Tyre Pyrolysis | Gas Chromatography | Gas Chromatography–Mass Spectrometry


Emissions of polycyclic aromatic hydrocarbons (PAHs) from the pyrolysis of scrap tires
Shui-Jen Chena,c, Hung-Bin Sua, Juu-En Changb,c, Wen-Jhy Leeb,c, Kuo-Lin Huanga,c,Ã, Lien-Te Hsieha, Yi-Chu Huanga, Wen-Yinn Lind, Chih-Chung Lina
Department of Environmental Engineering and Science, National Pingtung University of Science and Technology, Nei Pu, PingTung 91201, Taiwan, ROC b Department of Environmental Engineering, National Cheng Kung University, Tainan 70101, Taiwan, ROC c Subtainable Environment Research Center, National Cheng Kung University, Tainan 70101, Taiwan, ROC d Institute of Environmental Planning and Management, National Taipei University of Technology, Da An 106, Taipei, Taiwan, ROC Received 17 June 2006; received in revised form 5 September 2006; accepted 22 September 2006

Abstract This work investigated the PAHs generated in a waste-tire pyrolysis process and the PAHs removal by a wet scrubber (WSB) and a flare. IND, DBA, and BaP were found to dominate in the powders of scrap tires before the pyrolysis. The PAHs in the carbon blacks formed in the pyrolysis were mainly 2-, 3-, 6-, and 7-ring PAHs. Nap was the most predominant water-phase PAH in the WSB effluent. About 40% of the water-phase total-PAHs in the WSB effluent were contributed by nine carcinogenic PAHs. NaP, IND, and COR displayed higher mean gas- and particulate-phase concentrations than the other PAHs in the flare exhaust. The mean removal efficiencies of individual PAHs, total-PAHs, and high carcinogenic BaP+IND+DBA were 39.1–90.4%, 76.2%, and 84.9%, respectively for the WSB. For the flare, the mean removal efficiencies of gaseous, particulate, and combined (gaseous+particulate) total-PAHs were 59.8%, 91.2%, and 66.8%, respectively, whereas the removal efficiencies were 91.0%, 80.1%, and 89.1%, respectively for the total-BaPeq. However, the gaseous BaA displayed a negative mean removal efficiency. The total PAH emission rate and factor estimated for the scrap tire pyrolysis plant were 42.3 g dÀ1 and 4.00 mg kg-tireÀ1, respectively. r 2006 Elsevier Ltd. All rights reserved.
Keywords: PAHs; Pyrolysis; Tires; Air pollution control devices (APCDs)

1. Introduction In the past few years, over 2,500,000 ton of tires were produced per year in the European Union and
ÃCorresponding author. Department of Environmental Engineering and Science, National Pingtung University of Science and Technology, Nei Pu, PingTung 91201, Taiwan, ROC. Tel.: +886 8 7703202X7092; fax: +886 8 7740256. E-mail address: huangkL@mail.npust.edu.tw (K.-L. Huang).

this figure was similar in the USA (Mastral et al., 2000). About 103,054 ton of scrap tires were recovered in Taiwan in 2005 (Taiwan EPA, 2005). The production/consumption of tires is growing recently; however, it is environmentally concerned for the disposal and recycling of waste tires. Pyrolysis techniques can be used to treat or recycle the waste tires. Via pyrolysis, scrap/waste tires can be decomposed in the absence of oxygen in

1352-2310/$ - see front matter r 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.atmosenv.2006.09.041

Table 1 lists the specified operating conditions for the different units in the scrap tire pyrolysis process. Moreover. especially under pyrolytic conditions in N2. In the oil from tire pyrolysis. Therefore. They also found that the char had a high fixed-carbon content and could be used to manufacture category-A briquettes. pyrolysis products. 1). They suggested that pyrosynthesis was the major contributing mechanism to the PAH emissions from the combustion of these fuels and the survivability of parent PAHs was a minor mechanism at very high equivalence ratios. The contents/concentrations of PAHs in the scrap tires. the upcast location of the carbon black storage (Site B). The sampling system of PAHs For solid material sampling (at Sites A and B). and polybutadiene rubber (BR). CO2. $30 g of scrap tire powders and a similar amount of carbon black powders were collected using aluminum foils. (2001) reported that the products of automobile tire waste pyrolysis in an N2 atmosphere were approximately 37–40% char.and polycyclic aromatic species that can subsequently form PAHs (Williams and Bottrill. and naphthothiophenes and their methyl derivatives). The thermal decomposition of tires could be related to tire composition and temperature. little information about the characteristics of PAHs emitted from the pyrolysis of scrap tires is available. Laresgoiti et al. (2002) using a pyrolyzer with high heating rates. sulfur and chorine are concentrated in solid carbon residues although the chlorine in liquid and gas fractions is negligible (Diez et al.1. Therefore.. rinsed with . Gonzalez et al. The samples were taken at five sites (A–E) in the pyrolysis process as shown in Fig. 55% oil. the location of WSB effluent (Site C). the product distribution ratio of gas/tar/char was about 21/44/35 at 800 1C and more gases were identified in a study performed by Leung et al. liquid.. 2004). leading to the production of solid carbon residues. Moreover. They indicated that SBR and NR decomposed mainly at high and low temperatures. CH4. (2000) found that no significant influence of temperature on tire pyrolysis for the yields of solid. whereas BR decomposed at both high and low temperatures.ARTICLE IN PRESS high temperature. and the exit of stack flue gas (Site E). After the pyrolysis of tires. and the samples collected before/after the APCDs were determined.2. increasing pyrolysis temperature increased the concentrations of PASHs due to a Diels–Alder-type aromatization reaction. and the gases were identified as H2. the char yield from the rubber tire pyrolysis was about 32–42 wt% but that from the pure rubber component pyrolysis were all o4 wt% to suggest that the main source of char was the carbon black component in tires. condensable fractions and gases (Diez et al. In another study. The scrap tire pyrolysis plant and its operating condition The scrap tires used in this work were from a pyrolysis plant (in southern Taiwan) that collected used or waste tires mainly from scrap heaps or motor repair shops. 2. it is also possible to generate PAHs in the pyrolysis of tires. 2004). aliphatic and aromatic hydrocarbons and hydroxyl compounds were the major components of the oil. Williams and Bottrill (1995) identified sulfur-polycyclic aromatic hydrocarbons (PASHs. During operation. These five sampling points include the feeding inlet of scrap tires (Site A). The removal efficiencies of these APCDs were compared and the total PAH emission rate and factor for the scrap tire pyrolysis plant were estimated. respectively. 1. Williams and Besler (1995) pyrolyzed the major components of rubber tires: styrene–butadiene rubber (SBR). Atal et al. the alkenes and dienes generated from alkanes pyrolysis may react together to produce mono. Experimental 2. the sampling time covered all the consumed time periods at the five sites. and gas at temperatures over 500 1C. 2. However. 1995). methyl/dimethyl/ trimethyl dibenzothiophenes. CO. mainly dibenzothiophene. The samples ($200 ml each) of WSB effluent (Sites C) were collected using glass bottles (pretreated with 10% nitric acid. Nevertheless. the center of pipe between the 2-stage WSB and flare (Site D). Dissimilarly. this study investigated the PAH emission from a scrap tire pyrolysis plant equipped with two air pollution control devices (APCDs) (a WSB and a flare). and 4–11% gas. (1997) observed significant amounts of PAHs in the effluent of the combustion of pulverized coal and tire crumbs under sufficiently fuel-rich conditions. natural rubber (NR). C2H4 and C2H6. batch feeding of scrap tires was used and the processing time was 4 h for each batch. Through the Diels–Alder aromatization reactions. The scrap tires were powdered by crumbling machines before the pyrolysis (Fig.

For stack flue gas sampling (Sites D and E).. Pyrene [Pyr]. To ensure the good reproducibility. 2001a. the sampling train was rinsed with n-hexane. After each sampling cycle. six . Chrysene [CHR])..90 NA NA NA NA 8200 500 NA 800 distilled water.. all the experiments were repeated at least three times. Acenaphthene [Acp]. four 4-ring compounds (Fluoranthene [FL]. 2001. Tsai et al. Tubetype glass fiber filters (cleaned by heating up to 450 1C) were used to collect particle-phase PAHs. and then wrapped with aluminum foils). The PAH sampling system was equipped with a sampling probe. Lee et al. and a control computer. 1. Each stage sample of the cartridge was analyzed individually and compared to examine the PAH mass collected. a flow meter.ARTICLE IN PRESS Crumbling machines D Vacuumed Scrap tire feeding A Carbon black storage B pyrolysis reactor Oil and gas cooling 2-stage WSB Flare Flue Gas E Oil and water separation WSB effluent C Fig.44 NA NA 0. Phenanthrene [PA]. Anthracene [Ant]). Table 1 Specified operational conditions for the scrap tires pyrolysis process Unit Feeding rate of scrap tires (ton hÀ1) Production rate of carbon blacks (ton hÀ1) Flowrate of wastewater effluent (ton hÀ1) NA 0. 2. the modification of USEPA’s sampling method 5 (MM5) (40CFR60) by Graseby was adopted for the sampling of stack flue gases. A glass cartridge packed with XAD-2 resins and supported by a polyurethane foam (PUF) plug was used to collect the gas-phase PAHs in each sampling. Mi et al. a glass cartridge. 0. Breakthrough tests were investigated using a three-stage XAD-2/PUF cartridge. five 3-ring (Acenaphthylene [AcPy].17 NA Flowrate of stack flue gas (m3 hÀ1) Combustion temperature (1C) Thermal pyrolysis reactor Wet scrubber (WSB) Flare NA: not available.. All samples were stored at 0 1C in an ice chest until they were received at our analytical laboratory. Chen et al. 2001. PAH sampling sites (A–E) in the scrap tire pyrolysis process. The extraction and analysis of PAHs The PAH species determined included a 2-ring (Naphthalene [Nap]). a cooling device. Breakthrough test results showed that no significant PAH mass was collected in the third stage of cartridge. a pump. 1998. 2002). Benzo(a)anthracene [BaA]. Fluorene [Flu]. The flue gases were isokinetically sampled from the stack by a PAH sampling system that has been adopted for sampling PAHs in various industrial stacks (Yang et al. after which they were refrigerated at 4 1C.3..

ion source temperature ¼ 310 1C. IND. and WSB effluent samples were between 0.47 mg LÀ1. carbon black. cleaned via a silica column. 2. The LOQ values of the 21 PAH compounds for scrap tire powder. 0. The response factors of the PAH standard solution were used to calculate the masses of sampled PAHs at the same GC/MS relative retention time (RRT). 100 to 290 1C at 3 1C minÀ1.-cd)pyrene [IND].1%. and reconcentrated by purging with ultra-pure nitrogen to 1. The total recovery efficiencies of PAHs ranged from 74. 4-ring PAHs). middle molecular weight (MMW-PAHs. bottom ash. Perylene [PER]). Controlled by a computer workstation and equipped with a HP-7673A automatic sampler.102 and 2. Benzo(b)fluor anthene [BbF]. The extracts were then concentrated. Quality control and assurance Procedural blanks were analyzed concurrently with the samples. and 0.ARTICLE IN PRESS 5-ring (Cyclopenta(c. 3. The limit of quantification (LOQ) was defined as the limit of detection divided by the sampling volume. splitless injection ¼ 300 1C.023 and 0.8–5. The mean content of total-PAHs was 77 mg gÀ1 in the ..0 or 0. the GC/MS instrument operated with the following conditions: injection volume ¼ 1 ml. and a 7-ring (Coronene [COR]) PAH compounds. For PAHs extraction and analysis. 2-/3-ring PAHs). Field blanks were treated exactly as samples except that no air was drawn through the filter/adsorbent cartridge assemblies. and PUF/XAD-2 cartridges. Quantification of PAHs was according to the retention times and peak areas of the calibration standards.d.d)pyrene [CYC]. and then 290 1C-held for 40 min.524 mg for the 21 PAH compounds.4. Benzo(e)pyrene [BeP]. 0.5 ml prior to analysis. The quantification of PAHs was performed using a selectivity ionmonitoring (SIM) mode. four 6-ring (Indeno(1. The total-PAHs concentration was regarded as the sum of the concentrations of 21 PAH species for each collected sample.17 mm film thickness). Correlation coefficients of the calibration curves were X0. and WSB effluent samples) were extracted in a Soxhlet extraction apparatus for 24 h with 1:1 (v/v) n-hexane/dichloromethane. Benzo(k)fluoranthene [BkF]. Benzo(a)pyrene [BaP].h)anthrance [DBA]. all samples (including stack flue gas.008 and 0.2. glass fiber filters. and high molecular weight (HMW-PAHs. Results and discussion 3.3% and averaged 86. No significant contamination (GC/MS integrated areaodetection area) was found for the field blanks including the aluminum foils. The sums of the concentrations of BaP.32 mm i. A scan mode was employed to determine the masses of molecular and fragment ions of pure PAH standards in GC/MS analysis.999.016 mg gÀ1.3. Analyses of serial dilutions of PAH standards showed the detection limit of GC/MS between 0. Ten consecutive injections of a PAH 610-M standard yielded an average relative standard deviation (RSD) of GC/MS integration area of 3. bottles. oven heating from 50 to 100 1C at 20 1C minÀ1. Benzo(ghi)perylene [BghiP]). No detectable PAHs were present in the procedural blanks. The identification and quantification of PAHs was performed via gas chromatograph/mass spectrometer (GC/MS) measurements using a GC (Hewlett-Packard 5890A) with a Hewlett-Packard capillary column (HP Ultra 2-50 m  0.076 and 0. the GC/MS was routinely calibrated with a diluted standard solution containing 16 PAH compounds (PAH Mixture-610 M from Supleco) plus five additional individual PAHs obtained from Merck.1%. the concentrations of PAH species with low molecular weight (LMWPAHs. Benzo(b)chrycene [BbC]. The recovery efficiencies of 21 individual PAHs were determined by processing a solution with known PAH concentrations through the same experimental procedures used for the samples. To assess the PAH homolog distribution of each sample. PAHs in the feeding scrap tire powders (Site A) The PAH contents in scrap tire powders collected at the A sampling site may provide the inherent PAHs information in the feeding materials. a mass selective detector (MSD) (Hewlett-Packard 5972).8% to 110.1. The system was calibrated with a diluted standard solution containing sixteen PAH compounds (PAH Mixture 610-M from Supelco) plus five individual PAH compounds (from Merk). Dibenzo(a.175 mg N mÀ3.0% with a range of 0. and DBA were also determined to evaluate the carcinogenic potencies of PAH for different cases discussed. In each week. respectively. Mean RSDs of the recovery efficiencies were about 17% and the potential errors for PAHs analysis were around 16%. At least five standard concentrations covering the concentrations of interest were used in PAH analysis calibration. 5-/6-/7-ring PAHs) were determined.

3.1. the content of BaP+IND+DBA was $210 mg gÀ1 and the contents of LMW-. and DBA in the WSB effluent were 8. the IND displayed the highest content (207 mg gÀ1) among the PAHs. The mean content of total-PAHs was dominated by HMW-PAHs. IND.. and 8.16 mg gÀ1) of the mean content of total-PAHs in the feeding powders of scrap tires. 3. Carbon blacks are very fine-powdered elemental carbon and can be obtained from the process of partial combustion or thermal decomposition of hydrocarbons. 2004).. The formation of carbon blacks involves the combustion of vapor-phase hydrocarbons such as semi-volatile organic compounds (e. The PAHs are expected to be formed due to the free radical reactions resulted from the cracking of the feedstocks. respectively. MMW-.e. Contents of 21-PAHs in the scrap tires.e. The contents of other PAHs were less than 2 mg gÀ1.45) mg LÀ1.. The butadiene may precede a series of reactions to form PAHs with different rings (Catallo. IND. The concentration sum of nine carcinogenic PAHs (BaA+CHR+BbF+BkF+ . PAHs in WSB effluent (Site C)/exhaust (Site D) The water-phase PAH concentrations in effluent of the wet scrubber were higher for the 2.82–63. CO2. AcPy. powders of scrap tires (Fig.g. The pyrolysis of scrap tires can produce commercial carbon blacks (Sahouli et al.38 mg gÀ1).76–23...7). and HMW-PAHs were 48. DBA.. 2. respectively. IND and DBA) PAHs than for the others.e. 1998). additionally. 2). PAHs in WSB effluent/exhaust and PAH removal by the WSB 3. and COR). the combustion of these rubbers may generate low-carbon hydrocarbons (e. BghiP.0% (6.9% (8. LMW-PAHs were the predominant water-phase PAHs in the wet-scrubber effluent because the water solubilities were commonly higher for LMW-PAHs than for HMW-PAHs (Lee et al. NaP. 10. and BaP accounted for 71. and 240 mg gÀ1.. 3 shows that the contents of 21 PAHs in the carbon blacks formed in the pyrolysis at Site B were mainly 2–3 rings PAHs (i.3% (54. 1998). Acp. IND. 5. CO.. PAHs). H2) (Diez et al.e.3. 3. and 0. 1996).e. 4).3 (mean ¼ 16. In the carbon blacks.g.8 (mean ¼ 7. and Flu) and 6–7 rings PAHs (i. Nap) and 6-ring (i.9 mg gÀ1). respectively (Fig.22–46.(i. 12. Cryres and Bettens (1989) also indicated that both Nap and PA might be formed from the reactions of gas products generated in the pyrolysis of scrap tires.5 (mean ¼ 46).. The water-phase concentrations of Nap. butadiene) and other compounds (i. PAHs in the carbon blacks (Site B) Fig.ARTICLE IN PRESS 50 Content (µg/g) 40 10 8 6 4 2 0 BghiP Acp CYC AcPy BaA BkF BeP CHR BaP IND Flu PA Ant FL Pyr BbC COR BbF PER DBA Nap PAHs Fig. Styrene–butadiene and NRs are the major components in scrap tires.2.

60 Liquid-PAHs Concentration (µg/l) 40 20 15 10 5 0 Acp CYC BaA BeP BaP PER IND CHR DBA Flu FL BbC AcPy COR Pyr BbF Nap BkF PA Ant PAHs Fig. 3. Concentrations of individual liquid-phase PAHs in the WSB effluent (Site C). 4.ARTICLE IN PRESS 250 200 150 100 Content (µg/g) 50 20 10 0 Pyr BghiP Bghip CYC BbF BkF Acp Ant FL PER IND DBA AcPy PAHs Fig. 1992) was 41. Contents of 21-PAHs in the carbon blacks (Site B). BeP+BaP+IND+DBA+BghiP) with toxicity equivalence factors (TEFs)X0.5 mg LÀ1 accounting for 40% of the water-phase total-PAHs in the WSB effluent.01 (Nisbet and LaGoy. The water-phase mean concentration of IND was approximately 2 folds higher than that of DBA and COR CHR Nap Flu PA BaA BeP BaP BbC .

80% distribution in gaseous phase was observed for AcPy. PER. the mean removal efficiency of LMW-PAHs (74. 3.17 and 11. The high PAH removal by the WSB is possibly associated with the efficient grasp of the PAHs by scrubbing water.5 mg LÀ1 and the mean content of total-PAHs was 104 mg LÀ1 (Table 2). and 76. respectively. the mean effluent rates of individual PAHs and that of total-PAHs were 0. Concentrations of PAHs in the exhaust of flare (Site E) According to Table 3.8%) was similar to that of HMW-PAHs (75.80. and 3. and COR displayed higher mean gaseous phase concentrations (150.9%.17.2%. For the WSB effluent.08. the NaP. respectively) than the others. the mean concentrations of Nap.46 mg N mÀ3. About 90% of CYC and BaP were retained in the gaseous phase.39.05–150 and 182 mg N mÀ3 for individual PAHs and total-PAHs. among the nine compounds. 3. respectively.4. 5). CHR. On the other hand.47 mg N mÀ3. and COR) displayed more fractions in gaseous phase than in particulate phase (Fig. 3.04–3. respectively) than the others.8% of the water-phase total-PAHs. and 5. the two were responsible for 15. the mean residual . IND. the NaP. 5. In the WSB exhaust.378 mg kg-wasteÀ1.ARTICLE IN PRESS 160 Gas-PAHs 140 120 Distribution (%) 100 80 60 40 20 0 Ant FL BbF BkF Flu Pyr PA IND Bghip CYC CHR AcPy DBA COR Nap Acp BaA BeP BaP PER BbC Regression line (Gas-PAHs) Particulate-PAHs Regression line (Particulate-PAHs) PAHs Fig. most PAH compounds (except Pyr.18 mg N mÀ3. Acp. furthermore. respectively) were apparently higher than those of the others. additionally. IND.87 mg minÀ1. With a concentration summation of 94.8 mg mÀ3. For the residual PAHs in sampling tubes. correspond- ing to the mean emission factors of 0.8%) but lower than that of MMW-PAHs (81. Flu. Again. DBA.2. the IND displayed the highest concentration of 51. That the Nap dominated in the flare exhaust is similar to the observations reported by Yang et al. and IND (5.47. 6. the mean particulate phase PAHs concentrations in the flare exhaust were not detected (ND)—1.5 mg mÀ3 whereas the concentration of BaP (the most toxic) was 3.001–0. and COR displayed higher mean particulate phase concentrations (1. respectively. (1998) for various industrial stack gases. the mean gaseous phase PAH concentrations in the flare exhaust were 0. and BghiP. Individual PAH distribution (%) between gaseous and particulate phases in the exit stack flue gas of WSB. 7. and 0. the nine carcinogenic PAHs also distributed mainly in gaseous phase. The mean removal efficiencies of individual PAHs and total-PAHs were 39. Among the PAH species.3.73 and 8. For the WSB.1–90.164 and 0. 4).2% and 6. PAH removal by the WSB The concentrations of individual PAHs in WSB effluent (Site C) ranged 0. BbC. in the effluent (Fig. Nap exhibited the highest effluent rate among the PAHs. PA.4 mg N mÀ3 for the individual PAHs and totalPAHs.4%.40 mg mÀ3. respectively. BkF.03–51. The mean removal efficiency of high carcinogenic BaP+ IND+DBA was 84.1%). respectively. respectively.

0 104 NA 75.and MMW-PAHs than for the HMW-PAHs .06 0.378 NA PAHs mean effluent rate (mg minÀ1) 3.4 84.42 0.39 0.012 0.56 0.39 3.03 0.07 0.7 53.01 0.1 85.03 0.36 2.4 77.2%.22 3.61 0.15 0.10 5.6 Including solid.1 74.01 0.53%).08 0. All the three molecular PAH groups distributed more in the gaseous phase than in the particulate phase.09 1.001 0. respectively.7 78.09 1.05 0.004 0.4 79.8%).16 0. the BaA displayed a negligible mean gaseous+particulate removal efficiency (0.16 and 21.01 2.8 84.012 0.77 26.9 76.8%.229 0.04 0.and water-phase PAHs.6–98. This phenomenon was not found for the particulate BaA.09 0. Catallo. As a result. respectively. the residual LMW.4 68. NA: not available. the combined (gaseous and particulate phases) mean removal efficiencies of individual PAHs and total-PAHs were 39.7 75.9–98.20 0.2 86.4 81.7 76.06 4. BaP+IND+DBA and total-PAHs in the sampling tubes were 5.019 0.7 80.3 84.91 2.004 0.20 0.8 83.70%.1 90.03 0.010 0.22 1.5 2. The mean removal efficiency of particulate PAHs was higher for the LMW.ARTICLE IN PRESS Table 2 PAH removal rates/efficiencies for the WSB (Sites C and D) (N ¼ 7) PAHs Effluent of WSB Site C PAHsa mean concentration (mg LÀ1) Nap AcPy Acp Flu PA Ant FL Pyr CYC BaA CHR BbF BkF BeP BaP PER IND DBA BbC Bghip COR LMW-PAHs MMW-PAHs HMW-PAHs BaP+IND+DBA Total PAHs Total BaPeq (mg-BaPeq/m3) a Exhaust flue gas of WSB Site D PAHs mean emission rate (mg minÀ1) 1.12 0.91 7.35 0.15 0.7 88.15 0. with a removal efficiency of 97.29 0.001 0.6 86.003 0.28 0.85 2.4 PAHs mean Emission Factor (mg kg-wasteÀ1) 0.14 0.2–100% and 91.87 24.12 0.26 1.003 0.08 0.02 0.1 39.0%.3 1.34 2.016 0.7 78.13 0.004 0.60 0.13 1. possibly associated with the aromatization reactions via Diels–Alder mechanisms (Williams and Bottrill.06 0.016 0.31 21. Table 4 shows the removal efficiencies of PAHs for the flare.73 0.164 0.68 0.79 1.39 0.012 0. whereas the mean removal efficiencies of individual particulate PAHs and total-PAHs were 47.01 0.57 0.008 0.05 0.7 mg N mÀ3.02 8.1 75.8 (except the BaA) and 63. respectively.02 0. 1998). 1995.70 0.21 0.8 81.07 0.94 0.81 0.033 0.9 (except the BaA and COR) and 59.and HMW-PAHs whereas the concentration was higher for HMW-PAHs than for LMW.007 0.09 0.9 53.138 0.011 0. Therefore.001 0. The concentration of LMW-PAHs was significantly higher than those of MMW.32 0.21 0.047 0.01 0.03 0.87 171 PAHs mean removal efficiency (%) 51.24 0.005 0. Note that the mean concentration of gaseous BaA increased after the flare treatment to display a negative mean removal efficiency (À38.and MMW-PAHs in the particulate PAHs.21 0. The mean removal efficiency of gaseous COR was only 2.6 84.and HMW-PAHs were apparently more abundant than the MMW-PAHs in the tubes. As a result.16 0.1% for the flare.044 0. For the gaseous PAHs. The mean removal efficiencies of individual gaseous PAH species and total-PAHs were 24.04 0.

65 0.03–0.55 0.2 and 60.47 0. respectively.52 0.57–2.00–533 0.15 0. the emission rates of gaseous.94 0.5 232–11.86 0.23–3. and residual (in sampling tubes) PAHs calculated were 24.55 0. respectively. 2002).4 0.96 ND–0.71 20. APCDs.32 0.23 8. and 66.44 ND 0.7 ND–3.79 0.71–25.7 0.20 0.91 1.58 5.16–16.01–0.39 0.30 0.09–9.54 0.77 ND 0.49 0.93 Range 0.08–2.3% removed by the flare.04–0.01–1.821 Range 0.45 8. when comparing the performance of these APCDs.84 3.35 11.53 ND–13.01–0.8 ND–0.6 0.15 0.72 0.15 0. As a result. 1998).8 114–2685 Residual PAHsa (mg N mÀ3) Mean 5.21. particulate.2 8. the emission factor observed in this study for the scrap tire pyrolysis plant.17–4.01 0. 3.. 2004) in Taiwan.16 ND–0.11–3.57 0.03–0.19 0.56.15 1.68 2.12 0.43 0. This phenomenon cannot be evaluated only using the very limited information from the flare combustion operation (Table 1) because PAHs’ decomposition and formation are very complicated in the thermal treatment.01–0.3 g dÀ1 and 4. The gaseous and particulate BaP+IND+ DBA were 85.95 0.3 0.54 ND–0.02–1.88 0.0 0.4 7.71 0. even after applying APCDs for the PAH emission reduction.9 8.72 0.20 0.34 4.06–17.57 ND–0.54 1.3 0.67 6.15 0.22 0.20 ND–0. respectively.11–6.30 0.24–1.02–29.18 1.6 ND–1.35 0.47 159 2.90 0. and 3. 0.08 0. This observation discrepancy is attributed to the different feeding materials.40 1.07 0.05–53.16 21.39 0. respectively for the pyrolysis plant.03 0.36 Range 0.ARTICLE IN PRESS Table 3 Mean concentrations of gaseous phase and particulate phase PAHs in the exhaust of flare (Site E) (N ¼ 7) PAHs Gaseous phase PAHs (mg N mÀ3) Mean Nap AcPy Acp Flu PA Ant FL Pyr CYC BaA CHR BbF BkF BeP BaP PER IND DBA BbC Bghip COR LMW-PAHs MMW-PAHs HMW-PAHs BaP+IND+DBA Total-PAHs Total-BaPeq a Particulate phase PAHs (mg N mÀ3) Mean 1.49 0.04 0.03–9. to obtain corresponding emission factors of 3.28 0.94 0.6 1.11 0.60 0.13–0.7 2.00–569 125–5251 150 2.25 0.11–543 0.17 0. more PAHs were removed by the WSB than by the flare.8%.82–5.08–22.63 5.57 0.00 mg kg-tireÀ1.03–0.28 0. 1.05 ND–0.02–1.63 0. ND: not detected.09–61. steel/iron plants (Yang et al.17 0.8%. This emission rate was apparently greater but the emission factor was significantly smaller when compared with those reported by Lee et al.40 mg kg-tireÀ1.6 0.36 ND–0.2%. The mean removal efficiencies of gaseous.15 0. and processes used in the two different studies mentioned.6 3.05–7.03–0..01–1.43 ND–2.54 0.26 0.39.00 mg minÀ1.25–11.02–31.07–0.52 0.7 0.01–0.05 1.12 0.05 0.73 ND–4.15 ND–1.46 0. and combined (gaseous+ particulate) total-PAHs were 59.74 ND–4.25 0.47 0.001–0.23–18.95 Residual PAHs in sampling tubes.05–1. respectively (Table 5). and 0.5.25 0. However.61 ND–0.01–3.49 7.76 1.75 1.56 0.60 1.23 0.22 182 1.09–28.15 0.09 0.90 6. particulate.56–20.02 0.8 8.11 ND–0.08–23. The above results warrant .36 ND–9.06 0.79–26.44 0.46 0.13 0.01–0.19–2.9. was close to that for a heavy-oil-fired boiler but higher than those for a power plant (Yang et al.25–7. Emission rate and factor According to Tables 1–4.46 3.97 ND–0.46 2..64 0.22–20. but a reverse trend was found for their gaseous phase removal efficiencies.06–0. the total PAH emission rate and factor estimated for the scrap tire pyrolysis plant were 42.68 0. (2002) for two medical waste incinerators (MG-MWI and FG-MWI) although the PAH emission concentration was smaller in this study (Table 5).6 1.33 0.39 0. Nevertheless.77 0.83 11. and a coal-fired boiler (Chen et al.02–0.80 0.78 ND–0.86 0.19 0. 91.09 0.92 ND–3.29–6.19–4.02 0.49 ND–3.10–27.80 0.

8 2.6 86.8 0.15 0.c.25 4. a The mean concentration of total-PAHs with APCD treatments. c The mean value of twelve steel/iron plants. 587b NA NA NA 844a.12 0.13 3. (2002) Chen et al.60 0.91 1.5 93.0 92.68 2.62 279 11.95 POUT 1.69 65.98 3.15 0.09 10.3 91. P: particulate phase.9 2.6 8.47 159 2.60 1.8 98.28 0.93 1.3 26.5 92.0 99. (2002) Lee et al.44 ND 0.25 0.4 95.6 80.67 6.9 53.8 97.6 85.87 5.1 (G+P)R 39.00 24.12 0.1 163 55.34 1.3 80. 1360b.15 1.06 0.17 0. PR ¼ [(PINÀPOUT)/PIN] Â 100%.3 95.86 0.09 0.8 94.12 3.6 70.3 NA NA NA NA Emission factors (mg kg-wasteÀ1) 4.3 97.8 9.97 0.2 100 86.49 7.40 0.2 12.05 0.75 8.1 78.08 0.72 0.7 98.47 0.8 91.90 6. (1998) Yang et al.30 0.4 88.60 2.4 60.5 88.0 69.40 1. G: gaseous phase.8 89.5 91.55 1.7 PIN 52.5 96.2 80.0 95.6 66.9 85.83 0.4 79.6 0. MWI: medical waste incinerator.02 0.6 96.40 1.23 0.17 0.2 98.46 2.47 2.9 20.0 94.11 0.6 87.43 1.70 43.2 97. (2004) Yang et al.ARTICLE IN PRESS Table 4 Removal efficiencies of PAHs for the flare (N ¼ 7) PAHs PAHs mean concentrations in the entrance of flare (mg N mÀ3) GIN Nap AcPy Acp Flu PA Ant FL Pyr CYC BaA CHR BbF BkF BeP BaP PER IND DBA BbC Bghip COR LMW-PAHs MMW-PAHs HMW-PAHs BaP+IND+DBA Total PAHs Total BaPeq (mgBaPeq/Nm3) 199 21.25 0.6 16.4 71.71 20.9 97.55 0.4 453 21.8 89.7 73.5 57.79 9.95 0.32 2. b The mean concentration of total-PAHs without APCD treatments. (2002) MG: mechanical grate.78 2.0 75.7 83.58 5.30 0.5 60.36 5.2 8.1 53.5 13.9 À38.51 5.6 83.2 91.5 21.01 0.93 PAHs mean removal efficiencies (%) GR 24.6 87.7 12.1 82.0 PR 97.1 98. (1998) Yang et al. 1290b 497a.35 11.4 0.23 8.3 83.2 3. .2 59.4 89.3 80.4 62.4 89. PAHs mean removal efficiencies (%): GR ¼ [(GINÀGOUT)/GIN] Â 100%.13 0.38 12.3 91.6 95.6 95. and (G+P)R ¼ {[(GIN+PIN)À (GOUT+POUT)]/(GIN+PIN)} Â 100%.c Emission rates (g dÀ1) 42.1 83.0 91. FG: fixed grate.0 129 4.53 94.7 1.35 0.15 0.4 97.06 2.4 2.0 94.68 5.0 82.9 90.0 93.1 86.5 47.75 1. Table 5 Comparison of PAH emission rates and factors for different sources in Taiwan Sources Concentrations (mg N mÀ3) 215a 1094a. NA: not available.08 13.22 182 1.8 91.06a References Scrap tires pyrolysis plant MG-MWI FG-MWI Coal-fired boiler Heavy oil boiler Power plant Steel/iron plant This study Lee et al.24 2.9 38.9 84.05 1.1 ND: not detected.69 3.59 2.7 PAHs mean concentrations in the exit from the flare (mg N mÀ3) GOUT 150 2.47 0.12 0.9 88.04 50.7 99.

H. The total-BaPeq mean removal efficiencies for the gaseous and particulate PAHs were 91.. additionally. IND.46 mg N mÀ3.. P. References Atal..F. NSC92-2211-E020-009.7 mg N mÀ3 for gaseous and particulate phases PAHs. Production of Benzoles and active carbon from waste rubber and plastic materials by means of Pyrolysis with simultaneous post-cracking. Aerosol Air Quality Research 1. respectively. the mean removal efficiencies of gaseous individual (except the BaA and COR) and total-PAHs were 24. Chemosphere 37. the highest content]. Evaluation of BaP-equivalent carcinogenicity The TEFs estimated by Nisbet and LaGoy (1992) were adopted in this study to obtain the toxic potency (relative to that of BaP) of each PAH species.08.. 76.1–90... respectively. Fuel 83.9%. more PAHs were removed by the WSB than by the flare.95 and 0. and 84. B. 2004. Combustion and Flame 110. and the combined (gaseous and particulate phases) total-BaPeq mean removal efficiency was 89.2%. Acknowledgments The authors would like to thank the Taiwan National Science Council for financially supporting this research under Contract No..0% and 80.93 mg N mÀ3. Therefore..J. respectively.. respectively. 143–157. B. Y. 2001b)) It is found that the total-BaPeq content in carbon black was about 24. 91. G. The total emission rate and factor estimated for the scrap tire pyrolysis plant were 42. respectively) than the other PAHs. Chen.. Cryres.. Acp and Flu). Distributing mainly in gaseous phase.2%. 3. respectively. DBA. 781–790.36 mg N mÀ3 (Table 3). and high carcinogenic BaP+IND+DBA were 39. Y.. Fu. (BaPeq ¼ TEF Â PAH concentration (Mi et al. whereas these efficiencies were 47. R. the mean content of totalPAHs was 77 mg gÀ1 dominated by HMW-PAHs (IND.A. Chen.2% % for particulate individual. For the flare.6–98. LMW-PAHs (Nap) were the predominant water-phase PAHs in the wet-scrubber effluent.Y. 1989. Bettens. respectively. The flare displayed 91. Catallo.47 mg N mÀ3. In the flare exhaust. Bi.6% in total-BaPeq (Table 2)..00 mg kg-tireÀ1.. Dunayevskiy.6. AcPy. particulate. Vouros. 4. the WSB exhibited a removal efficiency of 86..C. Y. total-PAHs.0%. BeP. X. Wei. G. for the flare. Furthermore. particulate.8%. respectively) and particulate-phase concentrations (1. whereas the concentrations were lowered to 1. BghiP and COR). Y.1%.3 g dÀ1 and 4. 80. and BghiP) accounted for 40% of the water-phase total-PAHs in the WSB effluent. NaP.4 mg minÀ1 for the exhaust flue gas of WSB at Site D. respectively. C. the nine carcinogenic PAHs (BaA.4%. B. S.. At Site E. For the powders of scrap tires. and 89. Shue. On the survivability and pyrosynthesis of PAH during combustion of pulverized coal and tire crumb. the mean removal efficiencies of gaseous. J. The mean removal efficiencies of individual PAHs. and 5. and 0. and BaP). 2001. IND. Nap and IND were also dominant in sampling-tube. respectively for the WSB. 462–478. and 6-/7-ring PAHs (IND [207 mg gÀ1.2–100% and 91. furthermore. Huang. Sheng. Mai. the BaA displayed a negative mean removal efficiency in gaseous phase and the mean removal efficiency of gaseous COR was small. Emission characterization of particulate/gaseous phase and size association of polycyclic aromatic hydrocarbons from residential coal combustion. Hsieh. Conclusions PAHs emission from a waste-tire pyrolysis process was investigated in this work.1%.ARTICLE IN PRESS the need for seeking better technologies to remove the PAH compounds from the scrap tires pyrolysis process investigated.8%. The totalBaPeq mean effluent rate reached 171 mg minÀ1 for the effluent wastewater of WSB at Site C and the mean emission rate of total-BaPeq was 26. the total-BaPeq of sampling-tube residual PAHs in flare exhaust was 2.and total-PAHs. Levendis.. . 7. W. however. 1998. 6.9% and 59. In: Ferrero. M. Polycyclic aromatic hydrocarbons in combustion residues from 1. The PAHs in the carbon black formed in the pyrolysis were mainly 2-/3-ring PAHs (NaP. J. 57–67. A. DBA. BkF. BbF.M.L.17.X.J..1% for the flare. CHR.J.47. and combined (gaseous+particulate) total-PAHs were 59. Carlson.7 and 4.C. BaP. and combined (gaseous+particulate) PAHs. These TEFs are termed by BaP equivalent (BaPeq) (the carcinogenic potency of the individual PAH divided with the carcinogenicity of BaP).3-Butadiene... 1997.L.8%. the total-BaPeq concentrations in the entrance of flare were 21. and 66. and COR displayed higher mean gas (150. respectively in the exit of flare (Table 4).1% removal efficiencies in total-BaPeq for the gaseous.. W. PAHs and aerosol carbons in the exhaust of a gasoline powered engine. Jian.J.9 mg gÀ1.

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