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Catalytic conversion of waste particle board and polypropylene over H-beta and HY zeolites
Renewable Energy xxx (2014) 1e5
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Catalytic conversion of waste particle board and polypropylene over H-beta and HY zeolites Hyung Won Lee a, Suek Joo Choi a, Jong-Ki Jeon b, Sung Hoon Park c, Sang-Chul Jung c, Young-Kwon Park a, d, * a
Graduate School of Energy and Environmental System Engineering, University of Seoul, Seoul 130-743, South Korea Department of Chemical Engineering, Kongju National University, Cheonan 330-717, South Korea Department of Environmental Engineering, Sunchon National University, Suncheon 540-950, South Korea d School of Environmental Engineering, University of Seoul, Seoul 130-743, South Korea b c
a r t i c l e i n f o
a b s t r a c t
Article history: Received 17 March 2014 Accepted 22 July 2014 Available online xxx
The catalytic copyrolysis of waste particle board (WPB) and polypropylene (PP) was investigated for the first time over HY (5.1), HY (30), H-Beta and Ga/H-Beta catalysts. The catalysts were characterized by BET and NH3-TPD analyses. The catalytic pyrolysis of the WPB increased the production of gas products (CO, CO2, C1eC4) compared to non-catalytic pyrolysis. Acids and levoglucosan, which are the main components of bio-oil produced from non-catalytic pyrolysis, were converted to more valuable aromatics, phenolics, and furans through dehydration, deoxygenation and aromatization. The most abundant products from the copyrolysis of WPB and PP were large-molecular-mass hydrocarbons (C10). However, catalytic copyrolysis increased the yields of small-molecular-mass hydrocarbons in the gasoline range, aromatics and phenolics. The water content in bio-oil was reduced significantly by copyrolysis with PP, contributing to the improvement in oil quality. HY (5.1) with the largest number of acid sites showed higher catalytic activity than HY (30) and H-Beta because the decomposition and reforming reactions during catalytic copyrolysis occurred on the acid sites of the catalysts. Ga/H-Beta showed even higher selectivity toward the aromatics than H-Beta despite the smaller quantity of acid sites, suggesting that Ga promoted the dehydrocyclization of the reaction intermediates. © 2014 Elsevier Ltd. All rights reserved.
Keywords: Waste particle board Polypropylene Catalytic copyrolysis Bio-oil H-beta HY
1. Introduction The production of bio-fuel from biomass, which is aimed at replacing conventional petroleum-derived fuels, has attracted considerable attention. Among these bio-fuels, bio-oil is produced from the pyrolysis of biomass [1,2]. In general, the bio-oil produced from biomass pyrolysis has the following characteristics: heating value of 16e19 MJ/kg, carbon content of 54e58%, oxygen content of 35e40%, and moisture content of 15e30%, which are quite different from those of petroleum-derived fuels [3]. Bio-oil has a low heating value and poor miscibility in petroleum-derived fuels of bio-oil owing to its high oxygen and moisture content [3], which stems from its low carbon content (47e51 wt%) and high oxygen content (42e46 wt%) of the feedstock biomass. Therefore, pyrolyzing
* Corresponding author. School of Environmental Engineering, University of Seoul, Seoul 130-743, South Korea. Tel.: þ82 2 6490 2780; fax: þ82 2 6490 2859. E-mail address: [email protected] (Y.-K. Park).
biomass together with another material with a high carbon and hydrogen content can be an effective method for improving the bio-oil quality and its miscibility in petroleum-derived fuels. Although biomass is a natural polymer, plastic materials, such as polyethylene and polypropylene (PP) are synthetic polymers composed only of carbon and hydrogen. These synthetic polymers can be used as auxiliary materials that can provide carbon and hydrogen to biomass upon copyrolysis. Copyrolysis of a variety of different biomass materials and synthetic polymers has been examined [4e16]. These studies reported that the interaction between the biomass material and synthetic polymer affected the quality and yield of product bio-oil [4,5,17]. On the other hand, the bio-oil produced from copyrolysis consisted mostly of largemolecular-mass species, resulting in relatively low oil quality. Therefore, the oil quality needs to be improved by additional upgrading processes, such as catalytic cracking. Although the catalytic pyrolysis of biomass and the catalytic pyrolysis of plastic materials have been carried out, there are few reports of the catalytic copyrolysis of a mixture of biomass and
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H.W. Lee et al. / Renewable Energy xxx (2014) 1e5
plastic materials. Liu et al. [18] reported the copyrolysis of pubescens and LDPE over catalysts based on a mesoporous material, AlMCM-41. Nevertheless, there are no reports of the catalytic copyrolysis over HY and H-Beta, which are microporous zeolite materials. The copyrolysis of biomass and plastic materials is important in terms of the waste fuel quality improvement because they are the main components of municipal solid waste. The catalytic copyrolysis of waste particle board (WPB), a representative waste wood material contained in municipal solid waste, and PP, a model compound of waste plastic, was carried out in this study. HY, H-Beta, and Ga/H-Beta were used as the catalysts. The pyrolysis of WPB only over HY, H-Beta, and Ga/H-Beta was also performed for comparison. The goal of this study was to obtain upgraded bio-oil with low moisture content and high contents of hydrocarbon and mono-aromatics using catalytic co pyrolysis. 2. Materials and methods 2.1. Biomass and plastic samples Proximate analysis and ultimate analysis of WPB and PP were performed using the method reported in Ref. [19]. Table S1 (Supplementary Information) lists the characteristics of WPB and PP. WPB was composed of moisture (2.6 wt%), volatiles (79.4 wt%), fixed carbon (15.9 wt%), and ash (2.1 wt%). PP exhibited a composition of volatiles (99.8 wt%) and ash (0.2 wt%). From elemental analysis, WPB showed the following: C: 44.42 wt%, H: 5.14 wt%, O: 48.85 wt%, and N: 1.29 wt%, whereas PP contained only C: 85.4 wt% and H:14.6 wt%. 2.2. Synthesis and characterization of catalyst Commercial zeolites, H-Beta, HY (5.1) and HY (30), were purchased from Zeolyst. Ga/H-Beta was synthesized by impregnating 1wt% Ga onto H-Beta using Ga(NO3)3 as the precursor. The catalysts were characterized using BET and temperature programmed desorption of NH3 (NH3-TPD). The detailed procedures of these analysis methods are described in Ref. [19]. 2.3. Catalytic pyrolysis using a fixed bed reactor A U-type quartz reactor, whose inlet/outlet diameter, height, and volume were 1.5 cm, 16 cm, and 50 cc, respectively, was used. The reactor was purged with N2 gas with a flow rate of 50 cc/min for 30 min prior to each experiment to create O2-free conditions. Two condensers connected in series were used to collect the bio-oil. The condensers were maintained at 20 C to allow the condensation of low volatility species. The gaseous products that passed through the condensers were collected in a Teflon gas bag. The experiments were carried out under a gas flow with a flow rate of 50 cc/min at 500 C. Each experiment was performed for 1 h with a 5 g sample. Catalytic upgrading was performed using a fixed bed reactor system. The reaction temperature of the catalytic bed was set to 500 C. The ratio of catalyst/wood was 1/10. In the case of copyrolysis, 2.5 g of biomass and 2.5 g of PP were mixed and used for the reaction. The detailed experimental procedures are described in Ref. [17]. All the experiments were repeated 3 times and average values were used for comparison.
analysis was also identical to that used in the previous study [19] except that a mixture of 1 mg each of the WPB and PP sample was used in each experiment. For catalytic copyrolysis, catalyst (2 mg) was laid over the reactants (mixture of WPB and PP). The experiments repeated 3 times and average value was used. 3. Results and discussion 3.1. Characterization of the catalysts Table S2 (Supplementary Information) lists the characteristics of the catalysts. Two different SiO2/Al2O3 ratios of HY zeolite, 5.1 and 30, were used. The specific surface areas corresponding to these SiO2/Al2O3 ratios were 730 and 623 m2/g, respectively. Also, the specific surface area of H-Beta (SiO2/Al2O3 ¼ 25) was a 680 m2/g. The impregnation of Ga onto H-Beta reduced the specific surface area slightly to 648 m2/g due to partial blocking of the pores by added Ga. HY showed a larger pore size (7.4 Å) than H-Beta (ca. 6.6 Å). Fig. S1 (Supplementary Information) shows the acid characteristics of the catalysts analyzed by NH3-TPD. All catalysts exhibited a peak at approximately 210 C representing the weak acid sites and a peak at approximately 350 C representing medium-strength acid sites, which indicates that the acidities of the catalysts were all similar. The quantity of acid sites decreased with increasing SiO2/ Al2O3 ratio. Ga/H-Beta had fewer acid sites than H-Beta, probably because of the added Ga replaced acid sites. The order of the acid site quantity was HY (5.1) > H-Beta > HY (30) z Ga/H-Beta. 3.2. Catalytic pyrolysis of WPB Fig. 1 presents the yields of the solid, liquid and gaseous products obtained from the pyrolysis of WPB under different catalytic conditions. In all catalytic pyrolysis experiments, the oil yield was 5e7% lower than that of the non-catalytic pyrolysis, whereas the gas yield was 5e7% larger. These changes in the oil and gas yields were attributed to the improved cracking and deoxygenation of the reaction intermediates on the acid sites of the catalysts. Park et al. [20] reported that the oil yield was reduced and the gas yield was increased by the catalyst in the pyrolysis of a range of biomass materials, such as radiata pine, and attributed these changes to the reactions occurring on the acid sites of the catalysts. The water content of bio-oil was increased by ca. 20 wt% using the catalyst (Table 1). This was attributed to the removal of oxygen
2.4. Catalytic copyrolysis using Py-GC/MS The same experimental instruments, a single-shot pyrolyzer (Frontier-Lab Co., Py-2020iD) and a GC/MS system, as those used in a previous study [19] were used in the present study for the copyrolysis of WPB and PP. The procedure of pyrolysis and GC/MS
Fig. 1. Gas, oil and char yields obtained from the pyrolysis of WPB.
Please cite this article in press as: Lee HW, et al., Catalytic conversion of waste particle board and polypropylene over H-beta and HY zeolites, Renewable Energy (2014), http://dx.doi.org/10.1016/j.renene.2014.07.040
H.W. Lee et al. / Renewable Energy xxx (2014) 1e5 Table 1 Gaseous product yields and water content in bio-oil obtained from the pyrolysis of WPB under different conditions. Non-catalyst
HY(5.1)
H-beta
Ga/H-beta
HY(30)
Yield (wt%)
4.71 13.62 1.53 35.50
8.36 15.92 3.14 58.59
7.97 15.23 2.86 56.40
7.44 15.19 2.70 55.52
7.15 15.14 2.44 54.93
CO CO2 C1 ~ C4 Water contents in bio-oil (wt%)
in the biomass by dehydration on the catalyst's acid sites. The main components of the product gas were CO, CO2 and hydrocarbons. The fractions of these species were also affected by the catalysts. Although their yields were increased by the catalysts, as mentioned above, the increases in the yields of CO and hydrocarbons were particularly large. CO, CO2 and CH4 are produced from the decarbonylation, decarboxylation, and demethylation of biomass, respectively [21]. Therefore, the data shown in Table 1 suggests that these reactions (particularly decarbonylation) were promoted by the catalysts. Overall, a large number of acid sites are advantageous to catalytic pyrolysis because deoxygenation (dehydration, decarbonylation, and decarboxylation) and demethylation are enhanced in the presence of acid sites. In this study, the gas yield and water content of bio-oil increased with increasing number of acid sites: HY (5.1) > H-Beta > Ga/H-Beta z HY (30). Fig. 2 shows the product distributions obtained from the pyrolysis of WPB determined using Py-GC/MS. The main products of non-catalytic pyrolysis were oxygenates, acids, large-molecularmass hydrocarbons, and phenolics. Considerable amounts of oxygenates and acids were removed by the catalysis, whereas the fraction of phenolics increased. The production of aromatics and PAHs, which were produced in small quantities from non-catalytic pyrolysis, were also enhanced to a large extent. As shown in Fig. 3, the main component of the oxygenates was levoglucosan, which was removed completely by catalysis. The removed levoglucosan is believed to have been converted to other species, such as furans, furanones and cyclopentanones. For example, furans are produced from the dehydration of levoglucosan. Therefore, the increase in the fraction of furans observed in this study (Fig. 3) was attributed to the conversion of levoglucosan to furans by the acidic catalysts. Because furans are used as basic petrochemical feedstock materials, their production contributes to the increase in the economic value of bio-oil. In general, HY (5.1), which has the largest number of acid
20
10
5
0 Fur
ans
Fur
ano
nes Cyc
lope
ntan
one
s og Lev
luco
san er Oth
-oxy
gen
ates
Fig. 3. Oxygenate species distributions obtained from the pyrolysis of WPB.
sites, showed the best deoxygenation performance, whereas HY (30), with the fewest acid sites, showed the lowest deoxygenation efficiency. Acids such as acetic acid showed a similar trend. The order of the aromatics production capability of the catalysts was Ga/H-Beta > HY (5.1) > H-Beta > HY (30). It is known that suf€nsted acid sites are effective for the production of aroficient Bro matics. This is why HY (5.1) produced a large quantity of aromatics. Ga/H-Beta, which had a smaller number of acid sites than HY (5.1) and H-Beta, produced more aromatics because Ga enhanced the aromatization of the reaction intermediates. Park et al. [20] reported that the addition of Ga increased the yield of aromatics in the catalytic pyrolysis of radiata pine, which is in agreement with this study. In particular, BTEX (benzene, toluene, ethylbenzene, and xylene), which are basic petrochemical feedstock materials, accounted for 77.9% of the total aromatics (Fig. 4), suggesting that the economic value of the bio-oil can be increased by catalysis. The production of phenolics is also welcomed because they can be used as feedstock to produce phenolic resins. As shown in Fig. 2, the productivity of phenolics increased with increasing number of acid sites, HY (5.1) produced the largest quantity of phenolics. In addition, the phenolics produced consisted of hydroxyl phenyl, guaiacyl phenyl, and syringyl phenyl (Fig. 5). Previous studies
50
3.0 Non-Catalyst H-Beta Ga/H-Beta HY(5.1) HY(30)
30
20
10
Non-Catalyst H-Beta Ga/H-Beta HY(5.1) HY(30)
2.5
Distribution(area%)
40
Distribution(area%)
Non-Catalyst H-Beta Ga/H-Beta HY(5.1) HY(30)
15
Distribution(area%)
Catalyst
3
2.0
1.5
1.0
0.5
0
0.0
s Acid
ns ates rbo gen roca d Oxy y h hH ig
Aro
mat
ics
PAH
s
P he
noli
cs
Fig. 2. Pyrolysis product distributions of WPB obtained over different catalysts.
zene Ben
ene Tolu
e nzen ylbe Eth
ics ics ene mat mat Xyl -aro -aro ono ono m m C9 C10
Fig. 4. Aromatic species distributions obtained from the pyrolysis of WPB.
Please cite this article in press as: Lee HW, et al., Catalytic conversion of waste particle board and polypropylene over H-beta and HY zeolites, Renewable Energy (2014), http://dx.doi.org/10.1016/j.renene.2014.07.040
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H.W. Lee et al. / Renewable Energy xxx (2014) 1e5 18 Non-Catalyst H-Beta Ga/H-Beta HY(5.1) HY(30)
16
Distribution(area%)
14 12 10
Table 2 Gaseous product yields and water content in bio-oil obtained from the copyrolysis of WPB and PP under different conditions. Catalyst
Non-catalyst
HY(5.1)
H-beta
Ga/H-beta
HY(30)
Yield (wt%)
3.42 10.07 4.55 2.08
5.54 12.12 8.68 9.82
5.27 12.03 8.53 9.36
4.89 11.68 8.52 9.04
4.46 11.94 8.61 8.58
CO CO2 C1 ~ C4 Water contents in bio-oil (wt%)
8 6 4 2 0
lics eno t-ph Ligh
ia Gua
cyl-
phe
noli
cs in S yr
gyl-
cs noli phe
Oth
s olic hen er- p
Fig. 5. Phenolic species distributions obtained from the pyrolysis of WPB.
[21,22] on the catalytic pyrolysis of lignin, from which phenolics are produced, reported that lignin was converted to phenolics by deoxygenation (decarbonylation, decarboxylation, and dehydration), demethoxylation, and cracking on the acid sites, leading to an increase in the yield of phenolics, which is in good agreement with the present study. The pore size of the catalyst might also affect the catalytic activity. For example, HY and H-Beta have different pore sizes. In this study, however, the effect of the pore size was negligible. The activity of HY (30), which has larger pores than H-Beta, was lower than that of H-Beta, suggesting that the acidity is a much more important factor in determining the catalytic activity than the pore size. 3.3. Catalytic copyrolysis of WPB and PP Fig. 6 shows the results of the catalytic copyrolysis of WPB and PP in a fixed bed reactor. As in the pyrolysis of WPB only, the gas yield was increased and the oil yield was decreased by the catalysis. HY (5.1) with the largest number of acid sites produced the largest amount of gas, whereas HY (30), with the fewest acid sites produced the smallest amount of gas. The increase in the yields of CO, CO2, and hydrocarbons by the catalysis (Table 2) were attributed to
decarbonylation, decarboxylation, and cracking promoted by catalysts, as mentioned in Section 3.2. In particular, the yield of hydrocarbons increased to a large extent, suggesting that PP had decomposed to hydrocarbons in the presence of acidic catalysts. A previous study reported that PP was decomposed to C3eC9 hydrocarbons over HY, which is in good agreement with the present study [23]. The water content of bio-oil produced from non-catalytic copyrolysis was 2.08%, which is much smaller than that obtained from the non-catalytic pyrolysis of WPB only (35.50%). This might be due to the supply of sufficient C and H by PP. Catalytic copyrolysis resulted in a larger water content (ca. 9%) in the bio-oil than non-catalytic copyrolysis, which was attributed to the enhanced dehydration by the catalysts. On the other hand, the water content of ca. 9% was much smaller than that of the catalytic pyrolysis of WPB only (ca. 55e60%). Fig. 7 shows the product distributions obtained from copyrolysis determined by Py-GC/MS. Although the oxygenates were the most abundant products in the non-catalytic pyrolysis of WPB only (Fig. 2), hydrocarbons derived from PP were the most abundant products in the non-catalytic copyrolysis of WPB and PP. The hydrocarbon fraction decreased, whereas those of aromatics and phenolics were increased by catalysis. This can be attributed to the conversion of hydrocarbons, oxygenates, and acids into aromatics and phenolics by cracking, oligomerization, deoxygenation, and aromatization occurring on the acid sites of catalysts as in Section 3.2. Ga/H-Beta showed the highest selectivity toward aromatics, whereas HY (30) with the lowest number of acid sites led to the lowest yield of aromatics. This suggests that aromatization occurring on the acid sites was promoted by Ga-induced dehydrocyclization. The yield of aromatics obtained from catalytic copyrolysis was slightly larger than that obtained from the catalytic pyrolysis of WPB only. On the other hand, the yield of PAHs obtained from
70 Non-Catalyst H-Beta Ga/H-Beta HY(5.1) HY(30)
Distribution(area%)
60
50
40
30
20
10
0
s
Acid
Fig. 6. Gas, oil and char yields obtained from the copyrolysis of WPB and PP.
gen Oxy
a tes
roca
Hyd
rbo
ns
Aro
ic mat
s
PAH
s
Phe
noli
cs
Fig. 7. Product distributions obtained from the copyrolysis of WPB and PP.
Please cite this article in press as: Lee HW, et al., Catalytic conversion of waste particle board and polypropylene over H-beta and HY zeolites, Renewable Energy (2014), http://dx.doi.org/10.1016/j.renene.2014.07.040
H.W. Lee et al. / Renewable Energy xxx (2014) 1e5
Appendix A. Supplementary data
40
Distribution(area%)
30
5
Non-Catalyst H-Beta Ga/H-Beta HY(5.1) HY(30)
Supplementary data related to this article can be found at http:// dx.doi.org/10.1016/j.renene.2014.07.040. References
20
10
0 C1~
C4
C9 C5~
C10
~C1
7
Ov e
r C1
7
Fig. 8. Product carbon number distributions obtained from the copyrolysis of WPB and PP over different catalysts.
copyrolysis was smaller than that from the pyrolysis of WPB only. Because PAHs are carcinogenic and can deactivate the catalyst, the suppression of their production by the catalysis in this study is encouraging. In terms of the carbon number distribution of the oil species (Fig. 8), the main products of non-catalytic copyrolysis were wax species (C17) and large-molecular-mass compounds (C10). On the other hand, catalytic copyrolysis produced small-molecularmass compounds, mainly in the gasoline range (C5eC9). 4. Conclusions The catalytic pyrolysis of WPB was carried out over the HY and H-Beta catalysts. HY (5.1) with the largest amounts of acid sites was most favorable to cracking and deoxygenation reactions. The main compounds obtained from the catalytic pyrolysis of WPB only were phenolics, furans and aromatics. On the other hand, the main products of the catalytic copyrolysis of WPB with PP were hydrocarbons, aromatics and phenolics. The water content in bio-oil was decreased significantly by copyrolysis with PP, contributing to the improvement in oil quality. Catalytic copyrolysis suppressed the formation of PAHs, which are carcinogenic and cause coke formation. C5eC9 hydrocarbons were mostly generated from the copyrolysis. The addition of Ga led to enhanced aromatics production (particularly BTEX) for both the catalytic pyrolysis of WPB only and the catalytic copyrolysis of WPB and PP. Acknowledgment This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2012R1A1B3003394).
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Contents lists available at ScienceDirect
Renewable Energy journal homepage: www.elsevier.com/locate/renene
Catalytic conversion of waste particle board and polypropylene over H-beta and HY zeolites Hyung Won Lee a, Suek Joo Choi a, Jong-Ki Jeon b, Sung Hoon Park c, Sang-Chul Jung c, Young-Kwon Park a, d, * a
Graduate School of Energy and Environmental System Engineering, University of Seoul, Seoul 130-743, South Korea Department of Chemical Engineering, Kongju National University, Cheonan 330-717, South Korea Department of Environmental Engineering, Sunchon National University, Suncheon 540-950, South Korea d School of Environmental Engineering, University of Seoul, Seoul 130-743, South Korea b c
a r t i c l e i n f o
a b s t r a c t
Article history: Received 17 March 2014 Accepted 22 July 2014 Available online xxx
The catalytic copyrolysis of waste particle board (WPB) and polypropylene (PP) was investigated for the first time over HY (5.1), HY (30), H-Beta and Ga/H-Beta catalysts. The catalysts were characterized by BET and NH3-TPD analyses. The catalytic pyrolysis of the WPB increased the production of gas products (CO, CO2, C1eC4) compared to non-catalytic pyrolysis. Acids and levoglucosan, which are the main components of bio-oil produced from non-catalytic pyrolysis, were converted to more valuable aromatics, phenolics, and furans through dehydration, deoxygenation and aromatization. The most abundant products from the copyrolysis of WPB and PP were large-molecular-mass hydrocarbons (C10). However, catalytic copyrolysis increased the yields of small-molecular-mass hydrocarbons in the gasoline range, aromatics and phenolics. The water content in bio-oil was reduced significantly by copyrolysis with PP, contributing to the improvement in oil quality. HY (5.1) with the largest number of acid sites showed higher catalytic activity than HY (30) and H-Beta because the decomposition and reforming reactions during catalytic copyrolysis occurred on the acid sites of the catalysts. Ga/H-Beta showed even higher selectivity toward the aromatics than H-Beta despite the smaller quantity of acid sites, suggesting that Ga promoted the dehydrocyclization of the reaction intermediates. © 2014 Elsevier Ltd. All rights reserved.
Keywords: Waste particle board Polypropylene Catalytic copyrolysis Bio-oil H-beta HY
1. Introduction The production of bio-fuel from biomass, which is aimed at replacing conventional petroleum-derived fuels, has attracted considerable attention. Among these bio-fuels, bio-oil is produced from the pyrolysis of biomass [1,2]. In general, the bio-oil produced from biomass pyrolysis has the following characteristics: heating value of 16e19 MJ/kg, carbon content of 54e58%, oxygen content of 35e40%, and moisture content of 15e30%, which are quite different from those of petroleum-derived fuels [3]. Bio-oil has a low heating value and poor miscibility in petroleum-derived fuels of bio-oil owing to its high oxygen and moisture content [3], which stems from its low carbon content (47e51 wt%) and high oxygen content (42e46 wt%) of the feedstock biomass. Therefore, pyrolyzing
* Corresponding author. School of Environmental Engineering, University of Seoul, Seoul 130-743, South Korea. Tel.: þ82 2 6490 2780; fax: þ82 2 6490 2859. E-mail address: [email protected] (Y.-K. Park).
biomass together with another material with a high carbon and hydrogen content can be an effective method for improving the bio-oil quality and its miscibility in petroleum-derived fuels. Although biomass is a natural polymer, plastic materials, such as polyethylene and polypropylene (PP) are synthetic polymers composed only of carbon and hydrogen. These synthetic polymers can be used as auxiliary materials that can provide carbon and hydrogen to biomass upon copyrolysis. Copyrolysis of a variety of different biomass materials and synthetic polymers has been examined [4e16]. These studies reported that the interaction between the biomass material and synthetic polymer affected the quality and yield of product bio-oil [4,5,17]. On the other hand, the bio-oil produced from copyrolysis consisted mostly of largemolecular-mass species, resulting in relatively low oil quality. Therefore, the oil quality needs to be improved by additional upgrading processes, such as catalytic cracking. Although the catalytic pyrolysis of biomass and the catalytic pyrolysis of plastic materials have been carried out, there are few reports of the catalytic copyrolysis of a mixture of biomass and
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Please cite this article in press as: Lee HW, et al., Catalytic conversion of waste particle board and polypropylene over H-beta and HY zeolites, Renewable Energy (2014), http://dx.doi.org/10.1016/j.renene.2014.07.040
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H.W. Lee et al. / Renewable Energy xxx (2014) 1e5
plastic materials. Liu et al. [18] reported the copyrolysis of pubescens and LDPE over catalysts based on a mesoporous material, AlMCM-41. Nevertheless, there are no reports of the catalytic copyrolysis over HY and H-Beta, which are microporous zeolite materials. The copyrolysis of biomass and plastic materials is important in terms of the waste fuel quality improvement because they are the main components of municipal solid waste. The catalytic copyrolysis of waste particle board (WPB), a representative waste wood material contained in municipal solid waste, and PP, a model compound of waste plastic, was carried out in this study. HY, H-Beta, and Ga/H-Beta were used as the catalysts. The pyrolysis of WPB only over HY, H-Beta, and Ga/H-Beta was also performed for comparison. The goal of this study was to obtain upgraded bio-oil with low moisture content and high contents of hydrocarbon and mono-aromatics using catalytic co pyrolysis. 2. Materials and methods 2.1. Biomass and plastic samples Proximate analysis and ultimate analysis of WPB and PP were performed using the method reported in Ref. [19]. Table S1 (Supplementary Information) lists the characteristics of WPB and PP. WPB was composed of moisture (2.6 wt%), volatiles (79.4 wt%), fixed carbon (15.9 wt%), and ash (2.1 wt%). PP exhibited a composition of volatiles (99.8 wt%) and ash (0.2 wt%). From elemental analysis, WPB showed the following: C: 44.42 wt%, H: 5.14 wt%, O: 48.85 wt%, and N: 1.29 wt%, whereas PP contained only C: 85.4 wt% and H:14.6 wt%. 2.2. Synthesis and characterization of catalyst Commercial zeolites, H-Beta, HY (5.1) and HY (30), were purchased from Zeolyst. Ga/H-Beta was synthesized by impregnating 1wt% Ga onto H-Beta using Ga(NO3)3 as the precursor. The catalysts were characterized using BET and temperature programmed desorption of NH3 (NH3-TPD). The detailed procedures of these analysis methods are described in Ref. [19]. 2.3. Catalytic pyrolysis using a fixed bed reactor A U-type quartz reactor, whose inlet/outlet diameter, height, and volume were 1.5 cm, 16 cm, and 50 cc, respectively, was used. The reactor was purged with N2 gas with a flow rate of 50 cc/min for 30 min prior to each experiment to create O2-free conditions. Two condensers connected in series were used to collect the bio-oil. The condensers were maintained at 20 C to allow the condensation of low volatility species. The gaseous products that passed through the condensers were collected in a Teflon gas bag. The experiments were carried out under a gas flow with a flow rate of 50 cc/min at 500 C. Each experiment was performed for 1 h with a 5 g sample. Catalytic upgrading was performed using a fixed bed reactor system. The reaction temperature of the catalytic bed was set to 500 C. The ratio of catalyst/wood was 1/10. In the case of copyrolysis, 2.5 g of biomass and 2.5 g of PP were mixed and used for the reaction. The detailed experimental procedures are described in Ref. [17]. All the experiments were repeated 3 times and average values were used for comparison.
analysis was also identical to that used in the previous study [19] except that a mixture of 1 mg each of the WPB and PP sample was used in each experiment. For catalytic copyrolysis, catalyst (2 mg) was laid over the reactants (mixture of WPB and PP). The experiments repeated 3 times and average value was used. 3. Results and discussion 3.1. Characterization of the catalysts Table S2 (Supplementary Information) lists the characteristics of the catalysts. Two different SiO2/Al2O3 ratios of HY zeolite, 5.1 and 30, were used. The specific surface areas corresponding to these SiO2/Al2O3 ratios were 730 and 623 m2/g, respectively. Also, the specific surface area of H-Beta (SiO2/Al2O3 ¼ 25) was a 680 m2/g. The impregnation of Ga onto H-Beta reduced the specific surface area slightly to 648 m2/g due to partial blocking of the pores by added Ga. HY showed a larger pore size (7.4 Å) than H-Beta (ca. 6.6 Å). Fig. S1 (Supplementary Information) shows the acid characteristics of the catalysts analyzed by NH3-TPD. All catalysts exhibited a peak at approximately 210 C representing the weak acid sites and a peak at approximately 350 C representing medium-strength acid sites, which indicates that the acidities of the catalysts were all similar. The quantity of acid sites decreased with increasing SiO2/ Al2O3 ratio. Ga/H-Beta had fewer acid sites than H-Beta, probably because of the added Ga replaced acid sites. The order of the acid site quantity was HY (5.1) > H-Beta > HY (30) z Ga/H-Beta. 3.2. Catalytic pyrolysis of WPB Fig. 1 presents the yields of the solid, liquid and gaseous products obtained from the pyrolysis of WPB under different catalytic conditions. In all catalytic pyrolysis experiments, the oil yield was 5e7% lower than that of the non-catalytic pyrolysis, whereas the gas yield was 5e7% larger. These changes in the oil and gas yields were attributed to the improved cracking and deoxygenation of the reaction intermediates on the acid sites of the catalysts. Park et al. [20] reported that the oil yield was reduced and the gas yield was increased by the catalyst in the pyrolysis of a range of biomass materials, such as radiata pine, and attributed these changes to the reactions occurring on the acid sites of the catalysts. The water content of bio-oil was increased by ca. 20 wt% using the catalyst (Table 1). This was attributed to the removal of oxygen
2.4. Catalytic copyrolysis using Py-GC/MS The same experimental instruments, a single-shot pyrolyzer (Frontier-Lab Co., Py-2020iD) and a GC/MS system, as those used in a previous study [19] were used in the present study for the copyrolysis of WPB and PP. The procedure of pyrolysis and GC/MS
Fig. 1. Gas, oil and char yields obtained from the pyrolysis of WPB.
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H.W. Lee et al. / Renewable Energy xxx (2014) 1e5 Table 1 Gaseous product yields and water content in bio-oil obtained from the pyrolysis of WPB under different conditions. Non-catalyst
HY(5.1)
H-beta
Ga/H-beta
HY(30)
Yield (wt%)
4.71 13.62 1.53 35.50
8.36 15.92 3.14 58.59
7.97 15.23 2.86 56.40
7.44 15.19 2.70 55.52
7.15 15.14 2.44 54.93
CO CO2 C1 ~ C4 Water contents in bio-oil (wt%)
in the biomass by dehydration on the catalyst's acid sites. The main components of the product gas were CO, CO2 and hydrocarbons. The fractions of these species were also affected by the catalysts. Although their yields were increased by the catalysts, as mentioned above, the increases in the yields of CO and hydrocarbons were particularly large. CO, CO2 and CH4 are produced from the decarbonylation, decarboxylation, and demethylation of biomass, respectively [21]. Therefore, the data shown in Table 1 suggests that these reactions (particularly decarbonylation) were promoted by the catalysts. Overall, a large number of acid sites are advantageous to catalytic pyrolysis because deoxygenation (dehydration, decarbonylation, and decarboxylation) and demethylation are enhanced in the presence of acid sites. In this study, the gas yield and water content of bio-oil increased with increasing number of acid sites: HY (5.1) > H-Beta > Ga/H-Beta z HY (30). Fig. 2 shows the product distributions obtained from the pyrolysis of WPB determined using Py-GC/MS. The main products of non-catalytic pyrolysis were oxygenates, acids, large-molecularmass hydrocarbons, and phenolics. Considerable amounts of oxygenates and acids were removed by the catalysis, whereas the fraction of phenolics increased. The production of aromatics and PAHs, which were produced in small quantities from non-catalytic pyrolysis, were also enhanced to a large extent. As shown in Fig. 3, the main component of the oxygenates was levoglucosan, which was removed completely by catalysis. The removed levoglucosan is believed to have been converted to other species, such as furans, furanones and cyclopentanones. For example, furans are produced from the dehydration of levoglucosan. Therefore, the increase in the fraction of furans observed in this study (Fig. 3) was attributed to the conversion of levoglucosan to furans by the acidic catalysts. Because furans are used as basic petrochemical feedstock materials, their production contributes to the increase in the economic value of bio-oil. In general, HY (5.1), which has the largest number of acid
20
10
5
0 Fur
ans
Fur
ano
nes Cyc
lope
ntan
one
s og Lev
luco
san er Oth
-oxy
gen
ates
Fig. 3. Oxygenate species distributions obtained from the pyrolysis of WPB.
sites, showed the best deoxygenation performance, whereas HY (30), with the fewest acid sites, showed the lowest deoxygenation efficiency. Acids such as acetic acid showed a similar trend. The order of the aromatics production capability of the catalysts was Ga/H-Beta > HY (5.1) > H-Beta > HY (30). It is known that suf€nsted acid sites are effective for the production of aroficient Bro matics. This is why HY (5.1) produced a large quantity of aromatics. Ga/H-Beta, which had a smaller number of acid sites than HY (5.1) and H-Beta, produced more aromatics because Ga enhanced the aromatization of the reaction intermediates. Park et al. [20] reported that the addition of Ga increased the yield of aromatics in the catalytic pyrolysis of radiata pine, which is in agreement with this study. In particular, BTEX (benzene, toluene, ethylbenzene, and xylene), which are basic petrochemical feedstock materials, accounted for 77.9% of the total aromatics (Fig. 4), suggesting that the economic value of the bio-oil can be increased by catalysis. The production of phenolics is also welcomed because they can be used as feedstock to produce phenolic resins. As shown in Fig. 2, the productivity of phenolics increased with increasing number of acid sites, HY (5.1) produced the largest quantity of phenolics. In addition, the phenolics produced consisted of hydroxyl phenyl, guaiacyl phenyl, and syringyl phenyl (Fig. 5). Previous studies
50
3.0 Non-Catalyst H-Beta Ga/H-Beta HY(5.1) HY(30)
30
20
10
Non-Catalyst H-Beta Ga/H-Beta HY(5.1) HY(30)
2.5
Distribution(area%)
40
Distribution(area%)
Non-Catalyst H-Beta Ga/H-Beta HY(5.1) HY(30)
15
Distribution(area%)
Catalyst
3
2.0
1.5
1.0
0.5
0
0.0
s Acid
ns ates rbo gen roca d Oxy y h hH ig
Aro
mat
ics
PAH
s
P he
noli
cs
Fig. 2. Pyrolysis product distributions of WPB obtained over different catalysts.
zene Ben
ene Tolu
e nzen ylbe Eth
ics ics ene mat mat Xyl -aro -aro ono ono m m C9 C10
Fig. 4. Aromatic species distributions obtained from the pyrolysis of WPB.
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H.W. Lee et al. / Renewable Energy xxx (2014) 1e5 18 Non-Catalyst H-Beta Ga/H-Beta HY(5.1) HY(30)
16
Distribution(area%)
14 12 10
Table 2 Gaseous product yields and water content in bio-oil obtained from the copyrolysis of WPB and PP under different conditions. Catalyst
Non-catalyst
HY(5.1)
H-beta
Ga/H-beta
HY(30)
Yield (wt%)
3.42 10.07 4.55 2.08
5.54 12.12 8.68 9.82
5.27 12.03 8.53 9.36
4.89 11.68 8.52 9.04
4.46 11.94 8.61 8.58
CO CO2 C1 ~ C4 Water contents in bio-oil (wt%)
8 6 4 2 0
lics eno t-ph Ligh
ia Gua
cyl-
phe
noli
cs in S yr
gyl-
cs noli phe
Oth
s olic hen er- p
Fig. 5. Phenolic species distributions obtained from the pyrolysis of WPB.
[21,22] on the catalytic pyrolysis of lignin, from which phenolics are produced, reported that lignin was converted to phenolics by deoxygenation (decarbonylation, decarboxylation, and dehydration), demethoxylation, and cracking on the acid sites, leading to an increase in the yield of phenolics, which is in good agreement with the present study. The pore size of the catalyst might also affect the catalytic activity. For example, HY and H-Beta have different pore sizes. In this study, however, the effect of the pore size was negligible. The activity of HY (30), which has larger pores than H-Beta, was lower than that of H-Beta, suggesting that the acidity is a much more important factor in determining the catalytic activity than the pore size. 3.3. Catalytic copyrolysis of WPB and PP Fig. 6 shows the results of the catalytic copyrolysis of WPB and PP in a fixed bed reactor. As in the pyrolysis of WPB only, the gas yield was increased and the oil yield was decreased by the catalysis. HY (5.1) with the largest number of acid sites produced the largest amount of gas, whereas HY (30), with the fewest acid sites produced the smallest amount of gas. The increase in the yields of CO, CO2, and hydrocarbons by the catalysis (Table 2) were attributed to
decarbonylation, decarboxylation, and cracking promoted by catalysts, as mentioned in Section 3.2. In particular, the yield of hydrocarbons increased to a large extent, suggesting that PP had decomposed to hydrocarbons in the presence of acidic catalysts. A previous study reported that PP was decomposed to C3eC9 hydrocarbons over HY, which is in good agreement with the present study [23]. The water content of bio-oil produced from non-catalytic copyrolysis was 2.08%, which is much smaller than that obtained from the non-catalytic pyrolysis of WPB only (35.50%). This might be due to the supply of sufficient C and H by PP. Catalytic copyrolysis resulted in a larger water content (ca. 9%) in the bio-oil than non-catalytic copyrolysis, which was attributed to the enhanced dehydration by the catalysts. On the other hand, the water content of ca. 9% was much smaller than that of the catalytic pyrolysis of WPB only (ca. 55e60%). Fig. 7 shows the product distributions obtained from copyrolysis determined by Py-GC/MS. Although the oxygenates were the most abundant products in the non-catalytic pyrolysis of WPB only (Fig. 2), hydrocarbons derived from PP were the most abundant products in the non-catalytic copyrolysis of WPB and PP. The hydrocarbon fraction decreased, whereas those of aromatics and phenolics were increased by catalysis. This can be attributed to the conversion of hydrocarbons, oxygenates, and acids into aromatics and phenolics by cracking, oligomerization, deoxygenation, and aromatization occurring on the acid sites of catalysts as in Section 3.2. Ga/H-Beta showed the highest selectivity toward aromatics, whereas HY (30) with the lowest number of acid sites led to the lowest yield of aromatics. This suggests that aromatization occurring on the acid sites was promoted by Ga-induced dehydrocyclization. The yield of aromatics obtained from catalytic copyrolysis was slightly larger than that obtained from the catalytic pyrolysis of WPB only. On the other hand, the yield of PAHs obtained from
70 Non-Catalyst H-Beta Ga/H-Beta HY(5.1) HY(30)
Distribution(area%)
60
50
40
30
20
10
0
s
Acid
Fig. 6. Gas, oil and char yields obtained from the copyrolysis of WPB and PP.
gen Oxy
a tes
roca
Hyd
rbo
ns
Aro
ic mat
s
PAH
s
Phe
noli
cs
Fig. 7. Product distributions obtained from the copyrolysis of WPB and PP.
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H.W. Lee et al. / Renewable Energy xxx (2014) 1e5
Appendix A. Supplementary data
40
Distribution(area%)
30
5
Non-Catalyst H-Beta Ga/H-Beta HY(5.1) HY(30)
Supplementary data related to this article can be found at http:// dx.doi.org/10.1016/j.renene.2014.07.040. References
20
10
0 C1~
C4
C9 C5~
C10
~C1
7
Ov e
r C1
7
Fig. 8. Product carbon number distributions obtained from the copyrolysis of WPB and PP over different catalysts.
copyrolysis was smaller than that from the pyrolysis of WPB only. Because PAHs are carcinogenic and can deactivate the catalyst, the suppression of their production by the catalysis in this study is encouraging. In terms of the carbon number distribution of the oil species (Fig. 8), the main products of non-catalytic copyrolysis were wax species (C17) and large-molecular-mass compounds (C10). On the other hand, catalytic copyrolysis produced small-molecularmass compounds, mainly in the gasoline range (C5eC9). 4. Conclusions The catalytic pyrolysis of WPB was carried out over the HY and H-Beta catalysts. HY (5.1) with the largest amounts of acid sites was most favorable to cracking and deoxygenation reactions. The main compounds obtained from the catalytic pyrolysis of WPB only were phenolics, furans and aromatics. On the other hand, the main products of the catalytic copyrolysis of WPB with PP were hydrocarbons, aromatics and phenolics. The water content in bio-oil was decreased significantly by copyrolysis with PP, contributing to the improvement in oil quality. Catalytic copyrolysis suppressed the formation of PAHs, which are carcinogenic and cause coke formation. C5eC9 hydrocarbons were mostly generated from the copyrolysis. The addition of Ga led to enhanced aromatics production (particularly BTEX) for both the catalytic pyrolysis of WPB only and the catalytic copyrolysis of WPB and PP. Acknowledgment This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2012R1A1B3003394).
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