Optimizing the Aromatic Yield via Catalytic Fast Co-pyrolysis of Rice

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Biofuels and Biomass

Optimizing Aromatic Yield via Catalytic Fast Co-pyrolysis of Rice Straw and Waste Oil over HZSM-5 Catalysts Zihao Zhang, Feng Zhou, Hao Cheng, Hao Chen, Jing Li, Kai Qiao, Kequan Chen, Xiuyang Lu, Pingkai Ouyang, and Jie Fu Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.9b00779 • Publication Date (Web): 18 Apr 2019 Downloaded from http://pubs.acs.org on April 21, 2019

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Optimizing Aromatic Yield via Catalytic Fast Co-pyrolysis of Rice Straw and Waste Oil over HZSM-5 Catalysts Zihao Zhanga#, Feng Zhouc#, Hao Chenga,b, Hao Chena, Jing Lia, Kai Qiaoc, Kequan Chenb, Xiuyang Lua, Pingkai Ouyanga,b, Jie Fua* a

Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of

Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China b

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Biotechnology

and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211816, China c

State Fushun Research Institute of Petroleum and Petrochemicals, SINOPEC, Fushun 113000,

China

#

These authors contributed equally.

* Corresponding author Jie Fu, Tel.: +86 571 87951065, E-mail address: [email protected]

Abstract: Catalytic fast pyrolysis (CFP) of lignocellulosic-based feedstocks into aromatics has attracted much interest owing to its economic feasibility. However, the low effective hydrogen index (H/Ceff) of lignocellulosic biomass adversely impacts the production of aromatics via CFP. Here, we report catalytic fast co-pyrolysis (CFCP) of hydrogen-deficient rice straw (an important lignocellulosicbiomass-derived feedstock) coupled with hydrogen-rich stearic acid, gutter oil, or microalgae oil over a series of selected HZSM-5 catalysts. The aromatic yield of CFP of these three reactants decreases slightly in the order stearic acid, microalgae oil, and gutter oil. CFP of rice straw has a lower aromatic yield than CFP of stearic acid, gutter oil, or microalgae oil. However, CFCP of rice straw along with 1

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each of the hydrogen-rich candidates produces higher aromatic yields than predicted by the theoretical yield values of CFP of the individual materials. Additionally, the mass ratios of the two reactants are optimized to improve the aromatic yield.

Keywords: Catalytic fast co-pyrolysis; Rice straw; Waste oil; Aromatics; HZSM-5

1. Introduction Development of alternative renewable and environment-friendly energy sources has attracted much interest owing to increasing fuel demand and environmental pollution.1-4 The use of lignocellulosic biomass as a carbon-neutral and sustainable feedstock has provided several routes to produce green fuels.5, 6 Among these techniques, catalytic fast pyrolysis (CFP) of abundant lignocellulosic biomass is the most prevalent and is considered the most economically feasible and promising route for production of bio-oil.7-9 In addition to bio-oil, aromatics as the important fuel and chemical can also be produced in large quantities over zeolites catalyst from the CFP of lignocellulosic biomass.10 Benzene, toluene, and xylene (BTX), derived primarily from petroleum, are the main aromatic products during CFP of lignocellulosic biomass.11, 12 HZSM-5 zeolite catalysts, which are used to produce aromatics, have been extensively studied in CFP of lignocellulosic biomass.1316

Although CFP of lignocellulosic biomass exhibits good potential for direct production of aromatics, especially BTX, the use of hydrogen-deficient feedstocks makes it difficult to enhance the aromatic yield by modifying HZSM-5 (by alkali treatment, introduction of a mesotemplate and metal, etc.).11, 17-19 Additionally, large amounts of coke are produced by conversion of the pyrolysis vapors obtained from dehydration of the biomass-derived oxygenates, significantly influencing the

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lifetime of the catalyst.20-22 It has been demonstrated that a higher effective hydrogen index (H/Ceff) contributes to increased production of aromatic and olefin products and decreased production of coke products, and that H/Ceff should be greater than 1 to achieve a high aromatic yield.23 To remedy this problem with CFP of lignocellulosic biomass, catalytic fast co-pyrolysis (CFCP) of them together with hydrogen-rich feedstocks has become an efficient route. Significant efforts have been invested to use CFCP to enhance the aromatic yield. Alvarez et al. reported on CFCP of pinewood sawdust (lignocellulosic biomass) and sewage sludge; they observed a significant synergistic effect compared with CFP of each raw material separately.24 Moreover, CFCP of hemicellulose and plastic has also been investigated for enhancing the aromatic yield.21, 23, 25, 26 Lubricating oil was also chosen as the co-feed in the CFP of bamboo residual, and the yield of aromatics was much higher than that of the CFP of bamboo residual and lubricating oil alone.27 In addition, CFCP of biomass with fusel alcohol and food waste as co-feeds exhibited a remarkably improved aromatic yield.1, 10 In addition to the hydrogen-rich co-feeds mentioned above, low-cost waste lipids like gutter oil and microalgae oil can act as hydrogen donors to lignocellulosic biomass during CFCP, to the best of our knowledge. Here, rice straw, an abundant biomass source from agricultural waste, was used for CFCP with three different co-feeds, i.e., stearic acid, gutter oil, and microalgae oil, over a series of HZSM-5 catalysts. First, CFP of rice straw, stearic acid, gutter oil, and microalgae oil as separate reactants was studied over four selected zeolite catalysts. Second, CFCP of rice straw combined with stearic acid, gutter oil, or microalgae oil was explored, and the corresponding aromatic distributions were summarized. Third, the aromatic yields of CFCP of rice straw along with each co-feed were compared with the theoretical yield values of CFP of each reactant alone.

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2. Materials and methods 2.1 Materials Rice straw procured from a farm was subjected to Soxhlet extraction with toluene and ethanol as solvents and dried at 110 °C overnight before use. Stearic acid was purchased from SigmaAldrich, USA. Microalgae oil was obtained from Jiangsu Tiankai Biotechnology Co., Ltd., China. Gutter oil was obtained from Xiamen Huayihong Import and Export Co., Ltd., China. Prior to use, the microalgae oil and gutter oil were hydrolyzed to obtain mixed fatty acids. An HZSM-5 catalyst with a SiO2/Al2O3 ratio of 38 (ZM5) was procured from Nankai University, Tianjin, China. This optimized SiO2/Al2O3 ratio was determined in our previous work.28 The AZM5 catalyst was synthesized by treating ZM5 with 0.2 M NaOH in accordance with our previous study.28 Metalmodified 0.1 wt.% Cu/AZM5 was synthesized by traditional equivalent-volume impregnation methods using AZM5 as the carrier.28 A hierarchical HZSM-5 catalyst (TZM5) was prepared using trimethoxyoctadecylsilane as the mesotemplate using a previously reported procedure.29 2.2 CFP experiments All the CFP and CFCP experiments were performed in a Tandem μ-reactor system (Rx-3050 TR, Frontier Laboratories, Japan). The schematic diagram of this Tandem μ-reactor system was shown in Figure 1. This system contains two reactors that can be controlled individually at temperatures between 40 and 900 °C. Identification and quantification analyses were carried out in a gas chromatography-mass spectrometry equipment (Agilent 7890 B-5977A MSD) with an ultra-alloy-5 capillary column. The products were diverted into three detectors, i.e., a mass spectrometer, flame ionization detector (FID), and thermal conductivity detector (TCD), for analysis. A liquid nitrogen bath in front of the column was used to stabilize the pyrolysis vapors 4


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of the volatile substances before they arrived at the column. Consequently, good separation was obtained. In a typical experiment, a certain number of mixtures of the catalyst and reactants (rice straw, stearic acid, microalgae oil, and gutter oil) in different mass ratios were injected into the furnaces at 600 °C. All experiments were conducted in triplicate to ensure the reliability of the data. 2.3 Analysis method An elemental analyzer (Vario Micro, Germany) was used for CHN elemental analysis of rice straw, microalgae oil, and gutter oil, as well as to determine the coke contents of the reactants and products. The liquid products were analyzed quantitatively using the FID, and their calibration standards determined under identical reaction conditions. The quantification of gaseous products was carried out in the TCD using the corresponding calibration curves (This technique is known as the external standard method.). The product yield was defined as the ratio of the number of moles of carbon in the product to the number of moles of carbon in the added reactants. The selectivity of the catalyst to the target aromatic was calculated as the ratio of the number of moles of carbons in the target aromatic to the total number of moles of carbons in all the aromatics. The main components unaccounted for were high-molecular-weight substances and undetected coke sticking to the sample cup. The theoretical aromatic yield (Y) from CFCP of rice straw and M (stearic acid, gutter oil, or microalgae oil) was calculated by the following equation. Here, w% is the mass ratio of rice straw to M, and the total loading of rice straw and M kept unchanged. In addition, Yrice straw and YM were the yield obtained from their CFP alone. Y = w% ×Yrice straw + (1-w%) ×YM

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3. Results and discussion 3.1 CFP of stearic acid During CFP process, aromatics were produced by a complex reaction route including decomposition, decarbonylation, decarboxylation, dehydration, Diels-Alder and oligomerization et al. In this work, CFP of rice straw over the four selected catalysts, i.e., ZM5, AZM5, Cu/AZM5, and TZM5, was studied in our previous works.28,

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The aromatic yields at 600 °C with a

catalyst/reactant mass ratio of 20:1 were 23%, 27.2%, 29.2%, and 26.8%, respectively. In contrast, almost no aromatics could be observed without catalysts used. The H/Ceff of stearic acid is close to 2, which is much higher than that of lignocellulosic biomass feedstocks such as rice straw. Consequently, CFP of stearic acid is very effective for production of aromatics. CFP of stearic acid was carried out over the four HZSM-5 catalysts under the same operating conditions, and the results are shown in Figure 2. Compared to CFP of rice straw, CFP of stearic acid had remarkably higher aromatic yields. The aromatic yields obtained over the ZM5, AZM5, Cu/AZM5, and TZM5 catalysts were 36.2%, 37.7%, 38.4%, and 38.0%, respectively. Additionally, a high olefin yield of approximately 18% was achieved; olefins are important building blocks for clean fuels. Because of its lower O content, CFP of stearic acid also yielded CO and CO2. More importantly, coke deposition, which is usually 40% when rice straw is employed, was significantly suppressed to less than 18% when stearic acid was used as the pyrolysis reactant. The other products (not shown in Figure 2) were mainly alkanes with various structures and highmolecular-weight substances. The selectivity of the catalysts to specific aromatics is also summarized in Table 1. Compared to the corresponding values for CFP of rice straw11, 29, the catalyst selectivity to BTX increased remarkably in CFP of stearic acid, at the expense of selectivity to naphthalene and

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methyl naphthalene. The total BTX selectivity approached 80%, which is significant, as these are extremely important components of petrochemical products. Moreover, the four screened catalysts exhibited similar BTX selectivity, and their selectivity to the other aromatic products was less than 20%. 3.2 CFCP of rice straw and stearic acid The CFCP performance of rice straw and stearic acid in mass ratios varying from 1:5 to 5:1 was investigated using ZM5 as a model catalyst. The reaction conditions were identical to those of CFP of stearic acid, and the same mass ratio of the catalyst/total reactant (including both rice straw and stearic acid) i.e., 20:1, was used. With increasing stearic acid content, the yields of both coke and COx decreased significantly, as shown in Figure 3. The decrease in coke yield was ascribed to the lower coke production in CFP of stearic acid compared to CFP of rice straw. The lower COx yield was due to the decrease in total O content with increase in the proportion of stearic acid. In contrast, the olefin yield increased as increasing stearic acid/rice straw ratio, which can be attributed to the higher H/C ratio. Interestingly, the aromatic yield first increased and then decreased with increase in the stearic acid/rice straw ratio, and peaked at a stearic acid loading of 50%. The theoretical aromatic yield of CFCP of rice straw and stearic acid was calculated by adding the actual yields of CFP of each individual reactant, as shown in Figure 4. Surprisingly, the addition of stearic acid to rice straw promoted the formation of aromatics via CFCP. The highest aromatic yield, 40.2%, was realized when 50% stearic acid was used as the co-feed; this value was higher than the yield of 36.2% obtained in CFP of stearic acid. These results reveal a significant synergistic effect between rice straw and stearic acid during CFCP. Additionally, using suitable mass ratio of rice straw/stearic acid enhanced the production of aromatics. Stearic acid could provide hydrogen for pyrolysis of rice straw owing to its higher H/Ceff value. In addition, the oxygenated products from rice straw might facilitate chain scission or cracking of long-chain stearic acid and the corresponding deoxygenated 7


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substances.7 Therefore, this process of CFCP between two sustainable substances can enhance the production of aromatics while ensuring good economic efficiency. Additionally, the BTX selectivity increased gradually with stearic acid content, at the expense of the yield of polycyclic aromatic hydrocarbons (naphthalene and methyl naphthalene), as seen in Table S1. In addition to ZM5, the AZM5, Cu/AZM5, and TZM5 catalysts were also used for CFCP of rice straw and stearic acid at the optimized mass ratio of 1:1. The product distribution in Figure 5 shows that the actual aromatic yield of CFCP increased to 40%; the yields were 41.3%, 41.9%, and 40.8% when AZM5, Cu/AZM5, and TZM5, respectively, were used. In addition, the coke yield was also controlled to below 25% in all three cases. More importantly, the theoretical aromatic yields of CFCP calculated from the yield of CFP of stearic acid and rice straw alone were much lower than the corresponding practical values. These results indicate that CFCP of rice straw and stearic acid over various HZSM-5 catalysts is an efficient approach to improving the aromatic yield. In addition, the BTX selectivity of each of the three selected catalysts was higher than 70%, as shown in Table S2. 3.3 CFCP of rice straw and gutter oil Gutter oil hydrolysate contains a large amount of fatty acids30 and can be used as a co-feed to enhance the CFP performance of rice straw. Moreover, compared to stearic acid, gutter oil has better application prospects owing to its low cost and abundant availability. Prior to the CFCP of rice straw and gutter oil, CFP of gutter oil alone was performed over different catalysts. The elemental composition of rice straw was 37.4% C, 5.4% H, 0.9% N and remaining 56.3% O.29 In comparison, the elemental composition of gutter oil hydrolysate was obtained using an elemental analyzer (Vario Micro, Germany), which showed that the mass fractions of C, H, and O were 75.0%, 12.4%, and 12.6%, respectively. The H/Ceff value of gutter oil as calculated by the equation H/Ceff = (H – 2O)/C is approximately 1.831, which is much higher than 0.6 achieved from rice 8


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straw.22 As a result, a very high aromatic yield of approximately 32% was achieved in the CFP of gutter oil, which is much higher than that obtained in CFP of rice straw under identical reaction conditions.29 Unlike CFP of stearic acid, CFP of gutter oil yielded more olefins than aromatics (Figure 6). This can be ascribed to the presence of C=C double bonds in the unsaturated fatty acids of gutter oil. The catalyst selectivity to aromatic products in CFP of gutter oil is summarized in Table S3. The total selectivity to BTX in CFP of gutter oil exceeded 70%. Next, CFCP of gutter oil and rice straw was studied to investigate their synergistic effect, as shown in Figure 7. The mass ratio of gutter oil/rice straw was 1:1, and the theoretical aromatic yields calculated using the yield of CFP of each feedstock separately are 27.5%, 30.0%, 30.9%, and 29.8% over ZM5, AZM5, Cu/AZM5, and TZM5, respectively. The practical values of the aromatic yield of CFCP of gutter oil and rice straw were higher than their theoretical counterparts over all four catalysts. In other words, the addition of gutter oil for the CFCP with rice straw significantly enhanced the aromatic product yield and is thus a very important technique for application of waste cooking oil and rice straw. Additionally, catalyst selectivity to both naphthalene and methyl naphthalene was higher in CFCP of rice straw and gutter oil than in CFP of gutter oil alone, as shown in Table S4. This finding in thought to be attributable to the higher yields of naphthalene and methyl naphthalene obtained in CFP of rice straw. 3.4 CFCP of rice straw and microalgae oil In addition to gutter oil, microalgae oil with a triglyceride content of more than 60% is a promising renewable energy resource due to rapid growth rate of algal biomass.32 The elemental composition of microalgae oil hydrolysate was determined using an elemental analyzer (Vario Micro, Germany), which showed that the mass fractions of C, H, and O were 76.5%, 11.5%, and 12.0%, respectively. H/Ceff was calculated to be approximately 1.6, suggesting that microalgae oil 9


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can also be considered a hydrogen-rich feedstock. The aromatic yield of CFP of microalgae oil was also much higher than that of CFP of rice straw. The aromatic and olefin yields of CFP of microalgae oil were slightly higher than those of CFP of gutter oil, as shown in Figures 6 and 8. These results were ascribed to the higher unsaturation of microalgae oil. The catalyst selectivity to aromatic products in CFP of microalgae oil is summarized in Table S5; a BTX selectivity of approximately 70% was observed. For CFCP process, the experimental yields of aromatics were all higher than the theoretical value at all CFCP runs. These suggested that the synergetic effects of rice straw and waste oil existed during CFCP process and were beneficial to produce higher aromatics yield. A reasonable explanation was that the intermediate products of CFP of rice straw and waste oil might react with each other, enhancing the possibility of aromatics formation. CFCP of microalgae oil and rice straw at a mass ratio of 1:1 was also conducted under identical reaction conditions. The aromatic yields obtained over the ZM5, AZM5, Cu/AZM5, and TZM5 catalysts were 37.2%, 37.9%, 39.2%, and 38.1%, respectively, as shown in Figure 9. The olefin yields were in the range 15%~16%, and the total yields of CO and CO2 were greater than 10%. The obtained aromatic yield was expected to be much higher than the theoretical yield value calculated using the yields of CFP of microalgae oil and rice straw alone. The selectivity to BTX was also approximately 70%, as shown in Table S6.

4. Conclusions CFCP of hydrogen-deficient rice straw combined with hydrogen-rich stearic acid, gutter oil or microalgae oil over a series of selected HZSM-5 catalysts was studied. The addition of stearic acid for the CFCP of rice straw significantly enhanced the aromatic yield compared to that obtained in CFP of rice straw alone. Further, CFCP of rice straw along with waste raw feedstocks, i.e., gutter oil and

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microalgae oil, also exhibited an enhanced aromatic yield. The use of CFCP increased the selectivity to BTX to 70%. Additionally, the mass ratios of the two reactants and types of catalysts were studied to optimize the aromatic yield. Thus, CFCP of hydrogen-deficient rice straw mixed with hydrogen-rich waste oil provided an efficient and low-cost technique to enhance the CFP performance.

Acknowledgments This work was supported by the Zhejiang Provincial Natural Science Foundation of China (No. LR17B060002), and the National Natural Science Foundation of China (Nos. 21436007, U1663227, 21706228).

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Dorado, C.; Mullen, C.A.; Boateng, A.A. H-ZSM5 catalyzed co-pyrolysis of biomass and plastics. ACS Sustain. Chem. Eng. 2013, 2(2), 301-11.

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Dorado, C.; Mullen, C.A.; Boateng, A.A. Origin of carbon in aromatic and olefin products derived from HZSM-5 catalyzed co-pyrolysis of cellulose and plastics via isotopic labeling. Appl. Catal. B: Environ. 2015, 162, 338-45.

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Wang, J.; Zhang, B.; Zhong, Z.; Ding, K.; Deng, A.; Min M, Chen, P.; Ruan, R. Catalytic fast co-pyrolysis of bamboo residual and waste lubricating oil over an ex-situ dual catalytic beds of MgO and HZSM-5: Analytical PY-GC/MS study. Energy Convers. Manage. 2017, 139, 222-31.

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Energy & Fuels

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Chen, H.; Cheng, H.; Zhou, F.; Chen, K.; Qiao, K.; Lu, X.; Ouyang, P.; Fu, J. Catalytic fast pyrolysis of rice straw to aromatic compounds over hierarchical HZSM-5 produced by alkali treatment and metal-modification. J. Anal. Appl. Pyrol. 2018, 131, 76-84.

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Zhang, Z.; Cheng, H.; Chen, H.; Li, J.; Chen, K., Lu, X.; Ouyang, P.; Fu, J. Catalytic Fast Pyrolysis of Rice Straw to Aromatics over Hierarchical HZSM-5 Treated with Different Organosilanes. Energy Fuels 2019, 33(1), 307-312.

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15


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 1. The schematic diagram of Tandem μ-reactor system

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Page 17 of 26

80

Aromatics

Olefins

CO+CO2

Coke

70 60

Yield (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

50 40 30 20 10 0

ZM5

AZM5

Cu/AZM5

TZM5

Figure 2. CFP performance of stearic acid over different catalysts

17


Energy & Fuels

Aromatics CO+CO2

45 40

Olefins Coke

35 Yield (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 26

30 25 20 15 10 5 0

1:0

5:1

4:1

3:1

2:1

1:1

1:2

1:3

1:4

1:5

0:1

Rice straw/stearic acid

Figure 3. CFCP of stearic acid and rice straw in different mass ratios over ZM5 catalyst

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Page 19 of 26

40 36

Yield (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

32 28 theoretical value practical value

24 0.0

0.2

0.4

0.6

0.8

1.0

Stearic acid content (wt%)

Figure 4. Comparison between theoretical and practical values of aromatic yield of CFCP of rice straw and stearic acid in different mass ratios. The stearic acid content (wt%) was calculated respectively by the selected mass ratios of rice straw and stearic acid including 1:0, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5 and 0:1.

19


Energy & Fuels

Aromatics CO+CO2

50

Olefins Coke

Theoretical aromatic yield

40 Yield (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 26

30 20 10 0

AZM5

Cu/AZM5

TZM5

Figure 5. CFCP of stearic acid and rice straw in a mass ratio of 1:1 over AZM5, Cu/AZM5, and TZM5 catalysts

20


Page 21 of 26

35

Aromatics

Olefins

CO+CO2

30 25 Yield (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

20 15 10 5 0

ZM5

AZM5

Cu/AZM5

TZM5

Figure 6. CFP of gutter oil over ZM5, AZM5, Cu/AZM5, and TZM5 catalysts

21


Energy & Fuels

50 40

Yield (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 26

Aromatics CO+CO2

Olefins Theoretical aromatic yield

30 20 10 0

ZM5

AZM5

Cu/AZM5

TZM5

Figure 7. CFCP of gutter oil and rice straw over ZM5, AZM5, Cu/AZM5, and TZM5 catalysts

22


Page 23 of 26

40 Aromatics

35

Olefins

CO+CO2

30 Yield (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

25 20 15 10 5 0

ZM5

AZM5

Cu/AZM5

TZM5

Figure 8. CFP of microalgae oil over ZM5, AZM5, Cu/AZM5, and TZM5 catalysts

23


Energy & Fuels

50 40

Yield (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 26

Aromatics CO+CO2

Olefins Theoretical aromatic yield

30 20 10 0

ZM5

AZM5

Cu/AZM5

TZM5

Figure 9. CFCP of microalgae oil and rice straw over ZM5, AZM5, Cu/AZM5, and TZM5 catalysts

24


Page 25 of 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Table 1. Selectivity (%) of catalysts to aromatic products during CFP of stearic acid Catalyst

Benzene

Toluene

Xylene

Naphthalene

Others

2.6

Methyl naphthalene 1.7

ZM5

11.9

37.7

28.7

AZM5

12.0

37.0

28.7

2.7

2.3

17.3

Cu/AZM5

12.0

35.8

28.7

2.7

2.4

18.4

TZM5

11.6

37.7

27.8

1.6

1.7

19.6

25


17.4

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Optimizing Aromatic Yield via Catalytic Fast Co-pyrolysis of Rice Straw and Waste Oil over HZSM-5 Catalysts Zihao Zhanga#, Feng Zhouc#, Hao Chenga,b, Hao Chena, Jing Lia, Kai Qiaoc, Kequan Chenb, Xiuyang Lua, Pingkai Ouyanga,b, Jie Fua*

26


Page 26 of 26

Optimizing the Aromatic Yield via Catalytic Fast Co-pyrolysis of Rice

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