOx [g/kWh] 3.9 2.4 3.9

CO [g/kWh] 0.56 0.17 1.1

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 17 Requirements for transportation of fast pyrolysis bio-oil

Mika Laihanen, Antti Karhunen, and Tapio Ranta of Lappeenranta University of Technology (LUT Energy) in Finland discuss how best to transport biomass fast pyrolysis bio-oil as production increases

Biomass fast pyrolysis bio-oil (pyrolysis oil) is a renewable liquid fuel which can replace fossil fuels in energy production. In Finland there are currently ongoing projects concerning the production of pyrolysis oil. As this is a new chemical product, transportation requirements and conditions must Figure 1: Pyrolysis oil labelling for be taken into consideration. transportation.

Pyrolysis oil is a liquid biofuel produced, for example, from liquid, acidic, organic, n.o.s.” and biomass or other raw materials that 80 stands for corrosiveness (8) contain carbon. Biomass fast without any secondary hazard (0). pyrolysis bio-oil is generally acidic, For waterway transport pyrolysis oil unstable at high temperatures or will also need IMO classifications. over long storage periods, highly polar and mainly non-volatile containing a large amount of Table 1 illustrates different chemically dissolved emulsified transportation methods, typical unit water. Due to acidity pyrolysis oil sizes and indicative annual will be classified as dangerous transportation flows in Finland goods in road, railway and when production of pyrolysis oil is waterway transport. However 100,000 tonnes per annum. For pyrolysis oil has never been calculation purposes, the transported on a large-scale in hypothesis is that all pyrolysis oil Finland. will be transported regularly using a single transportation method; usually, in practice, the logistical Pyrolysis oil requires specific chain could consist of equipment for loading, unloading combinations of different and handling. All surfaces in alternatives. For railway transport it contact with the product must be is assumed that one train consists acid proof materials. Suitable of ten chemical wagons and tank materials are, for example, acid containers are transported by road proof steel PTFE (Teflon). Acidic with semi-trailers. Maximum products are already transported payloads per unit can vary widely and suitable transport between different European equipment exists. countries.

When transporting dangerous Suitable transportation methods goods, labelling is always required From top: are always closely related to and it is also required for road, Mika Laihanen, Antti production sites and end-users’ railway and waterway Karhunen, and Tapio facilities, existing transport transportation of pyrolysis oil. In connections and annual production Ranta labelling (Figure 1) the lower UN number 3265 stands for “Corrosive (Continued on page 19) IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 18 Requirements for transportation ...continued

volumes. Transport distance is also Table 1: Different transportation method unit sizes and number of an- a very important factor. nual transports in Finland with a production of 100,000 tons p/a.

Road transportation with a truck Maximum Number of and full-trailer combination is Transportation Method payload per unit, transports per year currently the most cost-effective tonnes and flexible option if no railway 1. Roadway 36-42 ~2,500 connection or deep-water harbour 2. Railway (10 wagons) 540 ~200 exists near the production plant. The main advantages of road 3. Waterway 3,600* ~30 transport are the constant 4. Tank container 25-30 ~3,500 transportation flow from production 3 to end-users and that roads offer *volume of one tank in chemical tanker 3,000m the most extensive transport network. one load is at least 3,000m³. transported using all conventional Waterway transportation also dangerous goods transportation The advantage of railway and requires chemical ports and methods. Different methods have waterway transport methods is the sufficient storage capacity to limitations that must be taken into option of larger unit sizes per one operate. In Finland truck transport consideration as well as national transport. Railway transportation is often needed in some part of legislations. All challenges would be a good option for straight railway and waterway transport concerning transportation are long-distance domestic routes from logistical chains. solvable and more dangerous production plant to end-user; goods are transported constantly however, if extra loading and Requirements and classifications via European roads, railways and unloading are needed the for pyrolysis oil transportation are waterways. profitability of railway transport needed because large-scale could decrease. production should be Contact commercialised in Finland within Corresponding author: Waterway transport with chemical the next few years. Pyrolysis oil will Mika Laihanen tankers is the best method for large be classified as dangerous goods Lappeenranta University of -scale exportation when the size of in transportation but it can be Technology—LUT Energy P.O. Box 20, FI-53851 Lappeenranta, Finland

T: +358 40 194 7819 E: [email protected]

Antti Karhunen E: [email protected]

Tapio Ranta E: [email protected]

www.lut.fi/web/en/school-of- technology/lut-energy

Figure 2: Truck and full trailer combination for chemical transports in Finland.

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 19 Chemical fingerprinting of pyrolysis oil heavy ends with high-resolution mass spectrometry

Janne Jänis of the University of Eastern Finland looks at the best way to characterise pyrolysis oil at the molecular level

based techniques. This fraction spectroscopy (NMR) and high- contains a large number of non- resolution mass spectrometry volatile polymeric compounds, e.g. (HRMS).1 GC is superior in pyrolytic lignin and different cyclic, identification of small volatile polyhydroxy types of compounds organics but generally does not (“sugaric” compounds). work with high-MW species. IR and NMR provide information about In recent years, many types of functional groups but do not The chemical complexity of analytical techniques have been generally allow identification of pyrolysis oils poses a challenge for utilised for chemical fingerprinting individual compounds from the their characterisation at the of pyrolysis oils, such as mixture. molecular level. The heavy ends of conventional gas chromatoghraphy pyrolysis oils (i.e. polar fraction of (GC), comprehensive two- HRMS has been succesfully used high molecular weight species) are dimensional gas chromatography in the past for the characterisation difficult to characterise using (2D-GC), infrared spectroscopy of petroleum and its end-products.2 conventional gas chromatography (IR), nuclear magnetic resonance (Continued on page 21)

Figure 1: High-resolution FT-ICR spectrum of birch wood fast pyrolysis oil. About 1400 individual heteroatom compounds could be identified. The inset shows the magnified view (a half nominal mass unit) at around m/z327. All nine baseline-resolved peaks could be unequivocally assigned to different oxygen-containing species, with varying degree of aromaticity/unsaturation (DBE = 1–11).

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 20 Chemical fingerprinting of pyrolysis oil ...continued

Figure 2: 3D van Krevelen plot of all compounds identified from the phase-separated pine wood slow pyrolysis oil by FT-ICR MS: aqueous phase (left), oily phase (right). A colour coding of the dots represents the relative abundance of each detected species.

Even the heaviest parts of cyclotron resonance (FT-ICR) MS, IMS-MS should futher advance our petroleum (e.g. distillation combined with different selective understanding of pyrolysis oil residues), having thousands of ionisation techniques, for constituents, especially for different species, can be analysed by compositional analysis of different isomeric species. HRMS techniques.3 More recently, pyrolysis oils. Figure 1 shows the HRMS has also been applied for FT-ICR mass spectrum of birch References the analysis of pyrolysis oils from wood fast pyrolysis oil; about 1,400 1. Staš, M.; Kubička, D.; Chudoba, J.; different starting materials. HRMS unique heteroatom compounds, Pospíšil, M.; ACS Energy Fuels provides a chemical fingerprint of mainly oxygenated species, could 2014, 28, 385–402. pyrolysis oils’ polar compounds be detected.4 Figure 3 shows 3D 2. Rodgers, R.P.; McKenna, A.M.; without chromatographic van Krevelen diagrams (H/C vs. O/ Anal. Chem. 2011, 83, 4665–4687. 3. Kekäläinen, T.; Pakarinen, J.M.H.; separation. Large polymeric C ratio, relative abundance given Wickström, K.; Lobodin, V.V.; species can also be detected. by the colour) for the compounds McKenna, A.M.; Jänis, J.; ACS Currently, the combination of 2D- detected from the phase-separated Energy Fuels 2013, 27, 2002–2009. GC and HRMS looks most pine wood slow pyrolysis oil by FT- 4. Kekäläinen, T.; Venäläinen, T.; promising for detailed molecular ICR MS.5 A van Krevelen plot is a Jänis, J.; accepted, ACS Energy level characterisation of pyrolysis straghtforward visual means for Fuels 2014. oils.1 The biggest drawback of differentiating between lipids, 5. Miettinen, I.; Mäkinen, M.; Jänis, J., HRMS is that it is merely semi- phenolic and “sugaric” compounds unpublished results. quantitative as the peak intensities in pyrolysis oils. As can be seen, do not correlate with the absolute the oily phase has clearly higher Contact concentrations of analytes in an oil content of lipids while “sugaric” Janne Jänis sample. Relative quantitation compounds are concentrated in the University of Eastern Finland between different samples for a aqueous phase. Department of Chemistry given analyte class are, however, P.O. Box 111, FI-80101 Joensuu possible. Also, some of the In the near future, we wish to Finland smallest analytes (methanol, acetic combine our FT-ICR MS with 2D- acid etc) are not typically efficiently GC technique to obtain deeper T: +358 29 4453422 ionised, so a combination of GC- insights into the molecular +358 50 4601075 MS with HRMS is therefore complexity of different pyrolysis E: [email protected] desirable for more comprehensive oils. In addition, we will test the analysis. analytical capabilities of ion www.uef.fi mobility spectrometry combined We have recently used ultrahigh- with mass spectrometry (IMS-MS) resolution Fourier transform ion in pyrolysis oil characterisation. IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 21 Second generation bio-oil by selective decarbonylation via catalyst-impregnated pyrolysis

Paul Dauenhauer of the University of Massachusetts Amherst, USA,

discusses a new Figure 1: Tunable cellulose melt (liquid) chemistry by catalyst-impregnated method of pyrolysis converts reactive furans (e.g. HMF) to stable furans (e.g. 2 increasing the methylfuran). viscosity and bio-oil to be produced in sufficient to be transported over reasonable quantity and quality that it can be distances via pipeline. Despite the commercial value of traded on the open market as a need for higher quality bio-oils, the commodity. This approach severs technology and scientific bio-oil upstream pyrolysis and understanding needed to downstream refining processes, accomplish this are lacking, where the latter is accomplished especially with regards to High-temperature pyrolysis of with an approach similar to today’s controlling pyrolysis chemistry to lignocellulosic biomass produces centralised petroleum refineries. enhance selectivity to desirable gases, solid residue and For pyrolysis oil to become a products (stable bio-oil). condensable vapors which can be commodity, it must be produced to converted to biofuels and have sufficient energy density and We introduce a new technology biochemicals.1 The vapours, stability to be valuable and be able (Cat. Sci. & Tech., 2014), called referred to as ‘bio-oil,’ are Catalyst-Impregnated Pyrolysis,2 comprised of a large number of for tuning the reaction pathways of highly oxygenated chemical melt-phase pyrolysis of cellulose species, some of which have and lignocellulose to targeted multiple functional groups and are “We introduce products more desirable for the extremely reactive. Over periods of a new second generation of bio-oil. As weeks and months, these species shown in Figure 1, the global react to form heavier oligomers, technology pathways of cellulose pyrolysis which increase the viscosity and called Catalyst have been defined as transition reduce the overall value of bio-oil. from solid polymers, through a -Impregnated liquid melt rich in anhydro- Implementation of the Pyrolysis” oligomers, and the eventual thermochemical biorefinery formation of high-vapour-pressure concept relies on the capacity for (Continued on page 23)

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 22 Second generation bio-oil ...continued

impact proof-of-concept of the potential of the technology for the next generation of bio-oils, the approach opens the door for future research necessary for implementation. The future programme of research must identify multiple chemical targets for in situ melt-phase transformation, synthesise cheaper and more recoverable catalysts, and develop continuous flow pyrolysis reactors capable of impregnating, reacting, and recovering catalysts.

Support Work from the University of Massachusetts Amherst was supported by U.S. Department of Energy Early Career Program, Basic Energy Sciences – Catalysis, Award Number DE-SC0006640).

Contact Paul Dauenhauer UMass Amherst Dept. of Chemical Engineering 686 North Pleasant Street Figure 2: Pyrolysis oil yield versus selectivity to decarbonylated furans. Amherst, MA 01003 Pd/C achieves almost 90% selectivity to stable furans with only negligible USA 2 loss in bio-oil yield. T: +1 413 545 2819 E: [email protected] species which evaporate and are Figure 2 shows that selective 3 collected as bio-oil. Within the transformation (decarbonylation) of www.ecs.umass.edu melt, condensed-phase reactions aldehydic furan species at 500°C is accomplished with Pd and Pt break down biopolymers into non- supported on Al O , SiO or volatile anhydro-oligomers which 2 3 2 carbon. Additionally, ultimately form volatile species. decarbonylation occurs without a The composition of evaporated significant reduction of total bio-oil species is dictated by melt-phase yield. Pt-containing catalysts reactions, and controlling them is one approach to producing a more exhibit a strong capacity for C-C 4 References stable and energy dense bio-oil. cleavage, which produces more 1. C. Di Blasi, Progress in Energy and permanent gases and significant Combustion Science 2008, 34, 47- Impregnation of biomass loss in the overall pyrolysis oil 90 feedstocks with supported metal yield. However, Pd-containing 2. M.S. Mettler, A.D. Paulsen, D.G. catalysts enables the tuning of melt catalysts only minorly impact Vlachos, P.J. Dauenhauer, -phase reactions as melt species overall yield, with only a small Catalysis Science and Technology have sufficient mobility (and increase in permanent gases. 2014, DOI: 10.1039/c4cy00676c residence time) to interact with Moreover, Pd achieves almost 3. M.S. Mettler, D.G. Vlachos, P.J. catalyst active sites. In this work, 90% selectivity to carbonyl-free Dauenhauer, Energy & Environmental Science 2012, 5, we target one class of suspected furans including furan, methyl 7797-7809. “bad actors” – aldehydes and furan, and dimethylfuran. 4. M.S. Mettler, A.D. Paulsen, D.G. ketones – which can destabilise bio Vlachos, P.J. Dauenhauer, Energy -oil. While catalyst-impregnated & Environmental Science 2012, 5, pyrolysis with Pd provides a high 7864-7868.

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 23 Production of liquid feedstock via catalytic fast pyrolysis of biomass in the presence of steam

The use of metal modified zeolite unit is composed of five sections: catalysts for production of liquid the gas preheating section, the feedstock and a modified reaction feeding section, the fast pyrolysis environment (using steam) during reactor, the char–vapour biomass fast pyrolysis was separation section and the liquid investigated. The introduction of quenching and collection system. steam and the incorporation of The overview of the process is metal functions on the zeolite shown in Figure 1. The pyrolysis (multifunctional catalysts) can took place at 450°C with a steam promote in situ hydrogen to biomass ratio (S/B) of 0.5 with generation (steam reforming, the experimental duration at 90 WGS, dehydrogenation and minutes. decarbonylation), hydrogen transfer and hydrogenation Catalysts Efthymios reactions which are important to Silica supported Ni and V were Kantarelis of KTH produce olefins and aromatics as prepared by incipient wetness well as hydrogenated products of impregnation and tested for their in Sweden looks high market value.1,2 activity and effect on the liquid yield and composition during fast into the potential of Fast pyrolysis process pyrolysis of biomass. The metallic steam for the A continuous bubbling fluidised functions were then incorporated bed reactor was used to pyrolyse a into a hybrid catalyst comprising of biomass fast mixture of pine and spruce H-ZSM5 zeolite and bentonite as samples in the presence of binder. The different effects on pyrolysis process different catalysts. The pyrolysis (Continued on page 25)

Figure 1: Overview of fast pyrolysis process. H-401 Steam Boiler; H-402 and H-403 Gas preheaters; R-201 Fluidised bed reactor; V-101 Biomass hopper; SF-101 Metering screw feeder; SF-102 Injection Feeder; FG-201 Cyclone; V-301 Venturi Scrubber; P-301 Pump; E-301 Heat Exchanger.

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 24 Production of liquid feedstock ...continued liquid yield and composition were investigated by adjusting the metals to zeolite and binder ratios as well as the Weight Hourly Space Velocity (WHSV). Characterisation of the coke formed, assessment of its reactivity during regeneration, and evaluation of the structural stability of catalyst, were all carried out.

Results The effects of the different catalysts on the CHO composition of the liquid are shown in Figure 2. Straight lines represent the theoretically obtained composition (in terms of H/C and O/C) if dehydration (-H2O), decarbonylation (-CO) or decarboxylation (-CO2) were the only acting mechanisms of oxygen rejection (NC refers to non-catalytic pyrolysis). The figure shows that Ni Figure 2: Effect of different catalysts on the CHO composition of obtained is more active in de-oxygenation liquid (dry basis). (lower (O/C) than V; however, liquid with H/C content lower than production. Increased catalytic reduced the yield of liquid that obtained from the V-catalysed activity (at low WHSV) results in product which had significantly pyrolysis is obtained. This effect is oxygen rejection in the form of lower oxygen content. detrimental because hydrogen carbon oxides. However, increased zeolite scavenging results in low effective content results in increased hydrogen content (EHI), which will XRD patterns of the fresh and coke formation on the catalyst. make further upgrading difficult due 3 regenerated catalyst are shown in The metal/zeolite content did to excessive coking. V seems to Figure 3. Their examination not significantly affect the char selectively deoxygenate liquids by indicates no new phases, nor yields. decarboxylation and changes in the relative intensities,  Low WHSV favour oxygen decarbonylation reactions. The Ni- while the analysis of interplanar rejection as carbon oxides. V bimetallic system shows spacing, ‘d’, shows that the catalyst However, lower liquid yields enhanced deoxygenation activity retained its crystallinity and thus, it were obtained, while the char compared to V-containing can be said that no significant yield remained almost catalysts, while simultaneously structural alterations occurred. unaffected. The coke showing less hydrogen scavenging percentage on the catalyst is compared to Ni catalysts. The H/C Conclusions reduced. and O/C atomic ratios of the  Both selected metals (Ni and  Comparison of reactivity of obtained liquid show that V) are catalytically active in coked catalysts at different deoxygenation moves along the transforming the composition of WHSV showed that at low theoretical dehydration pathway up pyrolysis liquids. The H WHSV more reactive coke is to 50% of ZSM5 loading. The 2 concentration in the produced deposited on the catalysts dehydration is catalysed by the gases increased. Vanadium- which denotes that the main strong Brønsted acid sites and is containing catalysts are more deactivation mechanism is the rate limiting step for Diels-Alder selective in the reduction of coke formation inside the pore cyclisation and aromatics carbonyl-containing structure. production via the production of 4 compounds (mainly acids and  The XRD and microscopic olefins. The increased zeolite ketones). Both metals showed investigation of the regenerated content allows for olefins activity towards the production catalyst at low temperatures cyclisation and di-, tri- and oligo- of phenols. (550°C) did not show merisation reactions after olefins  Increased zeolite content significant structural defects,

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 25 Production of liquid feedstock ...continued

which suggests that the catalyst is hydrothermally stable.  Overall, the modified reaction environment and bimetallic (Ni- V) multifunctional catalysts based on ZSM5 zeolites promote hydrogen production and transfer within the reaction system to produce a de- oxygenated liquid with preserved H content.

Acknowledgements Energimyndiheten is greatly acknowledged for funding this work (contract no.33284-1), as well as BOSON Energy S.A. and Preem AB for technical support and help. SCA BioNorr and Süd Chemie are also thanked for generously providing the biomass and the zeolite respectively.

Contact Efthymios Kantarelis Royal Institute of Technology School of Industrial Engineering and Management Brinellvagen 23, 10044 Stockholm Sweden

T: +46 87908405 E: [email protected] www.kth.se

Figure 3: XRD patterns of fresh and regenerated catalyst (WHSV ½ h-1). (a) Fresh catalyst; (b) regenerated at 550°C (1st row). SEM and TEM microphotographs of fresh (2nd row) and regenerated catalyst (3rd row). References 1. G. W. Huber and A. Corma, Applied Catalysis A: General, vol. ch. 24, pp. 277-288. "Synergies between Bio- and Oil 116, pp. 5-47, 1994. 4. Y.T Cheng and G.W. Huber, Refineries for the Production of 3. Ν. Y. Chen, D. E. Walsh, and L. R. "Production of targeted aromatics Fuels from Biomass," Angewandte Koenig, "Fluidized-Bed Upgrading by using Diels-Alder classes of Chemie. Int. Ed., vol. 46, pp. 7184- of Wood Pyrolysis Liquids and reactions with furans and olefins 7201, 2007. Related Compounds," in Pyrolysis over ZSM-5," Green Chemistry, vol. 2. A.V. Bridgwater, "Catalysis in Oils from Biomass. Washington DC: 14, pp. 3114-3125, 2012. thermal biomass conversion," American Chemical Society, 1988,

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 26 EMPYRO: Realisation of a commercial scale, biomass fast pyrolysis plant

The company Empyro was The outline of the Empyro project founded to build and demonstrate was presented in PyNe News the fast pyrolysis technology of Issue 27 (June 2010). While it has BTG Bioliquids on a commercially taken more time than anticipated relevant scale in the Netherlands. the key objective of the Empyro Preparations for this plant began in project remains unchanged: to 2008/2009, and in February 2014 demonstrate the fast pyrolysis Empyro BV announced that technology on a 5t/hr capacity and financial close had been reached make use of pyrolysis oil to replace and actual construction of the natural gas. pyrolysis oil production plant started. By the end of this year Fast pyrolysis plant construction will have been The Empyro plant will be situated completed, and the production in Hengelo on the site of chemical capacity will then be gradually company AkzoNobel, and in April increased to its maximum of over site specific construction work Gerhard Muggen of 20 million litres of pyrolysis oil per began. All permits have been year. This amount of renewable oil obtained for the realisation and BTG-BTL updates will replace 12 million cubic meters operation of the plant on this site. of natural gas, the equivalent us on the work of annual consumption of 8,000 The feedstock is clean wood and Empryo in the Dutch households, which saves up long term biomass contracts could to 20,000 tonnes of CO2 emissions be concluded to guarantee the Netherlands per year. biomass supply. Final drying will (Continued on page 28)

Figure 1: Impression of the Empryo fast pyrolysis production plant.

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 27 EMPRYO ...continued

Figure 2: Schematic drawing of the boiler to be installed at FrieslandCampina in Borculo (left). On the right, the Stark double register burner applied in the boiler. take place on site, and the biomass The pyrolysis plant is being time as site preparation work can dryer has been engineered by constructed by Zeton, Enschede. A be done in parallel to plant German company Amandus Kahl. benefit of working with Zeton is that construction. Zeton will also be in This company will also supply and they assemble and mechanically charge of re-assembly on site, install the unit. The engineering of test the main processes of the which is actually only a few the pyrolysis plant itself was complete Empyro plant at their in- kilometres from their own performed by BTG-BTL together house workshop before partially premises. with Zeton, Stork and HoSt. In the dismantling the installation into skid plant 5 tonnes of dried biomass will mounted modules and transporting Pyrolysis oil application be converted hourly into about 3.2 these to site. This will also save Obviously, an extremely important tonnes of pyrolysis oil. Excess heat part of the realisation of the project generated from the combustion of is a guaranteed long-term demand the byproducts (gas and char) will for pyrolysis oil. FrieslandCampina be used for the generation of – one of the world's largest dairy steam. Subsequently, this steam “Due to the efficient companies – owns and operates a will be used to provide the heat for number of natural gas fired boilers the biomass dryer and to run a design of this plant a for the generation of process steam turbine to generate total of up to 90% of steam. Agreement has been reached on a 12 year delivery electricity. The excess steam will the energy in the be supplied to AkzoNobel (located contract for the majority of the next to Empyro) for salt production. biomass will be pyrolysis oil, which Due to the efficient design of this captured in the form FrieslandCampina will utilise as a plant a total of up to 90% of the substitute for natural gas to energy in the biomass will be of pyrolysis oil, steam generate 40t/h of 20 bar(g) process captured in the form of pyrolysis and power while no steam for use in milk powder oil, steam and power while no production. A big advantage of this external energy will be required to external energy will application is that every pyrolysis run the plant (apart from start-up). be required to run the oil/natural gas substitution ratio up To get a sense of the scale of this to 70% is possible with a 100% installation: the framework alone plant (apart from start redundancy of natural gas. weighs 225 tonnes while the -up).” Therefore, the co-firing of pyrolysis largest single component weighs oil will not affect or interrupt the another 52 tonnes; the height of core business of the plant will be close to 24 metres. (Continued on page 29)

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 28 EMPRYO ...continued

Figure 3: Due to the innovative nature of the technology, Empryo can cover almost 40% of the total investment using European, national and local grants.

FrieslandCampina. Through the the Empyro plant are around 19 Contact use of pyrolysis oil, the direct million Euros. Due to the innovative Gerhard Muggen CO2 emissions for the entire nature of the technology, Empyro BTG-BTL Borculo location - one of the was able to cover almost 40% of P.O. Box 835 largest production facilities of the this investment by European, 7500 AV Enschede company - will be reduced by national and local grants. More The Netherlands approximately 15%. specifically, financial support was obtained from the European E: [email protected] For these purposes, a new boiler Commission (FP7 Programme), has been designed by Stork. the Ministry of Economic Affairs via www.btg-btl.com Construction of the boiler has the Topsector Energie TKI-BBE recently begun, and it is scheduled Programme, the province of to be online in the first quarter of Overijssel, and the Energy Fund of 2015. Instrumental in the design Overijssel (EFO). Additionally, have been the pyrolysis oil firing equity was provided by EFO and a tests performed jointly by Stork and private investor from Enschede. BTG-BTL (see PyNe News Issue 31). These have given insight into Time schedule the NOx, CO and dust emissions of Both site work and construction pyrolysis oil as well as the fouling have started. It is expected that the behavior when fired using Stork’s Zeton skids will be ready to be standard Low NOx Double Register transported to site in October and gas and oil-burner. The pyrolysis reassembly will begin at that time. oil will be transported from the Mechanical completion is expected production site in Hengelo to to be reached before the end of FrieslandCampina in Borculo by 2014. Commissioning and start-up tank truck, which is just a 30km is scheduled for Q1-2015. In the distance. Locally, use will be made same period the construction and of a 100m3 storage tank. commissioning of the new boiler of FrieslandCampina will be Project financing completed, and ready to start firing The total investments for design, pyrolysis oil. construction and initial start-up of

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 29 In-line determination of the water content of pyrolysis oils

In previous test campaigns on the new pilot plant the pyrolysis products were analysed labour intensively in the laboratory. However, significant simplifications can be achieved by using well- chosen and adapted high frequency technologies for process Figure 1: Microwave analytics. Transmissions and Reflection cell

from hf-Sensor. Research efforts Concerning the analyses of ® BioSyncrudes (high-concentrated shifted and costly lab analyses are suspensions of pyrolysis undesirable. Hence, real-time and condensates and char) taking easy analyses without sample samples is very problematic. The handling are desirable, which composition of small sample provide direct information about the volumes for the purposes of actual composition of the process analysing a process medium is medium. During the process, in usually different to the composition situ, inline measuring methods - Franz-Peter Girke of the medium inside the process. ideally with real time results - are discusses the latest Furthermore, in lab analyses, required. different operating conditions research and (pressure, temperature, etc.) exist Measuring technology to those in the real process and According to preliminary developments in the therefore any transfer of lab results measurements, a special to real conditions can lead to microwave measuring technology multistep significant errors. All in all, time- was suitable for integration into a “bioliq® concept” at pipeline construction in order to detect the water and char content Karlsruhe Institute of pyrolysis-oil char suspensions. of Technology (KIT) “In previous test Microwaves with a frequency of in Germany approximately 1GHz up to campaigns on the approximately 10GHz are well new pilot plant the suited to displace polar substances into oscillation. This effect can be pyrolysis products Motivation used for measurement purposes. An important step in KIT´s were analysed labour Higher frequencies cause strong losses to occur from relaxations of multistep “bioliq® concept” for intensively in the synthetic fuel production from dry the molecules, while at lower lignocellulosic biomass is the laboratory. However, frequencies the conductivity mixing of slurries from the pyrolysis significant influence of the substance rises. products (oil and char) which are Therefore, the use of microwaves converted downstream in the simplifications can be in the region of 1GHz to 10GHz entrained flow-gasifier to synthetic achieved by using seems to be the best method to gas. As a long-term objective of determine water content of this work process improvements on well-chosen and pyrolysis oils. the relevant technologies need to adapted high be achieved with regard to safety For measurements like this metallic technology (e.g. the detection of frequency pipes form a so-called “circular phase separated volumes) and technologies for waveguide” in which transmission process control (e.g. by a fully modes of microwave signals are automated feed control for an process analytics.” injected in an ingenious way into optimal oxygen dosage to the the pipeline, and consequently also gasifier). into the medium inside the pipe as (Continued on page 31) IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 30 In-line determination of water content ...continued

Figure 2: Left: Transmission curves; Right: Reflection curves of the pyrolysis oil samples (y-axis arbitrary units, x-axis microwave frequency in MHz). longitudinal and transversal waves. the material to be examined and no For batch measurements the Depending on the dielectric warming effects are expected on microwave tube was filled with the properties of the medium the the test material because the medium and then closed, and the microwaves are absorbed, inserted microwave energy is much temperature was adjusted. After transmitted and/or reflected. too small. Moreover, a sufficient attaining the desired temperature, Microwaves have the advantage of penetration depth of the several measurements were penetrating non-destructively into microwaves into the bulk material carried out on the material samples under test allows the detection of with this configuration. chemical components further away from the sensor, so this measuring The first focus of the microwave technology is well-suited for online measurements was to determine “The first focus of the or inline analytics. the water content of the samples. microwave The Karl-Fischer-Method was measurements was to The microwave measuring cell of selected as a reference for the real the company hf sensor (Leipzig, water content. determine the water Germany) being used operates content of the within a microwave frequency Results range of 2.0GHz up to 3.0GHz and The emitted microwaves are samples. As a was developed especially as a absorbed, transmitted and reference the Karl- transmission and reflecting cell reflected in a substance. (see Figure 1). It has been Transmission and reflection do not Fischer-Method was specially adapted for necessarily depend on each other. selected as a measurements under high Insofar that transmission spectra pressure, for narrow internal pipe and reflecting spectra can deliver reference for the real diameters, and for the difficult independent information, it appears water content.” insertion of microwave signals into to be reasonable to consider and the pipe. combine both types of spectra for (Continued on page 32)

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 31 In-line determination of water content ...continued

Figure 3: Predicted water content (via PLSR method) versus the reference water content (by Karl-Fischer titration). statistical evaluations. and the water content. By the use Contact of three such Principal Franz-Peter Girke By means of the Components more than 95% of the Institute for Catalysis Research “UNSCRAMBLER X10.2” software data variance is explained. If a and Technology (IKFT) of the “CAMO” company (Oslo, PLSR (Partial Least Square Karlsruhe Institute of Technology Norway) the measured spectra Regression) is applied, a good Hermann-von-Helmholtz-Platz 1, have to be analysed as a data correlation between reference 76344 Eggenstein-Leopoldshafen, matrix. Because of the complicated value and measured value of the Germany curve progression it is not possible water content can be obtained by to evaluate them manually. These the common processing of T: +49 721 608 29133 recorded curves must be assigned transmission data and reflecting E: [email protected] to the samples and the data. transmission and reflection data is www.kit.edu combined in one single data matrix The predicted exactness of the after average centred weighting of water content calculated by the the values. PLSR model is fairly accurate. The maximum divergence of approx. First a PCA (Principal Component 6wt.% appears at very high and at Analysis) is carried out. This allows very low water concentrations. a first overview of possible Though the standard laboratory relationships between the different method of Karl-Fischer titration is pyrolysis oils. From the ample more precise and well validated, original spectral data, PCA delivers the water measurement by means a compressed data matrix, which of microwave spectroscopy as an can be used for the classification of inline method can show changes in pyrolysis oils and also for the water concentration very development of a correlation model quickly during production and between the microwave spectra handling of pyrolysis oil.

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 32 Pyro2014

Marianne Bell and Scott Banks, both of the European Bioenergy Research Institute at Aston University, UK, Delegates listening to one of the 70 presentations at Pyro2014. review The 20th International Symposium conference relevant to the future of on Analytical and Applied pyrolysis, with one of the most Pyrolysis, organised and chaired important being the increasing by Tony Bridgwater of the relevance in this area of catalysts. European Bioenergy Research The inclusion of catalysts is Institute (EBRI) at Aston University, becoming a major part of pyrolysis took place from the 19th – 23rd research due to their ability to May 2014, in the centre of enhance various compounds Birmingham, UK. produced during the process. A large proportion of Pyro2014’s oral The week-long conference was presentations featured research universally considered a great that made use of catalysts, and success, with 230 delegates from eight were specifically focused on 32 countries around the world. the topic of catalyst use itself in two Across the week, they heard from dedicated sessions. 70 presenters delivering the latest findings in topics including Another key point that emerged analytical pyrolysis; applied from the conference was that pyrolysis; pyrolysis kinetics and waste has become a more mechanisms; and catalysis in mainstream feedstock for pyrolysis pyrolysis, together with research conversion to either a fuel or a results from a huge number of chemical source. This was in posters. particular highlighted by presentations by Frank Riedwald, Themes and presentations “Waste printed circuit board Several themes emerged from the (Continued on page 34)

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 33 Pyro2014 ...continued

Pyro2014 delegates at the Gala Dinner on 23rd May 2014. pyrolysis with simultaneous sink- poster competition, with Pyro2016 float separation of glass and presentations for the winners The 21st International Symposium metals by contact with a molten taking place at the gala dinner on on Analytical and Applied Pyrolysis salt – a laboratory investigation”, the fourth night of the conference. will take place in 2016 at CRNS and Sam Haig, “Fuels from waste The winning poster was by Nancy in France. We wish all of the plastics: an independent review Wolfram Buss, from the University Pyro 2016 team all the best for the and economic assessment of of Edinburgh, entitled “Biochars organisation and delivery of current technologies”, among affected by re-condensation of another successful Analytical and others. pyrolysis vapours – investigation of Applied Pyrolysis conference. phytotoxic effects and Finally, perhaps the most unusual characterisation of re-condensed Contact feature of the conference was the products”. Frontier Laboratories Marianne Bell focus on pyrolysis uses outside of also awarded prizes for T: +44 121 204 3115 the typical thermal chemical knowledgeable and enthusiastic E: [email protected] conversion technique. presentations, with first prize Presentations focused on bacterial awarded to Guillermo Rosas Scott Banks identification (Kent Voorhees, Mayoral, from the University of T: +44 121 204 3419 “Catalytic pyrolysis for bacterial León, for his poster “Auto-thermal E: [email protected] identification”, carbon nanotube and mobile pyrolysis reactor for production (Aidan Smith, “A novel vineyard residues with low pre- Aston University process for hydrogen and carbon treatment”. European Bioenergy Research nanotubes production from the Institute pyrolysis-gasification of waste Sponsors School of Engineering and Applied plastics”), and many other Pyro2014 received great support Science innovative topics, particularly through sponsorship from: ERDF; Birmingham B4 7ET, UK among the large number of poster BioenNW; CDS Analytical; presentations. Shimadzu; Gerstel; Aston www.aston.ac.uk/eas/research/ University; Frontier Lab; Gas Data; groups/ebri/ Posters and prizes PyroLab; SciMed; SUPERGEN Pyro2014 benefitted from three Bioenergy Hub; and Elsevier, poster sessions spread across the without which the conference could week, and also featured its own not have taken place. For more detailed information on the conference proceedings, please visit www.pyro2014.co.uk IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 34 International Events

News Flash: Pyrolysis Workshop Further details will be

BRISK will be holding a fast pyrolysis workshop which is open to all to attend, announced shortly on the organised by Wolter Prins and Tony Bridgwater. BRISK website. Subject: Review of challenges and opportunities in biomass fast pyrolysis Alternatively, email processes [email protected] for Location: Ghent, Belgium Date: December 8th-9th 2014 further information. AUGUST 2014 SEPTEMBER 2014 continued 24th-28th 24th-25th Lignin 2014 Biofuels International Conference Umeå, Sweden Marriott Hotel, Ghent, Belgium

26th-28th 30th-2nd 2014 China Guangzhou International Biomass 7th European Forum for Industrial Biotechnology Exhibition and the Biobased Economy Guangzhou, China Champagne-Ardenne, France

SEPTEMBER 2014 OCTOBER 2014 2nd-5th 5th-11th TCS 2014: Symposium on Thermal and Catalytic XXIV IUFRO World Congress 2014 Sciences for Biofuels and Biobased Products Salt Lake City, Utah, USA Denver, Colorado, USA 13th-15th 2nd-4th 33rd International Conference on Thermal 4th International Symposium on Gasification and Treatment Technologies & Hazardous Waste its Applications Combustors Vienna, Austria Baltimore, Maryland, USA

8th-11th 15th-16th ISWA 2014 Solid Waste World Congress 8th SGC International Seminar on Gasification Sao Paulo, Brazil Malmö, Sweden

10th-12th 20th-22nd 12th International Chemical and Biological Argus Biofuels and Feedstocks 2014 Engineering Conference London, UK Porto, Portugal 26th-29th 15th-18th Lignobiotech III Bioenergy from Forest Concepción, Chile Marina Congress Centre, Helsinki, Finland NOVEMBER 2014 16th-19th 18th World Congress of CIGR 17th-20th Beijing, China Renewable Energy from Waste Conference 2014 San Jose, California, USA 21st-22nd GMEE2014 17th-20th Hong Kong, China 5th International Symposium on Energy from Biomass and Waste 21st-23rd Island of San Servolo, Venice, Italy 4th Annual World Congress of Bioenergy Qingdao, China 19th-21st RENEXPO® South East Europe Bucharest, Romania For further international events, visit www.pyne.co.uk. IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 35 Pyrolysis Related Events

Lignin 2014: biosynthesis and utilization Umeå Plant Science Centre warmly The sessions of the conference are: welcomes everyone to the 1) Cell and developmental biology international conference “Lignin of lignin 2014” in Umeå, Sweden, August 24 2) Lignin monomer biosynthesis and Contact -28 2014. transcriptional regulation For questions regarding the scientific 3) Lignification: Oxidative programme of the conference, please The Lignin 2014 conference aims to polymerisation of phenolic contact: strengthen our knowledge on the monomers [email protected] various aspects of lignin 4) Diversity of natural lignins [email protected] biosynthesis and utilisation, from 5) Modification of lignins in plants [email protected] the basic cell biology, molecular 6) Lignin characterisation For questions regarding hotel biology to pre-treatment of plant technologies bookings or travel, please contact: biomass and utilisation of lignin. 7) Lignocellulose processing and Elisabet Norlin The conference is organised with extraction of lignin [email protected] the support of the Formas-financed 8) Novel applications for lignin and 090-13 00 35 strong research environment lignin derivatives BioImprove and the strategic research environment Bio4Energy, supported by the Swedish www.Lignin2014.se government.

Symposium on Thermal and Catalyc Sciences for Biofuels and Biobased Products

September 2‐5, 2014 Denver, Colorado, USA

Tcs2014 brings together leading scientists and engineers to share the latest advances in thermal and catalytic science for biofuels and biobased products Topics

 Advances in pyrolysis and solvent liquefaction  Advances in gasification  Catalytic upgrading of bio-oil and syngas to fuels and chemicals

www.tcs2014.org

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 36 Pyrolysis Related Events

Welcome The ISWA World Congress is one of the world’s most important congresses in the field of waste management. The ISWA Congress offers you the opportunity to update your knowledge on the latest trends, developments and perspectives for the waste sector. This event provides you with the perfect setting for knowledge exchange, as well as meeting old friends and establishing new ones.

Telephone: + 55 (11) 3056 6000 Email: [email protected]

The production of energy from alternative sources and its impact on climate change are among the main strategic tools implicated in the sustainable development of our society. Numerous types of biomass and wastes contribute towards the production of energy and reduction in the use of fossil fuels by means of biological, chemical and thermal processes. Existing biomass and waste to energy technologies are currently undergoing rapid development. Despite growing interest in the use of these technologies, in many countries their implementation remains limited.

The aim of the Venice 2014 Symposium is to focus on the advances made in the application of technologies for energy recovery from biomass and waste and to encourage discussion in these fields. The previous edition of the Symposium, held in 2012, was attended by nearly 580 scientists and operators from approximately 62 different countries.

The fifth edition of the Symposium will be held in the stunning island of San Servolo in the Venetian Lagoon and will feature:  Three days of scientific presentations  One day of guided technical tours at biochemical and thermochemical plants  Six parallel oral sessions (one of which in Italian), poster sessions and an exhibition by companies working in the field  Expected attendance of over 600 delegates from tens of different countries worldwide

The Symposium is organised by the International Waste Working Group (IWWG) with the scientific support of the Universities of Queensland, Padova, Hokkaido, www.venicesymposium.it Rostock, Trento and Hamburg University of Technology.

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 37 Publications

Fuel - Volume 116 Published by Elsevier Publication date: January 2014

Within this journal is the following paper: Effects of CO2 on biomass fast pyrolysis: Reaction rate, gas yields and char reactive properties Authors: C Guizani, FJ Escudero Sanz, S Salvador

Journal of Analytical and Applied Pyrolysis - Volume 107 Published by Elsevier Publication date: May 2014

BRISK Newsletter - Issue 4 Published by Aston University Publication date: May 2014

The Selection Process of Biomass Materials for the Production of Bio-Fuels and Co-Firing (IEEE Press Series on Power Engineering) Published by Wiley-IEEE Press Publication date: June 2014 Author: Najib Altawell ISBN: 978-1-118-54266-8

EERA Bioenergy NEWS - Issue 3 Published by Aston University Publication date: June 2014

Transformation of Biomass: Theory to Practice Published by Wiley Publication date: September 2014 Edited by Andreas Hornung ISBN: 978-1-119-97327-0

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 38 PyNe Issue 34 Further Information

If you require further information about the PyNe newsletter, or you would like to contribute to future editions, please contact the Editor:

Kerri Lyon European Bioenergy Research Institute (EBRI) Aston University Aston Triangle Birmingham, B4 7ET UK

T: +44 121 204 3416 E: [email protected]

Past editions of PyNe newsletters are www.pyne.co.uk available on the website.

PyNe Issue 33

IEA Bioenergy Task 34 ‐ Pyrolysis

Disclaimer: The PyNe newsletter is edited and produced by the European Bioenergy Research Institute, Aston University, UK on behalf of IEA Bioenergy Task 34 Pyrolysis. Any opinions or material contained within are those of the contributors and do not necessarily reflect any views or policies of the International Energy Agency, Aston University or any other organisation.

IEA Bioenergy Agreement Task 34 Newsletter — PyNe 35 Page 39