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Catalytic cracking of tar from biomass gasification

Nikola Sundac
Department of Chemical Engineering,, Lund University, P. O. Box 124, SE-221 00 Lund, Sweden

One of the major issues in the biomass gasification technology is how to deal with the biomass tar. When so called tar cracking catalysts are used, the only thing that is reformed is the tar itself while low hydrocarbons e.g. methane, ethane and propane are left intact. Dolomites, olivine and FCC catalyst are identified and investigated as tar cracking catalysts in the biomass gasification process, together with the necessary experimental equipment. The aim of the experimental work was to investigate some of the well-known tar cracking catalysts like dolomite and olivine and some of the lessknown alternatives in a lab scale experimental setup. Due to a limited time for experimental work and writing of this paper, only a preparation phase of the experiment was actually conducted in the laboratory. An overview of the biomass gasification technology is also presented.
Introduction Gasification of biomass is an important process for utilization of biomass e.g. for production of fuels and chemicals. During the gasification, biomass is converted with air or oxygen and water vapor into a mixture of gases such as CO, CO2, H2, H20 etc. Besides the gases, a number of low, volatile hydrocarbons (mostly CH4) are built, together with tars. The tars represent a complex mixture of components, typically polyaromatic that are difficult to deal with in the downstream processes that accompany gasification as well as in utilization technologies. When a so called tar cracking catalysts are used for tar removal, only tar is reformed while the low hydrocarbons are left intact. The efficiency of the total biomass conversion is increased in this way. The most well-known tar cracking catalysts are calcinated dolomite and olivine. The aim of this paper is to be an initial study of technology, methodology and problems concerning tar cracking catalysis in biomass gasification process. The work is divided into a literature study and an experimental work. The purpose of the literature study is to serve as a solid ground and a starting point for the experimental work. The objective of the experimental work is to investigate and evaluate some of the well-known tar cracking catalysts and perhaps some less-known alternative tar cracking catalyst in a lab scale reactor. Gasification of biomass The gasification has already been identified as one of the most promising processes for the use of biomass and has been extensively studied so that the current status of this technology is at close to commercialization stage. The fact is that biomass is the only renewable carbon source and this makes it especially attractive as a feedstock for the production of transportation fuels and chemicals in the future. On the other hand, the CO2-neutral nature of biomass is very attractive from the environmental point of view [1]. An overview of the gasification technology is given in Figure 1.

Biomass pretreatment

Gasification Gas purification and conditioning

Synthesis of chemicals/fuels

Production of electricity

Production of heat

Figure 1 Overview of the gasification technology

Pretreatment of biomass lies outside the scope of this paper. The gasification step converts a solid fuel into a combustible gas with help of an oxidizing agent (e.g. air, oxygen, steam). There are four different design concepts for gasification: fixed bed gasifiers, fluidized bed gasifiers, entrained flow gasifiers and indirect gasifiers [2]. The gas purification has to eliminate all the components (particulates, sulfur compounds, nitrogen compounds, halogens, volatile metals, and tars) that could have a negative effect on downstream processing or utilization of the produced gas. The function of the gas conditioning

is to remove undesired main compounds (removal of CO2 or hydrocarbons like e.g. CH4) [1] and to adjust the gas composition for the utilization step. When it comes to utilization of gases from biomass gasification, it is very important to distinguish two main types of gasification gases: product gas and biosyngas. The product gas is formed by low temperature gasification (below 1000C) while biosyngas is formed by high temperature (above 1200C) or catalytic gasification. Different composition of these gases defines their field of application. The product gas is used for production of synthetic natural gas (SNG) and electricity while the biosyngas is applied for: production of Fischer-Tropsch diesel, methanol, ammonia and hydrogen, for various uses in chemical industry and for the production of electricity [1]. Tar from gasification of biomass One of the major issues in the biomass gasification process is how to deal with the tar formed during the process. Tars can be easily defined as undesirable and problematic organic products of biomass gasification but there are a large number of definitions for the tar in the literature. The diversity in the operational definitions of tars usually comes from the variable product gas compositions required for a particular end-use application and how the tars are collected and analyzed4. One typical composition of biomass tars is shown in Figure 2. Composition of a specific tar depends on a large number of factors like the type of fuel used and the gasification process itself [3].
Heterocyclic com pounds, 10% Others, 2%

Accepted levels of tar in gas produced from biomass depend on the tolerance of end-use devices to tar. There are still very few reliable, well-defined and long-term data on the tolerance of the great variety of end-use devices to tar [4]. The tars can cause quite a few problems in the different applications such as cracking in the pores of filters, forming coke and causing plugging of the filters, condensing in the cold spots and plugging the cold spots; all this resulting in serious operational interruptions and maintenance costs. Another vital issue regarding tars is that they contain carcinogenic compounds that have to be removed to achieve health and environmental demands. Tar removal technologies can be broadly divided into two approaches: treatments inside the gasifier (primary methods) and hot gas cleaning after the gasifier (secondary methods) [5]. Although primary methods theoretically eliminate the need for downstream clean-up creating tar-free gas at the exit of the gasifier, they have not yet resulted in satisfactory low level of tar. It is more likely that a combination of primary and secondary methods has to be used for total tar removal during technology development in the future [6]. Different catalysts are used as a part of both primary and secondary methods for tar removal. Catalysts for tar cracking There are a large number of different catalysts that have been used to eliminate the tars in the product gas from the gasification process. The two most researched groups are Ni-based catalysts and dolomites. When Ni-based catalysts are used, tar concentration in the product gas can be reduced significantly by means of reforming but since this process is endothermic, a part of the chemically bound energy of the gas has to be burned to sustain this process. This effect leads to a decreased efficiency of the gasification process. In contrast, when so called tar cracking catalysts such as dolomite are used, the only thing that is reformed is the tar itself while low hydrocarbons e.g. methane, ethane and propane are left intact. Simultaneously with this transformation of tar, the gas composition (CO2, CO, H2 etc.) changes as a consequence of reactions that will be described later in the text. Tar cracking can be defined as a process that breaks down the larger, heavier and more complex hydrocarbon molecules of tar into simpler and lighter molecules by the action of heat and aided by the presence of a catalyst but without the addition of hydrogen [3]. Two well known tar cracking catalysts are naturally occurring minerals: dolomite and olivine. Another type of material that has been recognized as a tar cracking catalyst is the Fluid Catalytic Cracking (FCC) catalyst.

Phenolic com pounds, 7%

Four ring aromatic hydrocarbons, 1% Three ring aromatic hydrocarbons, 6% Other two ring aromatic hydrocarbons, 13%

Toluene, 24% Other one ring aromatic hydrocarbons, 22%

Naphthalene, 15%

Figure 2 Typical composition of biomass tar [3]

Some of the most influential parameters for the tar composition are the process temperature and the gasifier type. There have been several attempts to identify and classify tar compounds based on specific criteria (e.g. reactivity, solubility, condensability etc) chosen by an author. Development of tar classification systems is especially important for improvement of kinetic models of tar conversion over a catalytic bed and for better understanding of the relationship between the composition of the tar and the operating conditions and design of the gasifier.

Dolomite is a calcium magnesium ore with the general chemical formula CaMg(CO3)2 with some minor impurities. In order for dolomite to become active for tar conversion, it has to be calcined. Calcination involves decomposition of the carbonate mineral, eliminating CO2 to form MgO-CaO, at high temperatures (usually 800-900C). The effective use of dolomite as a catalyst is restricted by relatively high temperatures4 and the partial pressure of CO2 [7]. When it comes to the importance of dolomites composition for catalytic activity, it has been shown that an increased content of iron in dolomites, i.e. Fe2O3, can raise its activity towards tar elimination by 20% [8]. The fact that dolomites are quite inexpensive and abundant materials makes them very attractive as tar cracking catalysts. On the other hand, calcined dolomites are rather soft and therefore erode quickly as a result of attrition phenomena in fluidized bed reactors. Another disadvantage of using dolomites is that they are not very active for tar elimination and as a result, they are often used in guard beds, in conjunction with highly active and more expensive Ni-based catalysts [9]. Olivine consists of: MgO, Fe2O3, SiO2 and some minor components [10]. Unlike dolomite, olivine is a nonporous material that has an extremely low surface area and negligible pore volume. The main advantage of olivine, in comparison to dolomite is its resistance to attrition. Price levels of olivine and dolomite are approximately the same [3]. The pretreatment of the olivine is as important for the activity of olivine as it was for dolomite. Corella et al. [11] conducted a study of several in-bed additives in biomass gasification with air and made the conclusion that calcined dolomite is more effective for in-bed tar removal (1.40 times) than untreated olivine but at the same time generates more particulates in the gasification gas (4-6 times). At this point of gasification development, there are no final conclusions as to whether olivine is better then dolomite for in-bed use in gasification of biomass. Further research and techno-economical analysis have to be conducted in the future. The FCC catalysts have been identified as tar cracking catalysts but more research on FCC catalysts is needed in order to decide whether they are suitable for use in the biomass gasification tar cracking process or not. Laboratory studies There are two methods that have been used in research on catalytic tar conversion10 in laboratories worldwide. The first method is with catalyst mixed with the feed biomass in so called catalytic gasification or pyrolysis (in situ). In this case tar is removed in the gasifier itself (usually in a fluidized

bed gasifier). In the second method tar is treated downstream of the gasifier in a secondary reactor, outside of the gasifier (fixed bed catalytic reactor). Examples of laboratory reactors from literature for each method are presented in Figure 3 and Figure 4.

Figure 3 Fluidized bed gasifiers: BFB biomass gasifier (left) and CFB biomass gasifier (right) [13]

Figure 4 Fixed bed catalyst [13]

There are a large number of different operational parameters that define composition and quantity of the produced tar, concerning both mentioned methods, such as temperature, pressure, gasifying medium, catalyst and additives used, equivalence ratio (ER), gasification ratio (GR), steam-to-biomass ratio (SB), gas residence time (or space time) etc. Experimental setups described in the literature that have been used in laboratory studies of tar elimination are quite diverse and numerous. Besides the catalytic reactor and/or the gasifier itself, the most important part of the equipment is the tar sampling and analysis apparatus. It is important to mention that, when working with fixed bed catalytic reactors, some authors have used one carefully chosen model compound for tar like naphthalene, toluene, benzene, cyclohexane, nheptane etc. as a basis for their research [4], [9]. The main criteria upon which these compounds are chosen is their abundance in tar and resistance to cracking.

There is a high variety of sampling methods and analytical techniques that still has not been standardized. That is why comparison of data and definition of clear maximum allowable concentrations for these contaminants is problematic. An attempt has been made on European level, supported by European Commission, to standardize measurement of organic contaminants in gas coming from biomass gasifiers that lead to Guideline for sampling and analysis of tar and particles in biomass producer gases [14]. The tars are usually separated from the gas by means of condensation in so called cold traps using water condensers and cooling traps, combined with solvent absorption and filters. A tar sampling method based on solid phase adsorption (SPAmethod) [15] has also been used in a number of studies. Experimental work Due to limited time, only a preparation phase of the experiment was actually performed in the laboratory. This preparation phase involved gathering of the equipment, adjustments of the equipment, installation, start-up tests, calibrations, leakage tests, development of the analysis method with gas chromatograph etc. Instead of using a real tar, a model compound was chosen for the experimental work. The first model compound was naphthalene. Naphthalene was chosen due to its abundance in real biomass tar and resistance to cracking. It has proved to be very inconvenient with regards to leakage and unwanted condensation in the system and it was replaced with o-xylene. Xylene has been chosen simply because it is a more convenient tar component to work with, and it was accessible in the laboratory. The experimental setup for naphthalene is shown in Figure 5.
T

Every gas is stored in a cylindrical tube and its flow is controlled by a mass flow controller (MFC). Water in dejonized state is added in form of steam to ensure steam reforming of naphthalene. To feed the water in to the system, a syringe pump is used with a 50 ml syringe. Water is then mixed with gases and gasified in a pre-heater before entering the catalytic reactor. Naphthalene is stored in a reservoir, placed before the catalytic reactor, which is externally warmed up by means of a heater. When heated up to a proper temperature, naphthalene melts to a liquid. A nitrogen stream is passed through the reservoir and saturated with naphthalene. The concentration of naphthalene can be adjusted by changing the temperature inside the reservoir with the heater. This solution is called naphthalene saturator28. A very important issue when using naphthalene is to prevent blockage of piping and reactor by condensation of naphthalene. That is why a line after the catalytic reactor is traced at a temperature of 200C with a heating coil. The catalytic reactor is in the form of a cylinder, with an inner diameter of 26 mm and 250 mm length. It has two K-type thermocouples, for measuring the temperature below and above the fixed catalytic bed. The catalyst itself is placed on a metal net supported by a cross. The reactor is placed inside an electric gold-coated reflecting furnace that can be heated up to maximum 1000C. In order to collect all the condensable components and naphthalene, a condenser system or a so called tar trap is needed. During the preparations of this experimental setup, a few different condenser formations were tested with water vapor and nitrogen. The best alternative of the tested condenser systems is shown in Figure 6.
From catalytic reactor

Heated line

To GCanalysis
Condenser for of-line GCanalysis of tar

Catalytic fixed bed reactor

Computer Electric gold furnace

Gas chromatograph for on-line analysis of the permanent gases


Dator

Condenser 1 Condenser 2

Syringe pump for water Heater


50 ml

Naphthalene reservoir Pre-heater Ventilation

Condenser 3

MFC

Figure 6 Condenser formation


N2

MFC

MFC

MFC

MFC

CH4

CO2

CO

H2

Figure 5 Experimental setup for naphthalene

All permanent gases except nitrogen (CO2, CO, CH4 and H2) are introduced in the system prior to the pre-heater (standard laboratory electric furnace).

The idea of the condensation tests was to measure changes in the mass of the sampling tubes and by comparing it to the mass of the water injected in to the system, to find losses. These losses represent the proportion of the tar that would not be trapped in the condenser during the experiment. The results show that an average loss of water was 25.37 % when the best condenser was used (Figure 6). Because the temperature of the gas stream after the

third condenser was 24C throughout the tests, a constant amount of water is swept away to the ventilation with the stream of nitrogen. This constant loss of water was calculated to be 8.86 % of the water that was fed in to the system. If this data is taken into account when calculating the average loss of water is 16.53 %. After all the condensable compounds have been separated for an off-line GC analysis in the condenser system, the stream with the permanent gases is sent for an on-line analysis in the gas chromatograph. The gas chromatograph was Varian 3800. In order to perform on-line analysis of permanent gases and off-line analysis of collected tars from the condenser system, two different columns have been installed in this unit: Packed column, for the analysis of the permanent gases; Label: HayeSep DB, 60-80 mesh; Dimensions: 6 m x 1/8 x 2 mm; Injection: automatic injection valve Capillary column, for the analysis of the tars; Label: PoraPlot type U, DB-5MS; Dimensions: 30m x 0,25mm x 0,25 micron; Injection: manual, with a syringe The first column has been used in both cases (with naphthalene and xylene) while the second column is only used in the case of naphthalene as a model compound. This gas chromatograph is connected to a computer, equipped with a thermal conductivity detector and as a carrier gas, helium is used. As mentioned earlier, naphthalene was replaced with xylene as a model compound. The experimental setup for xylene is illustrated in Figure 7.
Tapp water
P T

container. In this experimental setup, no tar trap is used but instead the analysis is performed by an online gas chromatograph, direct after the catalytic reactor. In general, the method development of gas chromatography analysis was one of the most timedemanding phases of the experimental work. Even if a lot of time was spent on this part of work, the only firm result that was obtained is the identification of peaks from the permanent gases. It was performed successfully with a following starting composition of the gas mixture: 48% N2, 20% CO2, 10% CO, 10% CH4 and 12 % H2. Total gas flow was constantly kept at 100ln/h by increasing the nitrogen flow. Discussions and conclusions Gasification of biomass is a technology whose importance, according to the present situation, is going to rise in the future. However, a development of this technology has a long way ahead with a number of obstacles, such as the removal of tar, to be cracked. One of these obstacles is the development of the tar classification systems. This is especially important for improvement of kinetic models of tar conversion over a catalytic bed and for better understanding of relationship between compositions of tar and operating conditions and design of the gasifier. The tar cracking catalysts (dolomite, olivine and FCC catalysts) have to be investigate more in the future in order to find the best solution for catalytic removal of the tar. In order to prolong the life of these catalysts and to increase their activity, it is very important to find an optimal set of operational conditions together with pretreatment methods. The use of FCC catalysts in the biomass gasification technology has to be studied further in order to be justified and accepted. The tar sampling and analysis equipment and methodology have to be standardized so that a comparison of data from different studies can be easily performed. Further investigation

Heated line

Pressurized water container

Water jet pump Drain

Catalytic fixed bed reactor

Gas chromatograph
Dator

Computer

Water reservoir Syringe pump for xylene

MFC

Electric gold furnace

Ventilation
50 ml

MFC

Pre-heater

N2

MFC

MFC

MFC

MFC

CH4

CO2

CO

H2

Figure 7 Experimental setup for xylene

The main changes in this setup, in comparison to the setup for naphthalene, are concerning: model compound feed, water feed and concept for analysis of the tars and permanent gases. Xylene is fed with a syringe pump. Throughout the preparation tests, use of a syringe pump for feeding of water has proven to be insufficient and unsuitable so another feeding system was created in form of a pressurized water

Any further experimental investigation of tar cracking catalysts that would start from this paper or use it as one of the references, should take the following remarks carefully. The things that have to be done cautiously and well thought out are: The choice of the model compound, The choice of laboratory equipment and the design of the experimental setup, Start up and control tests. These issues can lead to a great waste of time if its not taken care of properly. A special attention

should be given to assemble and dissemble of the equipment during the experiment. If the experimental setups presented in this paper are taken as a starting point, there are four important elements of the experimental work that need to be improved before initiating an actual experiment: The investigation of the temperature profile in the reactor, The construction of the reactor with the belonging thermo elements, The construction of a well functioning condenser system, The tar sampling and analysis. References
[1] Boerrigter H., Rauch R. Review of applications of gases from biomass gasification, ECN Biomass, Coal and Environmental Research, web address: www.ecn.nl, report number ECN-RX--06-066 (2006). [2] Olofsson I., Nordin A., Sderlind U., Initial Review and Evaluation of Process Technologies and Systems for Cost-Efficient Medium Scale Gasification for Biomass to Liquid Fuels, ISSN 1653-0551 ETPC Rapport, University of Ume (2005). [3] Z. Abu El-Rub, E.A. Bramer, and G. Brem, Review of Catalysts for Tar Elimination in Biomass Gasification Processes, Ind. Eng. Chem. Res., 43, pp. 6911-6919 (2004). [4] Milne T.A., Evans R.J., Biomass Gasifier Tars: Their Nature, Formation and Conversion, NREL/TP570-25357 (1998). [5] Devi L., Ptasinski K.J., Janssen F.J.J.G, A review of primary measures for tar elimination in biomass gasification process, Biomass and Bioenergy, Vol. 24., pp. 125-140 (2003). [6] Boerrigter H., S.V.B. van Paasen, P.C.A. Bergman, Knemann J.W., Emmen R., Wijnands A., OLGA Tar Removal Technology, ECN Biomass, Coal and Environmental Research, web address: www.ecn.nl, report number ECN-C--05-009 (2005). [7] Simell P.A., Leppalahti J.K., Kurkela E.A., Tardecomposing activity of carbonate rocks under high CO2 partial pressure, Fuel, Vol.74, No.6, pp.938-945 (1995). [8] Orio A., Corella J., Narvaez I., Performance of Different Dolomites on Hot Raw Gas Cleaning from Biomass Gasification with Air, Ind. Eng. Chem. Res., Vol. 36, pp.3800-3808 (1997). [9] D. Dayton, A Review of the Literature on Catalytic Biomass Tar Destruction-Milestone Completion Report, NREL/TP-510-32815, National Renewable Energy Laboratory, web address: www.osti.gov/bridge (2002). [10] Devi L., Ptasinski K.J., Janssen F.J.J.G, van Pasen S.V.B., Bergman P.C.A., Kiel J.H.A, Catalytic decomposition of biomass tars: use of dolomite and untreated olivine, Renewable energy, Vol. 30, pp.565587 (2005). [11] Corella J., Toledo J.M., Padilla R., Olivine or Dolomite as In-Bed Additive in Biomass Gasification with Air in a Fluidized Bed: Which is better? Energy & Fuels, Vol. 18, pp. 713-720 (2004).

[12] Warnecke R., Gasification of biomass: comparison of fixed bed and fluidized bed gasifier, Biomass and Bioenergy, Vol.18, pp.489-497 (2000). [13] Orio A., Corella J., Narvaez I., Performance of Different Dolomites on Hot Raw Gas Cleaning from Biomass Gasification with Air, Ind. Eng. Chem. Res., Vol. 36, pp.3800-3808 (1997). [14] Paasen, S.V.B. van, Kiel, J.H.A., Neeft, J.P.A., Knoef, H.A.M., Buffinga, G.J., Zielke, U., Sjstrm, K., Brage, C., Hasler, P., Simell, P.A., Suomalainen, M., Dorrington, M.A., Thomas, L., Guideline for sampling and analysis of tar and particles in biomass producer gases, ECN Biomass, Coal and Environmental Research, web address: www.ecn.nl, report number ECN-C--02-090 (2002). [15] Claes B., Qizhuang Y., Guanxing C., Sjstrm K., Use of amino phase adsorbent for biomass tar sampling and separation, Fuel Vol. 76, No. 2, pp.137142 (1997).

Received for review September 13, 2007

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