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Tar removal from biomass pyrolysis gas in two-step function of decomposition and adsorption
Thana Phuphuakrat a,*, Tomoaki Namioka a, Kunio Yoshikawa b
Department of Environmental Science and Technology, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan Frontier Research Center, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan
a r t i c l e
i n f o
a b s t r a c t
Tar content in syngas pyrolysis is a serious problem for fuel gas utilization in downstream applications. This paper investigated tar removal, by the two-step function of decomposition and adsorption, from the pyrolysis gas. The temperature of the tar decomposition process was ﬁxed at 800 °C both with and without steam, with air as the reforming agent. Both steam and air had a strong inﬂuence on the tar decomposition reaction. The reduction of the gravimetric tar mass was 78% in the case of the thermal cracking, whereas, it was in the range of 77–92% in the case of the steam and air forming. Under conditions of tar decomposition, the gravimetric tar mass reduced, while the yield of the combustible gaseous components in the syngas increased. Synchronously, the amount of light tars increased. This should be eliminated later by ﬁxed-bed adsorption. Three adsorbents (activated carbon, wood chip, and synthetic porous cordierite) were selected to evaluate the adsorption performance of light tars, especially of condensable tar. Activated carbon showed the best adsorption performance among all light tars, in view of the adsorption capacity and breakthrough time. On the other hand, activated carbon decreased the efﬁciency of the system due to its high adsorption performance with non-condensable tar, which is a combustible substance in syngas. Synthetic porous cordierite showed very low adsorption performance with almost all light tars, whereas, wood chip showed a high adsorption performance with condensable tar and low adsorption performance with non-condensable tar. When compared with other adsorbents, wood chip showed a prominent adsorption selectivity that was suitable for practical use, by minimizing the condensable tar without decreasing the efﬁciency of the system. Ó 2009 Elsevier Ltd. All rights reserved.
Article history: Received 12 August 2009 Received in revised form 29 November 2009 Accepted 1 December 2009 Available online 29 December 2009 Keywords: Biomass pyrolysis Tar removal Tar decomposition Thermal cracking Reforming Tar adsorption
1. Introduction Pyrolysis is one of the thermal conversion technologies for liquid fuel production and gas fuel production. Despite a low efﬁciency of gas fuel production, pyrolysis has the signiﬁcant advantage of a higher heating value for the producer gas when compared to the gasiﬁcation process. The pyrolysis process requires lesser carrier gas quantity, a small capacity of downstream gas cleaning. Moreover, controlling of the pyrolysis process is not complicated. For pyrolysis gas application, the liquid production as well as the tar should be converted to gas, or minimized, in order to prevent the damage of downstream applications and improve the gas production efﬁciency. Tar is an undesirable material typically described as a complex mixture of condensable hydrocarbons, which include single-ring to multiple-ring aromatic compounds along with other oxygen-containing hydrocarbons that easily condense in ambient conditions [1,2]. The condensable tar deposits on the gas pass-way may cause blockage and corrosion
* Corresponding author. Tel.: +81 45 924 5507; fax: +81 45 924 5518. E-mail address: email@example.com (T. Phuphuakrat). 0306-2619/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.apenergy.2009.12.002
of the downstream equipment. This problem necessitates frequent maintenance of the downstream equipment, resulting in lower plant reliability. Without the appropriate gas cleaning processes, higher investment is required for the duplicate installation of some downstream equipment, in order to operate the plant continuously . There are ﬁve classes of tar: (1) undetectable, (2) heterocyclic, (3) light aromatic hydrocarbons, (4) light polyaromatic hydrocarbons, and (5) heavy polyaromatic hydrocarbons [3,4]. Excluding the light aromatic hydrocarbons, the others are considered as problematic, as they condense at an ambient temperature. Thermal decomposition is one conventional method used to convert tar to gas with high temperature and long residence time. Besides this effect, the tar is also converted into refractory tar . In other words, thermal decomposition is able to minimize tar quantity and increase the yield of producer gas. In order to elucidate tar decomposition during the thermal tar decomposition process, many researchers have utilized one or numerous aromatics as model biomass tar compounds, to investigate the decomposition behavior [1,6–10]. Yet, those studies are based on aromatic combinations modeled as biomass tar compounds, and therefore, cannot be practically applied to the real process. Some papers have
% dry basis) Volatile matter Fixed carbon Ash High heating value (MJ/kg) Ultimate analysis (wt. was made of stainless steel with an inner diameter of 25 mm and a length of 1300 mm. ﬁxed-bed adsorption is installed to remove the refractory tar in the system in order to capture the remaining tar. Quantitative information on the major tar components on account of the ﬁrst step of thermal decomposition during the process is acquired.4 0. and their changes were compared with the result of the pyrolysis condition. before being supplied into the reformer for supporting the tar decomposition reaction. while the ER is deﬁned as the actual amount of air supplied to the reformer divided by the stoichiometric amount of air for complete combustion of the feedstock. / Applied Energy 87 (2010) 2203–2211 reported on the effect of thermal cracking and reforming by using real biomass. and synthetic porous cordierite.1. which were carried out of the pyrolyzer by nitrogen. but also in the concentration of major tar compounds. The parameters of steam and air reforming used to observe the effect on tar decomposition are given by the steam to biomass (S/B) ratio and the equivalent ratio (ER).% dry-ash free basis) C H N O S Cl 80. Phuphuakrat et al. This paper aims to improve pyrolysis production by converting pyrolysis tar to fuel gases and minimizing condensable tar by using the two-step function of decomposition and adsorption. for the purpose of fuel gas application. before it was packed in the feeder. we have contributed ﬁxed-bed adsorption as an additional equipment. wood chip. All experimental conditions of tar decomposition are summarized in Table 2.5 l/min. Although higher temperature and increasing reforming agents are able to meet the tar concentration requirement.00 mm. In the tar decomposition experiment. in order to prevent downstream equipment damage from the remaining tar. Wood chip is selected because they are low cost adsorbents. which was kept at 400 °C.6 g/min. Schematic diagram of the experimental equipments. to remove moisture. the pyrolyzer was heated up to a temperature of 600 °C and kept at this temperature for 30 min before starting the feeder. Biomass pyrolysis A schematic representation of the experimental setup is shown in Fig. When the feedstock was introduced into the pyrolyzer. 2. To optimize the system with maximum cold gas efﬁciency the remaining tar must be removed with the help of an additional approach. the effect of each reforming condition was investigated on the basis of the change in gravimetric tar mass and concentration of tar compounds.2204 T. the heating value and the cold gas efﬁciency will signiﬁcantly decrease . Their adsorption characteristics have been compared with those of activated carbon with real biomass tar. respectively. Activated carbon is the most widely utilized adsorbent selected for adsorption of volatile organic compounds (VOCs). using three kinds of adsorbents. The entire pyrolysis product in the form of gas was supplied directly into the reformer. 2. due to its high adsorption capacity.3 49. and consequently. the information on using real biomass tar is rare. The feedstock was introduced into the pyrolyzer by a controlled screw feeder with a continuous feed rate of 0. Material and methods 2. in order to avoid tar decomposition or condensation.1 43. but the qualitative and quantitative information of each refractory tar compound is rare. The proximate and ultimate analysis results of the feedstock are summarized in Table 1.71–1. Tar decomposition Pyrolysis tar decomposition experiments under different reforming agents were carried out in an externally heated reactor. 1. Moreover. Although many researchers have demonstrated the adsorption performance of many kinds of activated carbon by using tar model compounds [13–16]. and synthetic porous cordierite is selected because it is a re-usable (regenerable) adsorbent. In each experiment. Fig. where the S/B ratio is deﬁned as the steam mass ﬂow rate divided by the feedstock mass ﬂow rate on the dry basis. wood chip. In the studies of steam and air reforming. Japanese cedar Proximate analysis (wt.1 . water and fresh air were heated up to the temperature of reforming. especially for class 3 and class 4 of tar. activated carbon. that is. The product of the pyrolysis process was sampled at the exit of the reformer. Thus.1 <0. are compared by their adsorption in a wide range of tar compounds from the real biomass tar. the feedstock released its volatiles in the form of syngas and tar aerosols.8 <0. called as the reformer. of 1. The feedstock was dried at a temperature of 105 °C overnight in an oven. we studied the real biomass and investigated the change not only in the gravimetric tar mass (total mass of tar) .3 19. and was surrounded by an electric heater.7 6. and synthetic porous cordierite. the performances of the three adsorbents.8 18. which are activated carbon. which are components of biomass tar. it cannot be practically applied to the real process due to a decrease in the efﬁciency of the system. In this paper. The pyrolyzer reactor was made of stainless steel with an inner diameter of 30 mm and a length of 280 mm.9 0. used as a carrier gas. 1. in order to ensure that pyrolysis tar production should be done under a steady-state operation. and entered the gas cleaning equipment with the ﬂow rate Table 1 The proximate and ultimate analysis of wood chip. Finally. As the second step. the literature carried out on the model tar compound. The feedstock was prepared from Japanese cedar. has been conducted to study the adsorption characteristics of real biomass tar. The reactor.2. arranged in class 3 of tar (non-condensable tar) . crushed and sieved with a mesh size of 0. Fixed-bed adsorption.
Each impinger bottle was ﬁlled with approximately 100 ml of isopropanol. placed separately in two cold baths. the collection efﬁciency of light PAH (polycyclic aromatic hydrocarbon) tars and heavy PAH tars (larger than the four-ring aromatic hydrocarbon) by dry type sampling was lower (approximately 25% for light PAH tars) than that with the wet type sampling method. toluene. A simple method for dry type tar sampling and analysis has been introduced in our previous study. In contrast.5 200 37.. equivalence ratio = actual amount of air supplied to the reformer/stoichiometric amount of air for complete combustion of the feedstock. Ltd. Adsorbent Shape Mean particle diameter (mm) Volume of adsorbent (cm3) Weight of adsorbent (g) Advantage Manufacturer/ source material Activated carbon Granular 4 200 85. the content of the impinger bottles were ﬁltered through a ﬁlter paper. The tar aerosols were collected by both condensation and absorption in the solvent. using adsorption and condensation strategies. and synthetic porous cordierite were selected to study the adsorption ability of tar compounds and to compare them with the adsorption ability of activated carbon. the tar removal performance was indicated by a decrease in either gravimetric tar mass or concentration of light tar compounds.3. without any heat exchanger device. The isopropanol bath was cooled by a mechanical cooling device to maintain a temperature under À20 °C which tar and moisture will be completely collected. the next four impinger bottles were immersed in isopropanol. indene. The reformed gas was cooled down to the temperature of 25–30 °C by natural convection. Pyrolysis Pyrolyzer temperature Reformer temperature Reforming agent Steam to biomass ratio Equivalence ratio 600 400 – – – Thermal cracking 600 800 – – – Steam reforming 600 800 Steam 2 3 – – Air reforming 600 800 Air – 0.1 Good adsorption performance Ajinomoto Fine Techno Co. The wet type method This tar and particle sampling system consists of the tar collection module and the backup VOC collector as shown in Fig. which was considered to be the most suitable solvent for tar absorption . respectively. Therefore. the use of Table 3 Adsorbents for tar adsorption study. The charcoal tube mainly adsorbs non-polar organic compounds without any cooling requirement. On the other hand. The dry type sampling method was chosen for the purpose of tracing a change in tar concentration. Phuphuakrat et al. The previous study also reported higher measurement efﬁciency for light tar when compared to wet type tar sampling. the dry type was selected to investigate the change in concentrations of tar compounds by adsorption treatment. Tar adsorption Adsorption studies were carried out using a ﬁxed-bed type adsorber. the wet type needs long sampling period that cannot be used for a study on tar aerosol adsorption characteristics. which has a good adsorption performance to adsorb hydrocarbons. The accuracy of sampling is approximate 90. xylene. / Applied Energy 87 (2010) 2203–2211 Table 2 Experimental conditions for tar decomposition. anthracene.1. to facilitate the study on tar adsorption. and pyrene. phenanthrene.T.0–1. which contained a lot of heavy tar and products of the reformer. Tar sampling and analysis The sampling of tar was done using either the wet type or dry type of sampling method at each sampling port.3 2205 1 – – 0. whereas. in a glass tube with an outer diameter of 6 mm.2–29%) . due to the low sampling temperature . Inc. which may have passed through the impinger train. 2. These sampling tubes are commercially available. In case of wood chip. the ﬁrst was used to determine the gravimetric tar mass by means of solvent distillation and evaporation. Wood chip. whereas.4% tested by the manufacturer for some aromatic hydrocarbon standards. Before starting the tar adsorption experiments. In this study.4. 2. The charcoal tube contains a double layer of activated carbon of 100 mg and 50 mg.8 l/min was passed through a total of 10 impinger bottles (250 ml). Immediately after completing the sampling. 2. Wood chip Chip 1. which was installed downstream of the reformer. The dry type method The dry type sampling method collects tar aerosols. However. and the second was used to determine the concentrations of light tar compounds using ﬂame ionization detector type gas chromatography (GC-FID).. supplied by Sibata Scientiﬁc Technology Ltd. . The ﬁltered isopropanol solution was divided into two parts. 2.2 – 0.4 Re-usable (regenerable) Chemical Auto Co. phenol. at room temperature . The accuracy of sampling was taken by BTG which reported in term of repeatability (5. The entire reformer product was supplied directly into the adsorption bed through a high temperature resistance tube connector. Two sampling ports were located at the exits of the reformer and the adsorption bed as shown in Fig. A set of backup VOC adsorber was installed downstream of the series of impinger bottles to protect the column of the gas chromatography from the residual solvent or VOCs.4. in a glass tube with an outer diameter of 8 mm. The characteristics of each adsorbent are summarized in Table 3. naphthalene. The wet type (cold trap) is generally selected for the measurement of organic contaminants and particles in the producer gas from pyrolysis or the gasiﬁcation process. that is. styrene. Therefore. as the same type of feedstock. 1. under room temperature. the reformed gas was bypassed from the adsorption bed for 30 min in order to ensure that the upstream reactions were under a steady-state condition.9 Low cost Japanese cedar Synthetic porous cordierite Pellet 4 200 109. using a charcoal tube and a silica gel tube connected in a series. and the silica gel tube mainly adsorbs polar organic compounds. The wet type tar sampling used in this study was taken followed by the sampling and analysis tar of Biomass Technology Groups (BTGs). 2.9–97. with a short sampling time. The sampling gas with the controlled volume ﬂow rate of approximately 0. benzene. the silica gel tube contains a double layer of silica gel of 520 mg and 260 mg.4.4 Steam to biomass ratio = steam mass ﬂow rate/feedstock mass ﬂow rate in dry basis. the wet type was selected to collect and measure products of the pyrolysis. The ﬁrst six impinger bottles were immersed in a mixture of salt/ice/water at a temperature below 5 °C.2. it was dried in a controlled oven at a temperature of 105 °C overnight before using as an adsorbent. especially for light tar measurements. The set of backup VOC adsorber consists of two cotton ﬁlters and an activated carbon ﬁlter connected in a series. The tar collection module consists of two series of impinger bottles containing a solvent for tar absorption. so as to determine the tar removal efﬁciency of the reformer. respectively. as these tars might have condensed before sampling.
23.2206 T. a ﬂow control valve.05–0. Without any addition of reforming agents. and a suction pump. 3. to prevent evaporation of the adsorbed tar. these tubes were kept in a refrigerator.5. in accordance with the IUPAC recommendations. next to the sampling tubes.12 Gravimetric tar 0. Dry type tar sampling train. over the relative pressure range of 0. whereas. The Barrett–Joyner–Halenda (BJH) approach was used to calculate the pore size distribution using the adsorption data. USA). Sampling port Charcoal tube Silica gel tube Purge P Suction pump Flow control valve Flow meter Fig. Effects of tar decomposition by thermal cracking and reforming The high temperature reaction had a signiﬁcant effect on tar decomposition. using an Autosorb-I instrument (Quantachrome. a reduction of 78% in the 0. the silica gel tube was desorbed by acetone of 2 ml in each layer. Tar mass contribution before and after decomposition. More details about dry type tar sampling and analysis have been described in our pervious paper . The gas sampling controller consists of a ﬂow meter. 4. Wet type tar sampling train.5 K. The Bruanuer–Emmett–Teller (BET) approach using adsorption data in the linear part. respectively.02 0. 1.08 0. Phuphuakrat et al. 2. Results and discussion 3. The charcoal tube was desorbed by carbon disulﬁde of 1 ml in each layer.10 g/g-feedstock 0. 4. The effects of tar decomposition were observed by changing either the quality or quantity of the reforming agents. the sampling was done at the gas sampling ports located at the inlet and exit of the adsorption bed as shown in Fig.06 0. 3. both the charcoal tube and the silica gel tube ensures that all organic compounds will be collected in the sampling tubes.14 0. The experimental results for gravimetric tar mass reduction under different cracking and reforming conditions are summarized in Fig.04 0.1.999.00 Fig. The gas was sampled with the constant ﬂow rate of 0. was utilized to determine the speciﬁc area of the samples. 2. / Applied Energy 87 (2010) 2203–2211 Suction pump Purge Flow adjustor P Flow meter Activated carbon Cotton filter II Cotton filter I GC-TCD Sampling port COOLER Mixture of salt /water/ice bath (Temperature 3± 1° C) Isopropanol bath (Temperature -22± 1° C) Fig. at a constant temperature of 800 °C. Immediately after completing the sampling. The desorbed solution was allowed to settle for 2 h before determining light tar compounds and their concentrations by GC-FID. 3. . and upstream conditions. respectively. connected in a series.5 l/min for 3 min according to the recommendation of the manufacturer of the sampling tubes. as shown in Fig. After switching the gas ﬂow into the adsorption bed. The pore volume was determined from the maximum amount of adsorption at the relative pressure of 0. Porous texture characterizations Characterization of the porous texture of the adsorbents was investigated by determining N2 and Ar gas adsorption and desorption isotherms at 77 K and 87.
It can be attributed to the fact that benzene and naphthalene are stable aromatic compounds that are formed during the thermal cracking reaction. Benzene was present in the S/B ratio of 1. class 4 of tar). Light tar contribution before and after decomposition. Gas concentration before and after decomposition. An increase in carbon dioxide and carbon monoxide after thermal cracking indicated that pyrolysis tar was composed of hydrogen.2 ER = 0. carbon. the gravimetric tar mass decreased. The formation of benzene may need a longer gas residence time in order to break the chemical bonds of the function groups in other light aromatic hydrocarbon tars .4 C2H 4 C2H 6 Fig. By increasing the ER from 0. Phuphuakrat et al. With an increase in the amount of a reforming agent. while only a small portion of the pyrolysis tar can hardly be decomposed. With a high temperature reaction it is possible to break the chemical bonds of heavy tars. Similar gas production by thermal cracking 18 16 14 mol/kg-feedstock 12 10 8 6 4 2 0 H5 CH4 CO CO2 Pyrolysis Thermal cracking S/B = 1 S/B = 2 S/B = 3 ER = 0. It can be stated. It is remarkable that the pyrolysis tar was composed mainly of heavy tars (class 5 of tar). Both steam and air enhanced the tar decomposition reaction. but not in the S/B ratio of two or three. The increase in S/B ratio leads to a decrease in the gas residence time in the reformer. One of the reasons for the enhancement of the formation of light PAH tars in air reforming conditions can be explained by the incomplete combustion of carbon-containing fuels. The increase in the ER also led to a decrease in the formation of light aromatic hydrocarbon tars (class 3 of tar). which results in the formation of lower aliphatic or aromatic hydrocarbons. 5.4. 6. By increasing the amount of steam to the S/B ratio of three. A similar tar decreasing trend was reported with respect to an increase in the amount of a reforming agent . especially for light polyaromatic hydro- carbon tars (light PAH tars. that almost all the pyrolysis tar can be decomposed to light tars and gases. the yields of light tars were obviously increased. The effects of decomposition or formation of light tars are shown in Fig. Signiﬁcant improvement in tar decomposition was observed by using reforming agents. both reforming and thermal cracking increased almost all the light tars (class 3 and 4 of tar). 6 shows the detailed gas distribution before and after pyrolysis tar decomposition by thermal cracking or reforming. In contrast. In air reforming. therefore.2 ER = 0. and oxygen. Thermal cracking had a stronger effect on the production of benzene and naphthalene compared to reforming. gravimetric tar mass was observed under the thermal cracking condition. especially by the partial oxidation of pyrolysis tar. the increases in both light aromatic hydrocarbon tars and light PAH tars were observed by increasing the S/B ratio. Therefore. Fig. 5.3 ER = 0. an increase in all gas products was observed. The highest yield of each light aromatic hydrocarbon tar was observed at the S/B ratio of three. Despite a decrease in the gravimetric tar mass. . the formation of all light PAH tars decreased. / Applied Energy 87 (2010) 2203–2211 2207 6 5 mg/g-feedstock 4 3 2 1 0 Pyrolysis Thermal cracking S/B = 1 S/B = 2 S/B = 3 ER = 0. except for benzene and naphthalene. approximately 22% of the tar mass remained . Similar to the investigation by Rath and Staudinger. however.T.2 to 0. an increase in the S/B ratio resulted in the decrease in benzene content. only a slight decrease in gravimetric tar mass was observed.3 ER = 0. excluding benzene. During thermal cracking. The formation of benzene can proceed via the breakage of other light aromatic hydrocarbon tars.4 Fig.
3 and 0. and carbon monoxide. Comparison of the porous texture characteristics of each adsorbent The porous texture characteristics of each adsorbent were measured (see Table 4). It is remarkable that steam has a strong inﬂuence on their yield. Therefore. In order to clarify the reason for this. it can be considered that the large amount of weight increase in the wood chip is the cause of the adsorption of steam. 3.14.0058 0. in order to improve the porosity. whereas.5569 0. but also water in the form of steam. An increase in the ER led to a decrease in the yield of hydrogen. When we compared the summation of the adsorption capacities of all tar components shown in Table 6 with the overall adsorption capacity shown in Table 5.25]. but not as small as the microporous material.2. Signiﬁcant hydrogen production was observed in the steam reforming conditions. A decrease in the yield of ethylene and ethane was also clearly observed by increasing the S/B ratio.0001 0.0005 0.077 Synthetic porous cordierite 2. Amount adsorbed (g/g adsorbent) Activated carbon Benzene Toluene Xylene Styrene Phenol Indene Naphthalene Phenanthrene Anthracene Pyrene Sum 0.0001 <0. In case of the air reforming conditions.0001 0. which is contradictory to the earlier prediction based on the porous texture characteristics. The substances adsorbed on the adsorbents were not only tar.0004 0. Comparison of the adsorption capacity of each adsorbent The adsorption capacity of each adsorbent for the remaining tar coming from the reformer is presented in Table 5. The activated carbon has pore size in the range of micropore. the numerical integration technique was used to calculate the adsorption capacity of each tar component from their breakthrough curves as shown in Table 6.0083 0.045 0. The evidence of their combustion was observed by the increase in the concentration of carbon dioxide by increasing the ER. The yield of methane at ERs of 0.2.0002 0.0011 0.0001 0.0189 0. Adsorbent Average pore Speciﬁc surface Total pore size (nm) area (SBET. m2/g) volume (ml/g) 987. the one used in this study has been prepared by the manufacturer using its own technique.072 6. Their reactions with steam promoted the production of hydrogen and carbon monoxide [22–24].2.0975 0.0011 0. methane.0001 <0. we can expect activated carbon to show the best adsorption performance.128 Wood chip 10.0128 Fig.1 1.0004 0.2 showed the highest formation of fuel–gas products. 3. The decrease in the yield of each fuel gas was caused by their combustion reactions.0001 <0. The adsorption capacity was evaluated by the weight gain/weight of each adsorbent.1.0007 0. Breakthrough curves of activated carbon: (a) for light aromatic tar adsorption and (b) for light PAH tar adsorption. Moreover.0609 0.0001 0.0027 0.0001 <0. whereas. we can see that both the values are almost the same only in the case of activated carbon. Most practical adsorbents commonly selected for adsorption of hydrocarbons are porous materials in the range of micropore with a high surface area and high pore volume [13. The weight gain of each adsorbent was measured immedi- ately after completing the experiment.0002 0.0010 0.1091 Wood chip 0.4 was less than that in the pyrolysis condition.0007 0. synthetic porous cordierite has a smaller pore size. Phuphuakrat et al.0196 Synthetic porous cordierite <0. the formation of hydrogen and carbon dioxide increased. the results of gas distributions at the ER of 0. produced during pyrolysis and thermal cracking processes. Adsorbent Activated carbon Wood chip Synthetic porous cordierite Amount adsorbed (g/g adsorbent) 0.0001 <0. the steam content in the gas was not completely removed. a decrease in the yield of methane was observed in a condition where the S/B ratio was three. This table indicates that wood chip had better adsorption capacity than activated carbon. the activated carbon adsorbed less amount of steam when compared to the wood chip and Table 4 Porous texture characterization of the adsorbents. By increasing the S/B ratio. Because the hydrophilicity surface and mesoporous material favor water adsorption. / Applied Energy 87 (2010) 2203–2211 Table 6 Adsorption capacity of each tar component. but the formation of carbon monoxide decreased. 7.0001 0.743 Table 5 Adsorption capacity of tar remaining after decomposition. pores of wood chip and synthetic porous cordierite can be arranged in the range of mesopore.0005 0. However.1557 0.2208 T. Carbon monoxide reacted with steam during the water–gas reaction to produce hydrogen and carbon dioxide.0028 has been reported in the other study . As a result.0125 0. although cordierite is generally a macroporous material.0158 0. A huge difference of these two values was observed for wood chip and synthetic porous cordierite.0083 Activated carbon 1.0001 0.2.0033 0. the surface area and pore volume cannot be much improved. Performance of tar adsorption of each adsorbent for ﬁxed-bed adsorption 3. Therefore. . Although the gas stream was cooled down to the temperature of 25–30 °C before being introduced into the adsorption bed.0016 0.
the condensing problem in the downstream equipments will not occur.4. except phenol. the high adsorption performance of activated carbon for all light tars may lead to a decrease in the thermal efﬁciency of the gasiﬁcation system. due to its water solubility. Wood chip. The highest adsorption performance for both light aromatic hydrocarbon tars and light PAH tars was clearly observed from the breakthrough curves of the activated carbon adsorbent. This observation is in agreement with that reported in the study of the adsorption performance of different porous texture characterization materials [13–15].2. . 3. and the value of C/C0 reached 33% after passing for 54 min from the start of the adsorption experiment. From these ﬁgures. In this regard.28. 3. When water is adsorbed on the surface of the wood chip. If light tars can be delivered to a combustor or an engine without their condensation. From the viewpoint of tar decomposition. but the present experimental data do not show any such prominent adverse effects on the adsorption of both light aromatic hydrocarbon tars and light PAH tars.2. the adsorption performances of wood chip for light PAH tars were almost similar to that of activated carbon. according to Linders et al. Some researchers have reported on light tars condensation [3. only the condensable tar (light PAH tars) is recommended to be removed before supplying the syngas to downstream energy converters. where C0 is the inlet concentration of a certain tar component and C is the exit concentration of that tar component. Moreover. Fig. / Applied Energy 87 (2010) 2203–2211 2209 synthetic porous cordierite. under humid conditions.2. The highest adsorption for all light tars of activated carbon can be explained by its porous texture characterization.T. Breakthrough curves of synthetic porous cordierite: (a) for light aromatic tar adsorption and (b) for light PAH tar adsorption. phenol will be captured as it dissolves in the adsorbed water. due to its hydroxyl group structure.2. 9.1. Breakthrough curves of wood chip: (a) for light aromatic tar adsorption and (b) for light PAH tar adsorption. 7–9. Not all light tars cause condensing problem. Phuphuakrat et al. Activated carbon.. and thermal efﬁciency can be improved by the effective use of the caloriﬁc value of light tars.3. The present experiment showed that activated carbon could reduce the concentration of residual condensable tar down to approximately 65 mg/m3. the amount of residual tar in the syngas was very small and at the permissible level for downstream components. They argued that tar condensation is related to the properties and compositions of tar. their breakthrough times were longer than the period of experiments. Fig. due to its high adsorption performance for noncondensable tar. Some papers have also reported that the adsorbents had a negative inﬂuence of the presence of carbon dioxide and steam on hydrocarbon adsorption [13. Comparison of the adsorption performance of each adsorbent The breakthrough curves of each adsorbent for each tar component are shown in Figs.27]. except for naphthalene. On the other hand. most of heavy tars were cracked or reformed into light tars and gases in the reformer. the adsorption performance of each adsorbent can be found as follows: 3. the surface chemistry of wood chip also inﬂuences the adsorption of phenol. After passing through the activated carbon adsorbent. In addition. who studied the adsorption equilibrium of hexaﬂuoropropylene (HFP) on Norit R1 carbon. It is noted that this micropore material with a higher pore volume and larger surface area is the best adsorbent for all light tars. Moreover.3. Wood chip could not adsorb most of the light aromatic hydrocarbon tars. Therefore.3.29]. while the caloriﬁc value loss reaches to approximately 20%. The naphthalene concentration at the exit of the adsorption bed gradually increased. 8. HFP vapor was adsorbed in the mircopore volume left free by water due to the miscible solvent of HFP and water .
3. the gravimetric tar mass decreased. A smaller size of the wood chip and a lower gas ﬂow rate may improve the condensable tar adsorption performance. It was mainly designed to remove the light tars formed during the tar decomposition process in the reformer.2. References  Devi L. To improve the efﬁciency of tar reduction. ECN-02-090.  Könemann HWJ. Ind Eng Chem Res 2002. Effects of reactor severity on the gas-phase pyrolysis of cellulose. Version 3.  Antal MJ. Tar decomposition also had the beneﬁt of increasing syngas production. synthetic porous cordierite adsorbed light tars well at the beginning of the experiment. Berlin. The non-condensable tar could be combusted in the downstream combustion equipment. J Jpn Inst Energy 2007. the exit concentration was only less than 10% of the inlet concentration even at the end of the experiment. Callen MS. Farriol X. Boerrigter H. Lopez JM. Considering both the adsorption performance and the capacity of synthetic porous cordierite for light tars. Synthetic porous cordierite.44:1455–63.24:125–40. Thomas KM. van Paasen SVB.22:366–75.  Lillo-Ródenas MA. The maximum tar reduction rates were approximately 88% and 92% by steam and air reforming. Three different adsorbents were conducted to study their performance of light tar removal.42:155–61. / Applied Energy 87 (2010) 2203–2211 The breakthrough curves showed that wood chip did not adsorb non-condensable tar. for engines. That is. Smaller size of wood chip and slower gas ﬂow rate were expected to improve the adsorption performance of wood chip. Knoef HAM. Handling non-condensation tar led to an increase in the cost of gas treatment as well as a decrease in the thermal efﬁciency of the system. France: Strasbourg. Montané D. Catalytic upgrading of tarry fuel gases. Fuel 1996. without condensing.88:243–50.  Bergman PCA.3. as non-condensable tar adsorption was poor. 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