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Bioliquids-Chp.Eu in the Bioliquids-CHP Project, Several Different Bioliquids and These Are Summarized in Table 1 (Overleaf)

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Bioliquids-Chp.Eu in the Bioliquids-CHP Project, Several Different Bioliquids and These Are Summarized in Table 1 (Overleaf) Main Project Results 2011 Partner – BTG Summary Bioliquids selection, production This brochure presents an overview of the main and characterisation project achievements and highlights some conclusions and perspectives towards future development. The full title of this collaborative project was : Engine and turbine SELECTION AND PRODUCTION PROPERTIES OF BIOLIQUIDS combustion for combined heat and power production. OF BIOLIQUIDS More information, publications and reports are available For all bioliquids a range of properties were determined at the project website: www.bioliquids-chp.eu In the Bioliquids-CHP project, several different bioliquids and these are summarized in Table 1 (overleaf). Fast were evaluated for use in prime movers. The ‘primary’ pyrolysis oil differs significantly from (rapeseed-derived) bioliquids were biodiesel, pure vegetable oil and fast biodiesel and sunflower oil with respect to acidity (pH), PROJECT OBJECTIVES AND APPROACH pyrolysis oil. The biodiesel (FAME) was produced from tendency to carbon formation (MCRT), water content and rapeseed and purchased in Germany. The vegetable oil density. For use in prime movers relevant properties are for The Bioliquids-CHP project was set up to reduce the used was sunflower oil that was purchased in Italy. The example the heating value, Cetane number and viscosity. technical barriers preventing the use of advanced fast pyrolysis oil was produced in BTG’s pilot plant from The viscosity of liquids can be lowered by preheating bioliquids in prime movers to generate combined heat pinewood. Two batches of fast pyrolysis oil were produced the fuel as illustrated in Figure 2. and power (CHP) in the range of 50-1000 kWe. The and used for the experiments. ‘Secondary’ bioliquids Another important property of any bioliquid - but in objective was to adapt or develop engines and turbines used were bio-ethanol and bio-butanol, which were used particular for fast pyrolysis oil - is its ageing behaviour. to enable operation on a variety of bioliquids, including in several cases to improve fast pyrolysis oil properties. A suitable method to study this aspect is the change in fast pyrolysis liquids, and to find a technical and Additionally, bio-ethanol was added as a rinsing fuel in the kinematic viscosity over time. This change in viscosity economic optimum between fuel upgrading and BTG’s diesel engine when switching fuels from diesel to was monitored for the different bioliquids over several engine and turbine modification. fast pyrolysis oil and vice versa. months. The bioliquids were stored at 40°C and the viscosity was measured on a regular basis. The observed change in viscosity for biodiesel and sunflower oil was PROJECT ACTIVITIES negligible. The ageing behaviour of fast pyrolysis oil is a strong function of the storage temperature. Ageing can There were four main activities: be kept within acceptable limits as long as the temperature • Bio-liquids production, analysis, characterisation, upgrading is kept below 40-50°C as illustrated in Figure 3. and blending: improving the combustion properties of bioliquids by chemical and/or physical upgrading and blending or emulsification in order to enable their use in prime movers • Prime mover development and modification: modification and development of different engines and a micro gas turbine so that these can run efficiently on bioliquids including biodiesel, OBJECTIVES vegetable oil, and fast pyrolysis oil; and their blends The main objective was to evaluate different • Exhaust emissions reduction: the project developed methods bioliquids and to produce fast pyrolysis oil from and techniques to control exhaust emissions particularly different sources in sufficient quantities as including NOx, CO, and particulates, to improve the required in the project. All bioliquids used in the environmental sustainability of the CHP combinations project needed to be properly characterized. • Assessments: the project evaluated the complete chain in terms of sustainability, economics, technology, environment, Figure 2: Kinematic viscosity as a function and market opportunities for application in EU Member of temperature for the different bioliquids OUTCOMES States and Russia. For the testing of prime movers biodiesel, sunflower oil and fast pyrolysis oil were selected as fuel. Fast pyrolysis oil was produced in BTG’s Figure 1: Structure of project pilot plant from pine and straw. Additionally, IMPACT bioethanol and butanol have been characterized as these alcohols can be relevant for the • New opportunities to provide reliable and cost effective preparations of different fuel blends with fast electricity and heat from biomass at a small scale pyrolysis oil. • Development of existing technologies, including bioliquids, prime movers and cogeneration units so that they can be used together in an integrated system • Contributions to improving the environment, quality of life, health and safety and the security of energy supplies. Figure 3: Change in viscosity of fast pyrolysis oil as a function of the storage temperature 2 3 Partners – BTG, CREAR, Aston, BIC Bioliquids upgrading and blending Table 1: Properties of the primary liquids Fast pyrolysis oil is considered the REDUCING SOLIDS MILD HYDROTREATMENT most difficult fuel of the bioliquids Property unit Biodiesel Sunflower Fast Pyrolysis Oil Bio- Bio- tested. The quality of fast pyrolysis CONTENT IN FAST OF FAST PYROLYSIS OIL Oil ethanolA butanol oil was improved using various PYROLYSIS OIL Mild hydrotreatment implies catalytic Pine I Pine II Straw approaches: Untreated fast pyrolysis oil can have treatment of fast pyrolysis oil in the C wt% 77.3 77.5 42.8 45.5 48.6 50.9 64.9 a high solids content. When applied presence of hydrogen at elevated pressure but without complete H wt% 12.1 11.9 7.6 5.8 7.9 12.7 13.5 REMOVING WATER FROM in prime movers this can lead to plugging and wear of fuel pumps and oxygen removal. The resulting product N wt% <0.01 <0.01 <0.01 <0.01 0.4 <0.01 <0.01 FAST PYROLYSIS OIL injectors. Devices tested for their has reduced acidity, increased O (Balance) wt% 10.6 10.6 49.6 48.8 43.0 36.4 21.6 Fast pyrolysis oil from biomass suitability for solids removal include energy content and improved ignition and thermal stability properties. Water content wt% - - 21.7 25.4 21.2 - - typically contains about 25 wt% a self-cleaning scraper filter, a batch of water. This high water content centrifuge, a self-cleaning centrifuge, The hydrotreatment was performed Ash content wt% - - 0.047 0.016 0.053 - - reduces the calorific value and and a centrifugal filter separator. The in BTG’s hydrogenation unit using a patented catalyst developed Solids content wt% - - 0.27 0.04 1.28 - - has a negative impact on ignition best results of high solids removal, properties. Therefore, partial removal easy operation and limited oil loss jointly with the Boreskov Institute of Density kg/m3 871 910 1,207 1,170 1,184 780 810 of water may be advantageous. were obtained with the self-cleaning Catalysis (BIC) and Rijksuniversiteit LHV MJ/kg 27.1 37.4 17.1 16.1 20.1 27.1 34.4 However, removing water leads centrifuge. Groningen (RUG). The operating pressure is typically around 200 HHV MJ/kg 40.2 40.0 18.7 18.8 21.9 30 37.4 to an increase in oil viscosity and oil ageing becomes more severe. bar, with reactor temperatures up to LHV MJ/L 32.7 34.0 20.6 18.8 23.8 21.4 27.9 Adding ethanol to the dewatered 350°C. The hydrogen consumption is about 10-20 gram/kg oil. The fuel pH - - - 2.85 2.85 3.3 - - fast pyrolysis oil can offset these detrimental impacts. produced is referred to as “Mild- MCRT wt% - 0,06 - 15.1 - - - HDO” (see Table 2). Kinematic cSt 6.9 80.7 65.1 - 80.4 1.5 3.6 viscosity at 20°C at 40 °C cSt 4.2 40.6 20.0 13.0 21.2 1.1 2.8 Table 2: Properties of modified oils ESTERIFICATION OF Cetane Number - ~60 ~40 ~10 -25 - - ~8-15 17 Property unit Emulsion PO-Ester Mild HDO Blend (30/30/40) FAST PYROLYSIS OIL Contaminants ppm C wt% 44.4 58.4 67.6 65.8 Cl <10 <10 <10 n.d. 240 n.d n.d. Fast pyrolysis oil was treated with H wt% 6.4 7.4 8.1 10.8 an alcohol in a reactive distillation Fe 1.3 2.2 11 11 N wt% <0.1 <0.1 <0.1 <0.1 process in the presence of a catalyst. Mg 3.7 4.4 6 37 O (balance) wt% 49.2 34.2 24.2 23.3 The resulting product has a lower Mn <1 <1 1.2 12 Water content wt% 22.8 6.6 6.7 6.8 acidity and water content, and higher energy content. The operating Ca 1.3 5.2 15 135 Ash content wt% 0.298 0.018 0.017 pressure is typically 300 mbar. The Sr <1 <1 <1 1.3 Solids content wt% - - - best results were obtained at a Density kg/m3 1198 1158 1106 9331 reactor temperature of 85°C, with Sn <1 >1 <1 2.6 LHV, calculated MJ/kg 16.3 24.0 27.0 28.4 butanol as the reactant and using a Si 2.0 42.9 6.6 83 solid acid catalyst (Nafion SEC13). LHV MJ/ltr 19.5 28.0 29.9 P <1 2.3 <1 15 During the process the butanol reacts pH - 2.1 3.0 3.1 3.8 with the acids in the fast pyrolysis oil Al 5.3 6.6 35 48 MCRT wt% 18 20 11 to form esters. Water is removed by K 14.4 13.4 21 254 Kinematic viscosity cSt 36 115 149 evaporation.
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