Accepted Manuscript

Production of bio-oil from agricultural waste by using a continuous fast micro-

wave pyrolysis system

Yunpu Wang, Zihong Zeng, Xiaojie Tian, Leilei Dai, Ling Jiang, Shumei Zhang,
Qiuhao Wu, Pingwei Wen, Guiming Fu, Yuhuan Liu, Roger Ruan

PII: S0960-8524(18)31171-4
DOI: https://doi.org/10.1016/j.biortech.2018.08.067
Reference: BITE 20350

To appear in: Bioresource Technology

Received Date: 20 July 2018

Revised Date: 14 August 2018
Accepted Date: 16 August 2018

Please cite this article as: Wang, Y., Zeng, Z., Tian, X., Dai, L., Jiang, L., Zhang, S., Wu, Q., Wen, P., Fu, G., Liu,
Y., Ruan, R., Production of bio-oil from agricultural waste by using a continuous fast microwave pyrolysis system,
Bioresource Technology (2018), doi: https://doi.org/10.1016/j.biortech.2018.08.067

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 Production of bio-oil from agricultural waste by using a continuous fast

microwave pyrolysis system

Yunpu Wang a,b,d , Zihong Zeng a,b, Xiaojie Tian a,b, Leilei Dai a,b, Ling Jiang a,b,

Shumei Zhang a,b, Qiuhao Wu a,b, Pingwei Wen a,b, Guiming Fu a, Yuhuan Liu a,b*,

Roger Ruan a,b,c

a
Nanchang University, State Key Laboratory of Food Science and Technology,

Nanchang 330047, China

b
Nanchang University, Engineering Research Center for Biomass Conversion,

Ministry of Education, Nanchang 330047, China

c
Center for Biorefining and Department of Bioproducts and Biosystems Engineering

University of Minnesota, 1390 Eckles Ave., St. Paul, MN 55108, USA

d
Guangdong Provincial Key Laboratory of New and Renewable Energy Research and

Development, Guangzhou 510640, China

Abstract: In this study, a continuous fast microwave-assisted pyrolysis system was

developed to produce bio-oil, gas, and biochar from rice straw and Camellia oleifera

shell. The effects of different pyrolysis temperatures (400 °C, 500 °C, and 600 °C)

and feed rates (rice straw: 25, 45, and 66 g/min; C. oleifera shell: 100, 200, and 400

g/min) on bio-oil production were investigated. Experimental results showed that the

∗Corresponding author at: Nanchang University, State Key Laboratory of Food

Science and Technology, Nanchang 330047, China.
E-mail address: liuyuhuan@ncu.edu.cn (Yuhuan Liu)；
yields of bio-oil (31.86 wt%) and gas (54.49 wt%) produced by the

microwave-assisted pyrolysis of rice straw increased with increasing temperature. By

contrast, the yields of bio-oil (27.45 wt%) and biochar (35.47 wt%) produced by the

pyrolysis of C. oleifera shell decreased with increasing temperature. The contents of

phenols, aldehydes, and alcohols in bio-oil produced from the shell were higher than

those in bio-oil derived from rice straw.

Keywords: Microwave; Fast pyrolysis; Rice straw; Camellia oleifera shell; Bio-oil

1. Introduction

With the rapid depletion of fossil fuels, renewable and environment-friendly

energy sources have attracted much attention. Biomass is one of the most severely

wasted resources and has advantages, including carbon neutrality, abundance, and low

cost. Biomass is usually treated by direct combustion and anaerobic digestion. Direct

combustion is the main method for handling biomass (Yin et al., 2018; Zeng et al.,

2007). However, this method is harmful to the environment and can produce

substantial amounts of toxic and harmful gases and dust (Hong et al., 2016; Zhang et

al., 2008). These contaminants can easily trigger severe asthma attacks (Torigoe et al.,

2000). Therefore, scholars must develop pollution-free and efficient means for

handling biomass.

Conventional pyrolysis has developed rapidly in recent years; in developed

countries, such as the United States and Canada, this method is used to analyze

material components; treat urban sludge, garbage, plastic, waste biomass, and rock

(Clarke et al., 2017); and generate power (Jones, 2014). This technology has also been
commercialized for treatment of domestic and agricultural wastes. However, the

commercial application of conventional pyrolysis remains in infancy in developing

countries. Given its superficial heating mechanism that is mainly based on heat

transfer between adjacent molecules, conventional pyrolysis creates a barrier in the

material to block heat transfer from the outer surface to the core (Farag et al., 2016;

Miura et al., 2004; Thostenson & Chou, 1999; Wu et al., 2014). Conventional

pyrolysis yields lower gas amounts and higher biochar levels compared with

microwave pyrolysis, which generates heat inside the material, under the same

conditions (Farag et al., 2016; Xin-hui et al., 2011). Hence, conventional pyrolysis

exhibits lower heating efficiency, longer pyrolysis time, slower heating rate, and

lower product quality (Xin-hui et al., 2011). Compared with traditional pyrolysis

technology, microwave-assisted pyrolysis is simpler, easier to industrialize, and more

efficient and selective and can be precisely controlled to a certain degree (Dai et al.,

2017; Li et al., 2016; Wang et al., 2016; Yin, 2012; Leng et al., 2019; Wang et al., 2018a;

Wang et al., 2018b; Wang et al., 2018c). In recent years, the use of microwave-assisted

pyrolysis of biomass has surged in biomass research. Rice straw is the most common

type of biomass and has been considerably explored for microwave pyrolysis. Du et al.

(Du et al., 2010) found that rice straw can produce an oil yield of 38% within 20 min

of microwave heating. Ravikumar and his co-workers (Ravikumar et al., 2017)

observed that the yield of rice straw pyrolyzed by microwave with a maximum power

of 800 W is very low (15.3 wt%). Huang et al. (Huang et al., 2013) reported that the

liquid products of the microwave-assisted pyrolysis of rice straw are mainly

monoaromatic hydrocarbons, polycyclic aromatic hydrocarbons, and aliphatic

compounds. Camellia oleifera shell is an agricultural waste biomass with high

contents of lignin, cellulose, and hemicellulose (Hu et al., 2015). More than 3×106

tons of C. oleifera shell is annually discarded or burnt (Zhang et al., 2018). To date,

only the products of C. oleifera shell in the fluidized-bed fast pyrolysis system (Wu et

al., 2016), Foss method (Xie et al., 2018), and water extraction (Zhang et al., 2011)

have been explored. Few studies have investigated the microwave-assisted pyrolysis

of C. oleifera shell.

Rice straw and C. oleifera shell collected from countryside is biomass processed

through a newly developed continuous fast microwave-assisted pyrolysis (cfMAP)

system. Incineration and landfilling are mainly used for biomass treatment (Yin et al.,

2018; Zeng et al., 2007). Meanwhile, conventional pyrolysis is the main method for

utilizing biomass resources. Previous studies concluded that pyrolysis technology can

achieve 50% reduction in waste volume and obtain high total heat values for bio-oil

(28 MJ/kg) and syngas (25 MJ/m3) (Inguanzo et al., 2002). In contrast to conventional

pyrolysis, the use of a rapid microwave pyrolysis device involves the following

advantages. (1) Uniform heat transfer, high heating efficiency, and fast response are

attained. (2) The coke content is greatly reduced, and the quality of biochar is

improved. (3) When the heating effect is the similar, the required temperature is

relatively low, which relatively saves energy.

This study focuses on producing bio-oil from agricultural wastes by using a

continuous microwave-assisted pyrolysis system. The effects of pyrolysis temperature

and feed rate on product yield were determined. The liquid bio-oils were analyzed

using gas chromatography (GC)–mass spectrometry (MS) technique.

2. Materials and Methods

2.1. Materials

Rice straw and C. oleifera shell, which is the by-products of the agricultural

industry, was collected from Nanchang, Jiangxi Province, China. They were used as

raw materials and dried in an oven at 105 °C for 48 h. The samples were pulverized

by a pulverizer and screened with an 80-mesh sieve to obtain particles with 0.18 mm

diameter. The powders were dried again for 24 h for subsequent use. The cellulose,

hemicellulose and lignin content of the rice straw and C. oleifera shell was

determined according to the method of Phan et al. (Phan et al., 2014).

2.2. cfMAP experiments

The microwave pyrolysis system is shown in Fig. 1. This system can set the

target pyrolysis temperature and adjust the microwave power, feed rate and agitation

speed through the control system. When the spherical SiC in the microwave reaction

chamber reached the target temperature, the biomass was continuously fed into the

microwave reaction chamber through the screw feeder. Under the action of the

agitator, the residue generated after the reaction was discharged into the slag trap

through the orifice plate. The pyrolysis steam was condensed by the condenser into

bio-oil and collected in the liquid collector, and the non-condensable gas was
collected by the gas collector. The device has the advantages of that it can be operated

continuously and it is suitable for industrial production.

The pyrolysis of rice straw and C. oleifera shell was carried out at different

temperatures and feed rates to study the effect of these factors on bio-oil production

yield and quality. The microwave device was turned on to start heating before

pyrolysis. When the temperature of the reactor reached the desired value, 100 g of the

sample was fed to the reactor at different feed rates. We then investigated the

differences in the yield and quality of bio-oil from rice straw at different feed rates (24,

45, and 66 g/min) and temperatures (400 °C, 500 °C, and 600 °C). The temperature of

the microwave-assisted pyrolysis of C. oleifera shell was set to 400 °C, 500 °C, and

600 °C, and the feed rates were set to 100, 200, and 400 g/min. When no liquid

flowed into the condenser, the pyrolysis reactions were considered complete. After the

pyrolysis, the liquid product was weighed, and yield was calculated on the basis of the

actual weight. The yields of bio-oil and char were calculated based on their actual

weight. The condensed liquid in the condensers was considered as bio-oil. The solid

residue in the pyrolysis reactor was considered as biochar. The yields of bio-oil and

biochar were calculated basis on their actual weights. The gas weight was calculated

as follows:

Mg = Mf - Mo - Mc

where Mg, Mf, Mo, and Mc are the gas weight, initial feedstock weight, bio-oil

weight, and char weight, respectively. The temperatures of 400 °C, 500 °C, and

600 °C were selected based on previous literature indicating that 400 °C–600 °C is the
optimum temperature for the pyrolysis of straw (Balagurumurthy et al., 2015; Biswas

et al., 2017a; Jung et al., 2008; Park et al., 2014; Phan et al., 2014; Putun, 2004;

Ukaew et al., 2018). At these temperatures, differences in the yield of product and

quality of bio-oil in the pyrolysis of different varieties at different feed rates were

studied.

2.3. Analysis of liquid products

The bio-oil produced by pyrolysis was filtered through a 0.22 μm organic syringe

membrane. The chemical composition of the bio-oil was determined using an Agilent

gas chromatograph–mass spectrometer (Agilent 7890B) equipped with a capillary

column (HP-5ms; 30 m × 0.25 mm × 0.25 m). The gas chromatograph was

programmed to heat to 60 °C for 2 min and then to 280 °C at a rate of 10 °C/min. The

vaporizer temperature was set to 250 °C, the split ratio was set to 20:1, and the

sampling size was 0.2 L. The carrier gas (helium) was introduced at a rate of 1

mL/min. The electron multiplier voltage of the MS detector was set to 1941 V, the

interface temperature was set to 280 °C, the ion source temperature was set to 230 °C,

and the analysis mode was scan mode. The area percentage was used to determine the

relative proportion of each chemical compound in the bio-oil. Considering that the

material was raw crude oil, we assumed that the detector reacted similarly to all

compounds. Each compound was identified by comparing the experimental mass

spectra with those in the NIST Mass Spectral library.

3. Results and discussion

3.1. Characteristics of rice straw and C. oleifera shell

The characteristics of rice straw and C. oleifera shell are shown in Table 1. The

amounts of volatile combustible materials in rice straw and C. oleifera shell are very

high (approximately 76 wt%). The proportion of ash in rice straw (11.23 wt%) was

higher than that in C. oleifera shell (1.46 wt%).

The O/C and H/C molar ratios were 0.79 and 1.60, respectively, for rice straw

and 0.75 and 1.47, respectively, for C. oleifera shell. We expected that the C. oleifera

shell would produce more oxygenated volatile compounds than rice straw. We

inferred that the chemical composition of rice straw is C1.00H1.60O0.79N0.02, and that of

C. oleifera shell is C1.00H1.47O0.75N0.04.

3.2. Product yields

As shown in Table 2, the liquid product of the microwave-assisted pyrolysis of

rice straw achieved the highest yield of 31.86% at 24 g/min feed rate and 500 °C.

Consistent with results in previous studies, we considered that the optimum pyrolysis

temperature for rice straw was 500 °C (Jung et al., 2008; Park et al., 2014; Xiao et al.,

2010; Zhou et al., 2017). The bio-oil produced from the pyrolysis of C. oleifera shell

achieved the highest yield (27.45%) at 200 g/min feed rate and 400 °C, which is the

optimal pyrolysis temperature for biomass (Balagurumurthy et al., 2015; Biswas et al.,

2017a; Biswas et al., 2017b). The differences in the maximum bio-oil yield and

optimal pyrolysis temperature between rice straw and C. oleifera shell may be due to

their different lignocellulose compositions; moreover, the thermochemical behavior of

cellulose, hemicellulose and lignin differs from one another (Huang et al., 2013).

Therefore, different biomass feedstock may have different maximum bio-oil yields

and optimal pyrolysis temperatures.

At 500 °C, the high feed rate resulted in low bio-oil yield from the pyrolysis of

rice straw and C. oleifera shell. After pyrolysis of C. oleifera shell and straw at

600 °C and 400 °C, respectively, the bio-oil yield increased with increasing feed rate.

This finding requires further study.

The solid residue generated by the microwave-assisted pyrolysis of rice straw

and C. oleifera shell was identified to be biochar, which is an aromatized and

insoluble solid material produced by the pyrolysis of biomass under complete or

partial anoxic conditions (Capunitan & Capareda, 2012). Table 2 shows the yield of

biochar and gas produced by the microwave-assisted pyrolysis of rice straw and C.

oleifera shell at 400 °C, 500 °C and 600 °C. In previous studies, the yields of biochar

and gas produced by the pyrolysis of rice straw at 500 °C in a fluidized bed reactor

were 31.35% and 20.90%, respectively (Phan et al., 2014). In a laboratory-scale

pyrolysis reactor, the bio-char yields were 33.51%, 28.26%, and 25.81% and the gas

yields were 24.58%, 29.05%, and 28.08% at 400 °C, 500 °C, and 600 °C, respectively

(Park et al., 2014). In the present experiment, the microwave-assisted pyrolysis of rice

straw at 400 °C led to the yields of 37.41%, 38.67%, and 39.15% for biochar and

43.63%, 41.08%, and 39.39% for gas at the feed rates of 24, 45, and 66 g/min,

respectively. The biochar yields from the microwave-assisted pyrolysis of rice straw

were 32.44%, 34.83%, and 41.96% at 500 °C and 31.27%, 33.14%, and 34.52% at
600 °C; meanwhile, the gas yields were 35.70%, 38.14%, and 39.13% at 500 °C and

52.49%, 41.14%, and 49.20% at 600 °C at the feed rates of 24, 45, and 66 g/min,

respectively. The product yields of the pyrolysis reaction varied greatly at constant

temperature and under different reaction conditions. In particular, reaction conditions,

such as product particle size, reactor, and heating rate, caused the varying degrees of

pyrolysis of the material.

A high heating rate is favorable for rapid decomposition of biomass and produces

additional gas; this notion is consistent with the experimental results of the present

study (Kan et al., 2016). Given the high heating rate of microwave-assisted pyrolysis,

many types of chemical bonds are destroyed simultaneously before the rearrangement

reaction, leading to release of numerous volatile compounds. As the reactor

temperature rises above 550 °C, the fragmentation reaction increasingly ensues and

leads to the formation of low-molecular-weight compounds, some of which are not

easy to condense (Collard & Blin, 2014). Several studies have also shown that the

amount of volatile compounds produced increases with decreasing particle size in the

range of 0.18mm-0.50mm (Jung et al., 2008; Phan et al., 2014; Shen et al., 2009).

This finding is consistent with the present experimental results.

In this experiment, pyrolysis was conducted by varying the feed rate. When the

feed rate increased to a certain extent, the heat transferred in the reactor was

insufficient to rapidly increase the temperature of the biomass. Therefore, increasing

the feed rate increased the biochar yield. As shown in Table 2, the biochar yield

showed an increasing trend as the feed rate increased; thus, the biochar yields reported
are reasonable.

Previous studies reported that composition and mineral content may affect the

distribution and properties of the product because of the minerals’ catalytic effect on

biomass pyrolysis. For example, minerals can promote the rearrangement of the

aromatic ring and hence augment the biochar yield (Collard & Blin, 2014; Kan et al.,

2016), as exemplified by our experiment. The amount of biochar produced from rice

straw was higher than that from C. oleifera shell under the same conditions. Moreover,

differences in crystallinity and mineral content between rice straw contains and C.

oleifera shell can produce more biochar than cellulose during hemicellulose pyrolysis,

and rice straw contains more hemicellulose than C. oleifera shell. These observations

are consistent with the results of our experiment.

3.3. Bio-oil composition

3.3.1. Effect of pyrolysis temperature

The bio-oil obtained by the microwave-assisted pyrolysis of rice straw is

displayed in Fig. 2. In a vacuum environment and at different pyrolysis temperatures,

the amount of phenols was the highest (40.55%) at 600 °C. With increasing

temperature, the phenol yield increased gradually through lignin degradation (Biswas

et al., 2017b). The increase in the temperature promoted the cleavage of C–C and C–

O bonds in lignin and increased the yield of phenols (Ma et al., 2018). The aldehyde

and alcohol levels also increased with increasing pyrolysis temperature. The increase

in the temperature led to decrease in the ketone content, consistent with the reported
trend of ketones in literature (Ma et al., 2018; Nam et al., 2015; Xiong et al., 2018).

The content of organic acids also decreased with increasing temperature; the increase

in the temperature possibly increased the probability of cracking or polymerization of

the compounds and decreased their concentrations (Xiong et al., 2018).

The bio-oil obtained from the microwave-assisted pyrolysis of C. oleifera shell is

presented in Fig. 3. The contents of phenols, ketones, aldehydes, and alcohols

increased with increasing temperature and were higher during pyrolysis at 500 °C

(42.63%, 20.45%, 11.51%, and 8.65%, respectively) than at other temperatures. This

finding is inconsistent with the variations in the amount of bio-oil produced through

the pyrolysis of rice straw at different temperatures; the lignocellulose composition

and contents in the two biomass samples were dissimilar, thereby affecting the

interaction between different components (Kan et al., 2016). The organic acid content

gradually reduced with increasing temperature, and this trend was consistent with the

variation in bio-oil content with temperature during the pyrolysis of rice straw.

3.3.2. Effect of feed rate

Experiments on rice straw and C. oleifera shell were conducted at different

temperatures and feed rates, and the liquid product bio-oil was analyzed by GC–MS

(Agilent 7890 B) (Figs. 4 and 5). The bio-oil from the pyrolysis of rice straw contains

phenols, ketones, aldehydes, organic acids, and alcohols; of which, phenols are the

main components (35.14%–39.97%), followed by ketones (19.87%–23.32%). For the

bio-oil obtained by the microwave-assisted pyrolysis of rice straw, the contents of

these components varied at different feed rates. The content of phenolic compounds in
the bio-oil produced by the pyrolysis of rice straw was the highest, consistent with

previous studies (Balagurumurthy et al., 2015; Biswas et al., 2017b; Jung et al., 2008).

With increasing feed rate, the content of phenols increased initially and then

decreased; meanwhile, the contents of aldehydes, ketones, and alcohols gradually

increased, and that of organic acids decreased. As the feed rate increased, the heating

rate also decreased, and the heating temperature could not quickly reach the desired

temperature. According to previous studies, a low heating rate results in a high ketone

content (Xiong et al., 2018). Another study found that low heating temperatures of

400 °C–550 °C (low heating rate) led to higher contents of aldehydes, ketones, and

alcohols and lower contents of organic acids; meanwhile, the content of phenols

increased first and then decreased with increasing feed rate (Ma et al., 2018). This

observation shows that our experimental results are reasonable.

The bio-oil produced by the pyrolysis of C. oleifera shell was similar to that

produced from rice straw. The main components are phenols, ketones, aldehydes,

organic acids, and alcohols; of which, phenols accounted for 34.59–42.63 wt%,

followed by ketones (14.69–20.45 wt%). Similar to that in rice straw, the content of

phenols in bio-oil from C. oleifera shell was the highest under different

microwave-assisted pyrolysis conditions. The variations in phenol and acid contents

were consistent with the changes in bio-oil produced by rice straw; that is, with

increasing feed rate, the organic acid content decreased, whereas the phenol content

increased initially and then decreased. However, the variations in the contents of

aldehydes, ketones, and alcohols differed between bio-oil produced from rice straw
and C. oleifera shell. With increasing feed rate, the contents of aldehydes, ketones,

and alcohols increased first and then decreased; this effect was mainly due to the

difference in the composition and contents of lignocellulose between C. oleifera shell

and rice straw. The different levels of lignin, cellulose, and hemicellulose lead to

different interactions in the reaction (Kan et al., 2016). In addition, the changes in the

feed rate during the pyrolysis of C. oleifera shell and rice straw differed, which may

result in different degrees of reaction and trends.

3.4. Analysis of the advantages of C. oleifera shell

Based on previous studies, the present experiment used rice straw and compared

it with C. oleifera shell for microwave-assisted pyrolysis (Biswas et al., 2017a; Du et

al., 2010; Jung et al., 2008; Phan et al., 2014; Ravikumar et al., 2017). The

components of bio-oil produced by the pyrolysis reaction were identified by GC–MS

(Table 3). In the bio-oil compositions of the pyrolysis products from rice straw and C.

oleifera, phenols were the main components and specifically included phenol,

catechol, p-cresol, phenol, 2-methoxy-, phenol, 2-methyl-, phenol, 4-ethyl-,

1,2-benzenediol, 3-methyl-, phenol, 2,6-dimethoxy-, hydroquinone,

2-methoxy-5-methylphenol, and phenol, 2,4-dimethyl-, with contents of 8.29%,

4.49%, 5.44%, 3.32%, 3.15%, 3.82%, 1.71%, 1.22%, 1.95%, 0.17%, and 0.23%,

respectively, in the bio-oil from rice straw and 7.46%, 6.34%, 4.92%, 2.39%, 2.45%,

1.39%, 1.91%, 1.58%, 0.64%, 0.74%, and 0.57%, respectively, in the bio-oil from C.

oleifera shell. High amounts of phenolic compounds, such as catechol,

1,2-benzenediol, 3-methyl- and phenol, 2,6-dimethoxy-, were observed in the bio-oil

produced by the pyrolysis of C. oleifera shell (6.34%, 1.91%, and 1.58%,

respectively). Phenols are widely used as raw materials in the chemical, agricultural,

and food industries. The amounts of furfural, vanillin, and 3,4,5- trimethyl pyrazole

(5.63%, 1.21%, and 0.79%, respectively) in the bio-oil produced from the pyrolysis of

C. oleifera shell were higher than those in the bio-oil produced by rice straw pyrolysis

(3.71%, 0.23%, and 0.00%, respectively). In particular, the content of furfural, which

is a raw material for preparing many drugs and industrial products, was the highest.

The bio-oil produced from the pyrolysis of C. oleifera shell has higher furfural

content that from rice straw and is thus more suitable for industrial production. Figs. 2

and 3 suggest that the amount of phenols in the bio-oil produced from C. oleifera shell

is much higher, and the organic acid content is lower than that in the bi-oil from rice

straw. These properties resulted in the lower acidity and improved bio-oil stability and

quality of bio-oil produced from C. oleifera shell than from rice straw.

The compositions of the rice straw and C. oleifera shell differ, resulting in

different bio-oil components obtained after pyrolysis. The contents of cellulose,

hemicellulose, and lignin were 36.72%, 26.81%, and 14.53%, respectively, in rice

straw and 23.40%, 30.72%, and 36.37%, respectively, in C. oleifera shell. The

thermochemical changes in the contents of cellulose, hemicellulose, and lignin differ

from one another. Hemicellulose and cellulose degrade to form alkanes, aldehydes,

alcohols, ketones, carboxylic acids, furans, and derivatives as well as many aromatic

oxygenates. Phenolic derivatives and aromatic ethers are mainly derived from lignin

(Balagurumurthy et al., 2015; Biswas et al., 2017b). The lignin content in C. oleifera
shell was higher than that in rice straw. The contents of phenolic substances in the

bio-oil obtained from the pyrolysis of C. oleifera shell were higher than those in the

bio-oil obtained from rice straw pyrolysis.

4. Conclusions

This experiment studied the influence of feed rate and temperature on the

products of microwave-assisted pyrolysis of rice straw and C. oleifera shell.

Accelerating the feed rate helped raise the contents of aldehydes, ketones, and

alcohols in the bio-oil produced by the pyrolysis of rice straw. The contents of

phenolic substances, alcohols, and aldehydes increased, whereas the organic acid

content decreased, for the C. oleifera shell. Furthermore, the contents of phenols,

ketones, aldehydes, and alcohols were highest at 500 °C in the bio-oil produced by C.

oleifera shell, and the pyrolysis of it produced more gas and better bio-oil.

Acknowledgements

We gratefully acknowledge the financial support from the National Natural

Science Foundation of China (No. 21766019), the Key Research and Development

Program of Jiangxi Province (20171BBF60023), the International Cooperation

Project of MOST P. R. China (2015DFA60170-4), the Science and Technology

Research Project of Jiangxi Province Education Department (No. GJJ150213), the

China Scholarship Council (201806820035), and the Guangdong Provincial Key

Laboratory of New and Renewable Energy Research and Development (No.

Y707sb1001).
 References

1. Balagurumurthy, B., Srivastava, V., Vinit, Kumar, J., Biswas, B., Singh, R., Gupta,

P., Kumar, K.L.N.S., Singh, R., Bhaskar, T. 2015. Value addition to rice straw

through pyrolysis in hydrogen and nitrogen environments. Bioresource

Technology, 188, 273-279.

2. Biswas, B., Pandey, N., Bisht, Y., Singh, R., Kumar, J., Bhaskar, T. 2017a.

Pyrolysis of agricultural biomass residues: Comparative study of corn cob,

wheat straw, rice straw and rice husk. Bioresource Technology, 237, 57-63.

3. Biswas, B., Singh, R., Kumar, J., Singh, R., Gupta, P., Krishna, B.B., Bhaskar, T.

2017b. Pyrolysis behavior of rice straw under carbon dioxide for production of

bio-oil. Renewable Energy.

4. Capunitan, J.A., Capareda, S.C. 2012. Assessing the potential for biofuel

production of corn stover pyrolysis using a pressurized batch reactor. Fuel, 95,

563-572.

5. Clarke, K.M., Clarkson, C.R., Sanei, H. 2017. The Evolution of Petrophysical

Properties During Pyrolysis: Examples from the Montney Formation and

Duvernay Formation, Alberta, Canada.

6. Collard, F.-X., Blin, J. 2014. A review on pyrolysis of biomass constituents:

Mechanisms and composition of the products obtained from the conversion of

cellulose, hemicelluloses and lignin. Renewable and Sustainable Energy

Reviews, 38, 594-608.

7. Dai, L., He, C., Wang, Y., Liu, Y., Yu, Z., Zhou, Y., Fan, L., Duan, D., Ruan, R.

2017. Comparative study on microwave and conventional hydrothermal

pretreatment of bamboo sawdust: Hydrochar properties and its pyrolysis

behaviors. Energy Conversion and Management, 146, 1-7.

8. Du, J., Liu, P., Liu, Z.-h., Sun, D.-g., Tao, C.-y. 2010. Fast pyrolysis of biomass for

bio-oil with ionic liquid and microwave irradiation. Journal of Fuel Chemistry

and Technology, 38(5), 554-559.

9. Farag, S., Mudraboyina, B.P., Jessop, P.G., Chaouki, J. 2016. Impact of the heating

mechanism on the yield and composition of bio-oil from pyrolysis of kraft

lignin. Biomass and Bioenergy, 95, 344-353.

10. Hong, J., Ren, L., Hong, J., Xu, C. 2016. Environmental impact assessment of

corn straw utilization in China. Journal of Cleaner Production, 112,

1700-1708.

11. Hu, J., Chang, S., Peng, K., Hu, K., Thévenon, M.-F. 2015. Bio-susceptibility of

shells of Camellia oleifera Abel. fruits to fungi and termites. International

Biodeterioration & Biodegradation, 104, 219-223.

12. Huang, Y.-F., Chiueh, P.-T., Kuan, W.-H., Lo, S.-L. 2013. Microwave pyrolysis of

rice straw: Products, mechanism, and kinetics. Bioresource Technology, 142,

620-624.

13. Inguanzo, M., Domınguez, A., Menéndez, J.A., Blanco, C.G., Pis, J.J. 2002. On

the pyrolysis of sewage sludge: the influence of pyrolysis conditions on solid,

liquid and gas fractions. Journal of Analytical and Applied Pyrolysis, 63(1),
 209-222.

14. Jones, J.C. 2014. A Review of Generation Technologies with a Technical Due

Dilligence of Advanced Conversion Pyrolysis for Generating Electricity at a

Refinery Site in the UK. (Doctoral dissertation, Cardiff University).

15. Jung, S.-H., Kang, B.-S., Kim, J.-S. 2008. Production of bio-oil from rice straw

and bamboo sawdust under various reaction conditions in a fast pyrolysis plant

equipped with a fluidized bed and a char separation system. Journal of

Analytical and Applied Pyrolysis, 82(2), 240-247.

16. Kan, T., Strezov, V., Evans, T.J. 2016. Lignocellulosic biomass pyrolysis: A

review of product properties and effects of pyrolysis parameters. Renewable

and Sustainable Energy Reviews, 57, 1126-1140.

17. Leng, L., Huang, H., Li, H., Li, J., Zhou, W. 2019. Biochar stability assessment

methods: A review. Science of The Total Environment, 647, 210-222.

18. Li, J., Dai, J., Liu, G., Zhang, H., Gao, Z., Fu, J., He, Y., Huang, Y. 2016. Biochar

from microwave pyrolysis of biomass: A review. Biomass and Bioenergy, 94,

228-244.

19. Ma, S., Zhang, L., Zhu, L., Zhu, X. 2018. Preparation of multipurpose bio-oil

from rice husk by pyrolysis and fractional condensation. Journal of Analytical

and Applied Pyrolysis, 131, 113-119.

20. Miura, M., Kaga, H., Sakurai, A., Kakuchi, T., Takahashi, K. 2004. Rapid

pyrolysis of wood block by microwave heating. Journal of Analytical and

Applied Pyrolysis, 71(1), 187-199.

21. Nam, H., Capareda, S.C., Ashwath, N., Kongkasawan, J. 2015. Experimental

investigation of pyrolysis of rice straw using bench-scale auger, batch and

fluidized bed reactors. Energy, 93, 2384-2394.

22. Park, J., Lee, Y., Ryu, C., Park, Y.-K. 2014. Slow pyrolysis of rice straw: Analysis

of products properties, carbon and energy yields. Bioresource Technology, 155,

63-70.

23. Phan, B.M.Q., Duong, L.T., Nguyen, V.D., Tran, T.B., Nguyen, M.H.H., Nguyen,

L.H., Nguyen, D.A., Luu, L.C. 2014. Evaluation of the production potential of

bio-oil from Vietnamese biomass resources by fast pyrolysis. Biomass and

Bioenergy, 62, 74-81.

24. Putun, A. 2004. Rice straw as a bio-oil source via pyrolysis and steam pyrolysis.

Energy, 29(12-15), 2171-2180.

25. Ravikumar, C., Senthil Kumar, P., Subhashni, S.K., Tejaswini, P.V., Varshini, V.

2017. Microwave assisted fast pyrolysis of corn cob, corn stover, saw dust and

rice straw: Experimental investigation on bio-oil yield and high heating values.

Sustainable Materials and Technologies, 11, 19-27.

26. Shen, J., Wang, X.-S., Garcia-Perez, M., Mourant, D., Rhodes, M.J., Li, C.-Z.

2009. Effects of particle size on the fast pyrolysis of oil mallee woody biomass.

Fuel, 88(10), 1810-1817.

27. Thostenson, E.T., Chou, T.W. 1999. Microwave processing: fundamentals and

applications. Composites Part A: Applied Science and Manufacturing, 30(9),

1055-1071.
28. Torigoe, K., Hasegawa, S., Numata, O., Yazaki, S., Matsunaga, M., Boku, N., Ino,

H. 2000. Influence of emission from rice straw burning on bronchial asthma in

children. Pediatrics International, 42(2), 143-150.

29. Ukaew, S., Schoenborn, J., Klemetsrud, B., Shonnard, D.R. 2018. Effects of

torrefaction temperature and acid pretreatment on the yield and quality of fast

pyrolysis bio - oil from rice straw. Journal of Analytical and Applied Pyrolysis,

129, 112-122.

30. Wang, Y., Jiang, L., Dai, L., Yu, Z., Liu, Y., Ruan, R., Fu, G., Zhou, Y., Fan, L.,

Duan, D., Zhao, Y. 2018a. Microwave-assisted catalytic co-pyrolysis of

soybean straw and soapstock for bio-oil production using SiC ceramic foam

catalyst. Journal of Analytical and Applied Pyrolysis, 133, 76-81.

31. Wang, Y., Wu, Q., Duan, D., Ruan, R., Liu, Y., Dai, L., Zhou, Y., Zhao, Y., Zhang,

S., Zeng, Z., Jiang, L., Yu, Z. 2018b. Ex-situ catalytic upgrading of vapors

from fast microwave-assisted co-pyrolysis of Chromolaena odorata and

soybean soapstock. Bioresource Technology, 261, 306-312.

32. Wang, Y., Wu, Q., Duan, D., Zhang, Y., Ruan, R., Liu, Y., Fu, G., Zhang, S., Zhao,

Y., Dai, L., Fan, L. 2018c. Co-pyrolysis of microwave-assisted acid pretreated

bamboo sawdust and soapstock. Bioresource Technology, 265, 33-38.

33. Wang, Y., Dai, L., Wang, R., Fan, L., Liu, Y., Xie, Q., Ruan, R. 2016.

Hydrocarbon fuel production from soapstock through fast microwave-assisted

pyrolysis using microwave absorbent. Journal of Analytical and Applied

Pyrolysis, 119, 251-258.

34. Wu, C., Budarin, V.L., Gronnow, M.J., De Bruyn, M., Onwudili, J.A., Clark, J.H.,

Williams, P.T. 2014. Conventional and microwave-assisted pyrolysis of

biomass under different heating rates. Journal of Analytical and Applied

Pyrolysis, 107, 276-283.

35. Wu, S.-R., Chang, C.-C., Chang, Y.-H., Wan, H.-P. 2016. Comparison of oil-tea

shell and Douglas-fir sawdust for the production of bio-oils and chars in a

fluidized-bed fast pyrolysis system. Fuel, 175, 57-63.

36. Xiao, R., Chen, X., Wang, F., Yu, G. 2010. Pyrolysis pretreatment of biomass for

entrained-flow gasification. Applied Energy, 87(1), 149-155.

37. Xie, Y., Ge, S., Jiang, S., Liu, Z., Chen, L., Wang, L., Chen, J., Qin, L., Peng, W.

2018. Study on biomolecules in extractives of Camellia oleifera fruit shell by

GC–MS. Saudi Journal of Biological Sciences, 25(2), 234-236.

38. Xin-hui, D., Srinivasakannan, C., Jin-hui, P., Li-bo, Z., Zheng-yong, Z. 2011.

Comparison of activated carbon prepared from Jatropha hull by conventional

heating and microwave heating. Biomass and Bioenergy, 35(9), 3920-3926.

39. Xiong, Z., Wang, Y., Syed-Hassan, S.S.A., Hu, X., Han, H., Su, S., Xu, K., Jiang,

L., Guo, J., Berthold, E.E.S., Hu, S., Xiang, J. 2018. Effects of heating rate on

the evolution of bio-oil during its pyrolysis. Energy Conversion and

Management, 163, 420-427.

40. Yin, C. 2012. Microwave-assisted pyrolysis of biomass for liquid biofuels

production. Bioresource Technology, 120, 273-284.

41. Yin, H., Zhao, W., Li, T., Cheng, X., Liu, Q. 2018. Balancing straw returning and
 chemical fertilizers in China: Role of straw nutrient resources. Renewable and

Sustainable Energy Reviews, 81, 2695-2702.

42. Zeng, X., Ma, Y., Ma, L. 2007. Utilization of straw in biomass energy in China.

Renewable and Sustainable Energy Reviews, 11(5), 976-987.

43. Zhang, H., Ye, X., Cheng, T., Chen, J., Yang, X., Wang, L., Zhang, R. 2008. A

laboratory study of agricultural crop residue combustion in China: Emission

factors and emission inventory. Atmospheric Environment, 42(36), 8432-8441.

44. Zhang, L., He, Y., Zhu, Y., Liu, Y., Wang, X. 2018. Camellia oleifera shell as an

alternative feedstock for furfural production using a high surface acidity solid

acid catalyst. Bioresource Technology, 249, 536-541.

45. Zhang, Y., Chen, Q., Luo, X., Dai, T., Lu, B., Shen, J. 2011. Mutagenicity and

Safety Evaluation of the Water Extract of Camellia oleifera Abel. Journal of

Food Science, 76(3), T84-T89.

46. Zhou, Y., Wang, Y., Fan, L., Dai, L., Duan, D., Liu, Y., Ruan, R., Zhao, Y., Yu, Z.,

Hu, Y. 2017. Fast microwave-assisted catalytic co-pyrolysis of straw stalk and

soapstock for bio-oil production. Journal of Analytical and Applied Pyrolysis,

124, 35-41.

Figure captions

Fig. 1. A new continuous fast microwave pyrolysis (cfMAP) system (1)control system;

(2)screw feeder; (3)agitator; (4)insulation layer; (5)microwave magnetron;

(6)microwave reaction chamber; (7)thermocouple; (8)spherical silicon carbide;

(9)mesh; (10)char collector; (11)ash barrier; (12)gas outlet; (13)condenser; (14)liquid

collector; (15)vacuum pump; (16)gas collector.

Fig. 2. The composition of bio-oil produced from microwave-assisted pyrolysis of

rice straw at different temperatures.

Fig. 3. The composition of bio-oil produced from microwave-assisted pyrolysis of C.

oleifera shell at different temperatures.

Fig. 4. The composition of bio-oil produced from microwave-assisted pyrolysis of

rice straw at different feed rates.

Fig. 5. The composition of bio-oil produced from microwave-assisted pyrolysis of C.

oleifera shell at different feed rates.

Fig. 1. A new continuous fast microwave pyrolysis (cfMAP) system (1)control system;

(2)screw feeder; (3)agitator; (4)insulation layer; (5)microwave magnetron;

(6)microwave reaction chamber; (7)thermocouple; (8)spherical silicon carbide;

(9)mesh; (10)char collector; (11)ash barrier; (12)gas outlet; (13)condenser; (14)liquid

collector; (15)vacuum pump; (16)gas collector.

Fig. 2. The composition of bio-oil produced from microwave-assisted pyrolysis of

rice straw at different temperatures.

Fig. 3. The composition of bio-oil produced from microwave-assisted pyrolysis of C.

oleifera shell at different temperatures.

Fig. 4. The composition of bio-oil produced from microwave-assisted pyrolysis of

rice straw at different feed rates.

Fig. 5. The composition of bio-oil produced from microwave-assisted pyrolysis of C.

oleifera shell at different feed rates.

Table 1

Rice straw and C. oleifera shell characteristics.

Biomass characteristics Rice straw C. oleifera shell

Proximate analysis (wt%), db

Volatile combustible matter 77.93 75.46

Ash 11.23 1.46

Ultimate analysis (wt%), db

 C 40.09 45.24

H 5.34 5.53

N 1.07 0.21

O 42.27 45.50

Chemical composition (wt%), db

Cellulose 36.72 23.40

Hemicellulose 26.81 30.72

Lignin 14.53 36.37

db: dry basis.
Table 2

Product yields of pyrolysis of rice straw and C. oleifera shell at different

temperatures.

Temperature, Feed rate, Bio-oil, Gas, Bio-char, Conversion,

°C g/min wt% wt% wt% %
RS-400 24 18.96 43.63 37.41 62.59
RS-400 45 20.25 41.08 38.67 61.33
RS-400 66 21.46 39.39 39.15 60.85

RS-500 24 31.86 35.70 32.44 67.56

RS-500 45 27.03 38.14 34.83 65.17
RS-500 66 18.91 39.13 41.96 58.04

RS-600 24 16.24 52.49 31.27 68.73

RS-600 45 25.72 41.14 33.14 66.86
RS-600 66 16.28 49.20 34.52 65.48

COS-400 100 24.56 43.30 32.14 67.86

COS-400 200 27.45 38.95 33.60 66.4
COS-400 400 20.96 43.57 35.47 64.53

COS-500 100 26.52 44.00 29.48 70.52

COS-500 200 24.11 44.07 31.82 68.18
COS-500 400 17.28 47.61 35.11 64.89

COS-600 100 14.56 60.59 24.85 75.15

COS-600 200 17.08 54.29 28.63 71.37
COS-600 400 23.28 43.46 33.26 66.74
Table 3

Compounds identified by GC-MS: Bio-oil from rice straw and C. oleifera shell

produced by microwave-assisted pyrolysis system.

Compounds identified in bio-oil Relative content %

produced from rice straw and camellia
oleifera shells at 600 °C Rice straw C. oleifera shell
Phenol 8.29 7.46
Catechol 4.49 6.34
p-Cresol 5.44 4.92
Furfural 3.71 5.63
Acetic acid 4.42 2.54
Phenol, 2-methoxy- 3.32 2.39
Phenol, 2-methyl- 3.15 2.45
Phenol, 4-ethyl- 3.82 1.39
2-Cyclopenten-1-one,
2.95 1.60
2-hydroxy-3-methyl-
1,2-Benzenediol, 3-methyl- 1.71 1.91
2-Propanone, 1-hydroxy- 2.15 1.06
2-Cyclopenten-1-one, 3-methyl- 1.63 1.18
Phenol, 2,6-dimethoxy- 1.22 1.58
Hydroquinone 1.95 0.64
2(5H)-Furanone 1.52 1.06
1-Hydroxy-2-butanone 1.29 0.74
2-Cyclopenten-1-one, 2-methyl- 1.33 0.61
Butanoic acid 1.00 0.82
Pyridine 1.09 0.40
Vanillin 0.23 1.21
2-Propanone, 1-(acetyloxy)- 0.51 0.60
Ethanone, 1-(2-furanyl)- 0.77 0.27
2-Methoxy-5-methylphenol 0.17 0.74
Stigmasta-3,5-diene - 0.90
Phenol, 2,4-dimethyl- 0.23 0.57
3,4,5-Trimethylpyrazole - 0.79
1,2-Benzenediol, 3-methoxy- 0.04 0.70
2-Isopropoxyphenol 0.03 0.69
Phenol, 4-(ethoxymethyl)-2-methoxy- - 0.61
2-Cyclopenten-1-one, 2,3-dimethyl- 0.31 0.31
Highlights:

 A newly developed continuous fast microwave-assisted pyrolysis system was

used.

 It is the first time to pyrolysis Camellia oleifera shell with microwave.

 The effects of temperature and feed rate on pyrolysis were studied.