Final Report Summary - BRISK (The European Research Infrastructure for Thermochemical Biomass Conversion)
Enhancing biomass utilization without risking its sustainability is a European energy priority, and can be linked to targets for curbing greenhouse gas emissions by 20% by 2020 and 50% by 2050: enhanced energy security and integration with other industrial sectors, such as agriculture, also play a role. Improved use of biofuels and products in advanced biomass conversion units and bio-refineries are seen as a key element in achieving this goal. In recent years leading industrial nations have established facilities in which their researchers have addressed the challenges associated with the production of biofuels and the establishment of bio-refineries. There remains fragmentation in terms of access to high-level experimental equipment necessary for achieving significant advances in this field.
The overall objective of BRISK is to integrate leading European research infrastructures for advancing fundamental and applied research in thermochemical biomass conversion. Feedstocks like woody biomass, crop residues, sewage sludge, municipal solid waste and other traditional and novel biogenic sources will be employed for a wide spectrum of powerful and, in many cases, unique laboratory-based and pilot-scale equipment. By uniting the infrastructures available at different laboratories, it becomes possible to cover the entire value chain, allowing research to be performed at stages: from the first preparation of the biomass feedstock, to conversion, then treatment and finally through to utilisation.
Project Context and Objectives:
Conceptually this project addresses the following realities in the trans-European macroenvironment, as outlined by the EC Strategic Energy Technology (SET) Plan (COM(2007) 723 and COM(2009) 519):
i) Weakness in Energy Innovation Today
• Since the oil price shocks in the 70s and 80s, Europe has enjoyed inexpensive and plentiful energy supplies. The easy availability of resources, no carbon constraints and the commercial imperatives of market forces have not only left us dependent on fossil fuels, but have also tempered the interest for innovation and investment in new energy technologies.
• Public and private energy research budgets in the EU have declined substantially since 1980s. This has led to an accumulated under-investment in energy research capacities and infrastructures.
• If EU governments were investing today at the same rate as in 1980, the total EU public expenditure for the development of energy technologies would be four times the current level of investment.
• As a consequence of this scenario, several semi-industrial/pilot biofuel research infrastructures were dismantled in the nineties. Many industries have preferred to develop their components testing them in a few outside research centres, with high costs and long wait times. The strategic importance of large scale biofuel production has been increasing in the last years and those now operating are expected to be employed for the next 20 years.
• The costs of running industrial tests are high, and therefore a well-organised network of complementary facilities, from laboratory, pilot to semi-industrial scale, is needed to improve the quality and quantity of services provided by the infrastructures and lower the associated costs. The number of potential users is expected to increase dramatically.
ii) Combustion and Gasification of Fuels (including biofuels) will continue to play a key role in power generation for the next decades
• According to the Technology Map accompanying the SET Plan (COM(2007) 723), ‘All energy forecasts show that fossil fuels will remain the main fuel for electricity generation in the medium and long term, retaining a share in power generation of the order of at least 40-50% in 2030’. The situation since 2007 is largely unchanged, as mentioned in the 2nd Strategic European Energy Review (COM(2008) 781) and latest SET Plan (COM(2009) 519).
• As a winning power generation technology has not yet been defined, a mix of technological options is needed to reduce risk and “avoid locking-in to technologies that may not provide the best solution in the long run” (Green Paper, SEC(2006) 317).
In fact, the challenging 20-20-20 objectives adopted by the European Commission – saving at least 20 % of total primary energy by 2020; 20 % contribution of renewable energy to the EU energy consumption by 2020; and 20 % reduction of GHG emissions by 2020, as referred to 1990 levels – and the goals established by the European Industrial Initiative on Bioenergy (SET Plan Technology Roadmap COM(2009) 519)
• 14% bioenergy in the EU energy mix by 2020
• simultaneous greenhouse gas emission savings for biofuels and bioliquids under the sustainability criteria of the new RES directive
require not only an unprecedented push in developing innovative renewable energy technologies, but also proactive steps to optimise more developed, conventional biofuel production technologies to allow the conversion of the largest variety of fuels (from the most difficult such as some wastes and biomass to the cleanest but most difficult to produce such as hydrogen) in the most efficient way possible and in widest possible range of applications (e.g. electricity generation, pulp and paper, energy-intensive industries, transportation, etc.).
Given this background, the overall objective of BRISK is to integrate leading European research infrastructures for advancing fundamental and applied research in thermochemical biomass conversion. Feedstocks like woody biomass, crop residues, sewage sludge, municipal solid waste and other traditional and novel biogenic sources will be employed for a wide spectrum of powerful and, in many cases, unique laboratory-based and pilot-scale equipment. By uniting the infrastructures available at different laboratories, it becomes possible to cover the entire value chain, allowing research to be performed at stages: from the first preparation of the biomass feedstock, to conversion, then treatment and finally through to utilisation. The individual and aggregated combinations of these facilities are then opened to the European Research Community via Transnational Access, one of the three main pillars of this project.
Objectives related to Networking Activities (NA, second pillar) are embedded in the following Work Packages:
• WP2 will establish and execute a common framework for Coordination of Transnational Access (TA) with an emphasis on objectivity, transparency, quality and flexibility. Within this work package, a User Selection Panel will be established, and formal campaigns to attract potential users will be undertaken. This activity will also include a TA review process, and will administer the influx of users in partnership with the Infrastructure owners.
• The publicity of TA will be facilitated by the creation of a publicly accessible on-line database of Infrastructure owners and rigs within WP3. This database will allow an easy and permanently accessible search for a facility that may match specific user needs, as well as providing an up-to date picture of the current and upcoming access opportunities. It is envisaged that this rig database will survive the completion of the BRISK project, further maintained by the IFRF. While this will act as a minimum legacy of the BRISK Research Infrastructure, a Business Plan for a more comprehensive ongoing successor activity/infrastructure to BRISK will also be developed within WP3.
• General dissemination activity (WP4) will be divided into four main tasks, and will be based around the existing IFRF network and website (www.ifrf.net).
- A public website will be created for dissemination and awareness purposes. As a “communicative aggregator”, the website will form the backbone of the communications strategy, supporting other media.
- To stimulate awareness of project activities and opportunities, the production and distribution of printed and electronic material is envisaged. Examples include flyers, a project logo, posters, CDs, etc. which can be handed out at conferences).
- Press articles will be produced to reach extended audiences via newspapers and sector journals.
- An electronic newsletter will be published quarterly on the website.
- Best practice will be shared through meetings organised following the IFRF’s tried and tested “TOTeM” approach (Topic Oriented Technical Meetings). As with the IFRF’s own meetings, all presentations, discussions and conclusions will be summarised and published on the project website providing not only a valuable knowledge resource, but also a form of "virtual" participation for those who were not able to participate, due to distance or time constraints.
• WP5 – Protocols, Databases and Benchmarking will promote and support the establishment of protocols for the collection and storage of data in order to facilitate data exchange and use between the project beneficiaries in the first instance, and later between the BRISK beneficiaries and other organisations in the international scientific community. Benchmarking of experimental rigs will be undertaken based on round robin approaches. Information will be exchanged at Technical Workshops of coherent groups of rig owners with a view to enhancing test rig operation.
Objectives related to Joint Research Activities (JRA, third pillar) are embedded in the following Work Packages:
• WP6 focuses on the development of methodologies for characterization of new feedstocks, 2nd generation biofuels, and residues. Both laboratory- and pilot-scale experimental campaigns will be employed for developing relevant methodologies and protocols, and results will be entered into a database for ready access for the benefit of current and future users of BRISK installations, and even for other equipment outside the consortium.
• WP7 deals with the development of advanced measurement methods and operational procedures in thermochemical biomass conversion. Quantification of tough-to-measure constituents, namely particulates, tars, and sulphur, are considered via new in-situ and other measurement techniques, greatly augmenting the usefulness of data collected in gasification, pyrolysis, and other conversion steps. Gasification technology and gas cleaning/upgrading practices will be refined in order to improve the flexibility of the installations.
• WP8 will improve methods for advanced testing, examination, and optimization of catalytic conversion processes of biosyngas conversion to 2nd generation liquid or gaseous biofuels. Fischer-Tropsch fuels, higher alcohols, SNG, and DME/MeOH are in focus for this activity, and as such the results will be highly useful for putting follow-on experimental findings in even more proper context for end-use applications
A description of the main scientific and technological results has been organized according to work packages, and excludes those activities that are outside this scope.
WP2 Coordination of Transnational Access
S & T highlights from the 150 user projects offered in BRISK are listed below:
• A wide variety of feedstock (plant- and animal-origin) was used: virgin biomass (pine wood chips, cherry, sycamore, cork, and beech); energy crops (willow, Virginia mallow, miscanthus); agro-forestry biomass residual (such as straw, grape vine, sunflower husks, olive husks, olive stone, hazelnut shells, cocoa pod husk), industrial residue (Kraft lignin) along with sewage sludge, poultry litter and horse bedding material.
• Pretreated biomass (e.g. torrefied olive stone, pine, straw or acid pre-treated walnutshell) was also tested.
• Thermochemical techniques (catalytic and non-catalytic) such as pyrolysis, gasification and combustion were applied to convert biomass into different energy products.
• Co-processing: e.g. co-combustion of biomass and coal; co-pyrolysis of biomass and waste polymers or glycerol; co-gasification and co-combustion of poultry litter char with scrap tire char and lignite were investigated.
• Optimization of combustion/gasification/pyrolysis parameters in order to minimize particulate emissions, dust/tar formation and avoid sintering of ashes.
• Determination of pyrolysis, gasification and oxidation kinetics of biomass using TGA/DSC-FTIR and modelling using the Aspen Plus simulator were performed.
• Effect of iron-, nickel-, alkali- and zeolite-based catalysts was determined.
WP5 Protocols, databases and benchmarking
Task 5.1 Protocols (DTU) and Task 5.2 Databases (DTU)
A common database for reporting of JR activities fuel data was earlier defined as part of WP6. A slightly modified extension of this database format was adopted and implemented for fuel data from TA activities.
A significant number of TA reports, > 70, have been carefully studied, in order to extract relevant fuel data from these and add them to the BRISK fuel database. Several set of fuel data have been added to the fuel database.
Part of the BRISK WP5 activities deal with developing protocols for documentation of set-ups and experiments. Thus, the same TN partner reports were scanned for documentation of the equipment and the experimental work conducted.
Task 5.3 Benchmarking of Experimental Rigs (TUD)
Work conducted within this task is linked to WP7 and involves the comparison of different gasifiers for the conversion of various biomass feedstocks into product gas and syngas. TUD and IFRF contributed to the set-up of an inventory list of gasifiers within BRISK with the aim of organizing a benchmarking of the different reactor concepts. TUD promoted the interaction between BRISK partners in comparing measurement methodologies, in particular for particles, tar, and sulphur species.
WP6 Development of new methodologies for the characterisation of new feedstocks, 2nd generation biomass
Within WP 6 new methodologies for the characterisation of new feedstock and 2nd generation biomass fuels were developed to support activities within Transnational Access. The work package was divided into three tasks: Task 6.1 which focused on the characterisation of feedstock and fuels, based on small batch reactors. Task 6.2 which was conducted on larger scale continuously operated reactors. Finally, investigations regarding the characterisation of liquid 2nd generation biofuels were carried out within Task 6.3.
The numerous gained results have been combined in a common database.
Task 6.1 Methods for characterisation of feedstocks, 2nd generation fuels and residues based on small batch reactors (BE2020, AAU, TUD, WROC, KTH, ENEA)
Within this task new methods for the characterisation of feedstock, 2nd generation fuels and residues based on small batch reactors were developed. The methods and test rigs have been adapted during the previous reporting periods and have been applied and further developed during the second and third period.
Åbo Akademi University (AAU) has characterised the BRISK fuels in their Single Particle Reactor. The characterisation has focused on char gasification. In the project the reactor has been supplied with a steam generator so that also conversion in mixed atmospheres of CO2, H2O and O2 could be studied. Especially with H2O a slow conversion due to a low reactivity led to gas concentrations below the detection limit. Due to the large particle size used in the reactor, modelling assisted extraction of kinetic parameters is necessary at conditions typical of industrial processes. This is due to mass transfer limitations at these conditions.
At Bioenergy2020+ (BE2020) and Graz University of Technology (TUG) new methods for testing 2nd generation fuels on lab-scale fixed bed reactors as well as on single particle reactors have been successfully developed and applied. The lab-scale fixed bed reactor was applied for the characterisation biomass fuels with respect to combustion related issues. The results can be used to support grate designs (necessary length of a grate, residence time on a grate) of combustion plants. Furthermore, the results allow an estimation of emission ranges which have to be expected and therefore show if a necessity for secondary measures to reduce emissions (NOx, particulate matter) are needed. This reactor has been adapted for operation under inert/pyrolysis conditions. Test runs, to prove the applicability for the evaluation of torrefaction, were performed with softwood wood chips (comparable chemical composition like softwood pellets), DDGS and sunflower press cake. The achieved results were compared with results from a large-scale torrefaction plant and have shown that the reactor is well suited for torrefaction investigations. The single particle reactor at BE2020 was applied for the determination of the combustion behaviour of biomass fuels under rapid heating conditions. Furthermore, investigations under pyrolysis conditions have been conducted. The focus was put on investigations regarding the release behaviour of biomass fuels. ENEA has investigated the gasification of hydrolytic lignin in internal circulating gasifier and with the updraft reactors, with air, O2, and steam added mix has been completed. Additionally, TGA analyses have been performed, to set an evaluation basis for the gasification tests. The feedstock was analysed together with the biochemical composition (cellulose, hemicellulose and lignin). Residual cellulosic fibres in the residue made gasification in fixed bed possible without clogging the gasifier. A sequence of exothermic and endothermic reactions was highlighted along the bed because of the autothermal processing and lignin rich feedstock. The use of oxygen as gasification medium, as well the supplement of superheated steam, increase the H2/CO ratio. Lower flow rates in the reactor obtained with the use of oxygen reduce the tar production. The addition of steam, instead, increases the flow rate and the production of tars.
At KTH a batch type fixed bed reactor with a TG capability (measurement of mass during thermochemical treatment of sample) has been used. The reactor can operate in a single particle mode as well as in a macro TGA mode. Tests runs with softwood pellets, DDGS, torrefied chips and pyrolysis char were performed in macro TG mode. Even though that limited tests were carried out in single pellet mode, measurements showed that the conversion process is controlled by heat transfer within the particle and thus intrinsic kinetics cannot be determined using the Macro-TG mode. However, differences in devolatilisation time and the final char yield of different fuels were observed using the Macro TG mode. Those differences can lead to useful conclusions for the effects of heat and mass transfer on the devolatilisation rates and the overlapping between devolatilisation and gasification stages. Within task 6.1 TUBITAK conducted TGA measurements for all BRISK fuels at four different heating rates under nitrogen atmosphere. Pyrolysis kinetics of the BRISK fuels has been driven according to isoconversional method. For comparison, Coats-Redfern method was used alternatively to derive the pyrolysis kinetics of the samples. For two fuels, (straw and wood pellets), TGA-Mass Spectrometry was used to monitor the pyrolysis gases.
In brief, calculated activation energies and characterisation studies indicated that wood pellets might be more reactive to thermochemical conversions and less prone to agglomeration. Although sunflower oil cake gave comparable activation energies to wood pellet, its high ash content and agglomeration index are the potential drawbacks in front of its utilisation via thermochemical conversions.
The Technical University of Delft (TUD) used a heated grid (HG) reactor and a TGA to characterise the BRISK fuels. The former was used for rapid pyrolysis experiments, whereas the latter was used for slow pyrolysis and combustion tests. Tests have been performed with softwood pellets, straw pellets, DDGS, torrefied wood (spruce) and pyrolytic char in the TGA apparatus. The TGA tests have been focused on calculating the proximate analysis of the fuels and calculating kinetic parameters regarding decomposition with the reaction rate constant method. Finally, the collaboration and comparison of WROC and TUD results from slow devolatilisation of BRISK softwood pellets show, that the calculated activation energies are in agreement but the pre-exponential factors differ, maybe due to differences in the TGA apparatuses. Softwood pellets, straw pellets, DDGS, raw spruce, torrefied spruce, wood chips and torrefied biomass have been tested in the HG reactor under rapid pyrolysis conditions. The reactor is connected with the FTIR, which makes the quantification of gases possible. Characterisation of the fast pyrolysis behaviour with respect to the permanent carbon gases is possible with the HG-FTIR setup. Regarding the spruce fast pyrolysis tests, the mass yields of quantified gases, CO, CH4 and CO2, are influenced significantly by final temperature and increased with increasing temperature. Furthermore, the impact of torrefaction in holocellulose and lignin fractions of fuel sample is observed in the quantified gases. On the other hand, BRISK straw releases significantly higher CO2, but lower CO and CH4 than softwood at the final temperature of 900°C. Topell woodchips are releasing more permanent carbon gases than Topell torrefied pellets as expected, especially CH4. This was expected as Topell woodchips have been mildly pyrolysed and their hemicellulose, mainly, had reacted. Finally, from all samples DDGS is the only one that NH3 is detected above the instrument’s limit, even though the final temperature is lower than for the rest samples.
WROC investigated physicochemical properties of all 6 BRISK fuels. In order to investigate the decomposition behaviour of the fuels, test runs using TGA/DSC/FTIR were conducted. For straw pellets, softwood pellets, DDGS and torrefied wood, the experiments were performed for raw samples and for cellulose, holocellulose and lignin derived thereafter. Based on lab-scale reactor experiments the characterisation of the devolatilisation and char combustion process is possible. Although devolatilisation occurs on a time scale much shorter than the char oxidation, it is accounting for up to 95% of the initial weight loss from 2nd generation biomass and it has a critical impact of biomass conversion processes such as combustion, gasification and torrefaction. Obtained results may be essential for prediction of: the flame stability (the reactivity), the burnout (the reactivity), the heating value of pyrolysis products (composition of evolved gases), the distribution of tar/ char (amount and composition of volatiles and char) and pollutant emissions (CO2, NOx). The detailed fuel characterisation, including kinetic parameters determination, can be used as input parameter for CFD simulations. Obtained data may be beneficial to boiler/ gasifier geometry design and the overall process efficiency optimisation.
Task 6.2 New methods for characterisation of feedstocks, 2nd generation fuels and residues based on larger continuously fed reactors (DTU, ECN, TUM, IFRF, BE2020, ENEA)
Work conducted in this task involves larger scale continuously fed reactors operating under real-scale conditions. Both entrained flow and fixed-bed systems are being considered. The main aim of this task is the development of new and targeted characterisation methods concerning the thermal conversion behaviour of new feedstocks, 2nd generation fuels (torrefied and liquid fuels) and residues (char, hydrolytic lignin) and to derive/validate kinetics under real-scale conditions.
For this task the methods and test rigs have been adapted during the first period and have been applied as well as further developed during the second and third period. All data generated will be merged in a database.
At BE2020 and TUG a 50 kW grate furnace coupled with an electrically heated drop tube furnace has been applied for the investigations of two BRISK fuels. Test runs have been performed for softwood as well as straw. During these test runs the N-to-NOx conversion has been determined as well as the release of inorganic ash forming elements to the gas phase during combustion. Furthermore, the ash load in the flue gas after the boilers has been determined. Additionally, deposits probe measurements have been performed at high temperatures to determine the deposit build up rates (in g/(m²∙h)) on heat exchanger tubes – for instance superheater tube in a biomass combined heat and power plant. The major results show, that dust loads for straw are around 4 times higher than for softwood pellets. The analysis of the deposition sample shows a 2 times higher Cl amount for straw, whereas K is in the same magnitude of quantity. However, it must be highlighted, that especially dust loads and resulting depositions are strongly dependent on the reactor type and operation mode, which makes a comparison with other reactors hardly possible. This has also been shown in deliverable 6.6 when comparing the gained results with results of TUM. Additionally a newly developed method for the determination of high temperature corrosion rates has been tested using BRISK straw at the Drop-Tube Furnace. The method is based on the application of a mass loss probe and allows the determination of the corrosion rate trend over a certain period at selectable flue gas and material temperatures. The test run showed a paralinear corrosion rate trend for the superheater material. This method allows a rather quick comparison of the high temperature corrosion resistance of selectable material under combustion conditions close to real-scale plants.
At DTU an Entrained Flow Reactor has been used for the determination of the combustion and gasification behaviour of softwood and straw pellets. The two BRISK reference fuels have been tested at a fixed reactor temperature of 1400 °C, at different (gas) residence times. During the combustion tests, coarse and fine ash particles were collected in a cyclone and aerosol filter, respectively, and saved for later analyses. A number of chemical and physical analyses on these ash samples which include the characterisation of residual (cyclone ash) particles by thermogravimetry for determination of combustible matter / char burnout. These investigations show that the char burn-out level is time and fuel dependent, while less dependent on temperature. However, it should be noticed that the different fuels may not be directly comparable, as e.g. the particle size and shapes may vary significantly. Furthermore, selected coarse and fine ash samples have been analysed by wet chemical methods to determine the total content of Ca, Cl, K, Na, P, S, Si, and water soluble fractions of K, Cl and S. Additionally, SEM/EDX analyses of selected ash samples have been performed to determine the particle morphology (structure, size, shape) and elemental compositions.
At ECN the Lab-scale Combustion Simulator 2 (LCS2) Test Rig was employed for the characterisation of liquid fuel conversion: Ignition behaviour, conversion kinetics, nitrogen release and NOx formation, sooting, ash formation, deposition and emission investigation, pumpability and atomisation. Testing of an unknown bio-oil or suspension specimen has many similarities to solid fuels. Nonetheless there are specific issues to do with the liquid fuel, which call for specialised or at least more in-depth analyses.
At IFRF the devolatilisation and char combustion behaviour of five biofuels were tested using the Isothermal Plug Flow Reactor (IPFR). The fuels tested were torrefied pellets, Danish straw, lignin, palm kernel shell and softwood pellets. Sufficiently reliable conversion trends versus residence time and temperature were determined, which were later used for the calculation of kinetic parameters. Errors in determining the real ash content of the parent biofuel and of the IPFR products was found to be the controlling factor on the overall error, especially at low conversion levels. Consequently, it is highly advisable to sieve the milled biofuels into a specific and narrow granulometry range (e.g. 45-90 μm, 63-90 μm), and to repeat several times the proximate analysis, to reduce as much as possible the error on the initial ash content. Also the possibility of a loss of ashes occurring during the IPFR tests was taken into consideration, by applying a first-order ash loss kinetic model characterised by the same activation energy of devolatilisation. Finally, the results of the characterisation of the five biofuels were compared.
At TUBITAK all samples except DDGS were gasified at laboratory scale bubbling bed gasifier with O2/N2 mixture. Furthermore, the EPA 15 method was tested for the gasification of pyrolysis char. The method applies for sulfur compound analysis and uses the principle of gas chromatographic (GC) separation and flame photometric detection (FPD). Application of the method is relevant since it describes how to eliminate the interference effects of moisture condensation, CO and CO2, elemental sulfur, SO2 and alkali mist in gas emissions. During the tests with pyrolysis char the applicability of the method was proven regarding its applicability for biomass gasification.
At TUM the entrained flow reactor has been used to determine the combustion behaviour of softwood, straw and torrefied pellets. The results from the IR-flue gas analyser show deviations in the NOx, CO and SO2 emissions. The heights NOx emission shows straw with about 650 ppm were both softwood and torrefied material have about 190 ppm in the flue gas. A slight decrease in the SO2 emissions occurs by torrefied material with 9.6 ppm to 12.7 ppm (softwood) and 12.09 ppm (straw). Despite of the stable conditions the CO measurement is difficult. With this in mind the increase in the NOx emissions from about 14 ppm (softwood, Straw) to 1360 ppm (torrefied material) is significant but not very reliable. The online particle measurements were performed with the ELPI. Softwood pellets and torrefied spruce show a very similar particle size distribution which is typical for wood fired in this type of reactors. In the bimodal distribution curve the first peak occur at a particle size of 0.13 micro-m then drops and rises again at a particle size of 6 micro-m. A similar pattern also takes the curve of straw combustion: the peak is shifted slightly to a particle size of 0.3 micro-m drops well off and increases with increasing particle size. The highest dust load occurred at the torrefied spruce combustion (424 g/m³), while for straw the lowest dust load with 260 g/m³ has been determined. The EDX analysis of each ELPI stage shows similar trends. High concentrations of K and Cl have been determined, while Ca, Mg, and Na were detected in small amounts. The highest K to Cl ratio occurred for torrefied spruce. The all in all concentration of the K, Cl and S is decreasing from straw with the highest ratio over softwood pellets to torrefied spruce. At the torrefied material S is not detectable.
Task 6.3 Advanced characterisation of liquid 2nd generation biofuels (TUBITAK, UNA)
TUBITAK and UNA participate in this task, which focused on the characterisation of liquid fuels. It includes methods for the chemical characterisation of liquid tar compounds from fast pyrolysis and for the characterisation of Fisher-Tropsch (FT) fuels.
TUBITAK developed a new analysis method for FT-liquids. In order to gain a useful chromatographic characterization technique for FT liquids, the effect of carrier gas type, carrier gas velocity, injection temperature, split ratio and temperature program (initial temperature, hold time and heating rate) of the gas chromatography have been parametrically investigated. These parameters were seen to be effective on the resolution of the peaks and the total analysis time.
At UNA pyrolysis tests have been performed using a lab-scale and a bench-scale fixed-bed reactor. The fuels investigated are: softwood and straw pellets and torrefied spruce wood chips at a laboratory scale and DDGS pellets and torrefied softwood chips at bench scale. For the lab-scale tests, pyrolysis occurs under highly dynamic thermal conditions: temperatures, that at the feeding time are at the pre-determined heating value (800K), first decrease, owing to the cold feed and possibly the energetics of the decomposition process, and then return again to the initial value (char bed heating). Gas consists mainly of CO2, CO and CH4 with lower amounts of hydrogen and C2 hydrocarbons. Straw pellets give rise to lower amounts of liquid product and higher amounts of char and gas in comparison to wood pellets, as a result of both chemical composition (higher lignin and extractive contents) and the action of alkali compounds constituting the inorganic matter.
As a second part of the analysis, the combustion behaviour of DDGS and the corresponding char has been studied using a thermogravimetric system. Comparison with beech wood indicates that DDGS devolatilisation occurs with a slower rate and the char consists of two fractions with different reactivity. The oxidation reactivity of the pyrolytic char has also been investigated with a thermogravimetric analyser (heating rate 5K/min), showing values approximately coincident with those of low-temperature beech-wood chars.
A comparison among liquids produced from beech wood, softwood and straw pellets has aslo been made. The three samples present features qualitatively similar. In accordance with the GC-MS analysis, higher levoglucosan quantities are obtained for the two wood liquids, although the acetic acid peaks are approximately the same in all cases (GC-MS reports higher yields of acetic acid for beech wood). Also, the hydroxypropanone peak is lower for the beech wood liquid while GC-MS reveals that the yields of this species are almost the same in all cases. Another discrepancy, with respect to the GC-MS response, is the higher peak of hydroxyacetaldehyde for the softwood with comparable values for the other two samples (the GC-MS analysis reports higher values for the wood liquids). These results are most likely attributable to a slightly higher concentration of the softwood liquid with respect to the other two samples.
WP7 Advanced measurement methods and operational procedures in thermochemical biomass conversion
During the BRISK project, WP7 focussed on describing (via protocols) and improving advanced measurement techniques and operational practices for biomass conversion using thermo-chemical techniques, like pyrolysis, gasification and combustion, but rather concentrating on gasification.
Task 7.1 Particle sampling and analysis (TUD, BE2020+, TUG, AAU)
TUD summarized the findings of the research regarding particulate matter sampling and analysis in an overview paper presented at the IRFR 18th member conference and also finalized the writing of a protocol for particulate matter sampling in challenging biomass gasification conditions under conditions of high steam contents in the product gas.
The high temperature impactor (HTI) of BE2020+ was used for the in-situ determination of the particle size distributions and concentrations of submicron particles and has already been adapted and applied in gasification processes. The low sampling mass was seen as a critical, limiting value for the possibility to perform chemical analyses of the samples. Particles sampled an updraft gasifier at TUG have been successfully analysed during the work performed in WP7. To verify that the results obtained with the device were not altered due to the modifications, experiments were carried out using a combined packed bed / drop tube reactor of BE2020. The measurements were performed using the original as well as the modified HTI. In conclusion, the modification of the HTI for gasification processes is considered to be successful. It allows the determination of the chemical composition of particle samples and particle size distribution were shown to be not altered by the modification.
AAU has carried out a number of tests using the lab scale fluidized bed reactor. These tests have focused on bed agglomeration, but also on achieving stable conditions necessary for the repeatability. As a part of this work, the fuel feeding system installed earlier during the BRISK project has been revised. With the first system feeding of biomass pellets proved problematic. In the new setup a more powerful electrical motor is included as well as a flexible junction between feeding system and reactor. In this way, also pellets can be fed successfully. Nevertheless, the size of the pilot scale installation limits the accuracy of the control of the stoichiometric conditions in the reactor. The particle sampling setup that has been used for sampling in the lab scale reactor has also been tested in a large scale installation. Here too a discrepancy between the planned conditions and the realized ones was observed.
Task 7.2 Tar sampling and analysis (CIUDEN, KTH, ECN, TUBITAK, TUD)
CIUDEN performed valuable measurements regarding tar composition in their 3 MWth BFB gasifier for a novel fuel, torrefied wood.
KTH tested a tar sampling prototype (on-line PID detector) with implemented technical solutions for enhanced robustness. Experience from the operation of the new design indicates an enhanced stability
At ECN some of the tar guidelines and SPA samples, which were taken in October 2014 during a duration test of our SNG system, were analysed by partners PSI, Tübitak Marmara Research Center and TU Münich for tar and/or heavy organic sulphur compounds.
At TUBITAK two off-line methods for tar sampling during biomass gasification were performed: Conventional gravimetric method, CEN/TS 15439; and Solid Phase Adsorption method (SPA).Both methodswere applied successfully for bubbling bed gasification of BRISK samples within TA activities at TUBITAK MAM. For both methods, tar compounds trapped in isopropanol were analyzed using a gas chromatography (GC) equipped with flame ionization detector (FID). Two different standard mixtures were used for the calibrations of individual tar compounds. GC was calibrated for components from Benzene to Benzo(ghi)Perylene. In the last year of the project, round robin samples have been received from ECN for investigating both tar and tar-S compounds. It was seen that only the tar samples taken according to CEN/TS 15439 gave comparable results. SPA tubes seemed to have to be analyzed at the sampled laboratory since its long distance transfer without appropriate storage conditions deteriorated the adsorbed tar species in some way and made the results deviate from a good interpretation.
At TUD additional gasification experiments with torrefied wood and its parent material were performed and tars were sampled using two different methods, Tar protocol and SPA. Tar protocol is a time and labour intensive method, whereas SPA sampling is faster and more direct. Therefore, SPA samples were taken in triplo each time. In general Tar protocol was performed once per gasification experiment and SPA sampling was performed twice; both sampling methods were performed during steady state. The samples were analysed on HPLC combined with detection by UV and Fluorescence. Furthermore, TUD participated in round robin testing of tar samples that PSI delivered. ECN and BE2020+ also participated. TUD analysed the tar samples on HPLC combined with detection by UV and Fluorescence. The results showed that torrefaction influences the quantity of tars, but not the quality, as practically the same tar compounds are present in both cases. Naphthalene and toluene were the dominant tar species in both cases.
Task 7.3 Gaseous sulphur species sampling and analysis (PSI, TUBITAK)
PSI has further improved its liquid quench sampling techniques and the operation of the GC/SCD liquid phase analysis system. Due to that limit of detection (LOD) was increased by two orders of magnitude. In order to be able measuring online H2S, COS and Thiophene in the one ppm range, a gas sampling system was evaluated for GC/SCD gas phase analysis. A European working group was initiated with special interest in gaseous sulphur compounds sampling and analysis. At TUBITAK analysis of both sulphur-tar compounds (‘thiophenics’) and light sulfur compounds (H2S and COS) have been performed using off-line gas chromatographic technique with a Pulse Flame Photometric detector (PFPD). PFPD detector was chosen since it presents some significant advantages over Flame Photometric Detector (FPD) as known from the application notes of detector supplier (Agilent). Gas samples collected during bubbling bed gasification of biomass samples were analyzed with the GC-PFPD for light sulphur compounds. Moreover, round robin samples for sulphur-tar compounds were collected by ECN during the operation of MILENA gasifier at the start of a 500 hours test and distributed to TUBITAK MAM for investigating tar-S compounds. In the analysis; Thiophene, Benzothiophene and Dibenzothiophene were detected in round robin samples. Some unidentified tar-sulphur compounds were detected as well. It was seen that PFPD detector was found to be a well proven detector for the analysis of low boiling point gaseous components such as H2S and COS. Both online and offline sampling and analysis methods were applied and accurate results were obtained. PFPD detector has also been evaluated as a suitable option for the analysis of sulphur containing tar species. Although SCD detector is a more desirable detector for more complex samples like sulphur in gasoline and middle distillates, PFPD has shown acceptable sensitivity and selectivity for the measurement of heavy sulphur components like thiophenes in isopropanol.
Task 7.4 Improving gasification technology practices (CERTH, CIUDEN, INERCO, IFRF, KTH, TUD)
CIUDEN developed an Aspen PlusTM model of a larger fluidized bed gasifier with the help of data collected from the CIUDEN 3MWth Atmospheric Bubbling Fluidized Bed Gasifier and existing experience from the 50kWth gasification system at CERTH. The model for the prediction of syngas quality is a steady-state model based on thermodynamic equilibrium by Gibbs free energy minimization as well as kinetic parameter from the collected data. A special addition to the model including C2H4 formation was proven to be the most successful in providing data for all the major components measured during the experimental campaign. Therefore, the comparison between the experimental results and the simulation results are in very good agreement with respect to the major gas components, i.e. H2, CO, CO2 and CH4.
At CIUDEN air was used as oxidizer to gasify torrefied chips (second generation biomass) in a 3 MWth bubbling fluidized bed gasifier (BFB) whose design fuel was wood pellets. Considering the size of the rig (semi industrial size), and taking into account that the problems that normally appear in this installation are the same as those problems that appear in a commercial plant, the a new process management strategy was described. Apart from the operational procedures and considering the fuel used was not the ‘design fuel’, modifications in the design of the rig were tested during the R&D activities. INERCO supported the experimental work via data analysis and modeling.
IFRF’s-S.Piero infrastructure (GASTONE), downdraft gasifier with gas cleaning employed for this task. Additional testing/evaluation activities were carried out concerning improving operational practices.
KTH investigated operational parameters in pressurized steam/oxygen BFB gasification of biomass. Of special interests have been to investigate the stability of catalytically active dolomite and ilmenite materials undergoing repeated cycles of carbonation and calcination, along with the development of a process window with optimal performance regarding catalytic activity and mechanical strength. Examples of results of importance are knowledge gained on the importance of crystal structure, micro- and macro-pores, and the distribution of Si in the crystal lattice for the stability of the dolomite. The micro- and macro structure distribution determine if the shape is preserved during the calcination and the Si distribution the mechanical strength in the bed.
TUD’s 100 kWth oxygen-steam blown Circulating Fluidized Bed Gasifier (CFBG) was operated applying different gas cleaning strategies; e.g. a high temperature (HT) filter at 350 oC. TUD has further refined the protocol regarding the operation of the CFBG. The protocol was refined in a way so that more carbonaceous fuels would be gasified successfully. In this period TUD has focused on gasifying torrefied woody biomass and its parent material under the same conditions in order to investigate on the effect of torrefaction on main gas composition and tar formation. The focus on Equivalence Ratio and steam-to-biomass ratio were to be as close as possible to industrial practices, and two tar sampling methods were tested for their efficiency. TUD has also hosted one long duration experiment with corn stover (an agricultural residue) in order to investigate its applicability under the gasification parameters of TUD’s reactor (i.e. oxygen-steam blown circulating fluidised bed gasification, at 850 oC, etc.). During the test several temperatures were tested during steady state to investigate when agglomeration phenomena will occur and how they can be countered in the gasifier. The results show that due to the more brittle nature of torrefied biomass, certain process benchmarks are improved although the opposite is expected. Carbon conversion efficiency is improved with torrefied material, due to the smaller particle size when it is fed in the gasifier. The results of corn stover gasification showed that gasification is possible of such a challenging fuel when an additive is used to counteract agglomeration.
WP8 Improving methods for advanced testing / examination and optimisation the catalytic conversion processes
Task 8.1 Developing methodologies for catalysts testing for FT and higher alcohols (CERTH)
The work accomplished in CERTH included a detailed study of the effect of operating conditions on catalyst performance for CO hydrogenation to higher alcohols, the definition of optimum testing conditions and the evaluation of a K-NiMo/AC catalyst in the presence of ammonia and benzene in the syngas feed. Ammonia and benzene concentrations typical of those in syngas from biomass gasification were selected. CERTH successfully conducted those tests indicating the feasibility of impurity testing in a high pressure small scale bench test unit. The performance of the AC-supported K/NiMo catalyst remained unaffected in both cases, indicating that Mo-based catalysts constitute a very promising class of catalytic materials for the synthesis of higher alcohols which is resistant to typical syngas impurities. Post characterization of the catalyst showed that important structural modifications occur, such as high loss of surface area, together with coke deposition on the nickel active sites. Results showed that ammonia and benzene concentrations typical of those in syngas from biomass gasification are not critical for the catalytic performance, which remained stable even after 130-200 hours on stream.
Experimental and characterization studies showed that mixing rate was the most effective parameter on catalyst attrition due to the larger physical forces applied on the catalyst at higher mixing rates. High space velocity values also caused series catalyst break up. These studies showed that catalyst and Fischer-Tropsch process development work should take into account the mechanical attrition since the parameters affecting the activity and selectivity of the catalysts also determines the mechanical integrity of the catalyst.
Task 8.2 Developing methodologies for catalysts testing for SNG with synthetic and real biosyngas. (CERTH, ECN, TUM, PSI)
CERTH teamed up with ECN to analysis fresh and used catalysts in conversion tests.The gasifier employed was a 25 kWth indirect gasifier of ECN design, referred to as MILENA. About 20% of the gas production is led to the OLGA tar removal system. Based on the findings of these experiments, the catalyst research with producer gas from a biomass gasifier was analyzed. Test methods were developed and illustrated with examples from a 500 hr test (the system consisted of a biomass gasifier, tar removal, gas cleaning and reactors with three different types of catalyst).
TUM finalized the process evaluation in their real-gas test rig that enables long-term testing under realistic operation conditions including pressure and volume flow variations over time as well as the investigation of start-up and shut-down procedures including emergency handling similar to a commercial demo-scale plant. This gives the opportunity to compare lab-scale findings and test results to the real-gas application and identify problematic issues and drawbacks before scale-up. The investigation of trace compounds and contaminants on the performance of the system was analyzed.
A long-term test of >100h (2*50 with a short emergency interruption in between) was performed with coupled gasification, hot gas cleaning and methanation. Several successful 100h tests for the proposed process route for thermochemical SNG production in a small-scale test rig were also performed. CERTH contributed with analysis of the catalysts after testing.
PSI contributed with the implementation of an improved micro fluidised bed methanation system (BFB). One of the specialities of the test rig is a movable sampling tube, which can be submerged into the BFB. Temperatures and gas compositions can be measured with a very high local resolution. The dried gas composition is measured by GC. This allows to observe changes during the experiment and to determine deactivation phenomena much easier and earlier as this would be the case, if the gas composition is measured only at the exit of the mBFB reactor. The mBFB system is designed in such a way that typical temperatures in fluidisied methanation can be investigated, i.e. 250 up to 400 °C. The operation pressure is between 1 bara and 3 bara. The mBFB test rig has been designed for two main applications:
kinetic measurements of methanation catalysts for a variety of chemical reactions (methanation, water gas shift, reforming, hydrogenation); and measurement of activity and selectivity of a specific methanation catalyst for a specific syngas quality (bulk gas composition, impurities).
Task 8.3 Developing methodologies for catalysts testing with advanced synthesis gas impurities measurement for DME/MeOH syntheses. (CERTH, ETC)
CERTH contributed to the development and characterization of catalytic materials pre and post reaction. Physicochemical characterization of methanol synthesis CuZnAl catalysts showed that variation of composition induces small changes, while the amorphous nature of the catalysts was found, by XRD, to increase with decreasing Cu molar content. Activity testing identified methanol, carbon dioxide and hydrocarbons as the main products of the reaction, while temperature increase benefits activity as well as hydrocarbons and CO2 selectivity at the expense of methanol formation. The optimum catalytic performance towards methanol, exhibited by the material Cu60/Zn30/Al10, with the highest Cu content.
At SP ETC an already existing pressurised gasifier was used to full characterise biomass synthesis gas in detail for trace elements and impurities and development of methodologies for determination of the trace elements is necessary. Focus in the BRISK project was to understand what types of impurities that are present in syngas obtained from pressurized entrained flow gasification of woody biomass. This was extremely important for designing proper gas clean up systems downstream the gasifier before catalytic upgrading to transportation fuels. Impurities have been sampled and measured primarily using gas chromatography online during operation and via gas sampling bags offline. In addition to gas chromatography trace components have been samples using impinger bottles filled with certain solutions for absorption of certain compounds. Important methodologies and correlations are presented for these measurements. BRISK project has introduced a combination of efforts both on catalysts development and characterisation and bringing high pressure high temperature gasification to meet specifications for MeOH and DME synthesis. Many possibilities for further research on the topic are opened, some of which also started being explored in the frame of TA activities.
A description of the main impact, dissemination activities, and exploitation of results has been organized according to work packages, and excludes those activities that are outside this scope.
WP4 Dissemination and international coordination
General dissemination activity has been divided into six main tasks. The communication actions foreseen at a European level are the result of a global communication strategy tightly linked with the whole project. International Coordination seeks to promote and support clustering and coordinated actions between the project and other national/international related initiatives.
Workshops were organised following the TOTeM approach (Topic Oriented Technical Meetings) developed by IFRF, and will be configured to attract potential new users of the BRISK Research Infrastructure.
Task 4.1 Public Website (Aston):
The BRISK website www.briskeu.com has been created for dissemination and awareness purposes and has two levels of accessibility: a public level and a private level. The public site comprises the following key areas as well as a number of support pages:
(i) BRISK partner information;
(ii) How to apply for Transnational Access, including a Frequently Asked Questions section;
(iii) Case studies featuring BRISK Transnational Access (TA) visitors;
(iv) News and up-to-date information about project seminars, workshops and other relevant events;
(v) Dissemination material produced and all relevant public deliverables.
The private section of the website (i.e. BRISK partner use-only) was launched in April 2012. It is a password-protected portal for sharing BRISK documents including Transnational Access applications, minutes, Work Package reports etc. A user-guide to the site, and logon details have been distributed to all partners.
Traffic to the website is monitored using the web analytical tool, Google Analytics. Number of visitors is the following:
1 October 2011 to 31 March 2013 6176
1 April 2013 to 30 September 2014 5610
1 October 2014 to 30 September 2015 8112
Task 4.2 Dissemination Material (Aston):
A range of BRISK promotional material has been produced and distributed:
4-page brochure; 1 page flyer; promotional presentations (electronic slides); and newsletter (see below).
• 32 case studies were produced about researchers’ visits to various BRISK partner facilities. These are featured on the BRISK website and within editions of the BRISK newsletter.
Task 4.3 Press Articles (Aston):
A formal announcement about BRISK was sent to the international press in April 2012. The press release was distributed to 70 journals, magazines and newsletters, and contained details about how researchers can apply for Transnational Access to BRISK partner laboratories.
Task 4.4 BRISK Electronic Newsletters (Aston):
BRISK NEWS, the electronic newsletter of the project is produced biannually.
A closing post-project edition of the newsletter (Issue 8) was produced and circulated to 3700 contacts in October 2015.All BRISK partners were asked to distribute BRISK NEWS to their own databases of contacts. Both editions have been posted to the BRISK website.
Task 4.5 Promotion of BRISK at International Events (Aston):
During the 18-month period 1 October 2011 – 1 April 2013, BRISK was promoted at 38 events in 16 countries. Dissemination material prepared in WP4 has been used during these conferences, exhibitions and workshops as a general presentation of the project. See deliverable D4.3 - Report on International Events. A calendar of biofuel-related international events has been established and is available publicly on the BRISK website. All project partners have been encouraged to attend key targeted events in order to promote BRISK to other organizations not participating in the project.
A significant event where BRISK was publicised was the 20th European Biomass Conference and Exhibition (EU BC&E), held in Milan, Italy 18-22 June, 2012. It was attended by 1550 attendees from 63 countries, including 500 researchers.
During the event, the BRISK stand received 50 direct enquiries from visitors to the stand from 20 countries.
During the 18-month period 1 April 2013 to 30 September 2014, BRISK was promoted at 36 events in 14 countries. Dissemination material prepared in Work Package 4 has been used during these conferences, exhibitions and workshops as a general presentation of the project. other organizations not participating in the project.
Two significant events where BRISK was publicised was the 21st European Biomass Conference and Exhibition (EU BC&E), held in Copenhagen, Denmark on 3-7 June 2013, and the 22nd European Biomass Conference and Exhibition (EU BC&E) held in Hamburg, Germany on 23-26
During the 12-month period 1 October 2014 to 30 September 2015, BRISK was promoted at least 15 events in 10 countries. Dissemination material prepared in Work Package 4 has been used during these conferences, exhibitions and workshops as a general presentation of the project.
Task 4.6 Open Workshops (including TOTeMs) (IFRF):
During this reporting period Task 4.6 focused on events that supported specific JRA activities and the promotion of Transnational Access opportunities. Three themes have been adopted so far:
1. Gas Analysis – Tars, Sulphur Compounds, Particulates, Water, other species.
a. The first workshop of this theme was held alongside the 20th European Biomass Conference and Exhibition in Milan, June 2012. Approximately 60 people attended this event part-time or full-time. The scope of the content was broadened from 11 analytical questions regarding just ‘tar’ to all questions regarding the analysis of gases from thermochemical conversion including elemental trace contaminants such as sulphur, alkali metals and chlorine which are highly relevant in synthesis gas applications. The presentations and meeting summary are to be found at http://www.evur.tu-berlin.de/menue/forschung/veranstaltungen/gas- analysis_workshop/parameter/en/
b. The second workshop in this theme is organised and will take place on June 6th 2013 in Copenhagen, alongside the 21st European Biomass Conference & Exhibition. It will take the form of a TOTeM on the theme of Tar and Organic Sulphur Compounds, focusing in particular on the interim Benchmark/Tar Protocol CEN/TS 15439. This TOTeM will be a launch pad for round robins in the area of tar sampling and analysis, and support TA, JRA WP7 (Advanced Measurement Methods) and Networking Activity WP5 (Protocols and Benchmarking).
c. A third and final workshop in this series is planned as a stand-alone TOTeM for Summer 2014. It will bring together the results of the round robins launched in 2013, and have as an objective to develop some conclusions and recommendations to the CEN/TS 15439 Technical Committee.
2. Gasification. A stand-alone TOTeM on the topic of gasification will be held in late autumn 2013. The event will be hosted by Chalmers University of Technology, Gothenburg, Sweden. It will incorporate opportunities to visit GoBiGas, a new major biomass gasification test facility which is not part of the BRISK Infrastructure http://gobigas.goteborgenergi.se/English_version/Start. This is seen as an opportunity to promote BRISK gasification Transnational Access and to open a link between BRISK and GoBiGas which may be important in the ‘Beyond BRISK’ business planning activity (WP3).
3. Protocols: DTU/IFRF will host/organise a TOTeM on Protocols for data acquisition and sharing in the spring of 2014.
During the period 1 October 2014 to 30 September 2015, two BRISK open workshops were held as follows:
Fast Pyrolysis of Biomass Workshop, 8-9 December 2014, Europahotel, Ghent, Belgium
This event was organised by Aston University and was attended by 47 people. The purpose of the meeting was to bring together people who are active in biomass fast pyrolysis, to review and discuss the current situation in science, technology and project implementation. It explored the opportunities and limitations of biomass fast pyrolysis in order to identify the R&D needs of the future.
Gasification Workshop (TOTeM), 22 April 2015, Technical University of Delft, Netherlands
The workshop / Topic Oriented Technical Meeting (TOTeM) was entitled “Gasification: a versatile technology converting biomass to produce synfuels, heat and power” and it was a one day stand-alone event. The workshop was organised by IFRF together with Technical University of Delft with 41 participants from 14 countries.
In the first part of the meeting the keynote presentations highlighted the main challenges and opportunities in the commercial use of biomass gasification technology as well as a comparison of the various European markets for this technology. In the second part of the workshop each of the BRISK Work Package leaders gave a report on the status and achievements of the relevant Work Package. The third part of the workshop contained various BRISK Transnational Access (TA) case studies by researchers who had participated in the initiative. There then followed a panel discussion, exploring in detail the state of biomass and biofuels gasification technology, its applicability, its commercial benefits as well as areas for the further development. The slides of the workshop-presentations can be found at: http://briskeu.com/home/briskevents
List of Websites: